WO2024043327A1 - 重合体、樹脂組成物、成形体および重合体の製造方法 - Google Patents
重合体、樹脂組成物、成形体および重合体の製造方法 Download PDFInfo
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- WO2024043327A1 WO2024043327A1 PCT/JP2023/030668 JP2023030668W WO2024043327A1 WO 2024043327 A1 WO2024043327 A1 WO 2024043327A1 JP 2023030668 W JP2023030668 W JP 2023030668W WO 2024043327 A1 WO2024043327 A1 WO 2024043327A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
Definitions
- the present invention relates to a polymer having excellent water and oil repellency, a composition and a molded article containing the polymer, and a method for producing the polymer.
- Patent Document 1 describes a silicone-based thermosetting composition containing a silicone compound, a compound having a chemically blocked carboxyl group, and a compound having an epoxy group, and exhibiting water repellency and oil repellency.
- Patent Document 2 discloses that the polymer contains a structural unit derived from ethylene, a structural unit derived from an acrylate monomer having a fluoroalkyl group, and a structural unit derived from an acrylate monomer, and exhibits water repellency and oil repellency. Consolidation is described.
- Patent Document 3 describes a heat-resistant polysiloxane-containing polymer obtained by copolymerizing a polysiloxane having an unsaturated carbon bond, ethylene, and an ⁇ -olefin having 3 to 20 carbon atoms.
- the present invention provides a polymer that exhibits water repellency and oil repellency, and also has an excellent slime adhesion suppressing function and shape transferability during molding, a resin composition and a molded article containing the polymer, and a polymer comprising the polymer.
- the purpose is to provide a manufacturing method for.
- the present invention provides the following [1] to [26].
- R represents a hydrogen atom or a methyl group
- L 1 represents -CO-O-, -O-CO- or -O-
- L2 is a single bond, -CH2-, -CH2-CH2-, -CH2-CH2-CH2- , -CH2 - CH ( OH ) -CH2- or -CH2- CH( CH 2 OH)-
- L3 is a single bond, -CO-O-, -O-CO-, -O-, -CO-NH-, -NH-CO-, -CO-NH-CO-, -NH-CO-NH-, -NH- or -N(CH 3 )-
- L6 represents -( CH2 ) n- ( Rf2O ) p- ( Rf3 ) h- (Si( Rf4 ) 2O ) g -Si( Rf1 ) 3
- R f1 represents a hydrogen atom or a C 1-15 alkyl
- n represents an integer from 0 to 10
- p represents an integer from 0 to 15, and when p is an integer of 2 or more, the plurality of -(R f2 O)- may be the same or different
- h represents an integer from 0 to 15, and when h is an integer of 2 or more, the plurality of -(R f3 )- may be the same or different
- g represents an integer from 1 to 1000
- the plurality of -(Si(R f4 ) 2 O)- may be the same or different
- R represents a hydrogen atom or a methyl group
- L 1 represents -CO-O-, -O-CO- or -O-
- L 4 represents a single bond or an alkylene group having 1 or more and 8 or less carbon atoms
- L 5 represents a hydrogen atom, an epoxy group, -CH(OH)-CH 2 OH, a carboxy group, a hydroxy group, an amino group, or an alkylamino group having 1 or more and 4 or less carbon atoms.
- the left side corresponds to the upper side of the formula (2)
- the right side corresponds to the lower side of the formula (2).
- the number of the structural units (A) is 70 to 99 mol%, where the total number of the structural units (A), the structural units (B), and the structural units (C) is 100 mol%, and the structural units The polymer according to [1], wherein the total number of (B) and the structural unit (C) is 30 to 1 mol%.
- the number of the structural units (B) is 1 mol% or more and 99 mol% or less, and the number of the structural units (C) is 100 mol%. is 1 mol% or more and 99 mol% or less
- the total amount of the structural unit (A), the structural unit (B), and the structural unit (C) is 100 mol% or more.
- [8] The polymer according to any one of [1] to [7], which is crosslinked.
- the total number of the structural unit (A), the structural unit (B), and the structural unit (C) is 90 mol% or more, assuming that the total number of all structural units contained in the polymer is 100 mol%.
- [11] A composition containing the polymer according to any one of [1] to [10].
- [12] The composition according to [11], containing 1% by weight or more of the polymer.
- R represents a hydrogen atom or a methyl group
- L 1 represents -CO-O-, -O-CO- or -O-
- L 4 represents a single bond or an alkylene group having 1 or more and 8 or less carbon atoms
- L 5 represents a hydrogen atom, an epoxy group, -CH(OH)-CH 2 OH, a carboxy group, a hydroxy group, an amino group, or an alkylamino group having 1 or more and 4 or less carbon atoms.
- the left side corresponds to the upper side of the formula (2)
- the right side corresponds to the lower side of the formula (2).
- a polymer exhibiting water repellency and oil repellency and further having excellent slime adhesion suppressing function and shape transferability during molding, a resin composition and a molded article containing the polymer, and the polymer A manufacturing method can be provided.
- R R L +k * (R U ⁇ R L ), where k is a variable ranging from 1 percent to 100 percent in 1 percent increments, i.e., k is 1 percent, 2 percent, 3 percent. , 4 percent, 5 percent, ..., 50 percent, 51 percent, 52 percent, ..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent). Additionally, any numerical range defined by two R numbers as described above is also specifically disclosed.
- lower limit to upper limit representing a numerical range represents “more than or equal to the lower limit and less than or equal to the upper limit”
- upper limit to lower limit represents “below the upper limit and more than the lower limit”. That is, these descriptions represent numerical ranges that include the lower limit and the upper limit.
- the polymer according to the present invention is A structural unit (A) derived from at least one selected from the group consisting of ethylene and propylene, a structural unit (B) represented by the above formula (1), a structural unit represented by the above formula (2), and the above formula ( It is a polymer (hereinafter sometimes referred to as "polymer (1)") containing at least one structural unit (C) selected from the group consisting of the structural units shown in 3).
- the polymer (1) according to the present invention has a structural unit (A) derived from at least one selected from the group consisting of ethylene and propylene.
- the structural unit (A) is a structural unit obtained by polymerizing ethylene, a structural unit obtained by polymerizing propylene, or a structural unit obtained by polymerizing ethylene and propylene, and the structural unit (A) may form a branched structure in the polymer. From the viewpoint of moldability, it is preferably derived from ethylene.
- R is preferably a hydrogen atom.
- L 1 is preferably -CO-O- or -O-CO-, more preferably -CO-O- from the viewpoint of moisture permeability.
- L 2 is preferably a single bond, -CH 2 -, -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 -, and more preferably a single bond.
- L 3 is preferably a single bond, -O-CO-, -O-, -NH-, or -N(CH 3 )-, and more preferably a single bond.
- R f1 constituting L 6 represents a hydrogen atom or a C 1-15 alkyl group, and the three R f1 may be the same or different.
- Examples of the C 1-15 alkyl group include methyl group, ethyl group, propyl group, butyl group, and the like.
- R f2 constituting L 6 represents a C 1-15 alkylene group, such as an ethylene group, a propylene group, a butenylene group, and the like.
- R f3 constituting L 16 represents a C 1-15 alkylene group, such as an ethylene group, a propylene group, a butenylene group, and the like.
- R f4 constituting L 16 represents a hydrogen atom, a substituted or unsubstituted C 1-15 alkyl group, or a substituted or unsubstituted C 6-20 aryl group, and two R f4s may be the same or May be different.
- C 1-15 alkyl groups include alkyl groups such as methyl, ethyl, propyl, and butyl groups, and aryl groups such as phenyl, tolyl, and xylyl groups; Part or all of it may be substituted with a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, or the like. Since mold release properties during molding are improved, unsubstituted alkyl groups having 1 to 3 carbon atoms are preferred, and methyl groups are more preferred.
- n constituting L 6 represents an integer of 0 to 10, preferably an integer of 0 to 6, more preferably 0 to 4, and still more preferably 0 to 2.
- p constituting L 6 represents an integer of 0 to 15, preferably an integer of 0 to 10, more preferably an integer of 0 to 5, and still more preferably an integer of 1 or 2. Further, when p is an integer of 2 or more, the plurality of --(R f2 O)- may be the same or different.
- h constituting L 6 represents an integer of 0 to 15, preferably an integer of 0 to 10, more preferably an integer of 0 to 5, and even more preferably an integer of 0 to 3. Further, when h is an integer of 2 or more, the plurality of --(R f3 )- may be the same or different.
- g constituting L 6 represents an integer of 1 to 1000, preferably an integer of 1 to 250, more preferably an integer of 1 to 100, still more preferably an integer of 1 to 50. Further, when g is an integer of 2 or more, the plurality of -(Si(R f4 ) 2 O)- may be the same or different.
- Examples of the structural unit (B) represented by formula (1) include the following structural units.
- the structural unit (B) represented by formula (1) is preferably a structural unit represented by any of the following.
- the structural unit (B) represented by formula (1) is more preferably a structural unit represented by any of the following.
- the structural unit (B) represented by formula (1) is more preferably the structural unit shown below.
- the structural unit B is, for example, 2-(3- ⁇ -butyl-polydimethylsiloxanyl-propoxy)ethyl acrylate, 2-(3- ⁇ -propyl-polydimethylsiloxanyl-propoxy)ethyl acrylate, 2-(3- ⁇ -ethyl-polydimethylsiloxanyl-propoxy)ethyl acrylate, 2-(3- ⁇ -methyl-polydimethylsiloxanyl-propoxy)ethyl acrylate, 3- ⁇ -butyl-polydimethylsiloxanyl-propoxymethyl acrylate, 3- ⁇ -propyl-polydimethylsiloxanyl-propoxymethyl acrylate, 3- ⁇ -ethyl-polydimethylsiloxanyl-propoxymethyl acrylate, 3- ⁇ -methyl-polydimethylsiloxanyl-propoxymethyl acrylate, 3- ⁇ -butyl-polydimethylsiloxanyl-prop
- the polymer (1) according to the present invention may contain two or more types of structural units (B), for example, derived from 2-(3- ⁇ -butyl-polydimethylsiloxanyl-propoxy)ethyl acrylate. and a structural unit derived from 2-(3- ⁇ -methyl-polydimethylsiloxanyl-propoxy)ethyl acrylate.
- structural units (B) for example, derived from 2-(3- ⁇ -butyl-polydimethylsiloxanyl-propoxy)ethyl acrylate.
- the polymer (1) according to the present invention contains at least one structural unit (C) selected from the group consisting of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (3).
- R is preferably a hydrogen atom.
- L 1 is preferably -CO-O-, -O-CO- or -O-, more preferably -CO-O- or -O-CO- from the viewpoint of moisture permeability, and even more preferably , -CO-O-.
- Examples of the alkylene group having 1 to 8 carbon atoms represented by L 4 include methylene group, ethylene group, n-propylene group, 1-methylethylene group, n-butylene group, and 1,2-dimethylethylene group. , 1,1-dimethylethylene group, 2,2-dimethylethylene group, n-pentylene group, n-hexylene group, n-heptalene group, n-octylene group and 2-ethyl-n-hexylene group. .
- L 4 is preferably a single bond, a methylene group, an ethylene group or an n-propylene group, and more preferably a methylene group.
- Examples of the alkylamino group having 1 to 4 carbon atoms represented by L 5 include methylamino group, ethylamino group, propylamino group, butylamino group, dimethylamino group, and diethylamino group.
- L 5 is preferably a hydrogen atom, an epoxy group or -CH(OH)-CH 2 OH, and more preferably a hydrogen atom.
- Examples of the structural unit represented by formula (2) include the following structural units.
- the structural unit represented by formula (2) is preferably a structural unit represented by any of the following.
- the structural unit represented by formula (2) is more preferably a structural unit represented by any of the following.
- the structural unit represented by formula (2) is more preferably the structural unit shown below.
- Examples of the structural unit represented by formula (2) include a structural unit derived from acrylic acid, a structural unit derived from methacrylic acid, a structural unit derived from vinyl alcohol, a structural unit derived from methyl acrylate, and a structural unit derived from ethyl acrylate.
- the structural unit represented by formula (3) is a structural unit derived from maleic anhydride.
- the polymer (1) according to the present invention may contain two or more types of structural units (C), for example, a structural unit derived from methyl acrylate, a structural unit derived from ethyl acrylate, and a structural unit derived from glycidyl methacrylate. It may also be a polymer containing structural units derived from the above.
- Constituent unit (A) and R is a hydrogen atom or a methyl group
- L 1 is -CO-O-
- L 2 and L 3 are single bonds
- L 6 is -(CH 2 ) n -(R f2 O) p -(
- a polymer containing can be mentioned.
- the total number of the structural units (A), the structural units (B), and the structural units (C) is 90 mol% or more, assuming that the total number of all structural units contained in the polymer 1 is 100 mol%. be.
- the polymer 1 may be a random polymer or a block polymer. Block polymerization and random polymerization may be mixed.
- the number of the structural units (A) in the polymer (1) according to the present invention is preferably 100 mol% of the total number of the structural units (A), the structural units (B), and the structural units (C). It is 70 mol% or more and 99 mol% or less, and the molding processability of the molded article containing the polymer (1) is improved, so it is more preferably 75 mol% or more and 99 mol% or less, and even more preferably 80 mol% or more and 99 mol% or less. It is.
- the total number of the structural unit (B) and the structural unit (C) in the polymer (1) according to the present invention is the total number of the structural unit (A), the structural unit (B), and the structural unit (C).
- the number is 100 mol%, it is preferably 1 mol% or more and 30 mol% or less, and more preferably 1 mol% because the water repellency, oil repellency, and slime adhesion suppressing function of the molded article containing the polymer (1) are better. It is 25 mol% or less, more preferably 1 mol% or more and 20 mol% or less.
- the number of the structural units (B) in the polymer (1) according to the present invention is preferably 1 mol% or more and 99 mol% or less, with the total number of the structural units (B) and the structural units (C) being 100 mol%. It is more preferably 10 mol% or more and 99 mol% or less, and even more preferably 20 mol% or more and 99 mol%, since the water repellency, oil repellency, and slime adhesion suppressing function of the molded article containing the polymer (1) are better. % or less, and even more preferably 20 mol% or more and 90 mol% or less.
- the number of the structural units (C) in the polymer (1) according to the present invention is preferably 1 mol% or more and 99 mol% or less, with the total number of the structural units (B) and the structural units (C) being 100 mol%.
- the content is more preferably 1 mol% or more and 90 mol% or less, still more preferably 1 mol% or more and 80 mol% or less, and even more preferably It is 10 mol% or more and 80 mol% or less.
- the number of structural units (A), the number of structural units (B), and the number of structural units (C) contained in the polymer (1) according to the present invention are, for example, 13 C nuclear magnetic resonance spectrum (hereinafter referred to as 13 C-NMR spectrum) or 1 H nuclear magnetic resonance spectrum (hereinafter referred to as 1 H-NMR spectrum), it can be determined from the integral value of the signal attributed to each constitutional unit.
- the polymer (1) according to the present invention has a structural unit (A) derived from at least one selected from the group consisting of ethylene and propylene, a structural unit represented by the above formula (2), and a structural unit represented by the above formula (3).
- precursor polymer (1) a polymer containing at least one structural unit (C) selected from the group consisting of structural units
- precursor polymer (1) a polymer containing at least one structural unit (C) selected from the group consisting of structural units
- precursor polymer (1) a polymer containing at least one structural unit (C) selected from the group consisting of structural units
- precursor polymer (1) a polymer containing at least one structural unit (C) selected from the group consisting of structural units
- ⁇ a polymer manufactured by a manufacturing method that includes,
- the precursor polymer (1) is an ethylene-methyl acrylate copolymer
- the following integral values (A 1 , B 1 , C 1 , D 1 , and E 1 ), and from the content (number) of three types of dyads (EE, EA, AA) determined from the following formula the structural unit A 1 derived from ethylene and methyl acrylate Calculate the number of structural units C1 derived from.
- EE means ethylene-ethylene dyad
- EA means ethylene-methyl acrylate dyad
- AA means methyl acrylate-methyl acrylate dyad.
- Number of constituent unit A 1 100 - number of constituent unit C 1
- Number of constituent unit C 1 100 x (EA/2+AA)/(EE+EA+AA)
- Conversion rate X 1 of structural unit C 1 derived from methyl acrylate to structural unit B 2 represented by formula (1) (unit: %) For the 1 H-NMR spectrum of polymer 1 obtained by reacting the ethylene-methyl acrylate copolymer and compound ⁇ , calculate the integral values (F 1 and G 1 ) in the range of f 1 and g 1 below. . Next, from the following formula, the conversion rate X 1 of the structural unit C 1 derived from methyl acrylate contained in the ethylene-methyl acrylate copolymer converted into the structural unit B 2 shown by the formula (1) of polymer 1 Calculate.
- Number of structural units A2 contained in polymer 1 Number of structural units A1 contained in the ethylene-methyl acrylate copolymer
- Number of structural units B2 contained in polymer 1 (number of structural units D1 contained in ethylene-methyl acrylate copolymer) x conversion rate X 1 /100
- Number of structural units C2 contained in polymer 1 (number of structural units C1 contained in the ethylene-methyl acrylate copolymer) - (number of structural units B2 contained in polymer 1)
- the number of structural units A2 , the number of structural units B2 , and the number of structural units C2 obtained in this manner are respectively the structural unit A derived from ethylene contained in the polymer 1, and the number of structural units A derived from the above formula (1). It corresponds to the number (unit: %) of the structural unit B shown by and the structural unit C shown by the above formula (2) and the above formula (3).
- the content (weight %) of the structural unit A, the structural unit B, and the structural unit C contained in the polymer 1 according to the present invention can be calculated from the following formulas.
- Weight% of structural unit A (number of structural units A x molecular weight of structural unit A) / (number of structural units A x molecular weight of structural unit A + number of structural units B x molecular weight of structural unit B + molecular weight of structural unit C) number x molecular weight of structural unit C)
- Weight% of structural unit B (number of structural units B x molecular weight of structural unit B) / (number of structural units A x molecular weight of structural unit A + number of structural units B x molecular weight of structural unit B + molecular weight of structural unit C) number x molecular weight of structural unit C)
- Weight% of structural unit C (number of structural units C x molecular weight of structural unit C) / (number of structural units A x molecular weight of structural unit A + number of structural units B x molecular weight of structural unit B + molecular weight of structural unit C) number x molecular weight of structural unit C)
- the total amount of the structural unit (A) and the structural unit (C) contained in the polymer (1) according to the present invention is the structural unit (A), the structural unit (B), and the structural unit (C). If the total amount is 100% by weight, the molding processability of the molded article containing the polymer (1) will be good, so it is preferably 10% by weight or more, more preferably 20% by weight or more, and even more preferably is 30% by weight or more.
- the content of the structural unit (B) contained in the polymer (1) according to the present invention is 100% by weight of the total amount of the structural unit (A), the structural unit (B), and the structural unit (C).
- the amount is preferably 30% by weight or more, more preferably 50% by weight or more, since the water repellency, oil repellency, and slime adhesion suppressing function of the molded article containing the polymer (1) will be better.
- the method for producing the polymer (1) of the present invention includes, for example, The above precursor polymer (1), A compound represented by the above formula (11), a compound represented by the above formula (12), a compound represented by the above formula (13), a compound represented by the above formula (14), a compound represented by the above formula (15), A step of reacting with one or more compounds ( ⁇ ) selected from the group consisting of the compound represented by the above formula (16), the compound represented by the above formula (17), and the compound represented by the above formula (18). , a method for producing a polymer; and a method for copolymerizing ethylene, a monomer serving as a raw material for the structural unit (B), and a monomer serving as a raw material for the structural unit (C).
- the precursor polymer (1) is a raw material for producing the polymer (1) according to the present invention, and does not contain the structural unit (B) represented by formula (1).
- the precursor polymer (1) may include a structural unit different from the structural unit (A), the structural unit (B), and the structural unit (C).
- the copolymerization (1) may be random copolymerization or block copolymerization, or may be a mixture of block polymerization and random polymerization.
- the number of the structural units (A) contained in the precursor polymer (1) is preferably 70 mol% or more and 99 mol% or less, assuming the total number of the structural units (A) and the structural units (C) to be 100 mol%. , more preferably 75 mol% or more and 99 mol% or less, and even more preferably 80 mol% or more and 99 mol% or less, since the molded article containing the polymer (1) according to the present invention produced has good molding processability. .
- the number of the structural units (C) contained in the precursor polymer (1) is preferably 1 mol% or more and 30 mol% or less, with the total number of the structural units (A) and the structural units (C) being 100 mol%.
- the water repellency, oil repellency, and slime adhesion suppressing function of the produced molded article containing the polymer (1) according to the present invention will be better, so it is more preferably 5 mol % or more and 30 mol % or less, and even more preferably It is 10 mol% or more and 30 mol% or less.
- the structural unit (B) contained in the polymer (1) As a method for forming the structural unit (B) contained in the polymer (1) according to the present invention, for example, the structural unit (C) contained in the precursor polymer (1) is reacted with the compound ( ⁇ ). and a method of polymerizing a monomer serving as a raw material for the structural unit (B).
- the method for reacting the structural unit (C) contained in the precursor polymer (1) with the compound ( ⁇ ) is as follows: When the structural unit (C) contained in the precursor polymer (1) has an ester group as a functional group, a method of reacting it with a compound represented by the formula (11), the formula (12), or the formula (14).
- the structural unit (C) contained in the precursor polymer (1) has a carboxy group as a functional group
- the above formula (11), the above formula (12), the above formula (13), the above formula (15), the above Examples include a method of reacting with a compound represented by formula (16), the above formula (17) or the above formula (18)
- the structural unit (C) contained in the precursor polymer (1) has a hydroxyl group as a functional group, it is represented by the formula (13), the formula (14), the formula (16), or the formula (18).
- Examples include a method of reacting with a compound, When the structural unit (C) contained in the precursor polymer (1) has an amino group as a functional group, the above formula (13), the above formula (14), the above formula (15), the above formula (16), the above Examples include a method of reacting with a compound represented by formula (17) or the above formula (18), When the structural unit (C) contained in the precursor polymer (1) has an epoxy group as a functional group, the above formula (11), the above formula (12), the above formula (14), the above formula (15) or the above Examples include a method of reacting with a compound represented by formula (17).
- the method of reacting the structural unit (C) contained in the precursor polymer (1) with the compound ( ⁇ ) is preferably such that the structural unit (C) contained in the precursor polymer (1) is functional.
- the group has an ester group
- the reaction with a compound represented by the formula (11), the formula (12) or the formula (14), or the structural unit (C) contained in the precursor polymer (1). has an epoxy group as a functional group
- the method involves reacting with a compound represented by the formula (11), the formula (12), the formula (14), the formula (15), or the formula (17).
- the method of reacting the structural unit (C) contained in the precursor polymer (1) with the compound ( ⁇ ) is such that the structural unit (C) contained in the precursor polymer (1) is reacted with the structural unit (C) contained in the precursor polymer (1).
- it has an ester group as a functional group, it is a method of reacting with a compound represented by the above formula (11), the above formula (12) or the above formula (14).
- the method for reacting the structural unit (C) contained in the precursor polymer (1) with the compound ( ⁇ ) is such that the structural unit (C) contained in the precursor polymer (1) is reacted with the structural unit (C) contained in the precursor polymer (1).
- it has an ester group as a functional group, it is a method of reacting with a compound represented by the above formula (11).
- Examples of the method for polymerizing at least one monomer selected from the group consisting of ethylene and propylene and a monomer serving as a raw material for the structural unit (B) include: At least one monomer selected from the group consisting of ethylene and propylene, 2-(3- ⁇ -butyl-polydimethylsiloxanyl-propoxy)ethyl acrylate, 2-(3- ⁇ -propyl-polydimethylsiloxanyl-propoxy)ethyl acrylate, 2-(3- ⁇ -ethyl-polydimethylsiloxanyl-propoxy)ethyl acrylate, 2-(3- ⁇ -methyl-polydimethylsiloxanyl-propoxy)ethyl acrylate, 3- ⁇ -butyl-polydimethylsiloxanyl-propoxymethyl acrylate, 3- ⁇ -propyl-polydimethylsiloxanyl-propoxymethyl acrylate, 3- ⁇ -ethyl-polydi
- Examples of the precursor polymer (1) include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, Ethylene-n-propyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-n- Butyl methacrylate copolymer, ethylene-vinyl formate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl (n-butyrate) copolymer, ethylene-methyl vinyl ether copolymer Polymer, ethylene-ethyl vinyl ether copoly
- the polymer (1) according to the present invention is produced by a production method including a step of reacting a precursor polymer (1) and a compound ( ⁇ ), the desired polymer (1) is used as the compound ( ⁇ ).
- L 6 i.e., -(CH 2 ) n -(R f2 O) p -(R f3 ) h -(Si(R f4 ) 2 O) g -Si(R f1 )
- a compound ( ⁇ ) corresponding to 3 ) is used.
- examples and preferred ranges of R f1 , R f2 , R f3 , R f4 , p, g, h and n are R f1 , R f2 , R in formula (1)
- examples and preferred ranges of f3 , R f4 , p, g, h and n are the same.
- the halogen atom represented by X includes a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the compound represented by formula (11) include ⁇ -methyl- ⁇ -[3-(2-hydroxyethoxy)propyl]polydimethylsiloxane, ⁇ -ethyl- ⁇ -[3-(2-hydroxyethoxy)propyl ] polydimethylsiloxane, ⁇ -propyl- ⁇ -[3-(2-hydroxyethoxy)propyl]polydimethylsiloxane, and ⁇ -butyl- ⁇ -[3-(2-hydroxyethoxy)propyl]polydimethylsiloxane.
- Examples of the compound represented by formula (12) include ⁇ -methyl- ⁇ -[3-(2-aminoethoxy)propyl]polydimethylsiloxane, ⁇ -ethyl- ⁇ -[3-(2-aminoethoxy)propyl ] polydimethylsiloxane, ⁇ -propyl- ⁇ -[3-(2-aminoethoxy)propyl]polydimethylsiloxane, and ⁇ -butyl- ⁇ -[3-(2-aminoethoxy)propyl]polydimethylsiloxane.
- Examples of the compound represented by formula (13) include ⁇ -methyl- ⁇ -[3-(2-chloroethoxy)propyl]polydimethylsiloxane, ⁇ -ethyl- ⁇ -[3-(2-chloroethoxy)propyl ]Polydimethylsiloxane, ⁇ -propyl- ⁇ -[3-(2-chloroethoxy)propyl]polydimethylsiloxane, ⁇ -butyl- ⁇ -[3-(2-chloroethoxy)propyl]polydimethylsiloxane, ⁇ -methyl - ⁇ -[3-(2-bromoethoxy)propyl]polydimethylsiloxane, ⁇ -ethyl- ⁇ -[3-(2-bromoethoxy)propyl]polydimethylsiloxane, ⁇ -propyl- ⁇ -[3-(2 -bromoethoxy)propyl]pol
- Examples of the compound represented by formula (14) include ⁇ -methyl- ⁇ -[3-(2-carboxyethoxy)propyl]polydimethylsiloxane, ⁇ -ethyl- ⁇ -[3-(2-carboxyethoxy)propyl ] polydimethylsiloxane, ⁇ -propyl- ⁇ -[3-(2-carboxyethoxy)propyl]polydimethylsiloxane, and ⁇ -butyl- ⁇ -[3-(2-carboxyethoxy)propyl]polydimethylsiloxane.
- Examples of the compound represented by formula (15) include ⁇ -methyl- ⁇ -[3-(2-carboxamidoethoxy)propyl]polydimethylsiloxane, ⁇ -ethyl- ⁇ -[3-(2-carboxamidoethoxy)propyl ] polydimethylsiloxane, ⁇ -propyl- ⁇ -[3-(2-carboxamidoethoxy)propyl]polydimethylsiloxane, and ⁇ -butyl- ⁇ -[3-(2-carboxamidoethoxy)propyl]polydimethylsiloxane.
- Examples of the compound represented by formula (16) include 3-(3- ⁇ -methyl-polydimethylsiloxanyl-propoxy)propanoyl chloride, 3-(3- ⁇ -ethyl-polydimethylsiloxanyl-propoxy) ) propanoyl chloride, 3-(3- ⁇ -propyl-polydimethylsiloxanyl-propoxy)propanoyl chloride, 3-(3- ⁇ -butyl-polydimethylsiloxanyl-propoxy)propanoyl chloride, 3-( 3- ⁇ -Methyl-polydimethylsiloxanyl-propoxy)propanoyl bromide, 3-(3- ⁇ -ethyl-polydimethylsiloxanyl-propoxy)propanoyl bromide, 3-(3- ⁇ -propyl-polydimethyl Siloxanyl-propoxy)propanoyl bromide, 3-(3- ⁇ -butyl-polydimethyls
- Examples of the compound represented by formula (17) include 1-(2-(3- ⁇ -methyl-polydimethylsiloxanyl-propoxy)ethyl)urea, 1-(2-(3- ⁇ -ethyl-polyoxy) dimethylsiloxanyl-propoxy)ethyl)urea, 1-(2-(3- ⁇ -protyl-polydimethylsiloxanyl-propoxy)ethyl)urea, 1-(2-(3- ⁇ -butyl-polydimethylsiloxane) Sanyl-propoxy)ethyl)urea is mentioned.
- Examples of the compound represented by formula (18) include ⁇ -methyl- ⁇ -[3-(2-isocyanatoethoxy)propyl]polydimethylsiloxane, ⁇ -ethyl- ⁇ -[3-(2-isocyanatoethoxy) ) propyl]polydimethylsiloxane, ⁇ -propyl- ⁇ -[3-(2-isocyanatoethoxy)propyl]polydimethylsiloxane, ⁇ -butyl- ⁇ -[3-(2-isocyanatoethoxy)propyl]polydimethylsiloxane can be mentioned.
- the reactivity ratio of at least one monomer selected from the group consisting of ethylene and propylene used as a raw material during the production of the precursor polymer (1) was set as r1, and the reactivity ratio of the monomer forming the structural unit (C) was set as r2.
- the product r1 ⁇ r2 of the reactivity ratio is preferably 0.5 or more and 5.0 or less because the shape retention of the produced molded article containing the polymer (1) according to the present invention is good. , more preferably 0.5 or more and 3.0 or less.
- the reactivity ratio r1 of at least one monomer selected from the group consisting of ethylene and propylene is such that the reactivity ratio r1 of at least one monomer selected from the group consisting of ethylene and propylene is such that when copolymerizing ethylene with the monomer forming the structural unit (C), the polymer whose terminal end is the structural unit (A)
- This reactivity ratio r1 means that during copolymerization of at least one monomer selected from the group consisting of ethylene and propylene and the monomer forming the structural unit (C), the polymer whose terminal end is the structural unit (A), This is an index indicating which of at least one monomer selected from the group consisting of ethylene and propylene or the monomer forming the structural unit (C) reacts more easily.
- the reactivity ratio r2 of the monomers forming the structural unit (C) is such that when the monomer forming the structural unit (C) is copolymerized with at least one monomer selected from the group consisting of ethylene and propylene, the terminal is the structural unit.
- This reactivity ratio r2 is such that when copolymerizing at least one monomer selected from the group consisting of ethylene and propylene with the monomer forming the structural unit (C), the polymer whose terminal end is the structural unit (C) is ethylene. Or, it is an index showing which of the monomers forming the structural unit (C) is more likely to react. The larger r2 is, the easier it is for the polymer having the structural unit (C) at the end to react with the monomer forming the structural unit (C) to form a chain of the structural unit (C).
- the product r1r2 of the reactivity ratio is calculated by the method described in the literature "Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T. Macromolecules, 1982, 15, 1150".
- the product r1r2 of the reactivity ratio is calculated from the 13 C nuclear magnetic resonance spectrum of the precursor polymer (1) for each dyad AA, AC, of the structural unit (A) and the structural unit (C), It can be obtained by substituting the CC fraction into the following formula.
- r1r2 AA[CC/(AC/2) 2 ]
- the product r1r2 of reactivity ratios is an index representing the monomer chain distribution of the copolymer.
- the melt flow rate (MFR) of the precursor polymer (1) measured at a temperature of 190° C. and a load of 21 N according to JIS K7210 is preferably 0.1 g/10 minutes or more and 500 g/10 minutes or less, and more Preferably, it is 1 g/10 minutes or more and 100 g/10 minutes or less, and more preferably 5 g/10 minutes or more and 50 g/10 minutes or less.
- Examples of the method for producing the precursor polymer (1) include coordination polymerization, cationic polymerization, anionic polymerization, and radical polymerization, preferably radical polymerization, and more preferably under high pressure. This is a radical polymerization method.
- the temperature at which the precursor polymer (1) and the compound ( ⁇ ) are reacted is usually 40°C or higher and 250°C or lower.
- This reaction may be carried out in the presence of a solvent.
- solvents include hexane, heptane, octane, nonane, decane, toluene and xylene.
- the reaction when by-products are generated in this reaction, in order to accelerate the reaction, the reaction may be carried out while distilling off the by-products under reduced pressure, or the by-products are azeotroped with the solvent, and the vaporized by-products are and the solvent are cooled, the distillate containing the by-products and the solvent is separated into a by-product layer and a solvent layer, and only the recovered solvent layer is returned to the reaction system as a reflux liquid while the reaction is carried out. You may go.
- the reaction between the precursor polymer (1) and the at least two types of compounds ( ⁇ ) may be performed while melt-kneading the precursor polymer (1) and the at least two types of compounds ( ⁇ ). If by-products are generated when the precursor polymer (1) and at least two compounds ( ⁇ ) are reacted while melt-kneading, the by-products are distilled off under reduced pressure to accelerate the reaction.
- the reaction may be performed while Examples of the melt-kneading device used for melt-kneading include a single-screw extruder, a twin-screw extruder, and a Banbury mixer.
- the melt-kneading temperature is preferably 100°C or higher and 250°C or lower.
- a catalyst may be added to promote the reaction.
- the catalyst include alkali metal salts and Group 4 metal complexes.
- the alkali metal salt include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkali metal alkoxides such as lithium methoxide and sodium methoxide.
- Group 4 metal complexes include tetra(isopropyl) orthotitanate, tetra(n-butyl) orthotitanate, and tetraoctadecyl orthotitanate.
- the amount of the catalyst added is preferably 0.01 parts by weight or more and 50 parts by weight or less, more preferably 0.01 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the total amount of the precursor polymer (1) and compound ( ⁇ ) used in the reaction. is from 0.01 parts by weight to 5 parts by weight.
- the polystyrene equivalent weight average molecular weight Mw of the polymer (1) according to the present invention measured by gel permeation chromatography (GPC) is preferably 10,000 to 5,000,000, more preferably is from 50,000 to 1,000,000, more preferably from 100,000 to 500,000.
- the mobile phase is usually orthodichlorobenzene and the measurement temperature is 140°C.
- the polymer (1) according to the present invention contains a structural unit (A) derived from ethylene, since the moldability of the polymer (1) is improved. Since the polymer (1) according to the present invention has good blow moldability or foam moldability, it is preferable that the structural unit (A) derived from ethylene forms a branched structure in the polymer. More preferably, the structure is a long-chain branched structure that is long enough to allow entanglement of polymer chains.
- the ratio A defined by the following formula (I) is preferably 0.95 or less, more preferably 0.90 or less, and still more preferably 0.80 or less. It is.
- A ⁇ 1 / ⁇ 0 (I)
- ⁇ 1 measures the absolute molecular weight and intrinsic viscosity of the polymer by gel permeation chromatography using a device equipped with a light scattering detector and a viscosity detector, Plot the measured data with the logarithm of the absolute molecular weight as the horizontal axis and the logarithm of the intrinsic viscosity as the vertical axis.
- the measured data is plotted with the logarithm of the absolute molecular weight as the horizontal axis and the logarithm of the intrinsic viscosity as the vertical axis.
- the range that is greater than or equal to the logarithm and less than or equal to the logarithm of the z-average molecular weight it is obtained by performing least squares approximation using formula (I-II) and finding the slope of the straight line represented by formula (I-II): ⁇ 0 It is a value.
- the mobile phase is usually orthodichlorobenzene and the measurement temperature is 155°C.
- the polyethylene reference material 1475a (manufactured by the National Institute of Standards and Technology) is high-density polyethylene that does not contain branches.
- the polymer (1) according to the present invention may form a mixture with the unreacted compound ( ⁇ ) or a catalyst added to promote the reaction.
- the content of the unreacted compound ( ⁇ ) contained in the mixture is preferably less than 3 parts by weight based on 100 parts by weight of the polymer.
- the polymer (1) according to the present invention may be a crosslinked polymer or a non-crosslinked polymer.
- the polymer (1) is a non-crosslinked polymer (hereinafter sometimes referred to as "polymer ( ⁇ )").
- the polymer ( ⁇ ) described below has a gel fraction of less than 20% by weight.
- the total number of the structural units (A), the structural units (B), and the structural units (C) is 90%, with the total number of all structural units contained in the polymer being 100%. It is preferably at least 95%, more preferably at least 95%, even more preferably 100%.
- polymer (1) is crosslinked. That is, at least some of the molecules of the polymer (1) are linked by covalent bonds between molecules.
- Examples of the method of crosslinking the polymer ( ⁇ ) include a method of crosslinking by irradiating with ionizing radiation, and a method of crosslinking using an organic peroxide.
- the polymer ( ⁇ ) When crosslinking a polymer ( ⁇ ) by irradiating it with ionizing radiation, the polymer ( ⁇ ), which has been previously formed into a desired shape, is usually irradiated with the ionizing radiation.
- the molded article to be irradiated with ionizing radiation may be a molded article containing only the polymer ( ⁇ ), or may be a molded article containing the polymer ( ⁇ ) and a polymer different from the polymer ( ⁇ ).
- Examples of the polymer different from polymer ( ⁇ ) include polymer (2) described below. When the molded article contains polymer ( ⁇ ) and polymer (2), the total amount of polymer ( ⁇ ) and polymer (2) is 100% by weight, and the content of polymer ( ⁇ ) is 1% by weight. It is preferably at least 99% by weight.
- the ionizing radiation examples include ⁇ rays, ⁇ rays, ⁇ rays, electron beams, neutron beams, and X-rays, with cobalt-60 ⁇ rays or electron beams being preferred.
- the molded product containing the polymer is in the form of a sheet, at least one surface of the sheet-like molded product may be irradiated with ionizing radiation.
- Irradiation of ionizing radiation is performed using a known ionizing radiation irradiation device.
- the irradiation amount is usually 5 to 300 kGy, preferably 10 to 150 kGy.
- a polymer with a high degree of crosslinking can be obtained with a low irradiation dose.
- the molded article to be irradiated with ionizing radiation contains a crosslinking aid, so that the crosslinked polymer (1) has a higher degree of crosslinking. can be obtained.
- the crosslinking aid is for improving the mechanical properties by increasing the degree of crosslinking of the polymer (1), and a compound having multiple double bonds in the molecule is preferably used.
- crosslinking aids examples include N,N'-m-phenylene bismaleimide, toluylene bismaleimide, triallyl isocyanurate, triallyl cyanurate, p-quinone dioxime, nitrobenzene, diphenylguanidine, divinylbenzene, and ethylene glycol. Mention may be made of dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate and allyl methacrylate. The crosslinking aids may be used alone or in combination.
- the amount of the crosslinking aid added is from 0.01 to 100 parts by weight, based on 100 parts by weight of the polymer ( ⁇ ) contained in the molded article to be irradiated with ionizing radiation and a polymer different from the polymer ( ⁇ ).
- the amount is preferably 4.0 parts by weight, and more preferably 0.05 to 2.0 parts by weight.
- a method for crosslinking using an organic peroxide for example, a method of crosslinking the polymer ( ⁇ ) by molding a composition containing the polymer ( ⁇ ) and the organic peroxide by a known method involving heating.
- Known molding methods involving heating include, for example, extrusion molding, injection molding, and press molding.
- a composition containing a polymer ( ⁇ ) and an organic peroxide may contain only the polymer according to the present invention as a polymer component, or may contain a polymer according to the present invention and a polymer different from the polymer. May include.
- the composition containing the polymer ( ⁇ ) and the organic peroxide contains a polymer different from the polymer ( ⁇ )
- examples of the polymer include the below-mentioned polymer (2). It is preferable that the content of polymer ( ⁇ ) is 1% by weight or more and 99% by weight or less, assuming that the total amount of ( ⁇ ) and polymer (2) is 100% by weight.
- organic peroxide having a decomposition temperature equal to or higher than the flow start temperature of the polymer component contained in the composition containing the polymer ( ⁇ ) and the organic peroxide.
- Preferred organic peroxides include, for example, dicumyl peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane, and 2,5-dimethyl-2,5-di-tert-butyl peroxide.
- Oxyhexine, ⁇ , ⁇ -di-tert-butylperoxyisopropylbenzene, and tert-butylperoxy-2-ethylhexyl carbonate can be mentioned.
- the crosslinked polymer (1) may contain known additives, if necessary.
- additives include flame retardants, antioxidants, weathering agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, dripless agents, pigments, and fillers. These additives can be added by kneading with the polymer ( ⁇ ) before crosslinking the polymer ( ⁇ ).
- the crosslinked polymer (1) preferably has a gel fraction of 20% by weight or more, more preferably 40% by weight or more, still more preferably 60% by weight or more, and most preferably 70% by weight. That's all. Gel fraction indicates the degree of crosslinking of a crosslinked polymer.
- a high gel fraction of a polymer means that the polymer has more crosslinked structures and a stronger network structure is formed. means that it has been When the gel fraction of the polymer is high, the polymer has high shape retention and is difficult to deform.
- the gel fraction is determined by the method described below.
- Polymer-encapsulated mesh basket and xylene (manufactured by Kanto Kagaku Co., Ltd., Deka special grade or equivalent): A mixture of o-xylene, m-xylene, p-xylene and ethylbenzene; o-xylene, m-xylene and p- A total of 50 mL of xylene (the total weight of xylene is 85% by weight or more) is introduced into a 100 mL test tube, and heat extraction is performed at 110° C. for 6 hours.
- the mesh basket containing the extraction residue is taken out from the test tube and dried under reduced pressure at 80° C. for 8 hours in a vacuum dryer, and the dried mesh basket containing the extraction residue is weighed.
- the gel weight is calculated from the difference in weight between the mesh basket containing the extraction residue and the empty mesh basket after drying.
- the gel fraction (weight %) is calculated by the following formula.
- Gel fraction (gel weight/measured sample weight) x 100
- the composition of the present invention (sometimes referred to as "resin composition (B)") contains polymer (1).
- the proportion of the polymer in the composition is not particularly limited, but in one embodiment, the composition contains the polymer in an amount of 0.01 to 99.9% by weight, preferably 0.1 to 99.9% by weight in order to improve shape retention.
- the content is 50% by weight, more preferably 0.1 to 20% by weight, even more preferably 0.1 to 10% by weight.
- the composition has water repellency and oil repellency.
- the resin composition (B) may further contain a base resin (sometimes referred to as polymer (2)).
- the base resin is at least one selected from the group consisting of thermosetting resins and thermoplastic resins.
- the ratio of the polymer (1) to the composition is not particularly limited, but in one embodiment, the composition contains the polymer in a proportion of 0.1 to 99.9% by weight. %, and the content is preferably 0.5 to 50% by weight, more preferably 1 to 20% by weight, and even more preferably 1 to 10% by weight because it improves shape retention against moisture.
- thermoplastic resin any conventionally known thermoplastic resin can be used, such as the following: High density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, high molecular weight polyethylene, ultra high molecular weight polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, atactic polypropylene, stereoblock polypropylene , ethylene-propylene random copolymer, ethylene-propylene block copolymer, polyisobutylene, polybut-1-ene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4- Methylpent-1-ene, polyvinylcyclohexane, polyisoprene, polybutadiene, cycloolefin polymer, olefin thermoplastic elastomer, polyvinyl chloride, polyvinylidene chloride, polychloroprene, vinyl chloride,
- thermoplastic resin any conventionally known thermoplastic resin can be used as the thermoplastic resin, such as high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, high molecular weight polyethylene, ultra high molecular weight polyethylene, and isoplastic resin.
- Tactic polypropylene syndiotactic polypropylene, hemiisotactic polypropylene, atactic polypropylene, stereoblock polypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene , polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycaprolactone, polylactic acid, polyhydroxyalkanoate, polyhydroxybutyrate, polycarbonate, polyamide, polyvinyl acetal, polyacetal, polyvinyl alcohol, polyvinyl acetate, polyphenylene ether, modified polyphenylene ether , polyphenylene oxide, polyphenylene sulfide, polyamide imide, polyether ether ketone, ethylene-methyl (meth)acrylate copolymer, ethylene-ethyl (meth)acryl
- the composition (B) made of a thermoplastic resin contains 0.1 to 99.9% by weight of the base resin, preferably 50 to 99.5% by weight since shape retention is improved, and more preferably 80% by weight. It contains up to 99% by weight, more preferably 90 to 99% by weight.
- the resin composition (B) made of a thermoplastic resin may contain two or more types of polymers (1), or may contain two or more types of polymers (2). Further, the polymer (2) may be a homopolymer or a copolymer, and the copolymer may be composed of two or more types of arbitrary monomers.
- the ratio of the polymer (1) to the composition is not particularly limited, but in one embodiment, the composition has a ratio of the polymer (1) of 0.01 to 99.9. It is preferably contained in an amount of 0.1 to 50% by weight, more preferably 0.1 to 20% by weight, and still more preferably 0.1 to 10% by weight since it improves shape retention against moisture.
- thermosetting resin any conventionally known thermosetting resin can be used, such as epoxy resin, phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, alkyd resin, furan resin, polyimide, and unsaturated polyester.
- thermosetting resin any conventionally known thermosetting resin can be used, such as epoxy resin, phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, alkyd resin, furan resin, polyimide, and unsaturated polyester.
- examples include resin, DAP resin, polyurethane, silicone resin, thermosetting acrylic resin, and the like.
- thermosetting resin any conventionally known thermosetting resin can be used, such as epoxy resin, phenol resin, urea resin, melamine resin, alkyd resin, unsaturated polyester resin, DAP resin, polyurethane, and silicone.
- thermosetting acrylic resins examples include resins, thermosetting acrylic resins, and more preferably unsaturated polyester resins and thermosetting acrylic resins.
- the resin composition (B) made of a thermosetting resin may contain two or more types of polymers (1), and may contain two or more types of base resins.
- the resin composition (B) made of a thermosetting resin contains 0.1 to 99.99% by weight of the base resin, preferably 50 to 99.9% by weight, more preferably 50 to 99.9% by weight to improve shape retention.
- the content is 80 to 99.9% by weight, more preferably 90 to 99.9% by weight.
- the resin composition according to the present invention includes the following "resin composition (A)" as one of the embodiments.
- the content of the polymer (1) is 1% by weight or more and 99% by weight or less, and the content of the polymer (2) is 100% by weight, the total amount of the polymer (1) and the polymer (2) being 100% by weight.
- the content of the polymer (1) is 1% by weight or more and 99% by weight or less (hereinafter sometimes referred to as "resin composition (A)")
- the content of the polymer (1) is 1% by weight or more and 50% by weight or less
- the content of the polymer (2) is 50% by weight or more and 99% by weight or less
- the content of the polymer (1) is 1% by weight or more and 30% by weight or less
- the content of the polymer (2) is 70% by weight or more and 99% by weight or less
- the content of polymer (1) is 1% by weight or more and 10% by weight or less
- the content of polymer (2) is 90% by weight or more and 99% by weight or less.
- the resin composition (A) according to the present invention may contain two or more types of polymers (1), or may contain two or more types of polymers (2).
- the melting peak temperature or glass transition temperature of the polymer (2) observed by differential scanning calorimetry (DSC) is within the range of 50°C or higher and 180°C or lower.
- the melting peak temperature of the polymer (2) is the temperature at the extreme value of the melting peak obtained by analyzing the melting curve measured by differential scanning calorimetry below using a method based on JIS K7121-1987. This is the temperature at which the amount of heat absorbed is maximum.
- the glass transition temperature of the polymer (2) is the midpoint glass transition temperature obtained by analyzing the melting curve measured by differential scanning calorimetry below by a method based on JIS K7121-1987.
- step (1) Using a differential scanning calorimeter, under a nitrogen atmosphere, an aluminum pan containing approximately 5 mg of sample was held at 200°C for 5 minutes in step (1), and heated from 200°C at a rate of 5°C/min in step (2). The temperature is lowered to -80°C, step (3) is held at -80°C for 5 minutes, and step (4) is heated from -80°C to 200°C at a rate of 5°C/min.
- the differential scanning calorimetry curve obtained by calorimetry in step (4) is defined as a melting curve.
- Examples of the polymer (2) having a melting peak temperature in the range of 50° C. or higher and 180° C. or lower include high-density polyethylene (HDPE), high-pressure low-density polyethylene (LDPE), ethylene- ⁇ -olefin copolymer, Examples include ethylene-vinyl acetate copolymer (EVA) and polypropylene (PP).
- HDPE high-density polyethylene
- LDPE high-pressure low-density polyethylene
- EVA ethylene-vinyl acetate copolymer
- PP polypropylene
- Examples of the polymer (2) having a glass transition temperature in the range of 50°C or higher and 180°C or lower include cyclic olefin polymers (COP), cyclic olefin copolymers (COC), polystyrene (PS), and polyvinyl chloride.
- COP cyclic olefin polymers
- COC cyclic olefin copolymers
- PS polystyrene
- polyvinyl chloride examples of the polymer (2) having a glass transition temperature in the range of 50°C or higher and 180°C or lower.
- PVC acrylonitrile-styrene copolymer
- AS acrylonitrile-styrene copolymer
- ABS acrylonitrile-butadiene-styrene copolymer
- PMMA polymethyl methacrylate
- PMMA polyvinyl alcohol
- PET polyethylene terephthalate
- PAN polyacrylonitrile
- PA6 polyamide 6
- PA66 polycarbonate
- PC polyphenylene sulfide
- PEEK polyetheretherketone
- the ethylene- ⁇ -olefin copolymer which is the polymer (2) is a copolymer having a structural unit derived from ethylene and a structural unit derived from ⁇ -olefin.
- the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and 4-methyl-1-hexene. may be used, or two or more types may be used.
- the ⁇ -olefin is preferably an ⁇ -olefin having 4 to 8 carbon atoms, more preferably 1-butene, 1-hexene or 1-octene.
- the density of the polymer (2), high-density polyethylene, high-pressure low-density polyethylene, and ethylene- ⁇ -olefin copolymer is usually 860 kg/m 3 or more and 960 kg/m 3 or less.
- Examples of the polypropylene which is the polymer (2) include a propylene homopolymer, the propylene random copolymer described below, and the propylene polymer material described below.
- the content of structural units derived from propylene contained in polypropylene is usually more than 50% by weight and 100% by weight or less (provided that the total amount of structural units constituting polypropylene is 100% by weight).
- the polypropylene that is the polymer (2) preferably has a melting peak temperature of 100° C. or higher.
- the polypropylene that is the polymer (2) is preferably a propylene homopolymer.
- Propylene random copolymer It is a random copolymer containing a structural unit derived from propylene and at least one structural unit selected from the group consisting of a structural unit derived from ethylene and a structural unit derived from an ⁇ -olefin.
- Examples of the propylene random copolymer include propylene-ethylene random copolymer, propylene-ethylene- ⁇ -olefin random copolymer, and propylene- ⁇ -olefin random copolymer.
- the ⁇ -olefin is preferably an ⁇ -olefin having 4 to 10 carbon atoms.
- ⁇ -olefins examples include linear ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene, and 3-methyl-1-butene and 3-methyl-1-butene.
- linear ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene, and 3-methyl-1-butene and 3-methyl-1-butene.
- Branched ⁇ -olefins such as methyl-1-pentene are mentioned.
- the constituent units derived from ⁇ -olefin contained in the propylene random copolymer may be one type alone or two or more types.
- Propylene homopolymers and propylene random copolymers can be produced by slurry polymerization, solution polymerization, etc. using Ziegler-Natta catalysts, or complex catalysts such as metallocene complexes and non-metallocene complexes. Examples include polymerization methods such as legal polymerization, bulk polymerization, and gas phase polymerization.
- Propylene polymer material Propylene homopolymer component (I), An ethylene copolymer component (II ) is a polymeric material containing.
- Examples of the ⁇ -olefin having 4 or more carbon atoms for the ethylene copolymer component (II) include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, Mention may be made of 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene and 2,2,4-trimethyl-1-pentene.
- the ⁇ -olefin having 4 or more carbon atoms is preferably an ⁇ -olefin having 4 or more and 20 or less carbon atoms, more preferably an ⁇ -olefin having 4 or more and 10 or less carbon atoms, and 1-butene, 1-hexene or 1 -Octene is more preferred.
- the constituent units derived from ⁇ -olefins having 4 or more carbon atoms contained in the ethylene copolymer component (II) may be one type alone or two or more types.
- ethylene copolymer component (II) examples include propylene-ethylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and propylene-ethylene copolymer. -1-butene copolymer, propylene-ethylene-1-hexene copolymer and propylene-ethylene-1-octene copolymer. Ethylene copolymer component (II) may be a random copolymer or a block copolymer.
- the propylene polymer material can be produced by multistage polymerization using a polymerization catalyst.
- a propylene polymer material can be manufactured by manufacturing the propylene homopolymer component (I) in the first polymerization step and manufacturing the ethylene copolymer component (II) in the second polymerization step.
- polymerization catalysts used in the production of propylene polymer materials include catalysts used in the production of propylene homopolymers and propylene random copolymers.
- Examples of polymerization methods in each polymerization step when producing a propylene polymer material include bulk polymerization, solution polymerization, slurry polymerization, and gas phase polymerization.
- Inert hydrocarbon solvents used in solution and slurry polymerization methods include propane, butane, isobutane, pentane, hexane, heptane and octane. Two or more of these polymerization methods may be used in combination, and either a batch method or a continuous method may be used.
- the polymerization method for producing the propylene polymer material is preferably continuous gas phase polymerization or bulk-gas phase polymerization in which bulk polymerization and gas phase polymerization are performed continuously.
- the resin composition (A) contains 0.1 to 99.9% by weight of Polymer 2, preferably 50 to 99.5% by weight, more preferably 80 to 99% by weight since shape retention is improved. , more preferably 90 to 99% by weight.
- the melt flow rate (MFR) of the resin composition is 0.1 g/10 minutes or more and 100 g/10 minutes or less.
- melt flow rate (MFR) of the resin composition is measured in accordance with JIS K7210 at 230°C and under a load of 2.16 kgf. is preferably 1 g/10 minutes or more and 1000 g/10 minutes or less.
- Quorum Sensing Inhibitor The composition according to the present invention may contain a quorum sensing inhibitor. Quorum sensing inhibitors are compounds that inhibit quorum sensing in microorganisms.
- Inhibition of quorum sensing can be measured by a bioassay using bacteria that produce pigments, bacteria that exhibit bioluminescence, etc. using a substance that induces quorum sensing (e.g., Sensors 2013, 13, 5117-5129).
- Sensors 2013, 13, 5117-5129 describes C. N-hexanoyl homoserine lactone, which induces quorum sensing, is added to a reporter strain such as L. violaceum CV026, and then caffeine, which is a quorum sensing inhibitor, is added, and the bacteria are cultured while being kept warm. It is stated that caffeine has quorum sensing inhibiting properties because the amount of produced purple pigment (violacein) is smaller than the amount of purple pigment (violacein) when no caffeine is added.
- the quorum sensing inhibitor is preferably the following quorum sensing inhibitor: Based on the method described in Sensors 2013, 13, 5117-5129, C. After adding N-hexanoyl homoserine lactone and further adding a quorum sensing inhibitor to C. violaceum CV026 (reporter strain), the bacteria are cultured by keeping warm. The amount of purple pigment (violacein) produced is 85% or less (however, the amount of purple pigment produced is 100% when the bacteria are cultured while keeping warm without adding a quorum sensing inhibitor). ) Quorum sensing inhibitors.
- Quorum sensing inhibitors include, for example: Eugenol, methyl eugenol, cinnamaldehyde, cinnamic acid, vanillin, isovanillin, ferulic acid, chlorogenic acid, caffeic acid, P-coumaric acid, cinnamaldehyde, methyl cinnamate, phenylpropionic acid, 2-methoxycinnamic acid, 3-Methoxycinnamic acid, 4-methoxycinnamic acid, 3-bromocinnamic acid, 2-fluorocinnamic acid, 3-fluorocinnamic acid, 3-methylcinnamic acid, 4-acetoxycinnamic acid, 4 - Bromocinnamic acid, 4-ethoxycinnamic acid, 4-fluorocinnamic acid, 3,4-dimethoxycinnamic acid, 2,3-dimethoxycinnamic acid, 2,5-dimeth
- the logS of the quorum sensing inhibitor is the common logarithm of the amount (solubility) S (g/100g) of the quorum sensing inhibitor dissolved in 100g of water at a temperature of 25°C and a pH of 6 to 8, and is the value of logS. The smaller the value, the more difficult it is to dissolve in water.
- the logS is preferably less than 0.1, more preferably 0.01 or less, and still more preferably -0.1 from the viewpoint of sustainability of the effect of reducing biofilm adhesion of the molded article of the present invention. It is below, particularly preferably -0.4 or below.
- the logS of the quorum sensing inhibitor is usually -30 or more, preferably -12 or more.
- the logS of quorum sensing inhibitors can be easily estimated from the chemical structure of quorum sensing inhibitors for which literature values are not known by using the computer software Hansen Solubility Parameter in Practice (HSPiP). can.
- the logS of the quorum sensing inhibitor contained in the composition according to the present invention a value calculated by HSPiP ver5.0.04 or a literature value is usually used.
- the quorum sensing inhibitor contained in the resin composition according to the present invention is an ionic compound, a charge transfer complex, an inorganic compound, a compound having more than 120 atoms other than hydrogen atoms, or a compound containing multiple hydrogen atoms
- the logS of the quorum sensing inhibitor is a value calculated by solubility measurement that measures the amount of solute dissolved in 100 g of water.
- quorum sensing inhibitors with a logS of less than 0.1 examples include phenylpropanoids with a logS of less than 0.1, benzoic acid analogs with a logS of less than 0.1, and quorum sensing inhibitors with a logS of less than 0.1.
- agents phenazines with a logS of less than 0.1, ubiquinone analogs with a logS of less than 0.1, eicosanoids with a logS of less than 0.1, carotenoids with a logS of less than 0.1, logS of 0.1 mycotoxins with a logS of less than 0.1; macrolides with a logS of less than 0.1; polysaccharides with a logS of less than 0.1; boronic acids and boronic acid derivatives with a logS of less than 0.1; Examples include steroids, lactones with a logS of less than 0.1, and ptenolides with a logS of less than 0.1.
- phenylpropanoids with a logS of less than 0.1 Preferably, phenylpropanoids with a logS of less than 0.1, benzoic acid analogs with a logS of less than 0.1, tannins with a logS of less than 0.1, and stilbene analogs with a logS of less than 0.1.
- flavonoids with a logS of less than 0.1 diarylheptanoids with a logS of less than 0.1, terpenes and terpenoids with a logS of less than 0.1, sulfur-containing compounds with a logS of less than 0.1, logS nitrogen-containing compounds with a logS of less than 0.1, coumarin derivatives with a logS of less than 0.1, furanocoumarins with a logS of less than 0.1, quinone derivatives with a logS of less than 0.1, logS of 0.1 alkaloids with a logS of less than 0.1, phenols and polyphenols with a logS of less than 0.1, surfactants with a logS of less than 0.1 and having the ability to inhibit quorum sensing, phenazines with a logS of less than 0.1, logS of Ubiquinone analogs with a logS of less than 0.1, eicosanoids with a logS of less than 0.1,
- flavonoids with a logS of less than 0.1 diarylheptanoids with a logS of less than 0.1, terpenes and terpenoids with a logS of less than 0.1, sulfur-containing compounds with a logS of less than 0.1, Nitrogen-containing compounds with logS less than 0.1, coumarin derivatives with logS less than 0.1, quinone derivatives with logS less than 0.1, alkaloids with logS less than 0.1, logS less than 0.1 boronic acids and boronic acid derivatives, or lactones whose log S is less than 0.1, More preferably, 2,3,4-trimethoxycinnamic acid, 2-fluorocinnamic acid, eugenol, salicylic acid, tannic acid, resveratrol, (-)-epicatechin, flavone, curcumin, carvacrol, phytol, diphenyl disulfide, Indole, umbelliferone, purpurin, reserpine
- Phenylpropanoids with logS less than 0.1 include eugenol, methyleugenol, cinnamaldehyde, cinnamic acid, isovanillin, ferulic acid, cinnamaldehyde, methyl cinnamate, phenylpropionic acid, and 2-methoxycinnamic acid.
- benzoic acid analogs with a log S of less than 0.1 include salicylic acid, gallic acid, and ellagic acid.
- tannins with a log S of less than 0.1 include 1,2,3,4,6-pentagalloylglucose, punicalagin, hamamelitannin, and tannic acid.
- Stilbene analogs and polyketides with a log S of less than 0.1 include resveratrol, pterostilbene, and the like.
- Flavonoids with logS less than 0.1 include (-)-epicatechin, (-)-catechin gallate, (-)-epicatechin gallate, (-)-gallocatechin gallate, and (-)-gallic acid.
- Examples include epigallocatechin, naringenin, flavone, apigenin, chrysin, acacetin, flavonol, kaempferol, quercetin, quercitrin, flavanone, isosacranetin, pinostrobin, eriodictyol, malvidin, and the like.
- Diarylheptanoids with a log S of less than 0.1 include curcumin and the like.
- terpenes and terpenoids with a log S of less than 0.1 include carvacrol, salvipison, acanthospermolide, isolimonic acid, ichangin, betulinic acid, ursolic acid, gymnemic acid, obacunone, deacetylnomilinic acid glucoside, phytol, etc. Can be mentioned.
- sulfur-containing compounds with a log S of less than 0.1 examples include allicin, sulforaphane, allyl isothiocyanate, iberin, diphenyl disulfide, and the like.
- nitrogen-containing compounds with a log S of less than 0.1 examples include indole, 2-methyltryptoline, and the like.
- Coumarin derivatives with a log S of less than 0.1 include esculetin, umbelliferone, scopoletin, and the like.
- furanocoumarins with a log S of less than 0.1 examples include psoralen, angelicin, bergamotin, dihydroxybergamottin, and the like.
- Examples of quinone derivatives having a logS of less than 0.1 include chrysophanol, emodin, shikonin, purpurin, and embelin.
- alkaloids with a log S of less than 0.1 examples include berberine, berberine chloride hydrate, chelerythrine, sanguinarine, reserpine, oloidine, piperine, hordenine, and the like.
- Phenols and polyphenols with a log S of less than 0.1 include malvaricon C, taxifolin, rosmarinic acid, and the like.
- surfactants having a logS of less than 0.1 and having the ability to inhibit quorum sensing include rhamnolipid, trehalolipid, sophorolipid, cellobiopid, viscosin, emulzan, and the like.
- phenazines with a log S of less than 0.1 examples include pyocyanin.
- Examples of ubiquinone analogs with a log S of less than 0.1 include piericidin A, glucopiericidin A, and the like.
- Examples of eicosanoids with a log S of less than 0.1 include lipoxin A4.
- Examples of carotenoids with a log S of less than 0.1 include zeaxanthin.
- Mycotoxins with a logS of less than 0.1 include penicillic acid, patulin, and the like.
- Examples of macrolides with a log S of less than 0.1 include erythromycin and the like.
- Polysaccharides with a log S of less than 0.1 include polygalacturonic acid, pectin, and the like.
- steroids with a log S of less than 0.1 examples include cholesteryl chloride and the like.
- boronic acids and boronic acid derivatives having a log S of less than 0.1 examples include 3-fluoro-4-methylphenylboronic acid and 2-fluoro-4-trifluoromethylphenylboronic acid.
- Lactones with a log S of less than 0.1 include N-(3-oxododecanoyl)-L-homoserine lactone and the like.
- Examples of the ptenolide having a log S of less than 0.1 include 3,4-dibromo-2(5H)-furanone and the like.
- the distance Ra 1 between the Hansen solubility parameter (hereinafter also referred to as HSP D ) of the quorum sensing inhibitor and the Hansen solubility parameter (hereinafter also referred to as HSP A ) of the polymer 1 is preferably 3.2 MPa 1/ 2 , more preferably 3.5 MPa 1/2 or more, still more preferably 4.2 MPa 1/2 or more.
- Ra 2 is usually 50 MPa 1/2 or less, preferably 35 MPa 1/2 or less.
- HSP Hansen solubility parameter
- ⁇ D, ⁇ P, and ⁇ H can be calculated from the chemical structural formula of Polymer 1 and the quorum sensing inhibitor by using, for example, the computer software Hansen Solubility Parameters in Practice (HSPiP).
- HSPiP Hansen Solubility Parameters in Practice
- the molded article of the present invention is HSPiP ver. The value obtained by calculation according to 5.0.04 is used.
- the above program cannot directly calculate the Hansen solubility parameter. Can not. In such a case, the Hansen solubility parameter of each homopolymer consisting of each constitutional unit was calculated, and the calculated Hansen solubility parameters of each homopolymer were averaged by the volume ratio of the constitutional units contained in the copolymer. The value was taken as the Hansen solubility parameter of the copolymer.
- the "value averaged by volume ratio” is the value obtained by multiplying each of the Hansen solubility parameters ⁇ D, ⁇ P, and ⁇ H of the homopolymer consisting of each structural unit by the volume fraction of the structural unit, It refers to the sum of each of ⁇ D, ⁇ P, and ⁇ H.
- the "volume fraction" of a certain structural unit means (volume of the structural unit)/(total volume of the structural units in the copolymer).
- the distance Ra 1 between HSP A and HSP D indicates the distance between the Hansen solubility parameters (HSP) of the two substances.
- Ra 1 is an index representing the affinity of both substances, and it can be said that the smaller the value, the higher the affinity of both substances.
- the quorum sensing inhibitor may be supported on a carrier.
- carriers include: Zeolite; Montmorionite; activated carbon; Calcium phosphate compounds such as hydroxyapatite; Oxides such as silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, zirconium oxide; Nitrides such as silicon nitride, titanium nitride, aluminum nitride, zirconium nitride; Non-oxide ceramics such as silicon carbide; Silicates such as calcium silicate, aluminum silicate, magnesium silicate, diatomaceous earth; Alumina-silica compounds such as kaolinite, bentonite, pumice, feldspar, and quartz.
- the content of the quorum sensing inhibitor is preferably 0.01 to 30% by weight, assuming the total amount of all components constituting the composition to be 100% by weight. % by weight, more preferably 0.1 to 10% by weight, even more preferably 0.1 to 5% by weight.
- composition according to the present invention may contain an antibacterial/antifungal agent.
- antibacterial and antifungal agents include: Methyl-2,4-dihydroxy-6-methylbenzoate, ethyl-2,4-dihydroxy-6-methylbenzoate, methyl-2,4-dihydroxy-3,6-dimethylbenzoate, isopropyl-2,4-dihydroxy-6 -Methylbenzoate, 3-methoxy-5-methylphenyl-2,4-dihydroxy-6-methylbenzoate, Ethyl-2,4-dihydroxy-3,6-dimethylbenzoate, Ethyl-3-formyl-2,4-dihydroxy -6-methylbenzoate, isopropyl-3-formyl-2,4-dihydroxy-6-methylbenzoate, 3-hydroxy-5-methylphenyl-2,4-dihydroxy-6-methylbenzoate, 3-hydroxy-5-methyl Phenyl-2-dihydroxy-4-methoxy-6-methylbenz
- isothiazolone antibacterial and antifungal agents Anilide-based antibacterial and antifungal agents such as 4'-hydroxyacetanilide, N-(3-hydroxyphenyl)benzenecarboxamide, and N-(3-hydroxyphenyl)benzamide; Nitrile antibacterial and antifungal agents such as monobromocyanoacetamide, dibromocyanoacetamide, 1,2-dibromo-2,4-dicyanobutane, and tetrachlorophthalonitrile; Imidazole/thiazole-based antibacterial/fungal agents such as 2-(4-thiazolyl)benzimidazole, 2-benzimidazole methyl carbamate, 1-(butylcarbamoyl)-2-benzimidazole methyl carbamate; Aldehyde antibacterial and antifungal agents such as dehydroacetic acid; Carboxylic acid antibacterial and antifungal agents such as sorbic acid; Ester-based antibacterial and antifungal agents such
- phenol/alcohol-based antibacterial/antifungal agents pyridine/quinoline-based antibacterial/antifungal agents, isothiazolone-based antibacterial/antifungal agents, nitrile-based antibacterial/antifungal agents, and imidazole/thiazole-based antibacterial/antifungal agents are preferred.
- a fungicide an aldehyde-based antibacterial/antifungal agent, a carboxylic acid-based antibacterial/antifungal agent, an ester-based antibacterial/antifungal agent, a quaternary ammonium salt, a biguanide, a surfactant, or an inorganic antibacterial agent, and more preferably , a pyridine/quinoline type antibacterial/antifungal agent, an isothiazolone type antibacterial/antifungal agent, or an imidazole/thiazole type antibacterial/antifungal agent, and more preferably thiabendazole, zinc pyrithione, or octylisothiazolinone.
- composition according to the present invention contains an antibacterial/antifungal agent, it may contain only one type of antibacterial/antifungal agent, or it may contain two or more types of antibacterial/antifungal agents.
- the common logarithm logS of the solubility of the antibacterial/antifungal agent in water at 25°C at pH 6 to 8 is preferably 1 or less, more preferably -0.6 or less, still more preferably -1 or less, and even more preferably is in the range of -1.5 or less.
- the antibacterial/antifungal agent may be supported on a carrier.
- carriers for antibacterial and antifungal agents include those exemplified as carriers for quorum sensing inhibitors.
- the content of the antibacterial/antifungal agent is 0.01 to 10% by weight, with the total amount of all components constituting the composition being 100% by weight.
- the content of the antibacterial/antifungal agent is preferably 0.1 to 5% by weight.
- composition according to this title may also include a surface modifier.
- surface modifier refers to a compound that changes the surface free energy of a molded article depending on the presence or absence of the surface modifier.
- Examples of surface modifiers include: Nonafluoro-1-butanesulfonic acid, tridecafluoroheptanoic acid, heptadecafluorooctanesulfonic acid, heptadecafluorononanoic acid, heneicosafluoroundecanoic acid, 2H,2H,3H,3H-heptadecafluoroundecanoic acid, pentadeca Fluorine surfactants such as ammonium fluorooctanoate, lithium nonafluoro-1-butanesulfonate, potassium heptadecafluoro-1-octanesulfonate, Surflon S-431, Surflon S-461, Surflon S-420; Perfluoropolyether group-containing compound described in International Publication No.
- Fluorine monomers such as 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate; RSC Adv. Alkylsiloxy group-containing compound described in 2015, 5, 53054-53062; Polyalkylene ether group-containing compound described in JP 2017-115044; Betaine type compounds described in JP-A No. 2002-069178; Surfactants such as glycerin monostearate.
- fluorine-based surfactants preferred are fluorine-based surfactants, perfluoropolyether group-containing compounds, fluorine-based monomers, polyalkylene ether group-containing compounds, betaine type compounds, or surfactants, and more preferred are fluorine-based interfaces.
- the content of the surface modifier should be 0.1 to 30% by weight, with the total amount of all components constituting the composition being 100% by weight. is preferable, and more preferably 1 to 20% by weight.
- Resin composition A and resin composition B may contain known additives as necessary.
- additives include antioxidants, rust preventives, ultraviolet absorbers, light stabilizers, stabilizers, hydrolysis inhibitors, biofouling inhibitors, biorepellents, antibiotics, antiviral agents, and deodorants.
- additives may be added during the synthesis of the polymer (1), or may be added during the kneading of the polymer (1).
- antioxidants examples include phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and hindered amine-based antioxidants.
- phenolic antioxidants include N-octadecyl-3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, 2,6-di-tert-butyl-4-methylphenol, 2 , 2-thio-diethylene-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tri-ethylene glycol-bis-[3-(3-tert-butyl-5- methyl-4-hydroxyphenyl)propionate], 3,9-bis[2- ⁇ 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy ⁇ -1,1-dimethylethyl]-2 , 4,8,10-tetraoxaspiro[5,5]undecane, tetrakis ⁇ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid ⁇ pentaerythrityl ester,
- sulfur-based antioxidants examples include 3,3'-thiodipropionic acid di-N-dodecyl ester, 3,3'-thiodipropionic acid di-N-tetradecyl ester, and 3,3-thiodipropionate.
- sulfur-based antioxidants examples include 3,3'-thiodipropionic acid di-N-dodecyl ester, 3,3'-thiodipropionic acid di-N-tetradecyl ester, and 3,3-thiodipropionate.
- examples include acid di-N-octadecyl ester and tetrakis(3-dodecylthiopropionic acid) pentaerythrityl ester.
- phosphorus antioxidants include tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butylphenyl) phosphite.
- hindered amine antioxidants include sebacate bis(2,2,6,6-tetramethyl-4-piperidyl) ester, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, poly[ ⁇ 6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl)imino ⁇ -1,6-hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl)imino ⁇ ].
- rust inhibitors include alkanolamines, quaternary ammonium salts, alkanethiols, imidazolines, sodium metavanadate, bismuth citrate, phenol derivatives, polyalkenylamines, alkylimidazoline derivatives, dianoalkylamines, carboxylic acid amides, and alkylenes.
- ultraviolet absorbers and light stabilizers examples include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(A,A-dimethylbenzyl)phenyl]- 2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, methyl -3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol, hydroxyphenylbenzotriazole derivative, 2-(4,6-diphenyl-1, Examples thereof include 3,5-triazin-2-yl)-5[(hexyl)oxy]-phenol and 2-ethoxy-2'-ethyl-oxalic acid bisanilide.
- the stabilizer examples include dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin maleate, dibutyltin maleate polymer, dioctyltin maleate, dioctyltin maleate polymer, dibutyltin laurate, dibutyltin laurate polymer, and the like.
- Organotin stabilizers such as lead stearate, dibasic lead phosphite, tribasic lead sulfate, etc., calcium-zinc stabilizers, barium-zinc stabilizers, barium-cadmium stabilizers , stearate stabilizers (metallic soaps) such as calcium stearate, zinc stearate, barium stearate, and lead stearate.
- hydrolysis inhibitor examples include compounds containing functional groups such as carbodiimide groups, epoxy groups, and oxazoline groups.
- Examples of the above-mentioned compound having a carbodiimide group include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction.
- Examples of such diisocyanates include 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'- Diphenyl ether diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4, Examples include 4'-dicyclohexylmethane diisocyanate and tetramethylxylylene diisocyanate.
- carbodiimide group-containing compounds include, for example, Carbodilite (registered trademark) V-01, V-02B, V-03, V-04K, V-04PF, V-05, V-0 7 manufactured by Nisshinbo Chemical Co., Ltd. , V-09, V-09GB, HMV-15CA, LA-1, and HMV-5CA-LC.
- epoxy group-containing compound for example, a glycidyl ester compound, a glycidyl ether compound, etc. are preferable.
- glycidyl ester compounds include benzoic acid glycidyl ester, t-Bu-benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, pelargonic acid glycidyl ester, stearic acid glycidyl ester, and laurin.
- Acid glycidyl ester palmitic acid glycidyl ester, behenic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, behenolic acid glycidyl ester, stearic acid glycidyl ester, terephthalic acid diglycidyl ester , isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, a
- glycidyl ether compounds include phenylglycidyl ether, o-phenylglycidyl ether, 1,4-bis( ⁇ , ⁇ -epoxypropoxy)butane, 1,6-bis( ⁇ , ⁇ -Epoxypropoxy)hexane, 1,4-bis( ⁇ , ⁇ -epoxypropoxy)benzene, 1-( ⁇ , ⁇ -epoxypropoxy)-2-ethoxyethane, 1-( ⁇ , ⁇ -epoxypropoxy)-2- Benzyloxyethane, 2,2-bis-[p-( ⁇ , ⁇ -epoxypropoxy)phenyl]propane and 2,2-bis-(4-hydroxyphenyl)propane and 2,2-bis-(4-hydroxyphenyl) )
- Examples include bisglycidyl polyethers obtained by the reaction of bisphenols such as methane and epichlorohydrin.
- bisoxazoline compounds and the like are preferred. Specifically, for example, 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), 2,2'-bis(4,4-dimethyl-2- oxazoline), 2,2'-bis(4-ethyl-2-oxazoline), 2,2'-bis(4,4'-diethyl-2-oxazoline), 2,2'-bis(4-propyl- 2-oxazoline), 2,2'-bis(4-butyl-2-oxazoline), 2,2'-bis(4-hexyl-2-oxazoline), 2,2'-bis(4-phenyl-2- oxazoline), 2,2'-bis(4-cyclohexyl-2-oxazoline), 2,2'-bis(4-benzyl-2-oxazoline), 2,2'-p-phenylenebis(2-oxazoline) , 2,2'-m
- biofouling inhibitors include tetramethylthiuram disulfide, zinc bis(N,N-dimethyldithiocarbamate), 3-(3,4-dichlorophenyl)-1,1-dimethylurea, dichloro-N-(( dimethylamino)sulfonyl)fluoro-N-(P-tolyl)methanesulfenamide, pyridine-triphenylborane, N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio)sulfamide, primary thiocyanate Copper, cuprous oxide, tetrabutylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zinc ethylene bisdithiocarbamate, 2,3,5,6-tetrachloro-4-(methylsulfonyl) ) Pyridine, N-(2,4,6-trichlorophenyl)maleimide
- deodorants include organic acids, fatty acid metals, metal compounds, cyclodextrins, and porous materials.
- organic acids examples include lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediamine polyacetic acid, alkane-1,2-dicarboxylic acid, alkene-1,2-dicarboxylic acid, cycloalkane-1 , 2-dicarboxylic acid, cycloalkene-1,2-dicarboxylic acid, and naphthalenesulfonic acid.
- fatty acid metals examples include zinc undecylenate, zinc 2-ethylhexanoate, and zinc ricinoleate.
- metal compounds include iron oxide, iron sulfate, zinc oxide, zinc sulfate, zinc chloride, silver oxide, steel oxide, metals (iron, copper, etc.) chlorophyllin sodium, metals (iron, copper, cobalt, etc.) phthalocyanine, metals.
- metal compounds include (iron, copper, cobalt, etc.) tetrasulfonic acid phthalocyanine, titanium dioxide, and visible light-responsive titanium dioxide (nitrogen-doped type, etc.).
- cyclodextrins examples include ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, methyl derivatives thereof, hydroxypropyl derivatives, glucosyl derivatives, and maltosyl derivatives.
- components constituting the porous body include polyunsaturated carboxylic acids, aromatic polymers, chitin, chitosan, activated carbon, silica gel, activated alumina, zeolites, and ceramics.
- polyunsaturated carboxylic acids examples include polymethacrylic acid and polyacrylic acid.
- aromatic polymers examples include polydivinylbenzene, styrene-divinylbenzene-vinylpyridine copolymer, and divinylbenzene-vinylpyridine copolymer.
- dyes examples include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, Examples include dyes such as phthalocyanine dyes and cyanine dyes, and these may be used alone or in combination of two or more.
- pigments include carbon black, titanium oxide, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene pigments, perinine pigments, quinophthalone pigments, diketopyrrolo-pyrrole pigments, dioxazine pigments, and disazo condensation pigments.
- pigments and penzimidazolone pigments include carbon black, titanium oxide, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene pigments, perinine pigments, quinophthalone pigments, diketopyrrolo-pyrrole pigments, dioxazine pigments, and disazo condensation pigments.
- examples include pigments and penzimidazolone pigments.
- flame retardants examples include decabromo biphenyl, antimony trioxide, phosphorus flame retardants, and aluminum hydroxide.
- antistatic agent examples include cationic surfactants, amphoteric surfactants, anionic surfactants, and nonionic surfactants.
- lubricants examples include internal lubricants, external lubricants, and the like.
- the internal lubricant is not particularly limited, and examples thereof include butyl stearate, lauryl alcohol, stearyl stearate, epoxidized soybean oil, glycerin monostearate, stearic acid, bisamide, and the like. These may be used alone or in combination of two or more.
- the external lubricant is not particularly limited, and examples thereof include montanic acid wax, paraffin wax, polyolefin wax, polyethylene wax, polypropylene wax, and ester wax. These may be used alone or in combination of two or more.
- cationic surfactant examples include quaternary ammonium salts, primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, and pyridine derivatives.
- amphoteric surfactants examples include betaine type surfactants, carboxylic acid derivatives, and imidazoline derivatives.
- anionic surfactants include alkyl phosphate surfactants, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, sulfated olefin ester salts, fatty alcohol sulfate ester salts, and alkyl sulfate ester salts. , fatty acid ethyl sulfonate, alkylnaphthalene sulfonate, alkylbenzene sulfonate, phosphoric acid ester sulfonate, and phosphoric acid ester salt.
- nonionic surfactants include partial fatty acid esters of polyhydric alcohols, ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty aminos or fatty acid amides, and ethylene oxide adducts of alkylphenols.
- ethylene oxide adduct of partial fatty acid ester of polyhydric alcohol polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol copolymer, Polyglykol PR600 (manufactured by CLARIANT Co., Ltd., CAS No.: 9003-11-6), Polyglykol P41/300 (manufactured by CLARIANT Co., Ltd., CAS No.: 58205-99-5), polyethylene glycol acrylate, polyethylene glycol methacrylate, monomethoxy polyethylene glycol acrylate, monomethoxy polyethylene glycol methacrylate, polypropylene glycol acrylate, polypropylene glycol methacrylate, monomethoxy Examples include polypropylene glycol acrylate, monomethoxypolypropylene glycol methacrylate, monomethoxypolyethylene glycol, dimethoxypolyethylene glycol, monomethoxypolypropylene glycol, and dimethoxypolypropy
- oils such as lubricating oil, solid sliding agents, and the like.
- Lubricating oils include paraffinic and naphthenic mineral oils such as spindle oil, refrigeration oil, dynamo oil, turbine oil, machine oil, cylinder oil, and gear oil, as well as grease, hydrocarbons, esters, polyglycols, polyphenylene ethers, silicones, Examples include halocarbon-based synthetic oils.
- solid lubricants include polytetrafluoroethylene particles, molybdenum disulfide, silicone rubber, polyethylene, and graphite.
- curing agent examples include t-butyl peroxybenzoate, t-amyl peroxybenzoate, 1,1-dimethylbutyl peroxybenzoate, 1,1,2-trimethylpropyl peroxybenzoate, 1,1,3,3 - Tertiary (C4-C10) alkyl peroxybenzoates such as tetramethylbutylperoxybenzoate; t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, 1, 1-dimethylbutylperoxy-2-ethylhexanoate, 1,1,2-trimethylpropylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate Noate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1-dimethylbutylperoxypivalate,
- (C4-C10) Alkyl ester Alkyl ester; Ketone peroxides such as methyl ethyl ketone peroxide, methyl isopropyl ketone peroxide, methyl isobutyl ketone peroxide, and cyclohexanone peroxide; t-butyl peroxyisopropyl carbonate, t-amyl peroxy isopropyl carbonate, 1,1-dimethylbutylperoxyisopropyl carbonate, 1,1,2-trimethylpropylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, t-amylperoxy-2-ethylhexyl carbonate, 1,1-dimethyl Peroxymonocarbonates such as butylperoxy-2-ethylhexyl carbonate, 1,1,2-trimethylperoxypropyl carbonate, 1,1,3,3-tetramethylbutylperoxy-2-ethy
- polymerization inhibitor examples include quinones such as parabenzoquinone, tolquinone, naphthoquinone, phenanthraquinone, and 2,5 diphenylparabenzoquinone; toluhydroquinone, hydroquinone, tert-butylcatechol, monotert-butylhydroquinone, 2,5 Hydroquinones such as di-tert-butylhydroquinone; monophenols such as hydroquinone monomethyl ether and 2,6-di-t-butyl-p-cresol;
- low shrinkage agent examples include thermoplastic resins such as polystyrene, polymethyl methacrylate, polyvinyl acetate, saturated polyester, and styrene-butadiene rubber.
- Examples of the accelerator include cobalt naphthenate, cobalt octenoate, manganese naphthenate, copper naphthenate, cobalt octenoate, and copper octenoate.
- mold release agents include sodium dialkylsulfosuccinate such as sodium di(2-ethylhexyl)sulfosuccinate, metal soaps such as zinc stearate and calcium stearate, fluorine-based organic compounds, and phosphoric acid-based compounds. Can be mentioned.
- thickener examples include calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, and oxides or hydroxides of magnesium and calcium.
- fibers include organic fibers and inorganic fibers, and examples of organic fibers include carbon fibers and aramid fibers.
- examples of inorganic fibers include chopped glass strands, milled glass fibers, roving glass, and the like.
- fillers examples include glass beads, glass balloons, glass flakes, asbestos, mica, calcium carbonate, magnesium carbonate, magnesium sulfate, talc, silica, calcium silicate, potassium titanate whiskers, hydrotalcite, kaolin, diatomaceous earth.
- inorganic fillers such as carbon black, graphite, pumice, Evo powder, cotton flock, cork powder, barium sulfate, and organic fillers such as fluororesin, wood flour, cellulose powder, and other natural fine powders or fibers and synthetic fibers. Can be mentioned.
- the resin composition according to the present invention is extrusion molded, injection molded, vacuum molded, blow molded, or roll molded, from the viewpoint of moldability, the resin composition is molded at 230°C and under a load of 2.16 kgf in accordance with JIS K7210.
- the measured melt flow rate (MFR) of the resin composition is preferably 0.1 to 100 g/10 minutes.
- melt flow rate (MFR) of the resin composition is measured in accordance with JIS K7210 at 230°C and under a load of 2.16 kgf. is preferably 1 to 1000 g/10 minutes.
- the method for producing the resin composition according to the present invention is not particularly limited.
- the resin composition according to the present invention includes the polymer 1 and, if necessary, a thermoplastic resin, a thermosetting resin, a quorum sensing inhibitor, an antibacterial/antifungal agent, a surface modifier, and other additives. They may be produced by melt-kneading and then cooling, or they may be melt-kneaded and then produced as pellets using a pelletizer.
- the resin composition according to the present invention is prepared by adding the polymer 1 and, if necessary, a thermoplastic resin, a thermosetting resin, a quorum sensing inhibitor, an antibacterial/antifungal agent, a surface modifier, and other additives. After preparing a high-concentration masterbatch by melt-kneading the ingredients, a composition may be produced by further adding the polymer 1, a thermoplastic resin, or a thermosetting resin and melt-kneading the mixture.
- the resin composition according to the present invention can be prepared by simply mixing the polymer 1 with a thermosetting resin, a quorum sensing inhibitor, an antibacterial/antifungal agent, a surface modifier, other additives, etc. as necessary. After dissolving the polymer 1 in a solvent, a thermosetting resin, a quorum sensing inhibitor, an antibacterial/antifungal agent, a surface modifier, and other additives may be added as necessary. It may be produced by mixing Polymer 1 with a solvent or, if necessary, a thermosetting resin, a quorum sensing inhibitor, an antibacterial/antifungal agent, a surface modifier, other additives, etc.
- Polymer 1 may be produced by mixing with a solution dissolved in a solvent, and then a thermosetting resin, a quorum sensing inhibitor, an antibacterial/antifungal agent, a surface It may also be manufactured by dissolving the modifier, other additives, etc. in a solvent and then mixing.
- the resin composition according to the present invention is prepared by adding the polymer 1 and, if necessary, a thermoplastic resin, a thermosetting resin, a quorum sensing inhibitor, an antibacterial/antifungal agent, a surface modifier, and other additives. After preparing a high-concentration masterbatch by simply mixing materials, etc., or by dissolving them in a solvent and then mixing them, polymer 1, thermoplastic resin, thermosetting resin, etc. are added as is or dissolved in a solvent as necessary.
- the composition may be manufactured by adding the components after the addition and mixing.
- the resin composition according to the present invention comprises a monomer or prepolymer of the polymer 1, a thermoplastic resin, a thermosetting resin, a quorum sensing inhibitor, an antibacterial/antifungal agent, a surface modifier, as necessary,
- the composition may be manufactured by mixing other additives, etc., or may be further manufactured by polymerization. Examples of polymerization methods include bulk polymerization, cast polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
- a molded article and a coating film can be produced using Polymer 1 or Resin Composition A or Resin Composition B obtained by the above method as a raw material.
- the polymers and compositions according to the present invention can be used as sliding materials, flame retardant materials, mold release materials, and antifouling materials.
- the polymers and compositions according to the present invention have excellent moldability and can have any shape, such as spherical, angular (cube-shaped), bead-shaped (bead-shaped) , cylindrical (pellet-like), powder-like, rod-like (stick-like), needle-like, fibrous-like (fiber-like), strand-like, filament-like, string-like, rope-like, rope-like, plate-like, sheet-like, membrane-like ( Examples include film-like shapes, woven fabrics, non-woven fabrics, box-like (capsule-like) foam forms, and any three-dimensional shape, and the shape can be appropriately selected depending on the purpose of use.
- any shape such as spherical, angular (cube-shaped), bead-shaped (bead-shaped) , cylindrical (pellet-like), powder-like, rod-like (stick-like), needle-like, fibrous-like (fiber-like), strand-like, filament-like, string-like, rope-like, rope-like,
- Molded objects that are spherical, angular (cube-like), bead-like, cylindrical (pellet-like), or powder-like are made of a material in which the polymer according to the present invention is different from the polymer according to the present invention.
- a covered core-shell structure may be formed, and a material different from the polymer according to the invention may form a core-shell structure covered with the polymer according to the invention.
- materials different from the polymer according to the present invention include polymers different from the polymer according to the present invention, metals, and inorganic substances other than metals.
- Molded objects that are rod-shaped, needle-shaped, fibrous (fiber-shaped), strand-shaped, filament-shaped, cord-shaped, rope-shaped, or rope-shaped are different from the polymer according to the present invention when they are combined according to the present invention.
- a core-sheath structure covered with a different material may be formed, and a material different from the polymer according to the present invention may form a core-sheath structure covered with a polymer according to the present invention. good.
- a plate-like, sheet-like, membrane-like (film-like), woven fabric-like, non-woven fabric-like, box-like or capsule-like molded article is one in which the polymer according to the present invention is made of a material different from the polymer according to the present invention.
- a laminated structure covered on both sides or one side may be formed, and a material different from the polymer according to the present invention may form a laminated structure covered on both sides or one side with the polymer according to the present invention. Good too.
- a molded body having a shape different from that of a foam or a material different from the polymer according to the present invention means: It may form a core-shell structure, a core-sheath structure or a laminated structure.
- the fiber containing the polymer according to the present invention is produced by spinning a resin composition (hereinafter sometimes referred to as "resin composition (A) or resin composition (B)") containing the polymer (1). This can be obtained by
- the resin composition (A) or the resin composition (B) may contain only the polymer (1) as a polymer component, or may contain the polymer (1) and a polymer different from the polymer (1). May include.
- examples of the polymer include the polymer (2).
- the total amount of the polymer (1) and the polymer (2) is 100% by weight, It is preferable that the content of the polymer (1) is 1% by weight or more and 99% by weight or less, and the content of the polymer (2) is 1% by weight or more and 99% by weight or less.
- the resin composition (A) or the resin composition (B) contains a polymer (1) and a polymer different from the polymer (1), and the polymer different from the polymer (1) contains a polymer ( 1), the phase consisting of polymer (1) and the phase consisting of a polymer different from polymer (1) usually have a sea-island structure, a cylinder structure, a lamellar structure, or a common structure. Forms morphology such as a continuous structure.
- the cross-sectional shape of the fiber containing the resin composition (A) or the resin composition (B) may be an irregular cross-section such as a circular cross-section, a polygon, or a multilobal cross-section, or may be a hollow cross-section.
- the single fiber fineness of the fiber containing the resin composition (A) or the resin composition (B) is not particularly limited, but from the viewpoint of ease of fiberization, it is preferably 1 dtex or more, and from the viewpoint of fiber flexibility, 20 dtex or less. preferable.
- Methods for producing fibers containing the resin composition (A) or resin composition (B) include, for example, dry spinning, wet spinning, and melt spinning, with melt spinning being preferred.
- the general spinning method consists of two steps, a spinning step and a stretching step, using a chip containing a resin composition as a raw material.
- the spinning method is such that the resin composition is not made into chips but is continuously produced from the resin composition production process.
- spin draw method direct spinning and drawing method
- POY semi-drawn yarn
- Examples include the POY-DTY method, in which drawn yarn (DTY) is obtained by hand-drawn yarn, and the spunbond method. These methods are more streamlined than the general spinning methods.
- the fiber containing the resin composition (A) or the resin composition (B) may be a composite fiber.
- Composite fiber refers to a fiber in which two or more types of fibers made of different components are joined within a single yarn. Examples of the composite fibers include core-sheath type composite fibers, bonded type composite fibers, split type composite fibers, and sea-island type composite fibers.
- the single fiber fineness of the composite fiber containing the resin composition (A) or the resin composition (B) is not particularly limited, but is preferably 1 dtex or more from the viewpoint of ease of fiberization, and 20 dtex or less from the viewpoint of fiber flexibility. preferable.
- the structure of the core-sheath type composite fiber is, for example, a core-sheath structure in which a material different from the resin composition (A) or the resin composition (B) is covered with the resin composition (A) or the resin composition (B).
- structure and a core-sheath structure in which the resin composition (A) or the resin composition (B) is covered with a material different from the resin composition (A) or the resin composition (B), preferably, It has a core-sheath structure in which a material different from the resin composition (A) or the resin composition (B) is covered with the resin composition (A) or the resin composition (B).
- the material different from the resin composition (A) or the resin composition (B) is preferably the polymer (2), more preferably polypropylene (PP), polyethylene terephthalate (PET), or polytrimethylene.
- PP polypropylene
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PA6 polyamide 6
- PA66 polyamide 66
- the bonded composite fibers are crimped due to the difference in shrinkage rate of the fibers containing the resin composition (A) or the resin composition (B), but when the composite fibers are crimped in a spiral shape, the resin composition (A) or the resin composition (B) may be on the outside of the helix, and a material different from the resin composition (A) or the resin composition (B) may be on the outside of the helix, preferably, This is a bonded composite fiber in which the resin composition (A) or the resin composition (B) is on the outside of the spiral.
- the material different from the resin composition (A) or the resin composition (B) is preferably the polymer (2), more preferably polypropylene (PP), polyethylene terephthalate (PET), or polytriester. Methylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6) or polyamide 66 (PA66).
- the splittable composite fibers are split and opened by chemically treating fibers containing the resin composition (A) or the resin composition (B) to obtain ultrafine fibers.
- the resin composition (A) or the resin composition (B) may be the plurality of surrounding wedge-shaped fibers
- the resin composition A plurality of surrounding wedge-shaped fibers may be made of a material different from the material (A) or the resin composition (B), and preferably, the resin composition (A) or the resin composition (B) is a material different from the surrounding plurality of wedge-shaped fibers. It is a split type composite fiber that is a wedge-shaped fiber.
- the material different from the resin composition (A) or the resin composition (B) is preferably the polymer (2), more preferably polypropylene (PP), polyethylene terephthalate (PET), or polytriester. Methylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6) or polyamide 66 (PA66).
- PP polypropylene
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PA6 polyamide 6
- PA66 polyamide 66
- the sea-island type composite fiber is obtained by chemically treating fibers containing the resin composition (A) or the resin composition (B) to remove the sea fibers and obtain ultrafine fibers consisting of a plurality of island fibers.
- the resin composition (A) or the resin composition (B) may be an island fiber, and a material different from the resin composition (A) or the resin composition (B) may be an island fiber,
- the resin composition (A) or the resin composition (B) is an island-in-sea type composite fiber in which the resin composition (A) or the resin composition (B) is an island fiber.
- the material different from the resin composition (A) or the resin composition (B) is preferably the polymer (2), more preferably polypropylene (PP), polyethylene terephthalate (PET), or polytriester. Methylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6) or polyamide 66 (PA66).
- PP polypropylene
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PA6 polyamide 6
- PA66 polyamide 66
- Examples of the form of the fibers containing the resin composition (A) or the resin composition (B) include long fibers (multifilament, monofilament) and short fibers (staple).
- the long fibers (multifilament, monofilament) may be used as they are, may be made into a false twisted yarn by false twisting, or may be made into a mixed yarn by air mixing or the like.
- the short fibers (staples) may be used as they are, may be spun to form a spun yarn, or may be spun to form a blended yarn.
- the form of the fiber containing the resin composition (A) or the resin composition (B) may be a core spun yarn in which long fibers are combined with short fibers, and the resin composition (A) or the resin composition (B) By twisting the fibers containing the above, it may be made into plied threads, intertwisted threads, or covering threads.
- the fibers containing the resin composition (A) or the resin composition (B) contain antioxidants, pigments, dyes, antibacterial agents, deodorants, antistatic agents, flame retardants, inert fine particles, light-absorbing heat-generating materials, and moisture-absorbing materials. It may contain additives such as a heat generating material and a far infrared heat generating material. The additive can be added during or after spinning the resin composition (A) or the resin composition (B).
- a light-absorbing and heat-generating fiber containing a resin composition (A) or a resin composition (B) and a light-absorbing and heat-generating material contains a light-absorbing and heat-generating material such as zirconium carbide that absorbs a specific wavelength of sunlight and converts it into thermal energy with high efficiency. , fibers fixed inside and on the surface of the fibers. Cloth made of light-absorbing and heat-generating fibers can increase the temperature of the cloth surface exposed to the sun, compared to cloth made of fibers that do not contain light-absorbing and heat-generating material.
- the moisture-absorbing heat-generating fiber containing the resin composition (A) or resin composition (B) and the moisture-absorbing heat-generating material is a fiber that generates adsorption heat when absorbing moisture, and releases moisture in a low-humidity environment, reducing the temperature and humidity inside clothing. It is a fiber that has the effect of controlling
- a far-infrared processed fiber containing a resin composition (A) or a resin composition (B) and a far-infrared emitting material is a fiber in which ceramics or the like with high far-infrared radiation is fixed to the inside and surface of the fiber. It is a fiber that has a heat-retaining effect.
- the fabric made of fibers containing the resin composition (A) or the resin composition (B) may be any of woven fabrics, knitted fabrics, and nonwoven fabrics.
- Examples of the weave structure include plain weave, twill weave, satin weave, and variations thereof, dobby, and jacquard.
- Examples of the knitting structure include weft knitting, warp knitting, and variations thereof.
- the fabric weight and gauge of the fabric made of fibers containing the resin composition (A) or the resin composition (B) are not particularly limited.
- the fabric/fabric made of fibers containing the resin composition (A) or the resin composition (B) may be made of only the fibers containing the resin composition (A) or the resin composition (B), or may be made of fibers containing the resin composition (A) or the resin composition (B). It may be used by interweaving or knitting with.
- other fibers include inorganic fibers such as carbon fibers, inorganic fibers, and metal fibers; refined fibers such as Lyocell; recycled fibers such as rayon, cupro, and polynosic; semi-synthetic fibers such as acetate, triacetate, and Promix; and acrylic fibers.
- acrylic fibers acrylic fibers, vinylon, vinylidene, polyvinyl chloride, polyethylene, polyclar, aramid, polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyamide 66 (PA66), urethane, and other synthetic fibers; cotton, cellulose-based Fibers, plant fibers such as hemp (flax, ramie, hemp, jute, etc.) or wool; animal fibers such as wool, animal hair (Angora, cashmere, mohair, alpaca, camel, etc.), silk; down, feathers and other feathers.
- the proportion of the fiber containing the resin composition (A) or the resin composition (B) is not particularly limited, but is preferably 20% by weight to 100% by weight.
- the nonwoven fabric made of fibers containing the resin composition (A) or the resin composition (B) may contain heat-fusible binder fibers.
- the heat-sealing binder fiber is a core-sheath type, a bonded type, etc. made of a resin composition (A) or a resin composition (B) and a material having a melting point different from that of the resin composition (A) or the resin composition (B).
- Composite fibers are preferred.
- the material having a different melting point from the resin composition (A) or the resin composition (B) is preferably the polymer (2), more preferably polypropylene (PP), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyamide 6 (PA6) or polyamide 66 (PA66).
- PP polypropylene
- PET polyethylene terephthalate
- PTT polytrimethylene terephthalate
- PBT polybutylene terephthalate
- PA6 polyamide 6
- PA66 polyamide 66
- the content thereof is preferably 5 to 20% by weight based on the total fibers of the nonwoven fabric.
- the nonwoven fabric made of fibers containing the resin composition (A) or the resin composition (B) should have a basis weight of 100 g/m2 or less and a thickness of 5 mm or less, from the viewpoints of lightness, soft feel, fashionability of clothing, etc. It is preferable that the area weight is 60 g/m 2 or less, and it is more preferable that the thickness is 5 mm or less.
- a method for producing a nonwoven fabric made of fibers containing the resin composition (A) or the resin composition (B) usually includes a web forming step and a web bonding step.
- the web forming process include dry method, wet method, spunbond method, melt blown method, and air laid method
- examples of the web bonding process include chemical bonding method, thermal bonding method, needle punching method, and water jet method.
- One example is the confounding method.
- Molded object By molding the polymer 1, resin composition A, or resin composition B, a molded object containing the polymer or composition can be produced.
- the method for molding the polymer 1, resin composition A, or resin composition B is not particularly limited, and includes, for example, injection molding, extrusion molding, vacuum molding, pressure molding, press molding, transfer molding, and casting. Molding, compression molding, lamination molding, inflation molding, calendar molding, blow molding, blow molding, two-color molding, foam molding, insert molding, in-mold coating molding, rotational molding, hand lay-up molding, spray-up molding, matched die molding, Examples of molding methods include vacuum injection molding, filament winding molding, centrifugal molding, and pultrusion molding.
- Examples of the molded product of the present invention include injection molded products, extrusion molded products, vacuum molded products, pressure molded products, press molded products, transfer molded products, cast molded products, compression molded products, laminate molded products, and inflation molded products. , calendar molded products, blow molded products, hollow molded products, two-color molded products, foam molded products, insert molded products, in-mold coating molded products, rotary molded products, hand lay-up molded products, spray-up molded products, matched die molded products , a vacuum injection molded product, a filament winding molded product, a centrifugal molded product, a pultrusion molded product, a sheet, a film, etc.
- the molded article may have a single layer structure or a multilayer structure.
- the molded article of the present invention may be a multilayer structure including a layer made of Polymer 1, Resin Composition A, or Resin Composition B, and a layer different from the layer.
- the layer made of polymer 1 or resin composition A or resin composition B is preferably at least one surface layer of the multilayer structure.
- the material constituting the layer different from the layer consisting of the polymer 1 or the resin composition A or the resin composition B include a resin different from the resin composition A or the resin composition B, metal, paper, leather, etc. Can be mentioned.
- the multilayer structure can be manufactured by laminating a layer made of resin composition A or resin composition B and a layer different from the layer.
- One embodiment of the molded article according to the present invention includes the following coating film.
- Coating film Polymer 1, resin composition A or resin composition B is applied onto a substrate and dried, or after dissolving polymer 1, resin composition A or resin composition B in a solution, the solution is A coating film containing the polymer and composition can be produced by coating on a substrate.
- the method of applying the polymer 1, resin composition A, or resin composition B is not particularly limited, and examples include dip coating, roll coating, bar coating, screen printing, doctor blade, spin coating, and spray coating.
- coating methods include coating method, die coating method, and vapor deposition method.
- the medium for dissolving the polymer (1), resin composition (A) or resin composition (B) is not particularly limited as long as the polymer or resin composition can be dissolved or dispersed, and a solvent may be used. Often monomers may be used or solvents and monomers may be combined.
- solvents examples include water, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, toluene, xylene, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate.
- solvents include ethylene glycol dimethyl ether, dichloromethane, dichloroethane, N,N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, chloroform, ortho-dichlorobenzene, and examples of monomers include methyl acrylate, methyl methacrylate, and benzyl.
- (Meth)acrylic monomers such as methacrylate, epoxy monomers, styrene, vinyl monomers such as vinyltoluene, silane coupling agents such as trimethoxysilane and triethoxysilane, polymerizable unsaturated monomers, polyols, polyisocyanates etc.
- the medium may be a combination of two or more types of solvents or monomers, and compounds other than the polymer 1, the resin composition (A), or the resin composition (B) may be dissolved therein.
- Substrates to which the coating film of the present invention is applied include, for example, metals such as silicon, iron, copper, aluminum, and zinc, inorganic materials such as alloys, ceramics, stainless steel, and glass, acrylic resins, polycarbonate resins, and polyester resins.
- Thermoplastic resins such as styrene resin, acrylic-styrene copolymer resin, cellulose resin, polyolefin resin, polyvinyl alcohol; Organic resin such as phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, silicone resin, urethane resin, etc. Examples include wood, stone, cement, concrete, fiber, fabric, paper, and leather.
- the coating film may be a single layer or a multilayer.
- the shape of the substrate to which the coating film of the present invention is applied includes, for example, a flat plate, a film, a curved surface, a spherical shape, an angular shape (cube shape), a bead shape (bead shape), a cylindrical shape (pellet shape), a powder shape, and a rod shape.
- the coating film of the present invention may be a multilayer coating film including a layer consisting of polymer 1, resin composition A or resin composition B, and a layer different from this layer.
- the layer consisting of Polymer 1, Resin Composition A, or Resin Composition B is preferably at least one surface layer of the multilayer coating film.
- materials constituting a layer different from the layer consisting of polymer 1, resin composition A, or resin composition B include a resin different from polymer 1, resin composition A, or resin composition B, a primer, etc. Can be mentioned.
- a multilayer coating film can be produced by sequentially coating a layer consisting of Polymer 1, Resin Composition A or Resin Composition B, and a layer different from the layer on a substrate.
- Compositions, molded objects, fibers, coatings, and paints containing Polymer 1 have excellent water repellency, oil repellency, slime adhesion inhibiting function, and shape transferability.
- the at least one property further selected from antifouling properties, sliding properties, antistatic properties, heat resistance, chemical resistance, solvent resistance, low chemical permeability, flame retardance, electrical properties, and durability It is also excellent. Therefore, it can be used in various applications requiring the above characteristics.
- the molded article of the present invention has excellent stain resistance, so that it can be used, for example, in textile products, kitchen utensils and their parts, bathroom/wash basin/toilet products and their parts, housing equipment parts, water storage equipment parts, home appliances, etc.
- - can be suitably used as a member of coastal facilities.
- Examples of articles to which a molded article containing Polymer 1 or Resin Composition A or Resin Composition B can be applied include the following: Tableware, various cooking utensils, storage containers, water purification pods, water purifiers, drains, drain traps, triangular corners, various sink parts, water storage pods, insulation pods, wraps, IH heaters, drainer baskets, water supplies, faucets, kitchen hoods, Kitchen parts and utensils such as coffee grinders; Washbasin parts such as sinks, basins, vanities, mirrors, drains, drain traps, drain plugs, hair catchers, drain traps; Bathroom parts such as bathroom walls, bathroom floors, bathroom doors, counters, bathtubs, faucets, mirrors, ventilation fans, bathroom dryers, bath lids, showers, etc.; Laundry components such as washing machines, dryers, hoses, washing tubs, washing machine drain traps, washing machine drain ports; Toilet parts such as toilet seats, toilet seat lids, toilet bowls, water storage tanks, remote controls
- a method for measuring the amount of biofilm attached to a material containing the polymer or composition according to the present invention comprises a step of forming a biofilm on the material and a step of quantifying the formed biofilm.
- Biofilms used for measurement can be collected from various environments and used as they are. Furthermore, bacteria known to form biofilms can be used alone or in combination in combination. The types of bacteria contained in biofilms vary depending on the environment in which they are formed, and the types of bacteria also vary depending on the time of collection and environmental conditions. Therefore, even if the same material is measured, the results may differ from measurement to measurement. Therefore, in evaluating the biofilm adhesion of a material, it is preferable to use bacteria known to form biofilms alone or in combination of several types from the viewpoint of quantitative properties and reproducibility.
- the bacteria used to measure the amount of biofilm adhesion are not particularly limited as long as they have the ability to form biofilms.
- Examples of bacteria used in the measurement include bacteria of the genus Pseudomonas, bacteria of the genus Brevundimonas, bacteria of the genus Methylobacterium, bacteria of the genus Bacillus, and bacteria of the genus Staphylococcus. can be mentioned.
- the bacteria used in the measurement are preferably those that are easy to culture, have a large amount of adhesion to the material, and do not peel off from the material even with a weak stream of water.
- Staphylococcus epidermidis ATCC 35984 or Brevundimonas diminuta NBRC 14213 are preferred.
- a biofilm As a method for forming a biofilm on a material, it is possible to form a biofilm on the material by placing the material in a place where a biofilm is formed. Furthermore, a biofilm can be formed on the material by immersing the material in a culture solution using a general microorganism culturing method. To measure the amount of biofilm adhesion, it is preferable to use a general microbial culture method from the viewpoint of quantitativeness and reproducibility. It is more preferable to use conditions such as sterilizing the culture medium to prevent contamination with bacteria.
- the culture conditions for forming a biofilm on the material include temperature, ventilation, physical conditions such as shaking or standing still, medium components, concentration, nutritional conditions such as pH, material and size of the container used for culture, etc. Conditions can be set as appropriate as long as they are within a range where bacteria can proliferate.
- the shape and size of the material for forming a biofilm can be set as appropriate as long as it can be stored in a culture container and immersed in a culture solution.
- Biofilm detection methods include suspending the biofilm in water and counting the number of bacteria, and staining the biofilm with a staining reagent. Therefore, a method of staining the biofilm is preferred.
- reagents for staining biofilms include crystal violet, methylene blue, fuchsin, acridine orange, DAPI, and Alcian blue, but crystal violet is preferred from the viewpoint of ease of measurement, quantitative properties, and reproducibility. .
- the structural unit (C 1 ) derived from methyl acrylate contained in the ethylene-methyl acrylate copolymer is converted into the structural unit (B 2 ) represented by formula (1) of polymer (1).
- the conversion rate (X 1 ) was calculated.
- Number of structural units (A 2 ) contained in polymer (1) Number of structural units (A 1 ) contained in ethylene-methyl acrylate copolymer
- Number of structural units (B 2 ) contained in polymer (1) (number of structural units (C 1 ) contained in ethylene-methyl acrylate copolymer) x conversion rate (X 1 )/100
- Number of structural units (C 2 ) contained in polymer (1) (number of structural units (C 1 ) contained in ethylene-methyl acrylate copolymer) - (number of structural units (C 1 ) contained in polymer (1) B2 ) number)
- the number of structural units (A 2 ), the number of structural units (B 2 ), and the number of structural units (C 2 ) obtained in this way are respectively the structural units derived from ethylene contained in the polymer ( A) corresponds to the number (unit: %) of the structural unit (B) represented by the above formula (1) and the structural unit (C) represented by the above formula (2).
- Weight% of structural unit (A) (number of structural units (A) x molecular weight of structural unit (A)) / (number of structural units (A) x molecular weight of structural unit (A) + molecular weight of structural unit (B) number x molecular weight of structural unit (B) + number of structural unit (C) x molecular weight of structural unit (C))
- Weight% of structural unit (B) (number of structural units (B) x molecular weight of structural unit (B)) / (number of structural units (A) x molecular weight of structural unit (A) + molecular weight of structural unit (B) number x molecular weight of structural unit (B) + number of structural unit (C) x molecular weight of structural unit (C))
- Weight% of structural unit (C) (number of structural units (C) x molecular weight of structural unit (C)) / (number of structural units (A) x molecular weight of structural unit (A) + molecular weight of structural unit (B) number x molecular weight of structural unit (B) + number of structural unit (C) x molecular weight of structural unit (C))
- Polystyrene equivalent molecular weight of polymer (1) PS equivalent number average molecular weight Mn, PS equivalent weight average molecular weight Mw, PS equivalent z average molecular weight Mz (unit: g/mol)
- the polystyrene equivalent molecular weight of the polymer was measured using a gel permeation chromatography (GPC) device and software under the measurement conditions shown below.
- Standard materials 12 types of polystyrene standard samples listed in standards 1 to 4 below (Tosoh)
- Solvent Add 0.1 w/v of BHT to orthodichlorobenzene (Wako, special grade)
- Standard solution concentration Add the specified weight of each of the three types as shown in Standards 1 to 4 below to 5 mL of solvent Dissolution conditions: Room temperature Standard 1: F700 (0.4mg), F20 (0.9mg), A5000 (1.2mg) Standard 2: F288 (0.4mg), F10 (1.0mg), A2500 (1.2mg) Standard 3: F80 (0.7mg), F4 (1.1mg), A1000 (1.3mg) Standard 4: F40 (0.8mg), F2 (1.1mg), A500 (1.3mg)
- Example solution preparation conditions Solvent: 0.1 w/v of BHT added to orthodichlorobenzene (Wako, special grade) Sample solution concentration: 1 mg/mL Melting conditions: 140°C, 2 hours
- GPC device HLC-8121GPC/HT (Tosoh)
- GPC column GMHHR-H(S)HT x 3 (Tosoh)
- ⁇ GPC measurement conditions Mobile phase: 0.5 mg/mL of BHT added to orthodichlorobenzene (Wako, special grade) Flow rate: 1 mL/min Column oven temperature: 155°C Sample injection part temperature: 155°C Each detector temperature: 155°C Sample solution injection volume: 0.3mL Refractive index increment (dn/dc): The dn/dc of the polymer (1) and the polyethylene standard material 1475a was set to -0.078 mL/g, and the dn/dc of the polystyrene standard material was set to 0.079 mL/g. Scattering angle: 90°
- Example solution preparation conditions Solvent: 0.1w/V of BHT added to orthodichlorobenzene (Wako, special grade) Sample solution concentration: 2mg/mL Melting conditions: 145°C, 2 hours
- ⁇ 1 is calculated by plotting the measured data with the logarithm of the absolute molecular weight of polymer (1) as the horizontal axis and the logarithm of the intrinsic viscosity of polymer (1) as the vertical axis, and calculating the logarithm of the absolute molecular weight and the logarithm of the intrinsic viscosity. is approximated by the least squares method using formula (II) within the range where the horizontal axis is greater than or equal to the logarithm of the weight average molecular weight of the polymer (1) and less than or equal to the logarithm of the z-average molecular weight, and ) is the value obtained by finding the slope of the straight line: ⁇ 1 .
- ⁇ 0 is calculated by plotting the measured data with the logarithm of the absolute molecular weight of the polyethylene standard material 1475a as the horizontal axis and the logarithm of the intrinsic viscosity of the polyethylene standard material 1475a as the vertical axis, and calculating the logarithm of the absolute molecular weight and the logarithm of the intrinsic viscosity.
- the least squares approximation is performed using formula (I-II), and the expression is expressed by formula (I-II).
- a stainless steel mesh (6 mesh) measuring 30 mm long x 30 mm wide, a release PET measuring 50 mm long x 50 mm wide x 0.1 mm thick, and an aluminum plate measuring 50 mm long x 50 mm wide x 0.3 mm thick were placed on top of the molded body in this order. After applying pressure at 0.1 MPa for 30 seconds, it was cooled for 5 minutes on a press plate at 30°C. If 90% or more of the number of openings in the mesh were transferred, the shape transferability was evaluated as " ⁇ ". If less than 90% of the number of openings were transferred, the shape transferability was rated "x".
- Biofilm staining solution (0.2% by mass crystal violet solution: CV solution) 4 g of Crystal Violet (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to a 2000 mL polyethylene bottle, and then 2000 mL of pure water was added to dissolve it, thereby preparing a biofilm staining solution.
- - Stained biofilm eluate (2.0% by mass sodium dodecyl sulfate solution: SDS solution)
- Add 40 g of sodium dodecyl sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) to a 2000 mL polyethylene bottle, then add 2000 mL of pure water to dissolve it. , and stained biofilm eluate.
- the obtained diluted eluate was placed in a 1 mL spectrometer cell, and a UV-visible spectrophotometer (Shimadzu, UV2450 (used in Examples A1-A3, B1, B2, Comparative Examples A1, A2, B1, B2), The absorbance at a wavelength of 570 nm was measured using UV3150 (used in Examples B3-B5 and Comparative Examples B3-B5). The higher the absorbance, the greater the amount of biofilm attached.
- the absorbance of the test piece of each example (hereinafter referred to as "A (molded body 1)") and the surface area of the test piece of each example “S (molded body 1)”
- the absorbance of the test piece A-1 (hereinafter referred to as “A(A-1)”)
- the surface area “S(A-1)” of the test piece A-1 the following formula ( ⁇ 1) is calculated. was used to determine the "biofilm reduction rate 1" of the polymer of each example.
- test piece is a composition containing G-1 as polymer 2
- a (molded body 2) the absorbance of the test piece of each example
- S (molded body 2) the absorbance of the test piece of each example
- G-1 The absorbance (hereinafter referred to as "A (G-1)") of a test piece obtained from a sheet (CeB1-2) consisting of "S (molded body 2)” and the following G-1 contained in the composition of each example ) and the surface area "S(G-1)" of the test piece obtained from the sheet (CeB1-2) consisting of G-1, using the following formula ( ⁇ 2), the "biofilm Reduction rate 2'' was calculated.
- test piece is a composition containing G-2 as polymer 2
- a (molded body 3) the absorbance of the test piece of each example
- a (G-2) The absorbance (hereinafter referred to as "A (G-2)") of a test piece obtained from a sheet (CeB2-2) consisting of "S (molded body 3)” and the following G-2 contained in the composition of each example )) and the surface area "S(G-2)" of the test piece obtained from the sheet (CeB2-2) consisting of G-2, using the following formula ( ⁇ 3), the "bio A film reduction rate of 3 was determined.
- test piece is a composition containing G-3 as polymer 2
- the absorbance of the test piece of each example hereinafter referred to as "A (molded body 4)
- test piece is a composition containing G-4 as polymer 2
- the absorbance of the test piece of each example hereinafter referred to as "A (molded body 5)
- test piece is a composition containing G-5 as polymer 2
- the absorbance of the test piece of each example hereinafter referred to as "A (molded body 6)
- a (G-5) The absorbance (hereinafter referred to as "A (G-5)”) of a test piece obtained from a sheet (CeB5-2) consisting of "S (molded body 6)” and the following G-5 contained in the composition of each example )) and the surface area "S (G-5)” of the test piece obtained from the sheet (CeB5-2) consisting of G-5, using the following formula ( ⁇ 6), the "bio A film reduction rate of 6'' was determined.
- biofilm reduction rate the higher the level of A-1 below, G-1 below, G-2 below, G-3 below, G-4 below, G-5 below, G-6 below, and G-7 below. This means that the amount of biofilm attached to the test piece is smaller than the amount of biofilm attached to the sheet.
- Ethylene-methyl acrylate copolymer was produced as follows.
- Ethylene and methyl acrylate were copolymerized in an autoclave reactor at a reaction temperature of 195°C and a reaction pressure of 160 MPa using tert-butyl peroxypivalate as a radical polymerization initiator to obtain an ethylene-methyl acrylate copolymer.
- A-1 was obtained.
- the composition and MFR of the obtained copolymer A-1 were as follows.
- ⁇ Catalyst> C-1 Tetra orthotitanate (iso-propyl) [manufactured by Nippon Soda Co., Ltd.]
- G-1 Unsaturated polyester [Rigolac TR-254 M-LVK, manufactured by Showa Denko K.K., Rigorac TR-254 M-LVK contains styrene]
- G-2 Polyvinyl chloride [ZEST 1000H, manufactured by Shin Daiichi PVC Co., Ltd.]
- G-3 Polymethyl methacrylate [Sumipex MM, manufactured by Sumitomo Chemical Co., Ltd.]
- G-4 High density polyethylene [E8080, made by Keiyo Polyethylene]
- G-5 Linear low-density polyethylene [Sumikasen E FV101, manufactured by Sumitomo Chemical Co., Ltd.]
- Hardening agent H-1 Permec N [manufactured by NOF Corporation]
- H-2 2,2'-azobis(isobutyronitrile) [manufactured by Tokyo Chemical Industry Co., Ltd.]
- I-1 Polyglykol P41/300 [manufactured by Clariant Co., Ltd.]
- I-2 Sunwax 151-P [manufactured by Sanyo Chemical Industries, Ltd.]
- I-3 H-7579 [manufactured by Sakai Chemical Industry Co., Ltd.]
- I-4 Ethylene glycol dimethacrylate [manufactured by Tokyo Chemical Industry Co., Ltd.]
- I-5 Terpinolene [manufactured by Tokyo Chemical Industry Co., Ltd.]
- I-6 Sodium di(2-ethylhexyl) sulfosuccinate [manufactured by Tokyo Chemical Industry Co., Ltd.]
- I-7 Sumilizer GP [manufactured by Sumitomo Chemical Co., Ltd.]
- Example A1 (1) Synthesis and analysis of polymer (ex1-1) After purging the inside of a separable flask with an internal volume of 0.5 L equipped with a stirrer and finger baffles with nitrogen gas, 60.00 g of A-1 and 60.00 g of B- 1:149.70 g was added, the oil bath temperature was set at 130° C., and the mixture was heated and stirred for 1.5 hours under a reduced pressure of 10 kPa.
- Example 2 (1) Synthesis and analysis of polymer (ex2-1) Polymer (ex2-1) ( Ethylene-2-(3- ⁇ -butyl-polydimethylsiloxanyl-propoxy)ethyl acrylate-methyl acrylate copolymer) was obtained. The proportion of structural units in the polymer was analyzed by the method described above. The analysis results are shown in Table 1. (2) Production of molded body (sheet) made of polymer (ex2-1) Except for changing the polymer (ex1-1) to the polymer (ex2-1) obtained in Example A2 (1). A molded article (ex2-2) measuring 50 mm x 50 mm x 1 mm was produced in the same manner as in Example 1 (2).
- Example A3 (1) Synthesis and analysis of polymer (ex3-1) Polymer (ex3-1) ( Ethylene-2-(3- ⁇ -butyl-polydimethylsiloxanyl-propoxy)ethyl acrylate-methyl acrylate copolymer) was obtained. The proportion of structural units in the polymer was analyzed by the method described above. The analysis results are shown in Table 1. (2) Preparation of molded body (sheet) made of polymer (ex3-1) Except for changing the polymer (ex1-1) to the polymer (ex3-1) obtained in Example A3 (1). A molded article (ex3-2) measuring 50 mm x 50 mm x 1 mm was produced in the same manner as in Example 1 (2).
- Comparative example A1 (1) Synthesis and analysis of polymer (ce1-1) A stirrer was placed in a two-diameter eggplant flask with an internal volume of 0.2 L equipped with a three-way stopcock, and the flask was dried at 120° C. for 3 hours. After purging the inside of the dried eggplant flask with nitrogen gas, 8.00 g of 3- ⁇ -butyl-polydimethylsiloxanyl-propyl methacrylate (molecular weight 1000, FM-0711, manufactured by JNC Corporation) and methyl methacrylate (Tokyo Kasei Kogyo) were added.
- test piece made of polymer (ce1-1) Test was conducted in the same manner as in Example A1 (2) except that polymer (ex1-1) was changed to polymer (ce1-1).
- a piece (ce1-2) was prepared.
- (3) Contact angle measurement, shape transferability, and biofilm reduction rate evaluation Using the sheet (CE1-2) obtained in (2) above, the contact angle and shape transferability of pure water and hexadecane in the atmosphere were measured as examples. It was evaluated in the same manner as A1. The evaluation results are shown in Table 1. The biofilm reduction rate could not be measured because the sheet disintegrated in water.
- Comparative example A2 Preparation of test piece consisting of A-1 A test piece (ce2-2) was prepared in the same manner as Example A1 (2) except that the polymer (ex1-1) was changed to A-1. did. (2) Contact angle measurement, shape transferability, biofilm reduction rate evaluation Using the sheet (CE2-2) obtained in (1) above, the contact angle of pure water and hexadecane, biofilm reduction rate (formula ( ⁇ 1 ), and the shape transferability was evaluated in the same manner as in Example A1. The evaluation results are shown in Table 1.
- Example B1 A solution (exB1-1) was prepared by dissolving 600 mg of the polymer (ex1-1) in 6 mL of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.) in a glass vial.
- styrene manufactured by Tokyo Chemical Industry Co., Ltd.
- Into a polyethylene bottle add 25 g of G-1 as prepolymer, 6 ml of solution (exB1-1), 250 mg of I-1 as additive, and wash the styrene inside the glass vial of solution (exB1-1). 3 ml was added and stirred for 30 minutes using a magnetic stirrer. Further, 250 mg of H-1 was added as a curing agent, and the mixture was stirred with a magnetic stirrer for 5 minutes to obtain a solution.
- the obtained solution was poured into a butyl rubber frame (inner diameter: 110 mm long x 110 mm wide x 1 mm thick) that was placed on a glass plate measuring 200 mm long x 200 mm wide x 5 mm thick (inner diameter: 110 mm long x 110 mm wide x 1 mm thick).
- a cell is created by placing another glass plate measuring 200 mm long x 200 mm wide x 5 mm thick on the frame, so that one glass plate will be on the vertically lower side and the other glass plate will be on the vertically upper side. It was placed in an oven and left to stand at room temperature for 30 minutes. Thereafter, it was heated at 100° C.
- the unsaturated polyester sheet (exB1-2) is a sheet containing the polymer (ex1-1). Regarding the sheet, the biofilm reduction rate (using the formula ( ⁇ 2)) was evaluated. The evaluation results are shown in Table 2.
- Example B2 (1) Production of resin composition (exB2-1) (G-2) 93.90% by weight, polymer (ex1-1) 4.69% by weight, additive (I-2) 0.47% by weight % and 0.94% by weight of additive (I-3) were put into a laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd., R100) with a rotor rotating at 150°C and 20 rpm for 4 minutes to plasticize, and then A resin composition (exB2-1) was obtained by melt-kneading at 150° C. and 80 rpm for 2 minutes.
- a laboplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd., R100
- Example B3 A solution (exB3-1) was prepared by dissolving 1.50 g of polymer (ex1-1) in 13.50 g of methyl methacrylate (Tokyo Kasei Kogyo Co., Ltd.) in a glass vial. After purging the inside of a 0.5 L separable flask equipped with a stirrer with nitrogen, 17.84 g of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd.) was added with 76 g of methyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a prepolymer.
- polymethyl methacrylate manufactured by Sumitomo Chemical Co., Ltd.
- the obtained solution was poured into a glass cell using two glass substrates measuring 20 cm long x 20 cm wide x 1 cm thick and a 1.5 mm thick vinyl chloride tube as a spacer between the glass substrates, and heated at 65°C. It was heated for 8 hours. Thereafter, a sheet (exB3-2) with a thickness of 1.5 mm was obtained by heating at 120° C. for 2 hours. Regarding the sheet, the biofilm reduction rate (using the formula ( ⁇ 4)) was evaluated. The evaluation results are shown in Table 2.
- Example B4 (1) Production of resin composition (exB4-1) (G-4) 95.22% by weight, polymer (ex1-1) 4.76% by weight, additive (I-7) 0.02% by weight % was put into a laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd., R100) with a rotor rotating at 190°C and 20 rpm for 4 minutes to plasticize it, and then melted and kneaded for 5 minutes at 190°C and 80 rpm to form a resin. A composition (exB4-1) was obtained.
- Example B5 Production of resin composition (exB5-1) 95.00% by weight of (G-5) and 5.00% by weight of polymer (ex1-1) were mixed in a laboratory with a rotor rotated at 170°C and 20 rpm.
- the resin composition (exB5-1) was obtained by putting it into a plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd., R100) for 4 minutes and plasticizing it, followed by melting and kneading at 170° C. and 80 rpm for 5 minutes.
- Comparative example B1 25 g of G-1 as a prepolymer and 3 ml of styrene were added to a polyethylene bottle and stirred for 30 minutes using a magnetic stirrer. Further, 250 mg of H-1 was added as a curing agent, and the mixture was stirred with a magnetic stirrer for 5 minutes to obtain a solution. The obtained solution was poured into a butyl rubber frame (inner diameter: 110 mm long x 110 mm wide x 1 mm thick) that was placed on a glass plate measuring 200 mm long x 200 mm wide x 5 mm thick (inner diameter: 110 mm long x 110 mm wide x 1 mm thick).
- Comparative example B2 (G-2) is sandwiched between two pieces of 0.1 mm thick release PET film, placed within the frame of a spacer measuring 50 mm long x 50 mm wide x 1 mm thick, and sandwiched between 0.5 mm thick aluminum plates. It was further sandwiched between two 2 mm thick stainless steel plates. The obtained sample was placed in a hot press molding machine with a press plate set at 175°C, and the pressure was increased to 1 MPa over 5 minutes, and then cooled at 30°C and 0.5 MPa for 5 minutes to form a 1 mm thick mold. A sheet (CeB2-2) was produced. Regarding the sheet, the biofilm reduction rate (using the formula ( ⁇ 3)) was evaluated. The evaluation results are shown in Table 2.
- Comparative example B3 After purging the inside of a 0.5 L separable flask equipped with a stirrer with nitrogen, 17.84 g of polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd.) was added with 81 g of methyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a prepolymer. .46 g, 0.40 g of I-4 as additives, 0.1 g of a solution of 0.1 g of I-5 dissolved in 0.9 g of methyl methacrylate, and 0.1 g of I-6 in 0.6 g of methyl methacrylate.
- Comparative example B4 (G-4) was sandwiched between two 0.1 mm thick release PET films, placed within the frame of a 50 mm long x 50 mm wide x 1 mm thick spacer, and then placed between 0.5 mm thick aluminum plates. It was then sandwiched between two 2mm thick stainless steel plates. The obtained sample was placed in a hot press molding machine with a press plate set at 190°C, and the pressure was increased to 5 MPa over 5 minutes, and then cooled at 30°C and 5 MPa for 5 minutes to form a 1 mm thick sheet ( CeB4-2) was produced. Regarding the sheet, the biofilm reduction rate (using the formula ( ⁇ 5)) was evaluated. The evaluation results are shown in Table 2.
- Comparative example B5 (G-5) was sandwiched between two 0.1 mm thick release PET films, placed within the frame of a 50 mm long x 50 mm wide x 1 mm thick spacer, and then placed in a 0.5 mm thick aluminum plate. It was then sandwiched between two 2mm thick stainless steel plates. The obtained sample was placed in a hot press molding machine with a press plate set at 190°C, and the pressure was increased to 5 MPa over 5 minutes, and then cooled at 30°C and 5 MPa for 5 minutes to form a 1 mm thick sheet ( CeB5-2) was produced. Regarding the sheet, the biofilm reduction rate (using the formula ( ⁇ 6)) was evaluated. The evaluation results are shown in Table 2.
- the polymer exhibits water repellency and oil repellency, and is also excellent in slime adhesion suppressing function and shape transferability during molding. It is possible to provide a polymer that exhibits oiliness and can provide a resin composition that has an excellent slime adhesion suppressing function and shape transferability during molding.
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Abstract
Description
そこで、本発明は、撥水性および撥油性を示し、さらに、ぬめり付着抑制機能と成形時の形状転写性に優れる重合体と、該重合体を含む樹脂組成物および成形体、並びに、該重合体の製造方法を提供することを目的とする。
重合体。
(式(1)中、
Rは、水素原子またはメチル基を表し、
L1は、―CO―O―、―O―CO―または―O―を表し、
L2は、単結合、―CH2―、―CH2―CH2―、―CH2―CH2―CH2―、―CH2―CH(OH)―CH2―または―CH2―CH(CH2OH)―を表し、
L3は、単結合、―CO―O―、―O―CO―、―O―、―CO―NH―、―NH―CO―、―CO―NH―CO―、―NH―CO―NH―、―NH―または―N(CH3)―を表し、
L6は、―(CH2)n―(Rf2O)p―(Rf3)h―(Si(Rf4)2O)g―Si(Rf1)3を表し、
Rf1は、水素原子又はC1~15のアルキル基を表し、3つのRf1は、同一でも異なっていてもよく、
Rf2は、C1~15のアルキレン基を表し、
Rf3は、C1~15のアルキレン基を表し、
Rf4は、水素原子又はC1~15の置換もしくは非置換のアルキル基又は置換もしくは非置換のC6~20のアリ―ル基を表し、2つのRf4は、同一でも異なっていてもよく、
nは0~10の整数を表し、
pは0~15の整数を表し、pが2以上の整数である場合、複数の―(Rf2O)―は、同一でも異なっていてもよく、
hは0~15の整数を表し、hが2以上の整数である場合、複数の―(Rf3)―は、同一でも異なっていてもよく、
gは1~1000の整数を表し、gが2以上の整数である場合、複数の―(Si(Rf4)2O)―は、同一でも異なっていてもよく、
なお、L1、L2およびL3で表される横書きの化学式の各々は、その左側が式(1)の上側に対応し、その右側が式(1)の下側に対応する。)
(式(2)中、
Rは、水素原子またはメチル基を表し、
L1は、―CO―O―、―O―CO―または―O―を表し、
L4は、単結合または炭素原子数1以上8以下のアルキレン基を表し、
L5は、水素原子、エポキシ基、―CH(OH)―CH2OH、カルボキシ基、ヒドロキシ基、アミノ基または炭素原子数1以上4以下のアルキルアミノ基を表す。
なお、L1で表される横書きの化学式の各々は、その左側が式(2)の上側に対応し、その右側が式(2)の下側に対応する。)
[2]前記構成単位(A)と前記構成単位(B)と前記構成単位(C)の合計数を100mol%として、前記構成単位(A)の数が70~99mol%であり、前記構成単位(B)と前記構成単位(C)の合計数が30~1mol%である、[1]に記載の重合体。
[3]前記構成単位(B)と前記構成単位(C)の合計数を100mol%として、前記構成単位(B)の数が1mol%以上99mol%以下であり、前記構成単位(C)の数が1mol%以上99mol%以下である、[1]又は[2]に記載の重合体
[4]前記構成単位(A)と前記構成単位(B)と前記構成単位(C)の合計量を100重量%として、前記構成単位(B)の含有量が30重量%以上である、[1]~[3]のいずれかに記載の重合体。
[5]前記構成単位(A)と前記構成単位(B)と前記構成単位(C)の合計量を100重量%として、前記構成単位(B)の含有量が50重量%以上である、[1]~[4]のいずれかに記載の重合体。
[6]前記式(1)で示される構成単位(B)において、L6のgが1以上250以下である、[1]~[5]のいずれかに記載の重合体
[7]前記式(1)で示される構成単位(B)において、L11が―CO―O―である、[1]~[6]のいずれかに記載の重合体。
[8]架橋されている、[1]~[7]のいずれかに記載の重合体。
[9]ゲル分率が20%以上である、[1]~[8]のいずれかに記載の重合体。
[10]前記重合体に含まれる全ての構成単位の合計数を100mol%として、前記構成単位(A)と前記構成単位(B)と前記構成単位(C)の合計数が90mol%以上である、[1]~[9]のいずれかに記載の重合体。
[11][1]~[10]のいずれかに記載の重合体を含有する組成物。
[12]前記重合体を1重量%以上含有する[11]に記載の組成物。
[13]ベース樹脂を含有する[11]又は[12]に記載の組成物。
[14]前記ベース樹脂が熱可塑性樹脂である、[13]に記載の組成物。
[15]前記ベース樹脂がポリ塩化ビニルである、[13]に記載の組成物。
[16]前記ベース樹脂が熱硬化性樹脂である、[13]に記載の組成物。
[17]前記ベース樹脂が不飽和ポリエステルである、[13]に記載の組成物。
[18][1]~[10]のいずれかに記載の重合体を含有する成形体。
[19][11]~[17]のいずれかに記載の組成物を含有する成形体。
[20]防汚材である[18]又は[19]に記載の成形体。
[21]抗ぬめり材である[18]又は[19]に記載の成形体。
[22][1]~[10]のいずれかに記載の重合体を含有する塗膜。
[23][11]~[17]のいずれかに記載の組成物を含有する塗膜。
[24]防汚材である[22]又は[23]に記載の塗膜。
[25]抗ぬめり材である[22]又は[23]に記載の塗膜。
[26]エチレン及びプロピレンからなる群より選ばれる少なくとも一種に由来する構成単位(A)と、下記式(2)で示される構成単位および下記式(3)で示される構成単位からなる群より選ばれる少なくとも一種の構成単位(C)とを含む重合体と、
下記式(11)で示される化合物、下記式(12)で示される化合物、下記式(13)で示される化合物、下記式(14)で示される化合物、下記式(15)で示される化合物、下記式(16)で示される化合物、下記式(17)で示される化合物および下記式(18)で示される化合物からなる群より選ばれる1種以上の化合物(α)と
を反応させる工程を含む、[1]~[10]のいずれかに記載の重合体の製造方法。
(式(2)中、
Rは、水素原子またはメチル基を表し、
L1は、―CO―O―、―O―CO―または―O―を表し、
L4は、単結合または炭素原子数1以上8以下のアルキレン基を表し、
L5は、水素原子、エポキシ基、―CH(OH)―CH2OH、カルボキシ基、ヒドロキシ基、アミノ基または炭素原子数1以上4以下のアルキルアミノ基を表す。
なお、L1で表される横書きの化学式の各々は、その左側が式(2)の上側に対応し、その右側が式(2)の下側に対応する。)
HO―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(11)
H2N―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(12)
X―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(13)
HO-C(=O)―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(14)
H2N-C(=O)―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(15)
X-C(=O)―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(16)
H2N-C(=O)-HN―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(17)
OCN―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(18)
式中、Rf1、Rf2、Rf3、Rf4、p、g、h及びnは、式(1)で規定した通りであり、Xはハロゲン原子を表し、
複数の化合物αを用いる場合、各Rf1、Rf2、Rf3、Rf4、p、g、h及びn並びにXは、同一でも異なっていてもよい。)
[27][26]に記載の製造方法によって、得られうる重合体。
本明細書において開示されている全ての数は、「約」又は「概ね」という単語がそれと関連して使用されようとなかろうと、近似値である。それらは、1パーセント、2パーセント、5パーセント、又は時には10~20パーセントで変動してもよい。下限RL及び上限RUを伴う数値の範囲が開示されている場合はいつも、範囲に含まれる任意の数が特に開示される。特に、範囲内の下記の数が特に開示される。R=RL+k*(RU-RL)(式中、kは、1パーセントずつ増加する1パーセント~100パーセントの範囲の変数であり、すなわち、kは、1パーセント、2パーセント、3パーセント、4パーセント、5パーセント、...、50パーセント、51パーセント、52パーセント、...、95パーセント、96パーセント、97パーセント、98パーセント、99パーセント、又は100パーセントである)。さらに、上記に記載の2つのRの数によって定義される任意の数値の範囲もまた、特に開示される。
エチレン及びプロピレンからなる群より選ばれる少なくとも一種に由来する構成単位(A)と、上記式(1)で示される構成単位(B)と、上記式(2)で示される構成単位および上記式(3)で示される構成単位からなる群より選ばれる少なくとも一種の構成単位(C)とを含む重合体(以下、「重合体(1)」と記載することがある)である。
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
3-α-ブチル-ポリジメチルシロキサニル-プロポキシメチルアクリレート、
3-α-プロピル-ポリジメチルシロキサニル-プロポキシメチルアクリレート、
3-α-エチル-ポリジメチルシロキサニル-プロポキシメチルアクリレート、
3-α-メチル-ポリジメチルシロキサニル-プロポキシメチルアクリレート、
3-α-ブチル-ポリジメチルシロキサニル-プロピルアクリレート、
3-α-プロピル-ポリジメチルシロキサニル-プロピルアクリレート、
3-α-エチル-ポリジメチルシロキサニル-プロピルアクリレート、
3-α-メチル-ポリジメチルシロキサニル-プロピルアクリレート、
2-α-ブチル-ポリジメチルシロキサニル-エチルアクリレート、
2-α-プロピル-ポリジメチルシロキサニル-エチルアクリレート、
2-α-エチル-ポリジメチルシロキサニル-エチルアクリレート、
2-α-メチル-ポリジメチルシロキサニル-エチルアクリレート、
2-(2-α-ブチル-ポリジメチルシロキサニル-エトキシ)エチルアクリレート、
2-(2-α-プロピル-ポリジメチルシロキサニル-エトキシ)エチルアクリレート、
2-(2-α-エチル-ポリジメチルシロキサニル-エトキシ)エチルアクリレート、
2-(2-α-メチル-ポリジメチルシロキサニル-エトキシ)エチルアクリレート、
2-(4-α-ブチル-ポリジメチルシロキサニル-ブトキシ)エチルアクリレート、
2-(4-α-プロピル-ポリジメチルシロキサニル-ブトキシ)エチルアクリレート、
2-(4-α-エチル-ポリジメチルシロキサニル-ブトキシ)エチルアクリレート、
2-(4-α-メチル-ポリジメチルシロキサニル-ブトキシ)エチルアクリレート、
4-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)ブチルアクリレート、
4-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)ブチルアクリレート、
4-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)ブチルアクリレート、
4-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)ブチルアクリレート、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
2-(4-α-ブチル-ポリジメチルシロキサニル-ブトキシ)エチルメタクリレート、
2-(4-α-プロピル-ポリジメチルシロキサニル-ブトキシ)エチルメタクリレート、
2-(4-α-エチル-ポリジメチルシロキサニル-ブトキシ)エチルメタクリレート、
2-(4-α-メチル-ポリジメチルシロキサニル-ブトキシ)エチルメタクリレート、
3-α-ブチル-ポリジメチルシロキサニル-プロピルメタクリレート、
3-α-プロピル-ポリジメチルシロキサニル-プロピルメタクリレート、
3-α-エチル-ポリジメチルシロキサニル-プロピルメタクリレート、
3-α-メチル-ポリジメチルシロキサニル-プロピルメタクリレート、
2-α-ブチル-ポリジメチルシロキサニル-エチルメタクリレート、
2-α-プロピル-ポリジメチルシロキサニル-エチルメタクリレート、
2-α-エチル-ポリジメチルシロキサニル-エチルメタクリレート、
2-α-メチル-ポリジメチルシロキサニル-エチルメタクリレート、
3-(2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
3-(2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
3-(2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
3-(2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
3-α-ブチル-ポリジメチルシロキサニル-1-プロペン、
3-α-プロピル-ポリジメチルシロキサニル-1-プロペン、
3-α-エチル-ポリジメチルシロキサニル-1-プロペン、
3-α-メチル-ポリジメチルシロキサニル-1-プロペン、
4-α-ブチル-ポリジメチルシロキサニル-1-ブテン、
4-α-プロピル-ポリジメチルシロキサニル-1-ブテン、
4-α-エチル-ポリジメチルシロキサニル-1-ブテン、
4-α-メチル-ポリジメチルシロキサニル-1-ブテン、
2-α-ブチル-ポリジメチルシロキサニル-エテン、
2-α-プロピル-ポリジメチルシロキサニル-エテン、
2-α-エチル-ポリジメチルシロキサニル-エテン、
2-α-メチル-ポリジメチルシロキサニル-エテン、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エテン、
2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)エテン、
2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)エテン、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エテン、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)-1-プロペン、
2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)-1-プロペン、
2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)-1-プロペン、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)-1-プロペン
に由来する構成単位であることができ、
好ましくは、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
3-α-ブチル-ポリジメチルシロキサニル-プロピルアクリレート、
3-α-メチル-ポリジメチルシロキサニル-プロピルアクリレート、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
3-(2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
3-(2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
2-α-ブチル-ポリジメチルシロキサニル-エテン、
2-α-メチル-ポリジメチルシロキサニル-エテン、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エテン、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エテン、
に由来する構成単位であり、
より好ましくは、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
3-(2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
2-α-ブチル-ポリジメチルシロキサニル-エテン、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エテン、
に由来する構成単位であり、
さらに好ましくは、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
に由来する構成単位である。
に由来する構成単位と、2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレートに由来する構成単位とを含んでもよい。
好ましくは、アクリル酸に由来する構成単位、メタクリル酸に由来する構成単位、ビニルアルコールに由来する構成単位、メチルアクリレートに由来する構成単位、エチルアクリレートに由来する構成単位、イソプロピルアクリレートに由来する構成単位、メチルメタクリレートに由来する構成単位、エチルメタクリレートに由来する構成単位、イソプロピルメタクリレートに由来する構成単位、ビニルホルメートに由来する構成単位、ビニルアセテートに由来する構成単位、グリシジルアクリレートに由来する構成単位、グリシジルメタクリレートに由来する構成単位、2,3-ジヒドロキシプロピルアクリレートに由来する構成単位、2,3-ジヒドロキシプロピルメタクリレートに由来する構成単位、3-(ジメチルアミノ)プロピルアクリレートに由来する構成単位、または、3-(ジメチルアミノ)プロピルメタクリレートに由来する構成単位であり、
より好ましくは、アクリル酸に由来する構成単位、メタクリル酸に由来する構成単位、メチルアクリレートに由来する構成単位、エチルアクリレートに由来する構成単位、メチルメタクリレートに由来する構成単位、ビニルアセテートに由来する構成単位、グリシジルメタクリレートに由来する構成単位、または、2,3-ジヒドロキシプロピルメタクリレートに由来する構成単位であり、
さらに好ましくは、メチルアクリレートに由来する構成単位である。
構成単位(A)と、
Rが水素原子またはメチル基であり、L1が-CO-O-であり、L2およびL3が単結合であり、L6が―(CH2)n―(Rf2O)p―(Rf3)h―(Si(Rf4)2O)g―Si(Rf1)3である式(1)で示される構成単位(B)と、
Rが水素原子またはメチル基であり、L1が-CO-O-であり、L4が炭素原子数1のアルキレン基であり、L5が水素原子である式(2)で示される構成単位(C)とを含む重合体
が挙げられる。
前記構成単位(A)の数、前記構成単位(B)の数、および、前記構成単位(C)の数は、例えば、以下の方法により求めることができる。
前駆重合体(1)(エチレン-メチルアクリレート共重合体)の13C-NMRスペクトルについて、以下のa1、b1、c1、d1、及びe1の範囲の積分値(A1、B1、C1、D1、及びE1)を求め、下記式から求められる3種のダイアッド(EE、EA、AA)の含有量(数)から、エチレンに由来する構成単位A1及びメチルアクリレートに由来する構成単位C1の数を算出する。なお、EEは、エチレン-エチレンダイアッドを意味し、EAは、エチレン-メチルアクリレートダイアッドを意味し、AAは、メチルアクリレート-メチルアクリレートダイアッドを意味する。
b1:31.9-32.6ppm
c1:41.7ppm
d1:43.1-44.2ppm
e1:45.0-46.5ppm
EA=E1
AA=C1+D1
構成単位C1の数=100×(EA/2+AA)/(EE+EA+AA)
エチレン-メチルアクリレート共重合体と、化合物αとを反応させて得られる重合体1の1H-NMRスペクトルについて、以下のf1及びg1の範囲の積分値(F1及びG1)を求める。次に、下記式から、エチレン-メチルアクリレート共重合体に含まれるメチルアクリレートに由来する構成単位C1が、重合体1の式(1)で示される構成単位B2に転化した転化率X1を算出する。
g1:3.9-4.3ppm
重合体1に含まれる、エチレンに由来する構成単位A2、式(1)で示される構成単位B2、メチルアクリレートに由来する構成単位C2の数は、それぞれ、下記式から算出する。
上記前駆重合体(1)と、
上記式(11)で示される化合物、上記式(12)で示される化合物、上記式(13)で示される化合物、上記式(14)で示される化合物、上記式(15)で示される化合物、上記式(16)で示される化合物、上記式(17)で示される化合物および上記式(18)で示される化合物からなる群より選ばれる1種以上の化合物(α)と
を反応させる工程を含む、重合体の製造方法;および
エチレンと、前記構成単位(B)の原料となるモノマーと、前記構成単位(C)の原料となるモノマーとを共重合する方法;が挙げられる。
前駆重合体(1)に含まれる前記構成単位(C)が官能基としてエステル基を有する場合、前記式(11)、前記式(12)または前記式(14)で示される化合物と反応させる方法が挙げられ、
前駆重合体(1)に含まれる前記構成単位(C)が官能基としてカルボキシ基を有する場合、前記式(11)、前記式(12)、前記式(13)、前記式(15)、前記式(16)、前記式(17)または前記式(18)で示される化合物と反応させる方法が挙げられ、
前駆重合体(1)に含まれる前記構成単位(C)が官能基として水酸基を有する場合、前記式(13)、前記式(14)、前記式(16)または前記式(18)で示される化合物と反応させる方法が挙げられ、
前駆重合体(1)に含まれる前記構成単位(C)が官能基としてアミノ基を有する場合、前記式(13)、前記式(14)、前記式(15)、前記式(16)、前記式(17)または前記式(18)で示される化合物と反応させる方法が挙げられ、
前駆重合体(1)に含まれる前記構成単位(C)が官能基としてエポキシ基を有する場合、前記式(11)、前記式(12)、前記式(14)、前記式(15)または前記式(17)で示される化合物と反応させる方法が挙げられる。
エチレン及びプロピレンからなる群より選ばれる少なくとも一種のモノマーと、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート、
3-α-ブチル-ポリジメチルシロキサニル-プロポキシメチルアクリレート、
3-α-プロピル-ポリジメチルシロキサニル-プロポキシメチルアクリレート、
3-α-エチル-ポリジメチルシロキサニル-プロポキシメチルアクリレート、
3-α-メチル-ポリジメチルシロキサニル-プロポキシメチルアクリレート、
3-α-ブチル-ポリジメチルシロキサニル-プロピルアクリレート、
3-α-プロピル-ポリジメチルシロキサニル-プロピルアクリレート、
3-α-エチル-ポリジメチルシロキサニル-プロピルアクリレート、
3-α-メチル-ポリジメチルシロキサニル-プロピルアクリレート、
2-α-ブチル-ポリジメチルシロキサニル-エチルアクリレート、
2-α-プロピル-ポリジメチルシロキサニル-エチルアクリレート、
2-α-エチル-ポリジメチルシロキサニル-エチルアクリレート、
2-α-メチル-ポリジメチルシロキサニル-エチルアクリレート、
2-(2-α-ブチル-ポリジメチルシロキサニル-エトキシ)エチルアクリレート、
2-(2-α-プロピル-ポリジメチルシロキサニル-エトキシ)エチルアクリレート、
2-(2-α-エチル-ポリジメチルシロキサニル-エトキシ)エチルアクリレート、
2-(2-α-メチル-ポリジメチルシロキサニル-エトキシ)エチルアクリレート、
2-(4-α-ブチル-ポリジメチルシロキサニル-ブトキシ)エチルアクリレート、
2-(4-α-プロピル-ポリジメチルシロキサニル-ブトキシ)エチルアクリレート、
2-(4-α-エチル-ポリジメチルシロキサニル-ブトキシ)エチルアクリレート、
2-(4-α-メチル-ポリジメチルシロキサニル-ブトキシ)エチルアクリレート、
4-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)ブチルアクリレート、
4-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)ブチルアクリレート、
4-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)ブチルアクリレート、
4-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)ブチルアクリレート、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エチルメタクリレート、
2-(4-α-ブチル-ポリジメチルシロキサニル-ブトキシ)エチルメタクリレート、
2-(4-α-プロピル-ポリジメチルシロキサニル-ブトキシ)エチルメタクリレート、
2-(4-α-エチル-ポリジメチルシロキサニル-ブトキシ)エチルメタクリレート、
2-(4-α-メチル-ポリジメチルシロキサニル-ブトキシ)エチルメタクリレート、
3-α-ブチル-ポリジメチルシロキサニル-プロピルメタクリレート、
3-α-プロピル-ポリジメチルシロキサニル-プロピルメタクリレート、
3-α-エチル-ポリジメチルシロキサニル-プロピルメタクリレート、
3-α-メチル-ポリジメチルシロキサニル-プロピルメタクリレート、
2-α-ブチル-ポリジメチルシロキサニル-エチルメタクリレート、
2-α-プロピル-ポリジメチルシロキサニル-エチルメタクリレート、
2-α-エチル-ポリジメチルシロキサニル-エチルメタクリレート、
2-α-メチル-ポリジメチルシロキサニル-エチルメタクリレート、
3-(2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルアクリレート、
3-(2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
3-(2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
3-(2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
3-(2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エトキシ)-2-ヒドロキシプロピルメタクリレート、
3-α-ブチル-ポリジメチルシロキサニル-1-プロペン、
3-α-プロピル-ポリジメチルシロキサニル-1-プロペン、
3-α-エチル-ポリジメチルシロキサニル-1-プロペン、
3-α-メチル-ポリジメチルシロキサニル-1-プロペン、
4-α-ブチル-ポリジメチルシロキサニル-1-ブテン、
4-α-プロピル-ポリジメチルシロキサニル-1-ブテン、
4-α-エチル-ポリジメチルシロキサニル-1-ブテン、
4-α-メチル-ポリジメチルシロキサニル-1-ブテン、
2-α-ブチル-ポリジメチルシロキサニル-エテン、
2-α-プロピル-ポリジメチルシロキサニル-エテン、
2-α-エチル-ポリジメチルシロキサニル-エテン、
2-α-メチル-ポリジメチルシロキサニル-エテン、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エテン、
2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)エテン、
2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)エテン、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)エテン、
2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)-1-プロペン、
2-(3-α-プロピル-ポリジメチルシロキサニル-プロポキシ)-1-プロペン、
2-(3-α-エチル-ポリジメチルシロキサニル-プロポキシ)-1-プロペン、
2-(3-α-メチル-ポリジメチルシロキサニル-プロポキシ)-1-プロペン
等の前記構成単位(B)の原料となるモノマーとを、
tert-ブチルパーオキシピバレート等の有機過酸化物、または、アゾビスイソブチロニトリル等のアゾ化合物を重合開始剤に用いて重合する方法が挙げられる。
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r1r2=AA[CC/(AC/2)2]
A=α1/α0 (I)
[式(I)中、
α1は、光散乱検出器と粘度検出器とを備えた装置を用いるゲル・パーミエイション・クロマトグラフィーにより、重合体の絶対分子量と固有粘度とを測定し、
絶対分子量の対数を横軸とし、固有粘度の対数を縦軸として、測定したデータをプロットし、絶対分子量の対数と固有粘度の対数とを、横軸が前記重合体の重量平均分子量の対数以上でありz平均分子量の対数以下である範囲において、式(I-I)で最小二乗法近似し、式(I-I)で表される直線の傾き:α1を求めることで得られる値である。
log[η1]=α1logM1+logK1 (I-I)
(式(I-I)中、[η1]は重合体の固有粘度(単位:dl/g)を表し、M1は重合体の絶対分子量を表し、K1は定数である。)
α0は、光散乱検出器と粘度検出器とを備えた装置を用いるゲル・パーミエイション・クロマトグラフィーにより、ポリエチレン標準物質1475a(米国国立標準技術研究所製)の絶対分子量と固有粘度とを測定し、
絶対分子量の対数を横軸とし、固有粘度の対数を縦軸として、測定したデータをプロットし、絶対分子量の対数と固有粘度の対数とを、横軸が前記ポリエチレン標準物質1475aの重量平均分子量の対数以上でありz平均分子量の対数以下である範囲において、式(I-II)で最小二乗法近似し、式(I-II)で表される直線の傾き:α0を求めることで得られる値である。
log[η0]=α0logM0+logK0 (I-II)
(式(I-II)中、[η0]はポリエチレン標準物質1475aの固有粘度(単位:dl/g)を表し、M0はポリエチレン標準物質1475aの絶対分子量を表し、K0は定数である。)]
本発明に係る一つの態様において、重合体(1)は架橋されている。すなわち、重合体(1)の分子の少なくとも一部が分子間で共有結合により連結されている。
ゲル分率=(ゲル重量/測定試料重量)×100
本発明の組成物(「樹脂組成物(B)」と称することもある)は重合体(1)を含有する。当該組成物に対する当該重合体の割合は特に限定されないが、一態様において、当該組成物は当該重合体を0.01~99.9重量%、形状保持性が向上するため好ましくは0.1~50重量%、より好ましくは0.1~20重量%、さらに好ましくは0.1~10重量%含有する。当該組成物は撥水性及び撥油性を有する。
高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、線状低密度ポリエチレン、高分子量ポリエチレン、超高分子量ポリエチレン、アイソタクチックポリプロピレン、シンジオタクチックポリプロピレン、 ヘミアイソタクチックポリプロピレン、アタクチックポリプロピレン、ステレオブロックポリプロピレン、エチレン-プロピレンランダム共重合体、エチレン-プロピレンブロック共重合体、ポリイソブチレン、ポリブタ-1-エン、ポリ-3-メチル-1-ブテン、ポリ-3-メチル-1-ペンテン、ポリ-4-メチルペンタ-1-エン、ポリビニルシクロヘキサン、ポリイソプレン、ポリブタジエン、シクロオレフィンポリマー、オレフィン系熱可塑性エラストマー、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリクロロプレン、塩化ビニル系熱可塑性エラストマー、ポリスチレン、アクリロニトリル-ブタジエン-スチレン、アクリロニトリル-スチレン、スチレン系熱可塑性エラストマー、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリトリメチレンテレフタレート、ポリアリレート、ポリカプロラクトン、ポリ乳酸、ポリヒドロキシアルカノエート、ポリヒドロキシブチレート、ポリグリコール酸、ポリエチレンアジペート、ポリカーボネート、ポリアミド、ポリイミド、シリコーン樹脂、ポリビニルアセタール、ポリアセタール、ポリビニルアルコール、エチレン-ビニルアルコール樹脂、セルロース樹脂、アクリルポリオール系樹脂、ポリエステルポリオール系樹脂、ポリエステル系熱可塑性エラストマー、ウレタン樹脂、ポリウレタン系熱可塑性エラストマー、ポリテトラフルオロエチレン、ポリフッ化ビニル、ボリフッ化ビニリデン、フッ素樹脂、ポリ酢酸ビニル、エチレン-酢酸ビニル、メチル(メタ)アクリレート重合体、エチル(メタ)アクリレート重合体、オクタデシル(メタ)アクリレート重合体、ヘキサデシル(メタ)アクリレート重合体、テトラデシル(メタ)アクリレート重合体、ポリメタクリル酸メチル、ポリアクリル酸メチル、アクリロニトリル-アクリルゴム-スチレン樹脂、アクリロニトリル-エチレンゴム-スチレン樹脂、(メタ)アクリル酸エステル-スチレン樹脂、スチレン-ブタジエン-スチレン樹脂、スチレン-ブタジエン共重合体、ポリフェニレンエーテル、変性ポリフェニレンエーテル、ポリフェニレンオキサイド、ポリフェニレンサルファイド、ポリアミドイミド、ポリスルホン、ポリエーテルスルホン、ポリエーテルエーテルケトン、ポリエーテル-ポリプロピレンブロック共重合体、ポリエーテルエステルアミド、1H,1H,2H,2H-トリデカフルオロ-1-オクチル(メタ)アクリレート重合体、1H,1H,2H,2H-ヘプタフルオロ-1-ヘキシル(メタ)アクリレート重合体、エチレン-(メタ)アクリル酸メチル共重合体、エチレン-(メタ)アクリル酸エチル共重合体、エチレン-(メタ)アクリル酸ブチル共重合体、エチレン-オクタデシル(メタ)アクリレート共重合体、エチレン-ヘキサデシル(メタ)アクリレート共重合体、エチレン-テトラデシル(メタ)アクリレート共重合体、エチレン-オクタデシル(メタ)アクリレート-メチル(メタ)アクリレート共重合体等のエチレン-(メタ)アクリル酸エステル共重合体及びそれらのアイオノマー樹脂、エチレン-(メタ)アクリル酸樹脂及びそのアイオノマー樹脂。
<樹脂組成物(A)>
前記重合体(1)と、
示差走査熱量測定によって観測される融解ピーク温度またはガラス転移温度が50℃以上180℃以下である重合体(但し、上記の重合体(1)を除く)である重合体(2)とを含有し、
前記重合体(1)と前記重合体(2)の合計量を100重量%として、重合体(1)の含有量が1重量%以上99重量%以下であり、重合体(2)の含有量が1重量%以上99重量%以下である樹脂組成物(以下、「樹脂組成物(A)」と記載することがある)であり、
好ましくは、重合体(1)の含有量が1重量%以上50重量%以下であり、重合体(2)の含有量が50重量%以上99重量%以下であり、
より好ましくは、重合体(1)の含有量が1重量%以上30重量%以下であり、重合体(2)の含有量が70重量%以上99重量%以下であり、
さらに好ましくは、重合体(1)の含有量が1重量%以上10重量%以下であり、重合体(2)の含有量が90重量%以上99重量%以下である。
示差走査熱量計を用いて、窒素雰囲気下で、約5mgの試料を封入したアルミニウムパンを、工程(1)200℃で5分間保持し、工程(2)5℃/分の速度で200℃から-80℃まで降温し、工程(3)-80℃で5分間保持し、工程(4)5℃/分の速度で-80℃から200℃まで昇温する。工程(4)における熱量測定により得られた示差走査熱量測定曲線を融解曲線とする。
重合体(2)であるポリプロピレンは、融解ピーク温度が100℃以上であることが好ましい。
プロピレンに由来する構成単位と、エチレンに由来する構成単位およびα-オレフィンに由来する構成単位からなる群より選ばれる少なくとも一種の構成単位とを含むランダム共重合体である。プロピレンランダム共重合体としては、例えば、プロピレン-エチレンランダム共重合体、プロピレン-エチレン-α-オレフィンランダム共重合体、および、プロピレン-α-オレフィンランダム共重合体が挙げられる。該α-オレフィンとしては、炭素原子数4~10のα-オレフィンが好ましい。このようなα-オレフィンとしては、例えば、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、1-デセン等の直鎖状α-オレフィン、および、3-メチル-1-ブテン、3-メチル-1-ペンテン等の分岐状α-オレフィンが挙げられる。プロピレンランダム共重合体に含まれるα-オレフィンに由来する構成単位は、1種単独であってもよく、2種以上であってもよい。
プロピレン単独重合体成分(I)と、
プロピレンに由来する構成単位および炭素原子数4以上のα-オレフィンに由来する構成単位からなる群から選ばれる少なくとも一種の構成単位と、エチレンに由来する構成単位とを含むエチレン共重合体成分(II)と
を含有する重合材料である。
エチレン共重合体成分(II)に含まれる炭素原子数4以上のα-オレフィンに由来する構成単位は、1種単独であってもよく、2種以上であってもよい。
エチレン共重合体成分(II)は、ランダム共重合体であってもよく、ブロック共重合体であってもよい。
本発明に係る組成物はクオラムセンシング阻害剤を含有してもよい。クオラムセンシング阻害剤は、微生物のクオラムセンシングを阻害する化合物である。
Sensors2013,13,5117-5129に記載の方法に基づき、培地中のC. violaceum CV026(レポーター株)に対してN-ヘキサノイルホモセリンラクトンを添加し、さらに、クオラムセンシング阻害剤を添加した後、保温して菌を培養する。生産された紫色色素(violacein)の量が85%以下である(ただし、クオラムセンシング阻害剤を添加することなく、保温して菌を培養し、生産された紫色色素の量を100%とする)クオラムセンシング阻害剤。
オイゲノール、メチルオイゲノール、シンナムアルデヒド、けい皮酸、バニリン、イソバニリン、フェルラ酸、クロロゲン酸、カフェ酸、P-クマル酸、けい皮アルデヒド、けい皮酸メチル、フェニルプロピオン酸、2-メトキシけい皮酸、3-メトキシけい皮酸、4-メトキシけい皮酸、3-ブロモけい皮酸、2-フルオロけい皮酸、3-フルオロけい皮酸、3-メチルけい皮酸、4-アセトキシけい皮酸、4-ブロモけい皮酸、4-エトキシけい皮酸、4-フルオロけい皮酸、3,4-ジメトキシけい皮酸、2,3-ジメトキシけい皮酸、2,5-ジメトキシけい皮酸、2,3,4-トリメトキシけい皮酸、3,4,5-トリメトキシけい皮酸、リグニン等のフェニルプロパノイド;
サリチル酸、バニリン酸、没食子酸、エラグ酸等の安息香酸類縁体;
1,2,3,4,6-ペンタガロイルグルコース、プニカラギン、ハマメリタンニン、タンニン酸等のタンニン類;
レスベラトール、プテロスチルベン等のスチルベン類縁体及びポリケタイド;
(-)-カテキン、(-)-エピカテキン、(-)-ガロカテキン、(-)-エピガロカテキン、(-)-没食子酸カテキン、(-)-没食子酸エピカテキン、(-)-没食子酸ガロカテキン、(-)-没食子酸エピガロカテキン、ナリンゲニン、フラボン、アピゲニン、クリシン、アカセチン、フラボノール、ケンフェロール、ケルセチン、クェルシトリン、フラバノン、イソサクラネチン、ピノストロビン、エリオジクチオール、シアニジン、マルビジン等のフラボノイド;
クルクミン等のジアリールヘプタノイド;
カルバクロール、サルビピソン、アカントスペルモリド、イソリモニン酸、イチャンギン、ベツリン酸、ウルソール酸、ギムネマ酸、プロトアネモニン、オバクノン、デアセチルノミリン酸グルコシド、フィトール等のテルペン及びテルペノイド;
アリシン、アホエン、スルフォラファン、アリルイソチオシアネート、イベリン、チアゾリジンジオン、ジフェニルジスルフィド等の硫黄含有化合物;
インドール、2-メチルトリプトリンなどの窒素含有化合物;
ウンベリフェロン、スコポレチン等のクマリン誘導体;
プソラレン、アンゲリシン、ベルガモチン、ジヒドロキシベルガモチン等のフラノクマリン類;
クリソファノール、エモジン、シコニン、プルプリン、エンベリン等のキノン誘導体; ベルベリン、塩化ベルベリン水和物、ケレリトリン、サンギナリン、レセルピン、カフェイン、オロイジン、ピペリン、ホルデニン等のアルカロイド;
ピロガロール、マラバリコンC、タキシフォリン、ロスマリン酸等のフェノール類又はポリフェノール類;
ラムノリピッド、トレハロリピッド、ソホロリピッド、セロビオピッド、ビスコシン、サーファクチン、エマルザン等のクオラムセンシング阻害能を有する界面活性剤;
ピオシアニン等のフェナジン類;
ピエリシジンA、グルコピエリシジンA等のユビキノン類縁体;
リポキシンA4等のエイコサノイド;
ポリガラクツロン酸、ペクチン等の多糖類;
エリスロマイシン等のマクロライド;
ゼアキサンチン等のカロテノイド;
ペニシリン酸、パツリン等のマイコトキシン;
コレステリルクロリド等のステロイド;
3-フルオロ-4-メチルフェニルボロン酸、2-フルオロ-4-トリフルオロメチルフェニルボロン酸等のボロン酸及びボロン酸誘導体;
アシル化シクロペンチルアミド、N-(3-オキソドデカノイル)-L-ホモセリンラクトン等のラクトン類;
3,4-ジブロモ-2(5H)-フラノン等のプテノライド。
但し、本発明に係る樹脂組成物に含まれるクオラムセンシング阻害剤が、イオン性の化合物、電荷移動錯体、無機化合物、水素原子以外の原子数が120を超える化合物、又は、化合物同士で多重水素結合を形成する化合物である場合は、該クオラムセンシング阻害剤のlogSは、100gの水に溶解する溶質量を測定する溶解度測定により算出した値を用いる。
好ましくは、logSが0.1未満であるフェニルプロパノイド、logSが0.1未満である安息香酸類縁体、logSが0.1未満であるタンニン類、logSが0.1未満であるスチルベン類縁体及びポリケタイド、logSが0.1未満であるフラボノイド、logSが0.1未満であるジアリールヘプタノイド、logSが0.1未満であるテルペン及びテルペノイド、logSが0.1未満である硫黄含有化合物、logSが0.1未満である窒素含有化合物、logSが0.1未満であるクマリン誘導体、logSが0.1未満であるフラノクマリン類、logSが0.1未満であるキノン誘導体、logSが0.1未満であるアルカロイド、logSが0.1未満であるフェノール、ポリフェノール類、logSが0.1未満でありクオラムセンシング阻害能を有する界面活性剤、logSが0.1未満であるフェナジン類、logSが0.1未満であるユビキノン類縁体、logSが0.1未満であるエイコサノイド、logSが0.1未満であるカロテノイド、logSが0.1未満であるマイコトキシン、logSが0.1未満であるマクロライド、logSが0.1未満である多糖類、logSが0.1未満であるステロイド類、logSが0.1未満であるボロン酸及びボロン酸誘導体、logSが0.1未満であるラクトン類、又は、logSが0.1未満であるプテノライドであり、
より好ましくは、logSが0.1未満であるフェニルプロパノイド、logSが0.1未満である安息香酸類縁体、logSが0.1未満であるタンニン類、logSが0.1未満であるスチルベン類縁体及びポリケタイド、logSが0.1未満であるフラボノイド、logSが0.1未満であるジアリールヘプタノイド、logSが0.1未満であるテルペン及びテルペノイド、logSが0.1未満である硫黄含有化合物、logSが0.1未満である窒素含有化合物、logSが0.1未満であるクマリン誘導体、logSが0.1未満であるキノン誘導体、logSが0.1未満であるアルカロイド、logSが0.1未満であるボロン酸及びボロン酸誘導体、又は、logSが0.1未満であるラクトン類であり、
さらに好ましくは、2,3,4-トリメトキシけい皮酸、2-フルオロけい皮酸、オイゲノール、サリチル酸、タンニン酸、レスベラトール、(-)-エピカテキン、フラボン、クルクミン、カルバクロール、フィトール、ジフェニルジスルフィド、インドール、ウンベリフェロン、プルプリン、レセルピン、塩化ベルベリン水和物、3-フルオロ-4-メチルフェニルボロン酸、N-(3-オキソドデカノイル)-L-ホモセリンラクトン、又は、2-フルオロ-4-トリフルオロメチルフェニルボロン酸である。
HSP2=(δD)2+(δP)2+(δH)2 ・・・(H)
δD:London分散力項
δP:分子分極項(双極子間力項)
δH:水素結合項
HSPα=(δDα、δPα、δHα)
HSPβ=(δDβ、δPβ、δHβ)
と仮定すれば、HSPαとHSPβとの距離(Ra)は、下記式(R)により計算することができる。
ゼオライト;
モンモリオナイト;
活性炭;
ハイドロキシアパタイト等のリン酸カルシウム系化合物;
酸化ケイ素、酸化アルミニウム、酸化マグネシウム、酸化チタン、酸化ジルコニウム等の酸化物;
窒化ケイ素、窒化チタン、窒化アルミニウム、窒化ジルコニウム等の窒化物;
炭化ケイ素等の非酸化物セラミックス;
珪酸カルシウム、珪酸アルミニウム、珪酸マグネシウム、珪藻土などの珪酸塩;
カオリナイト、ベントナイト、軽石、長石、石英等のアルミナ-シリカ系化合物。
本発明に係る組成物は抗菌・防カビ剤を含有してもよい。抗菌・防カビ剤としては、例えば以下が挙げられる:
メチル-2,4-ジヒドロキシ-6-メチルベンゾエート、エチル-2,4-ジヒドロキシ-6-メチルベンゾエート、メチル-2,4-ジヒドロキシ-3,6-ジメチルベンゾエート、イソプロピル-2,4-ジヒドロキシ-6-メチルベンゾエート、3-メトキシ-5-メチルフェニル-2,4-ジヒドロキシ-6-メチルベンゾエート、エチル-2,4-ジヒドロキシ-3,6-ジメチルベンゾエート、エチル-3-ホルミル-2,4-ジヒドロキシ-6-メチルベンゾエート、イソプロピル-3-ホルミル-2,4-ジヒドロキシ-6-メチルベンゾエート、3-ヒドロキシ-5-メチルフェニル-2,4-ジヒドロキシ-6-メチルベンゾエート、3-ヒドロキシ-5-メチルフェニル-2-ジヒドロキシ-4-メトキシ-6-メチルベンゾエート、3-メトキシ-5-メチルフェニル-2-ヒドロキシ-4-メトキシ-6-メチルベンゾエート、3-クロロ-2,6-ジヒドロキシ-4-メチルベンゾエート等のフェノール・アルコール系抗菌・防カビ剤;
(2-ピリジルチオ-1-オキシド)ナトリウム、ナリジクス酸、ガチフロキサシン、ピリチオン銅、ピリチオン亜鉛等のピリジン・キノリン系抗菌・防カビ剤;
ヘキサヒドロ-1,3,5-トリス(2-ヒドロキシエチル)-S-トリアジン等のトリアジン系抗菌・防カビ剤;
1,2-ベンズイソチアゾリン-3オン、2-メチル-5-クロロ-4-イソチアゾロン錯体、オクチルイソチアゾリノン、メチルイソチアゾリノン、クロロメチルイソチアゾリノン、ジクロロオクチルイソチアゾリノン、エンズイソチアゾリノン等のイソチアゾロン系抗菌・防カビ剤;
4’-ヒトロキシアセトアニリド、N-(3-ヒドロキシフェニル)ベンゼンカルボアミド、N-(3-ヒドロキシフェニル)ベンズアミド等のアニリド系抗菌・防カビ剤;
モノブロモシアノアセトアミド、ジブロモシアノアセトアミド、1,2-ジブロモ-2,4-ジシアノブタン、テトラクロロフタロニトリル等のニトリル系抗菌・防カビ剤;
2-(4-チアゾリル)ベンゾイミダゾール、2-ベンズイミダゾールカルバミン酸メチル、1-(ブチルカルバモイル)-2-ベンズイミダゾールカルバミン酸メチル等のイミダゾール・チアゾール系抗菌・防カビ剤;
デヒドロ酢酸等のアルデヒド系抗菌・防カビ剤;
ソルビン酸等のカルボン酸系抗菌・防カビ剤;
パラオキシ安息香酸エステル等のエステル系抗菌・防カビ剤;
ジチオ-2,2-ビス(ベンズメチルアミド)、テトラメチルチウラムジスルフィド、ジメチルフェニルスルファミド等のジスルフィド化合物;
マンゼブ、マンネブ、ジネブ、ポリカーバメート等のチオカーバメート化合物;
1,1-ジブロモ-1-ニトロプロパノール、1,1-ジブロモ-1-ニトロ-2-アセトキシプロパン等のニトロ化合物;
塩化ベンザルコニウム、塩化ベンゼトニウム、塩化メチルベンゼトニウム、塩化セチルピリジニウム、セトリモニウム、塩化ドファニウム、臭化テトラエチルアンモニウム、塩化ジデシルジメチルアンモニウム、臭化ドミフェン等の4級アンモニウム塩;
メトホルミン、ブホルミン、フェンホルミン、プログアニル、クロロプログアニル、クロルヘキシジン、アレキシジン、ポリアミノプロピルビグアニド、ポリヘキサニド等のビグアナイド;
アルキルベンゼンスルホン酸ナトリウム、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンステアリルアミン、ラウリルジメチルベンジルアンモニウムクロライド等の界面活性剤;
銀担持ゼオライト、銅担持ゼオライト、亜鉛担持ゼオライト、銀担持リン酸カルシウム、銅担持リン酸カルシウム、亜鉛担持リン酸カルシウム、酸化チタン等の無機系抗菌剤。
抗菌・防カビ剤の担体としては、クオラムセンシング阻害剤の担体として例示したものが挙げられる。
本圧名に係る組成物は表面改質剤を含んでもよい。本明細書において、「表面改質剤」とは、該表面改質剤の有無により、成形体の表面自由エネルギーが変化する化合物を意味する。
ノナフルオロ-1-ブタンスルホン酸、トリデカフルオロヘプタン酸、ヘプタデカフルオロオクタンスルホン酸、ヘプタデカフルオロノナン酸、ヘンエイコサフルオロウンデカン酸、2H,2H,3H,3H-ヘプタデカフルオロウンデカン酸、ペンタデカフルオロオクタン酸アンモニウム、ノナフルオロ-1-ブタンスルホン酸リチウム、ヘプタデカフルオロ-1-オクタンスルホン酸カリウム、サーフロンS-431、サーフロンS-461、サーフロンS-420等のフッ素系界面活性剤;
国際公開公報2014/080873号に記載のパーフルオロポリエーテル基含有化合物;
1H,1H,2H,2H-ヘプタデカフルオロデシルアクリレート等のフッ素系モノマー;
RSC Adv. 2015,5,53054-53062に記載のアルキルシロキシ基含有化合物;
特開2017-115044号公報に記載のポリアルキレンエーテル基含有化合物;
特開2002-069178号公報に記載のベタイン型化合物;
グリセリンモノステアレート等の界面活性剤。
を100重量%として、表面改質剤の含有量は0.1~30重量%であることが好ましく、より好ましくは、1~20量%である。
発泡体状とは異なる形状の成形体、または、本発明に係る重合体とは異なる材料とは、
コア-シェル構造、芯-鞘構造または積層構造を形成していてもよい。
本発明に係る重合体を含む繊維は、前記重合体(1)を含む樹脂組成物(以下、「樹脂組成物(A)又は樹脂組成物(B)」と記載することがある)を紡糸することにより得ることができる。
重合体1又は樹脂組成物A又は樹脂組成物Bを成形することにより、当該重合体又は組成物を含有する成形体を製造することができる。
本発明の成形体は、重合体1又は樹脂組成物A又は樹脂組成物Bからなる層と、該層とは異なる層との多層構造体でもよい。多層構造体において、重合体1又は樹脂組成物A又は樹脂組成物Bからなる層は、該多層構造体の少なくとも一方の表層であることが好ましい。重合体1又は樹脂組成物A又は樹脂組成物Bからなる層とは異なる層を構成する材料としては、例えば、樹脂組成物A又は樹脂組成物Bとは異なる樹脂、金属、紙、皮革等が挙げられる。多層構造体は、樹脂組成物A又は樹脂組成物Bからなる層と、該層とは異なる層とを張り合わせて製造することが可能である。
塗膜
重合体1、樹脂組成物A又は樹脂組成物Bを基材上に塗布し乾燥する、または重合体1、樹脂組成物A又は樹脂組成物Bを溶液に溶解させた後、該溶液を基材上に塗布することにより、当該重合体及び組成物を含有する塗膜を製造することができる。
当該媒体は2種類以上の溶媒またはモノマーを組み合わせてもよく、重合体1、樹脂組成物(A)又は樹脂組成物(B)以外の化合物が溶解していてもよい。
本発明の塗膜は、重合体1、樹脂組成物A又は樹脂組成物Bからなる層と、該層とは異なる層との多層塗膜でもよい。多層塗膜において、重合体1、樹脂組成物A又は樹脂組成物Bからなる層は、該多層塗膜の少なくとも一方の表層であることが好ましい。重合体1、樹脂組成物A又は樹脂組成物Bからなる層とは異なる層を構成する材料としては、例えば、重合体1、樹脂組成物A又は樹脂組成物Bとは異なる樹脂、プライマー等が挙げられる。多層塗膜は、重合体1、樹脂組成物A又は樹脂組成物Bからなる層と、該層とは異なる層とを順に基材上塗布することにより製造することが可能である。
食器、各種調理器具、保存容器、浄水ポッド、浄水器、排水口、排水トラップ、三角コーナー、シンクの各種部品、貯水ポッド、断熱ポッド、ラップ、IHヒーター、水切りかご、水道、蛇口、キッチンフード、コーヒーミル等の台所用部材及び台所用品;
洗面台、洗面器、洗面化粧台、鏡、排水口、排水トラップ、排水栓、ヘアキャッチャー、排水トラップ等の洗面用部材;
浴室壁、浴室床、浴室ドア、カウンター、浴槽、蛇口、鏡、換気扇、浴室乾燥機、風呂フタ、シャワー等の浴室用部材;
洗濯機、乾燥機、ホース、洗濯槽、洗濯機用排水トラップ、洗濯機用排水口等の洗濯用部材;
便座、便座のフタ、便器、貯水タンク、リモコン、温水洗浄便座、温水洗浄便座ノズル、携帯ウォシュレット(登録商標)等のトイレ用部材;
各種配管;
各種パッキン;
各種コック;
各種ネット;
貯水タンク、貯水槽、太陽熱温水器、水槽、プール等の各種貯水物品・設備;
養殖用水槽、展示・観賞用水槽、組立水槽、循環ろ過設備、自動給餌器、加温・冷却ユニット、温度計、水槽用ファン、エアー供給機器、酸素発生機、魚類標識タグ、泡沫分離装置、攪拌パドル、水底活性機、孵化装置、アクアフレーム、ポンプ、などの飼育・養殖設備;
活魚タンク、コンテナ、ブロワー、冷却装置などの活魚輸送用機器設備;
食品用包材、化粧品用包材等の各種包装材料;
換気扇、窓枠、網戸、サッシ、窓ガラス、人工大理石、畳、フローリング床、照明、絨毯、壁紙、机天板、住宅内壁、住宅天井、排水溝等の各種屋内設備;
送電線、アンテナ、屋根材、住宅外壁、電柱、埋設配管、等の住宅屋外設備;
エアコン、エアコンドレンパン、エアコン室外機、各種ホース、各種リモコン、熱交換器、加湿装置、乾燥器、冷蔵庫、食器洗浄機、食器乾燥機、洗濯機、掃除機、ドリンクサーバー、コーヒーサーバー、電子レンジ、アイロン、スチーマー、アロマディフューザー、ホームクリーニング機、高圧洗浄機、ポット、ウェアラブルデバイス、プリンター、画像形成装置用の液体吸収体、等の各種電気機器及びその付属する物品;
鼻腔栄養チューブ、創傷接触層、カテーテル、チューブステント、ペースメーカーシェル、心臓弁、整形外科用インプラント、歯周インプラント、歯列矯正器、他の歯列矯正器具、入れ歯、歯冠、フェイスマスク、コンタクトレンズ、眼内レンズ、軟組織インプラント、外科用器具、縫合糸、蝸牛インプラント、鼓室形成チューブ、シャント、術後廃液チューブ、廃液デバイス、気管内チューブ、心臓弁、絆創膏、創傷包帯、他のインプラント可能デバイス、並びに他の留置デバイス、細胞培養基材、人工皮膚、人工筋肉、心筋シート等の各種医療用物品;
船舶、船底塗料、ロープ、漁網、漁具、浮き子、ブイ、生け簀、釣り針、浮子、釣り糸、浮き球、コンテナ、バケツ、延縄、ワイヤー、水中灯等の漁業部材;
火力・原子力発電所の給排水口等の水中構造物;
海水ポンプ等の海水利用機器類;
洋上風力発電機、メガフロート、湾岸道路、海底トンネル等の発電設備及び港湾・湾岸設備;
風力発電機ブレード、太陽光発電パネル、太陽電池カバー、熱交換器、熱交換機用放熱フィンなどの発電設備の部材;
運河・水路等における各種海洋土木工事の汚泥拡散防止膜等の土木設備;
自動車用窓ガラス、車体、シート、自動車用塗装、グレージング剤、ヘッドランプレンズ、ドアミラー、カメラレンズ、ラジエーターフィン、エバポレーター、ポップアップディスプレイ、フロントウィンドウ、二輪車車体などの車両用物品および車両用部材;
鉄道車体、バス車体、シート、車両床、窓ガラス、手摺、つり革、車内トイレ、などの公共車両用物品;
航空機機体、シート、機体床、窓ガラス、機内トイレ、などの航空機用物品;
橋梁、道路鏡、防塵カバー、看板、交通標識、各種表示装置、広告塔、防音壁、屋外広告、橋梁、ガードレール、トンネル、浄化槽、冷却塔、排水溝等の野外設備;
油水分離槽、グリストラップ、グリス阻集器、オイルトラップ、オイル阻集器、排水ピットなどの分離槽及び止油槽;
植物ポッド、土壌、灌水チューブ、配管、ビニールハウス、フロートパネル、育苗用トレー、育苗用スポンジ、水耕栽培養液供給流路、花瓶、プランター等の農業資材;
油水分離膜、ガス分離膜、逆浸透膜、ナノろ過膜、限外ろ過膜、精密濾過膜、などの分離膜;
衣服、ハンカチ、エプロン、枕、布団、マットレス、毛布、敷布、カーテン、テーブルかけ、タオル、布団カバー、枕カバーなどの繊維系物品;
ロボット、ロボット用部材;
テレビ、スマートフォン、タブレットPC、パソコン、タッチパネルディスプレイ、VRゴーグル等の表示装置。
本発明に係る重合体又は組成物を含有する素材に付着したバイオフィルムの量を測定する方法は、素材にバイオフィルムを形成させる工程、形成したバイオフィルムを定量する工程で構成される。
核磁気共鳴分光器(NMR)を用い、以下に示す測定条件にて、重合体の核磁気共鳴スペクトル(以下、NMRスペクトル)を測定した。
装置:ブルカー・バイオスピン(株)製 AVANCE III 600HD
測定プローブ:10mmクライオプローブ
測定溶媒:1,2-ジクロロベンゼン/1,1,2,2-テトラクロロエタン-d2=50/50(容積比)の混合液
試料濃度:100mg/mL
測定温度:135℃
測定方法:プロトンデカップリング法
積算回数:5000回
パルス幅:45度
パルス繰り返し時間:4秒
測定基準:テトラメチルシラン
装置:日本電子(株)製 JNM―AL400
測定プローブ:10mmオートチューンプローブ
測定溶媒:1,2-ジクロロベンゼン/1,1,2,2-テトラクロロエタン-d2=85/15(容積比)の混合液
試料濃度:100mg/mL
測定温度:135℃
積算回数:256回
パルス幅:45度
パルス繰り返し時間:5秒
測定基準:テトラメチルシラン
上記の13C-NMR測定条件に従って得られたエチレン-メチルアクリレート共重合体の13C-NMRスペクトルについて、以下のa1、b1、c1、d1およびe1の範囲の積分値を求め、下記式から求められる3種のダイアッド(EE、EA、AA)の含有量(数)から、エチレンに由来する構成単位(A1)およびメチルアクリレートに由来する構成単位(C1)の数を算出した。なお、EEは、エチレン-エチレンダイアッドを意味し、EAは、エチレン-メチルアクリレートダイアッドを意味し、AAは、メチルアクリレート-メチルアクリレートダイアッドを意味する。
b1:31.9-32.6ppm
c1:41.7ppm
d1:43.1-44.2ppm
e1:45.0-46.5ppm
EA=e1
AA=c1+d1
構成単位(C1)の数=100×(EA/2+AA)/(EE+EA+AA)
エチレン-メチルアクリレート共重合体と、後述のB-1とを反応させて、エチレンに由来する構成単位(A2)と式(1)で示される構成単位(B2)とメチルアクリレートに由来する構成単位(C2)とからなる重合体を得た実施例において、上記の1H-NMR測定条件に従って得られた該重合体の1H-NMRスペクトルについて、以下のf1およびg1の範囲の積分値を求めた。次に、下記式から、エチレン-メチルアクリレート共重合体に含まれるメチルアクリレートに由来する構成単位(C1)が、重合体(1)の式(1)で示される構成単位(B2)に転化した転化率(X1)を算出した。
g1:3.9-4.3ppm
重合体(1)に含まれる、エチレンに由来する構成単位(A2)、式(1)で示される構成単位(B2)、メチルアクリレートに由来する構成単位(C2)の数は、それぞれ、下記式から算出した。
重合体(1)に含まれるエチレンに由来する構成単位(A)、上記式(1)で示される構成単位(B)および上記式(2)で示される構成単位(C)の重量%は、それぞれ、下記式から算出した。
ゲル・パーミエイション・クロマトグラフィー(GPC)装置およびソフトウェアを用い、以下に示す測定条件にて、重合体のポリスチレン換算平均分子量を測定した。
装置:HLC-8121GPC/HT(東ソー)
GPCカラム:TOSOH TSKgelGMH6-HT 7.8mm I.D.×300mm(東ソー) 3本
示差屈折率計(RI):GPC装置に付属
ソフトウェア:GPC-8020modelII(東ソー)
移動相:オルトジクロロベンゼン(和光、特級)にBHTを0.1w/v添加
流速:1mL/分
カラムオーブン温度:140℃
試料注入部温度:140℃
検出器温度:140℃
試料溶液注入量:0.3mL
標準物質:下記の標準1~4に記載の12種類のポリスチレン標準試料(東ソー)
溶媒:オルトジクロロベンゼン(和光、特級)にBHTを0.1w/v添加
標準溶液濃度:下記の標準1~4の通り3種類ごとに所定重量を5mLの溶媒に添加
溶解条件:室温
標準1:F700(0.4mg)、F20(0.9mg)、A5000(1.2mg)
標準2:F288(0.4mg)、F10(1.0mg)、A2500(1.2mg)
標準3:F80(0.7mg)、F4(1.1mg)、A1000(1.3mg)
標準4:F40(0.8mg)、F2(1.1mg)、A500(1.3mg)
溶媒:オルトジクロロベンゼン(和光、特級)にBHTを0.1w/v添加
試料溶液濃度:1mg/mL
溶解条件:140℃、2時間
<重合体(1)の絶対分子量と固有粘度の測定>
光散乱検出器と粘度検出器を備えた装置を用いるゲル・パーミエイション・クロマトグラフィー(GPC)により、重合体(1)およびポリエチレン標準物質1475a(米国国立標準技術研究所製)のそれぞれの絶対分子量と固有粘度を測定した。
GPC装置:HLC-8121GPC/HT(東ソー)
GPCカラム:GMHHR-H(S)HT × 3本(東ソー)
示差屈折率計(RI):GPC装置に付属
光散乱光度計(LS):PD2040(Precision Detectors社) 差圧粘度計(VISC):H502(Viscotek社)
ソフトウェア:OmniSEC(version4.7)(Malvern社)
LSおよびVISCはGPC装置のカラムオーブン内に設置し、LS、RI、VISCの順で接続した。
移動相:オルトジクロロベンゼン(和光、特級)にBHTを0.5mg/mL添加
流速:1mL/分
カラムオーブン温度:155℃
試料注入部温度:155℃
各検出器温度:155℃
試料溶液注入量:0.3mL
屈折率増分(dn/dc):重合体(1)とポリエチレン標準物質1475aのdn/dcは-0.078mL/gとし、ポリスチレン標準物質のdn/dcは0.079mL/gとした。
散乱角度:90°
溶媒:オルトジクロロベンゼン(和光、特級)にBHTを0.1w/V添加
試料溶液濃度:2mg/mL
溶解条件:145℃、2時間
以下の方法により、α1とα0を求め、これらを下記式(I)に代入してAを求めた。
A=α1/α0 (I)
log[η1]=α1logM1+logK1 (I-I)
(式(I-I)中、[η1]は重合体の固有粘度(単位:dl/g)を表し、M1は重合体の絶対分子量を表し、K1は定数である。)
log[η0]=α0logM0+logK0 (I-II)
(式(I-II)中、[η0]はポリエチレン標準物質1475aの固有粘度(単位:dl/g)を表し、M0はポリエチレン標準物質1475aの絶対分子量を表し、K0は定数である。)
自動接触角計DM-501(協和界面科学社製)を用い、成形体(シート)の接触角を測定した。試験液としては、純水またはヘキサデカン(東京化成工業株式会社製)を用い、滴下量は2μL、測定法はθ/2法とした。純水の接触角が大きいほど撥水性が高く、ヘキサデカンの接触角が大きいほど撥油性が高い。
実施例及び比較例に記載した方法で重合体をプレス成形し、縦30 mm×横30 mm×1mm厚にカットし、試験片を作製した。縦50mm×横50mm×0.3mm厚のアルミニウム板、縦50mm×横50mm×0.1mm厚の離型PETの上に試験片を載せた後、60℃まで加熱した熱プレス成形機のプレス板の上に設置し、5分間予熱した。その後、縦30mm×横30mmのステンレス製の網(6メッシュ)、縦50mm×横50mm×0.1mm厚の離型PET、縦50mm×横50mm×0.3mm厚のアルミニウム板の順に成形体の上に載せ、0.1MPaで30秒間保圧した後、30℃のプレス板の上で5分間冷却し、網の開孔部の数の90%以上を転写したものを形状転写性「〇」とし、網の開孔部の数の90%未満を転写したものを形状転写性「×」とした。
実施例及び比較例に記載した方法で重合体を成形し、縦20 mm×横40 mm×1mm厚にカットし、試験片を作製した。試験片は、表面の汚れを除くため、薄めた中性洗剤で洗浄し、表面の雑菌を死滅させるため、エタノールに数秒間浸漬して殺菌した。100人/日 程度使用する大浴場の排水口の排水カップに該試験片を貼り付け、2日間静置してぬめりを付着させた。
・バイオフィルム染色液(0.2質量%クリスタルバイオレット溶液:CV溶液)
クリスタルバイオレット(東京化成工業株式会社製)4gを2000mL容ポリエチレン製瓶に加え、次いで純水2000mLを加えて溶解させ、バイオフィルム染色液とした。
・染色バイオフィルム溶出液(2.0質量%ドデシル硫酸ナトリウム溶液:SDS溶液) ドデシル硫酸ナトリウム(東京化成工業株式会社製)40gを2000mL容ポリエチレン製瓶に加え、次いで純水2000mLを加えて溶解させ、染色バイオフィルム溶出液とした。
500mLビーカーに純水を500mL程度加えた後、取り出された試験片を純水に浸漬して軽く揺すって試験片を洗浄した。洗浄された試験片を取り出し、試験片に付いた余分な水分をペーパータオルで吸い取った。
500mLビーカーに純水を500mL程度加えた後、取り出された試験片を純水に浸漬して洗浄した。洗浄された試験片を取り出し、試験片に付いた余分な水分をペーパータオルで吸い取った。
<構成単位(A)と構成単位(C)とを有する前駆重合体(1)>
エチレン-メチルアクリレート共重合体A-1を以下のとおり製造した。
メチルアクリレートに由来する構成単位の数:14.7%(34.6重量%、13C-NMRにて上述の方法に従った求めた)
MFR(190℃、21Nで測定):41g/10分
B-1: α―ブチル-ω-[3-(2-ヒドロキシエトキシ)プロピル]ポリジメチルシロキサン(JNC株式会社製)
C-1:オルトチタン酸テトラ(iso-プロピル) [日本曹達株式会社製]
G-1:不飽和ポリエステル[リゴラックTR-254 M-LVK、昭和電工株式会社製、リゴラックTR-254 M-LVKはスチレンを含む]
G-2:ポリ塩化ビニル[ZEST 1000H、新第一塩ビ株式会社製]
G-3:ポリメチルメタクリレート[スミペックス MM、住友化学株式会社製]
G-4:高密度ポリエチレン[E8080、京葉ポリエチレン製]
G-5:直鎖状低密度ポリエチレン[スミカセンE FV101、住友化学株式会社製]
H-1:パーメックN[日油株式会社製]
H-2:2,2’-アゾビス(イソブチロニトリル)[東京化成工業株式会社製]
I-1:Polyglykol P41/300[クラリアント株式会社製]
I-2:サンワックス151-P[三洋化成工業株式会社製]
I-3:H-7579[堺化学工業株式会社製]
I-4:エチレングリコールジメタクリレート[東京化成工業株式会社製]
I-5:テルピノレン[東京化成工業株式会社製]
I-6:ジ(2-エチルヘキシル)スルホこはく酸ナトリウム[東京化成工業株式会社製]
I-7:スミライザーGP[住友化学株式会社製]
(1)重合体(ex1-1)の合成及び分析
攪拌機およびフィンガーバッフルを備えた内容積0.5Lのセパラブルフラスコの内部を窒素ガス置換した後、A-1:60.00gと、B-1:149.70gとを加え、オイルバス温度を130℃に設定し、10kPa減圧下にて1.5時間加熱攪拌を行った。その後、窒素ガス雰囲気下で、そこへC-1:3.55gを加え、オイルバス温度を140℃に設定し、3kPa減圧下にて25時間加熱攪拌を行い、重合体(ex1-1)(エチレン-2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート-メチルアクリレート共重合体)を得た。重合体(ex1-1)の構成単位の割合を上記記載の方法で分析した。その分析結果を表1に示す。
(2)重合体(ex1-1)からなる成形体(シート)の作製
実施例A1(1)で得られた重合体(ex1-1)を縦50mm×横50mm×厚み1mmのスペーサーの枠内に投入し、該スペーサーを2枚の0.3mm厚のアルミニウム板で挟み、更にその外側を2枚の2mm厚のステンレス板で挟んだ。プレス板の設定を140℃とした熱プレス成形機中に設置し、5分間予熱後、10MPaまで昇圧し5分間保圧した後、30℃、10MPaで5分間冷却し、ドライアイスで5分間冷却して、厚さ1mmのシート(ex1-2)を作製した。
(3)接触角測定、形状転写性、バイオフィルム低減率評価
上記(2)で得られたシート(ex1-2)について、純水及びヘキサデカンの接触角、形状転写性、バイオフィルム低減率(式(δ1)の数式を使用)を上記記載の方法で評価した。その評価結果を表1に示す。
(1)重合体(ex2-1)の合成及び分析
B-1の使用量を112.28gに変更したこと以外は、実施例A1(1)と同様にして、重合体(ex2-1)(エチレン-2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート-メチルアクリレート共重合体)を得た。当該重合体の構成単位の割合を上記記載の方法で分析した。その分析結果を表1に示す。
(2)重合体(ex2-1)からなる成形体(シート)の作製
重合体(ex1-1)を実施例A2(1)で得られた重合体(ex2-1)へ変更したこと以外は、実施例1(2)と同様にして、50mm×50mm×1mmの成形体(ex2-2)を作製した。
(3)接触角測定、形状転写性、バイオフィルム低減率評価
上記(2)で得られたシート(ex2-2)について、純水及びヘキサデカンの接触角、形状転写性、バイオフィルム低減率(式(δ1)の数式を使用)を上記記載の方法で評価した。その評価結果を表1に示す。
(1)重合体(ex3-1)の合成及び分析
B-1の使用量を74.85gに変更したこと以外は、実施例A1(1)と同様にして、重合体(ex3-1)(エチレン-2-(3-α-ブチル-ポリジメチルシロキサニル-プロポキシ)エチルアクリレート-メチルアクリレート共重合体)を得た。当該重合体の構成単位の割合を上記記載の方法で分析した。その分析結果を表1に示す。
(2)重合体(ex3-1)からなる成形体(シート)の作製
重合体(ex1-1)を実施例A3(1)で得られた重合体(ex3-1)へ変更したこと以外は、実施例1(2)と同様にして、50mm×50mm×1mmの成形体(ex3-2)を作製した。
(3)接触角測定、形状転写性、バイオフィルム低減率評価
上記(2)で得られたシート(ex3-2)について、純水及びヘキサデカンの接触角、形状転写性、バイオフィルム低減率(式(δ1)の数式を使用)を上記記載の方法で評価した。その評価結果を表1に示す。
(1)重合体(ce1-1)の合成及び分析
三方コックを備えた内容積0.2Lの2径ナスフラスコに撹拌子を入れ、120℃で3時間乾燥した。乾燥したナスフラスコの内部を窒素ガス置換した後、3-α-ブチル-ポリジメチルシロキサニル-プロピルメタクリレート(分子量1000、FM―0711、JNC株式会社製)8.00g、メチルメタクリレート(東京化成工業株式会社製)0.53g、再結晶により精製した2,2’-アゾビス(イソブチロニトリル)(東京化成工業株式会社製)0.011gをナスフラスコに投入した。当該溶液にシリンジ針を用いて窒素ガスを流入して30分間バブリングした。その後、オイルバスを60℃に設定し、16時間攪拌した。80℃の真空乾燥器で乾燥し、重合体(ce1-1)(3-α-ブチル-ポリジメチルシロキサニル-プロピルメタクリレート-メチルメタクリレート共重合体)を得た。当該重合体の評価結果を表1に示す。
(2)重合体(ce1-1)からなる試験片の作製
重合体(ex1-1)を重合体(ce1-1)へ変更したこと以外は、実施例A1(2)と同様にして、試験片(ce1-2)を作製した。
(3)接触角測定、形状転写性、バイオフィルム低減率評価
上記(2)で得られたシート(ce1-2)を使用し、純水及びヘキサデカンの大気下接触角、形状転写性を実施例A1と同様にして評価した。その評価結果を表1に示す。バイオフィルム低減率はシートが水中で崩壊するため測定することができなかった。
(1)A-1からなる試験片の作製
重合体(ex1-1)をA-1へ変更したこと以外は、実施例A1(2)と同様にして、試験片(ce2-2)を作製した。
(2)接触角測定、形状転写性、バイオフィルム低減率評価
上記(1)で得られたシート(ce2-2)を使用し、純水及びヘキサデカンの接触角、バイオフィルム低減率(式(δ1)の数式を使用)、形状転写性を実施例A1と同様にして評価した。その評価結果を表1に示す。
ガラス製バイアル瓶中で重合体(ex1-1)600mgをスチレン(東京化成工業株式会社製)6mLに溶解させ、溶液(exB1-1)を作製した。ポリエチレン製の瓶へ、プレポリマーとしてG-1 25g、溶液(exB1-1)6 ml、添加剤としてI-1を250 mg,さらに溶液(exB1-1)のガラス製バイアル瓶中を洗浄したスチレン3mlを加え、マグネチックスターラーを用いて30分間攪拌した。さらに、硬化剤としてH-1を250mgを加え、マグネチックスターラーで5分間攪拌することで溶液を得た。得られた溶液を、縦200mm×横200mm×厚み5mmのガラス板の上に載せた縦150mm×横150mm×厚み1mmのブチルゴム製の枠(内径:縦110mm×横110mm×厚み1mm)内に注液した後、もう一枚の縦200mm×横200mm×厚み5mmのガラス板を枠の上に載せることでセルを作製し片方のガラス板が鉛直下側、もう一方のガラス板が鉛直上側になるようにオーブンに設置し、室温で30分間静置した。その後、100℃で2時間加熱し、不飽和ポリエステルとスチレンとを重合し、架橋させることで厚さ1mmの不飽和ポリエステルシート(exB1-2)を得た。不飽和ポリエステルシート(exB1-2)は、重合体(ex1-1)を含むシートである。
当該シートについて、バイオフィルム低減率(式(δ2)の数式を使用)を評価した。その評価結果を表2に示す。
(1)樹脂組成物(exB2-1)の製造
(G-2)93.90重量%と、重合体(ex1-1)4.69重量%と、添加剤(I-2) 0.47重量%と、添加剤(I-3)0.94重量%を、ローターを150℃、20rpmで回転させたラボプラストミル(株式会社東洋精機製作所製、R100)に4分間で投入・可塑化し、続いて150℃、80rpm、2分間溶融混練することで樹脂組成物(exB2-1)を得た。
(2)シート(exB2-2)の製造
当該樹脂組成物を、縦50mm×横50mm×厚み1mmのスペーサーの枠内に投入し、該スペーサーを0.5mm厚のアルミニウム板で挟み、更に2枚の2mm厚のステンレス板で挟んだ。得られた試料をプレス板の設定を175℃とした熱プレス成形機中に設置し、5分間かけて1MPaまで昇圧した後、30℃、0.5MPaで5分間冷却して、厚さ1mmのシート(exB2-2)を作製した。
当該シートについて、バイオフィルム低減率(式(δ3)の数式を使用)を評価した。その評価結果を表2に示す。
ガラス製バイアル瓶中で重合体(ex1-1)1.50gをメタクリル酸メチル(東京化成工業株式会社)13.50gに溶解させ、溶液(exB3-1)を作製した。撹拌機を備えた容積0.5Lのセパラブルフラスコの内部を窒素置換した後、ポリメタクリル酸メチル(住友化学社製)17.84gに、プレポリマーとしてメタクリル酸メチル(東京化成工業社製)76.55g、溶液(exB3-1)を5.00g、添加剤としてI-4を0.40g、I-5をメタクリル酸メチル0.9g中に0.1g溶解させた溶液を0.1g、I-6をメタクリル酸メチル0.6g中に0.4g溶解させた溶液を0.2g加え、70℃で2時間攪拌した。加熱を止めて室温まで温度が下がってきたら硬化剤としてH-2を0.08g加え、15分攪拌した。得られた溶液は真空オーブン中、-0.065MPaで15分間脱気した。得られた溶液は、縦20cm×横20cm×厚さ1cmのガラス基板2枚と、厚さ1.5mmの塩化ビニルチューブをガラス基板間のスペーサーとして使用したガラスセル中に注液し、65℃で8時間加熱した。その後120℃で2時間加熱することで厚さ1.5mmのシート(exB3-2)を得た。
当該シートについて、バイオフィルム低減率(式(δ4)の数式を使用)を評価した。その評価結果を表2に示す。
(1)樹脂組成物(exB4-1)の製造
(G-4)95.22重量%と、重合体(ex1-1)4.76重量%と、添加剤(I-7)0.02重量%を、ローターを190℃、20rpmで回転させたラボプラストミル(株式会社東洋精機製作所製、R100)に4分間で投入・可塑化し、続いて190℃、80rpm、5分間溶融混練することで樹脂組成物(exB4-1)を得た。
(2)シート(exB4-2)の製造
当該樹脂組成物を2枚の0.1mm厚の離型PETフィルムで挟み、縦50mm×横50mm×厚み1mmのスペーサーの枠内に納まるように投入し、さらに0.5mm厚のアルミニウム板で挟み、更に2枚の2mm厚のステンレス板で挟んだ。得られた試料をプレス板の設定を190℃とした熱プレス成形機中に設置し、5分間かけて5MPaまで昇圧した後、30℃、5MPaで5分間冷却して、厚さ1mmのシート(exB4-2)を作製した。
当該シートについて、バイオフィルム低減率(式(δ5)の数式を使用)を評価した。その評価結果を表2に示す。
(1)樹脂組成物(exB5-1)の製造
(G-5)95.00重量%と、重合体(ex1-1)5.00重量%を、ローターを170℃、20rpmで回転させたラボプラストミル(株式会社東洋精機製作所製、R100)に4分間で投入・可塑化し、続いて170℃、80rpm、5分間溶融混練することで樹脂組成物(exB5-1)を得た。
(2)シート(exB5-2)の製造
当該樹脂組成物を2枚の0.1mm厚の離型PETフィルムで挟み、縦50mm×横50mm×厚み1mmのスペーサーの枠内に納まるように投入し、さらに0.5mm厚のアルミニウム板で挟み、更に2枚の2mm厚のステンレス板で挟んだ。得られた試料をプレス板の設定を190℃とした熱プレス成形機中に設置し、5分間かけて5MPaまで昇圧した後、30℃、5MPaで5分間冷却して、厚さ1mmのシート(exB5-2)を作製した。
当該シートについて、バイオフィルム低減率(式(δ6)の数式を使用)を評価した。その評価結果を表2に示す。
ポリエチレン製の瓶へ、プレポリマーとしてG-1 25g、スチレン3mlを加え、マグネチックスターラーを用いて30分間攪拌した。さらに、硬化剤としてH-1を250 mgを加え、マグネチックスターラーで5分間攪拌することで溶液を得た。得られた溶液を、縦200mm×横200mm×厚み5mmのガラス板の上に載せた縦150mm×横150mm×厚み1mmのブチルゴム製の枠(内径:縦110mm×横110mm×厚み1mm)内に注液した後、、もう一枚の縦200mm×横200mm×厚み5mmのガラス板を枠の上に載せることでセルを作製し片方のガラス板が鉛直下側、もう一方のガラス板が鉛直上側になるようにオーブンに設置し、室温で30分間静置した。その後、100℃で2時間加熱し、不飽和ポリエステルとスチレンとを重合し、架橋させることで厚さ1mmの不飽和ポリエステルシート(CeB1-2)を得た。
当該シートについて、バイオフィルム低減率(式(δ2)の数式を使用)を評価した。その評価結果を表2に示す。
(G-2)を2枚の0.1mm厚の離型PETフィルムで挟み、縦50mm×横50mm×厚み1mmのスペーサーの枠内に納まるように投入し、0.5mm厚のアルミニウム板で挟み、更に2枚の2mm厚のステンレス板で挟んだ。得られた試料をプレス板の設定を175℃とした熱プレス成形機中に設置し、5分間かけて1MPaまで昇圧した後、30℃、0.5MPaで5分間冷却して、厚さ1mmのシート(CeB2-2)を作製した。
当該シートについて、バイオフィルム低減率(式(δ3)の数式を使用)を評価した。その評価結果を表2に示す。
撹拌機を備えた容積0.5Lのセパラブルフラスコの内部を窒素置換した後、ポリメタクリル酸メチル(住友化学社製)17.84gに、プレポリマーとしてメタクリル酸メチル(東京化成工業社製)81.46g、添加剤としてI-4を0.40g、I-5をメタクリル酸メチル0.9g中に0.1g溶解させた溶液を0.1g、I-6をメタクリル酸メチル0.6g中に0.4g溶解させた溶液を0.2g加え、70℃で2時間攪拌した。加熱を止めて室温まで温度が下がってきたら硬化剤としてH-2を0.08g加え、15分攪拌した。得られた溶液は真空オーブン中、-0.065MPaで15分間脱気した。得られた溶液は、縦20cm×横20cm×厚さ1cmのガラス基板2枚と、厚さ1.5mmの塩化ビニルチューブをガラス基板間のスペーサーとして使用したガラスセル中に注液し、65℃で8時間加熱した。その後120℃で2時間加熱することで厚さ1.5mmのシート(CeB3-2)を得た。
当該シートについて、バイオフィルム低減率(式(δ4)の数式を使用)を評価した。その評価結果を表2に示す。
(G-4)を2枚の0.1mm厚の離型PETフィルムで挟み、縦50mm×横50mm×厚み1mmのスペーサーの枠内に納まるように投入し、さらに0.5mm厚のアルミニウム板で挟み、更に2枚の2mm厚のステンレス板で挟んだ。得られた試料をプレス板の設定を190℃とした熱プレス成形機中に設置し、5分間かけて5MPaまで昇圧した後、30℃、5MPaで5分間冷却して、厚さ1mmのシート(CeB4-2)を作製した。
当該シートについて、バイオフィルム低減率(式(δ5)の数式を使用)を評価した。その評価結果を表2に示す。
(G-5)を2枚の0.1mm厚の離型PETフィルムで挟み、縦50mm×横50mm×厚み1mmのスペーサーの枠内に納まるように投入し、さらに0.5mm厚のアルミニウム板で挟み、更に2枚の2mm厚のステンレス板で挟んだ。得られた試料をプレス板の設定を190℃とした熱プレス成形機中に設置し、5分間かけて5MPaまで昇圧した後、30℃、5MPaで5分間冷却して、厚さ1mmのシート(CeB5-2)を作製した。
当該シートについて、バイオフィルム低減率(式(δ6)の数式を使用)を評価した。その評価結果を表2に示す。
Claims (27)
- エチレン及びプロピレンからなる群より選ばれる少なくとも一種に由来する構成単位(A)と、下記式(1)で示される構成単位(B)と、下記式(2)で示される構成単位および下記式(3)で示される構成単位からなる群より選ばれる少なくとも一種の構成単位(C)とを含む
重合体。
(式(1)中、
Rは、水素原子またはメチル基を表し、
L1は、―CO―O―、―O―CO―または―O―を表し、
L2は、単結合、―CH2―、―CH2―CH2―、―CH2―CH2―CH2―、―CH2―CH(OH)―CH2―または―CH2―CH(CH2OH)―を表し、
L3は、単結合、―CO―O―、―O―CO―、―O―、―CO―NH―、―NH―CO―、―CO―NH―CO―、―NH―CO―NH―、―NH―または―N(CH3)―を表し、
L6は、―(CH2)n―(Rf2O)p―(Rf3)h―(Si(Rf4)2O)g―Si(Rf1)3を表し、
Rf1は、水素原子又はC1~15のアルキル基を表し、3つのRf1は、同一でも異なっていてもよく、
Rf2は、C1~15のアルキレン基を表し、
Rf3は、C1~15のアルキレン基を表し、
Rf4は、水素原子又は置換もしくは非置換のC1~15のアルキル基又は置換もしくは非置換のC6~20のアリ―ル基を表し、2つのRf4は、同一でも異なっていてもよく、
nは0~10の整数を表し、
pは0~15の整数を表し、pが2以上の整数である場合、複数の―(Rf2O)―は、同一でも異なっていてもよく、
hは0~15の整数を表し、hが2以上の整数である場合、複数の―(Rf3)―は、同一でも異なっていてもよく、
gは1~1000の整数を表し、gが2以上の整数である場合、複数の―(Si(Rf4)2O)―は、同一でも異なっていてもよく、
なお、L1、L2およびL3で表される横書きの化学式の各々は、その左側が式(1)の上側に対応し、その右側が式(1)の下側に対応する。)
(式(2)中、
Rは、水素原子またはメチル基を表し、
L1は、―CO―O―、―O―CO―または―O―を表し、
L4は、単結合または炭素原子数1以上8以下のアルキレン基を表し、
L5は、水素原子、エポキシ基、―CH(OH)―CH2OH、カルボキシ基、ヒドロキシ基、アミノ基または炭素原子数1以上4以下のアルキルアミノ基を表す。
なお、L1で表される横書きの化学式の各々は、その左側が式(2)の上側に対応し、その右側が式(2)の下側に対応する。)
- 前記構成単位(A)と前記構成単位(B)と前記構成単位(C)の合計数を100mol%として、前記構成単位(A)の数が70~99mol%であり、前記構成単位(B)と前記構成単位(C)の合計数が30~1mol%である、請求項1に記載の重合体。
- 前記構成単位(B)と前記構成単位(C)の合計数を100mol%として、前記構成単位(B)の数が1mol%以上99mol%以下であり、前記構成単位(C)の数が1mol%以上99mol%以下である、請求項1に記載の重合体
- 前記構成単位(A)と前記構成単位(B)と前記構成単位(C)の合計量を100重量%として、前記構成単位(B)の含有量が30重量%以上である、請求項1に記載の重合体。
- 前記構成単位(A)と前記構成単位(B)と前記構成単位(C)の合計量を100重量%として、前記構成単位(B)の含有量が50重量%以上である、請求項1に記載の重合体。
- 前記式(1)で示される構成単位(B)において、L6のgが1以上250以下である、請求項1に記載の重合体
- 前記式(1)で示される構成単位(B)において、L11が―CO―O―である、請求項1に記載の重合体。
- 架橋されている、請求項1に記載の重合体。
- ゲル分率が20%以上である、請求項1に記載の重合体。
- 前記重合体に含まれる全ての構成単位の合計数を100mol%として、前記構成単位(A)と前記構成単位(B)と前記構成単位(C)の合計数が90mol%以上である、請求項1に記載の重合体。
- 請求項1に記載の重合体を含有する組成物。
- 前記重合体を1重量%以上含有する請求項11に記載の組成物。
- ベース樹脂を含有する請求項11に記載の組成物。
- 前記ベース樹脂が熱可塑性樹脂である、請求項13に記載の組成物。
- 前記ベース樹脂がポリ塩化ビニルである、請求項13に記載の組成物。
- 前記ベース樹脂が熱硬化性樹脂である、請求項13に記載の組成物。
- 前記ベース樹脂が不飽和ポリエステルである、請求項13に記載の組成物。
- 請求項1に記載の重合体を含有する成形体。
- 請求項11に記載の組成物を含有する成形体。
- 防汚材である請求項18又は19に記載の成形体。
- 抗ぬめり材である請求項18又は19に記載の成形体。
- 請求項1に記載の重合体を含有する塗膜。
- 請求項11に記載の組成物を含有する塗膜。
- 防汚材である請求項22又は23に記載の塗膜。
- 抗ぬめり材である請求項22又は23に記載の塗膜。
- エチレン及びプロピレンからなる群より選ばれる少なくとも一種に由来する構成単位(A)と、下記式(2)で示される構成単位および下記式(3)で示される構成単位からなる群より選ばれる少なくとも一種の構成単位(C)とを含む重合体と、
下記式(11)で示される化合物、下記式(12)で示される化合物、下記式(13)で示される化合物、下記式(14)で示される化合物、下記式(15)で示される化合物、下記式(16)で示される化合物、下記式(17)で示される化合物および下記式(18)で示される化合物からなる群より選ばれる1種以上の化合物(α)と
を反応させる工程を含む、請求項1に記載の重合体の製造方法。
(式(2)中、
Rは、水素原子またはメチル基を表し、
L1は、―CO―O―、―O―CO―または―O―を表し、
L4は、単結合または炭素原子数1以上8以下のアルキレン基を表し、
L5は、水素原子、エポキシ基、―CH(OH)―CH2OH、カルボキシ基、ヒドロキシ基、アミノ基または炭素原子数1以上4以下のアルキルアミノ基を表す。
なお、L1で表される横書きの化学式の各々は、その左側が式(2)の上側に対応し、その右側が式(2)の下側に対応する。)
HO―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(11)
H2N―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(12)
X―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(13)
HO-C(=O)―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(14)
H2N-C(=O)―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(15)
X-C(=O)―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(16)
H2N-C(=O)-HN―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(17)
OCN―(CH2)n―(Rf2O)p―(Rf3)h-(Si(Rf4)2O)g―Si(Rf1)3 式(18)
式中、Rf1、Rf2、Rf3、Rf4、p、g、h及びnは、式(1)で規定した通りであり、Xはハロゲン原子を表し、
複数の化合物αを用いる場合、各Rf1、Rf2、Rf3、Rf4、p、g、h及びn並びにXは、同一でも異なっていてもよい。) - 請求項26に記載の製造方法によって、得られうる重合体。
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| EP23857435.4A EP4578895A4 (en) | 2022-08-26 | 2023-08-25 | POLYMER AND PROCESS FOR MANUFACTURING IT, RESIN COMPOSITION, AND MOLDED BODY |
| JP2024542884A JPWO2024043327A1 (ja) | 2022-08-26 | 2023-08-25 |
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| JPH02158645A (ja) * | 1988-12-09 | 1990-06-19 | Hitachi Cable Ltd | 難燃性電気絶縁組成物 |
| JPH08511825A (ja) * | 1993-06-24 | 1996-12-10 | ザ、プロクター、エンド、ギャンブル、カンパニー | シロキサン変性ポリオレフィン共重合体 |
| JP2002069178A (ja) | 2000-06-12 | 2002-03-08 | Mitsui Chemicals Inc | 重合体及びその製造方法 |
| JP2003226740A (ja) | 2002-02-04 | 2003-08-12 | Nippon Yushi Basf Coatings Kk | 含シリコーン系熱硬化性組成物 |
| WO2014080873A1 (ja) | 2012-11-20 | 2014-05-30 | 住友ゴム工業株式会社 | 表面改質方法及び表面改質弾性体 |
| JP2017115044A (ja) | 2015-12-25 | 2017-06-29 | 三菱ケミカルアグリドリーム株式会社 | 防曇組成物および防曇性フィルム |
| WO2019159863A1 (ja) | 2018-02-13 | 2019-08-22 | 住友化学株式会社 | 重合体、樹脂組成物、成形体および重合体の製造方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106255731A (zh) * | 2014-04-29 | 2016-12-21 | 3M创新有限公司 | 聚(乙烯‑共‑丙烯酸)和聚二有机硅氧烷的共聚物 |
-
2023
- 2023-08-25 EP EP23857435.4A patent/EP4578895A4/en active Pending
- 2023-08-25 WO PCT/JP2023/030668 patent/WO2024043327A1/ja not_active Ceased
- 2023-08-25 JP JP2024542884A patent/JPWO2024043327A1/ja active Pending
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| JPH02158645A (ja) * | 1988-12-09 | 1990-06-19 | Hitachi Cable Ltd | 難燃性電気絶縁組成物 |
| JPH08511825A (ja) * | 1993-06-24 | 1996-12-10 | ザ、プロクター、エンド、ギャンブル、カンパニー | シロキサン変性ポリオレフィン共重合体 |
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| WO2014080873A1 (ja) | 2012-11-20 | 2014-05-30 | 住友ゴム工業株式会社 | 表面改質方法及び表面改質弾性体 |
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| WO2019159863A1 (ja) | 2018-02-13 | 2019-08-22 | 住友化学株式会社 | 重合体、樹脂組成物、成形体および重合体の製造方法 |
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| JPWO2024043327A1 (ja) | 2024-02-29 |
| EP4578895A1 (en) | 2025-07-02 |
| EP4578895A4 (en) | 2026-07-29 |
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