WO2024253093A1 - Composé de fluorosilicone - Google Patents

Composé de fluorosilicone Download PDF

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Publication number
WO2024253093A1
WO2024253093A1 PCT/JP2024/020382 JP2024020382W WO2024253093A1 WO 2024253093 A1 WO2024253093 A1 WO 2024253093A1 JP 2024020382 W JP2024020382 W JP 2024020382W WO 2024253093 A1 WO2024253093 A1 WO 2024253093A1
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independently
group
integer
sir
organic group
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Japanese (ja)
Inventor
大貴 石井
亮介 三又
秀一 植畑
靖史 中前
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to CN202480037422.8A priority Critical patent/CN121241090A/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
    • B29C33/64—Silicone
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • This disclosure relates to fluorosilicone compounds.
  • silicone compounds having fluorine-containing groups have been known and are used, for example, as release agents for molding various rubbers and resins (see Patent Document 1).
  • the objective of this disclosure is to provide a fluorosilicone compound that has excellent release properties.
  • X is -(Ar) a1 -(CFH) b1 -(CH 2 ) c1 -(O) d1 -
  • Ar is a divalent aromatic group optionally substituted by a fluorine atom or R A ; a1 is an integer from 0 to 10, b1 is an integer from 0 to 200, c1 is an integer from 0 to 200, d1 is an integer from 0 to 10, The repeating units denoted by symbols a1, b1, c1, and d1 and enclosed in parentheses may be present in any order.
  • the fluorosilicone compound according to any one of the above [1] to [4], wherein the fluorosilicone compound is a group represented by the formula: [6]
  • X is -(Ar) a1 -(O) d1 -(CH 2 ) c1 - [Wherein: Ar is a divalent aromatic group which may be substituted by a fluorine atom
  • R Si is represented by the following formula (S1), (S2), (S3), (S4) or (S5): [Wherein: Each R 11 is independently a hydroxyl group or a hydrolyzable group; Each R 12 is independently a monovalent organic group; n1 is independently an integer of 0 to 3 for each (SiR 11 n1 R 12 3-n1 ) unit, Each X11 independently represents a single bond or a divalent organic group; Each R 13 is independently a hydrogen atom or a monovalent organic group.
  • Each t is independently an integer of 2 or more;
  • R 14 is each independently a hydrogen atom, a halogen atom or -X 11 -SiR 11 n1 R 12 3-n1 ;
  • R 15 is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms;
  • Each R a1 is independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 ;
  • Each Z1 is independently a divalent organic group;
  • Each R 21 is independently -Z 1' -SiR 21' p1' R 22' q1' R 23' r1' ;
  • Each R 22 is independently a hydroxyl group or a hydrolyzable group;
  • Each R 23 is independently a monovalent organic group;
  • Each p1 is independently an integer from 0 to 3;
  • Each q1 is independently an integer from 0 to 3,
  • Each n2 is independently an integer from 0 to 3;
  • Each R e1 is independently —Z 3 —SiR 34 n2 R 35 3-n2 ;
  • Each R f1 is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group,
  • Each k2 is independently an integer from 0 to 3;
  • Each l2 is independently an integer from 0 to 3;
  • Each m2 independently represents an integer of 0 to 3.
  • R g1 and R h1 are each independently -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , or -Z 4 -CR d1 k2 R e1 l2 R f1 m2 ;
  • Each Z4 is independently a single bond, an oxygen atom, or a divalent organic group, k3 is 1 or 2; l3 is 0 or 1; However, in formula (S1), (S2), (S3), (S4), or (S5), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded.]
  • a release composition comprising the fluorosilicone compound according to any one
  • (i) A method for forming a release agent coating comprising a step of applying the release composition according to any one of the above items [9] to [13] to an inner surface of a molding die to form a coating of the release composition.
  • the fluorosilicone compound disclosed herein can provide excellent release properties.
  • monovalent organic group refers to a monovalent group containing carbon.
  • the monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof.
  • a derivative of a hydrocarbon group refers to a group that has one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain.
  • divalent organic group is not particularly limited, but includes divalent groups in which one hydrogen atom has been removed from a hydrocarbon group.
  • hydrocarbon group refers to a group containing carbon and hydrogen, with one hydrogen atom removed from the molecule.
  • Such hydrocarbon groups are not particularly limited, but include hydrocarbon groups having 1 to 20 carbon atoms, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups.
  • the above-mentioned "aliphatic hydrocarbon group” may be linear, branched, or cyclic, and may be saturated or unsaturated.
  • the hydrocarbon group may contain one or more ring structures. Such a hydrocarbon group may be substituted with one or more substituents.
  • the hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at its terminal or in the molecular chain.
  • substituents for a "hydrocarbon group” include, but are not limited to, one or more groups selected from a halogen atom; a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5-10 membered heterocyclyl group, a 5-10 membered unsaturated heterocyclyl group, a C 6-10 aryl group, and a 5-10 membered heteroaryl group, each of which is optionally substituted by one or more halogen atoms.
  • hydrolyzable group refers to a group that can undergo hydrolysis, i.e., a group that can be removed from the main skeleton of a compound by hydrolysis.
  • R h examples include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
  • an alkyl group, particularly an unsubstituted alkyl group is preferred, and a methyl group or an ethyl group is more preferred.
  • R h is a methyl group, and in another embodiment, R h is an ethyl group.
  • R A can be CF 3 O—.
  • R A can be CF 3 NH-- or (CF 3 ) 2 N--, preferably CF 3 NH--.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
  • Substituents for the alkyl and aryl groups include halogen atoms, and one or more groups selected from a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5-10 membered heterocyclyl group, a 5-10 membered unsaturated heterocyclyl group, a C 6-10 aryl group, and a 5-10 membered heteroaryl group, each of which may be substituted by one or more halogen atoms.
  • the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom.
  • the alkyl group may be an alkyl group that may be substituted with a halogen atom, such as a chlorine atom.
  • the aryl group may be an aryl group that may be substituted with a halogen atom, such as a chlorine atom, or a C 1 -C 10 alkyl group, for example a methyl group.
  • a halogen atom such as a chlorine atom
  • a C 1 -C 10 alkyl group for example a methyl group.
  • the alkyl group may be preferably a C 1-20 alkyl group, more preferably a C 1-12 alkyl group, even more preferably a C 1-4 alkyl group, and even more preferably a methyl group.
  • the aryl group may be preferably a C 6-20 aryl group, more preferably a C 6-12 aryl group, and even more preferably a phenyl group.
  • R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 may each independently be an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, or a dodecyl group; a substituted alkyl group such as a chloromethyl group, an unsubstituted aryl group such as a phenyl group or a naphthyl group; or a substituted aryl group such as a 4-chlorophenyl group or a 2-methylphenyl group.
  • an alkyl group, particularly an unsubstituted alkyl group is preferred, and a methyl group is more preferred.
  • R 3 and R 10 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, R A -X-, or R Si -Y-.
  • substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group in R3 and R10 are the same as those described above for R1 and the like.
  • Each X is independently a divalent organic group.
  • X is -(Ar) a1 -(CFH) b1 -(CH 2 ) c1 -(O) d1 -
  • Ar is a divalent aromatic group optionally substituted by a fluorine atom or R A ;
  • aromatic groups include aromatic rings containing only carbon as ring atoms (so-called arylenes), as well as aromatic rings containing nitrogen, oxygen or sulfur (so-called heteroarylenes), and groups having multiple aromatic rings.
  • the aromatic group preferably has a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a corannulene ring, or an ovalene ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.
  • the aromatic group preferably has an indole ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring, more preferably an indole ring.
  • the aromatic group preferably has a biphenyl ring, a terphenyl ring, a triphenylmethane ring, or a benzophenone ring.
  • Ar is an unsubstituted divalent aromatic group.
  • Ar is a divalent aromatic group substituted with a fluorine atom.
  • a1 is an integer from 0 to 10, preferably 0 or 1.
  • a1 is 0.
  • a1 is 1.
  • c1 is an integer between 0 and 200, preferably between 0 and 30.
  • d1 is an integer from 0 to 10, preferably an integer from 0 to 3.
  • X is -(Ar) a1 -(O) d1 -(CH 2 ) c1 -
  • Ar is a divalent aromatic group which may be substituted by a fluorine atom or R A , preferably an unsubstituted divalent aromatic group; a1 is 0 or 1; c1 is an integer from 1 to 36, preferably an integer from 1 to 30, for example an integer from 1 to 9, an integer from 1 to 3, or an integer from 2 to 3; d1 is 0 or 1. It is a group represented by the following formula:
  • X is -(CH 2 ) c1 -
  • c1 is an integer from 1 to 36, preferably an integer from 1 to 30, and may be, for example, an integer from 1 to 9, or an integer from 1 to 3.
  • It is a group represented by the following formula:
  • X is -Ar-O-(CH 2 ) c1 -
  • Ar is a divalent aromatic group which may be substituted by a fluorine atom or R A , preferably an unsubstituted divalent aromatic group
  • c1 is an integer from 1 to 36, preferably an integer from 1 to 30, and may be, for example, an integer from 1 to 9, an integer from 1 to 3, or an integer from 2 to 3. It is a group represented by the following formula:
  • Each Y is independently a divalent organic group.
  • Y may be a divalent organic group preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms.
  • Y may preferably be an alkylene group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms), such as an ethylene group, a propylene group, a methylethylene group, an octylene group, and a decylene group, and an alkyleneoxyalkylene group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms), such as an ethyleneoxymethylene group, a propyleneoxymethylene group, a propyleneoxyethylene group, and an ethyleneoxybutylene group.
  • Y may more preferably be -(CH 2 ) r -, where r is an integer of 2 to 200, preferably an integer of 2 to 12.
  • R 3 Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto.
  • R 3 Si is preferably a group represented by formula (S1), (S2), (S3), (S4) or (S5).
  • Each R 11 independently represents a hydroxyl group or a hydrolyzable group.
  • each R 11 is independently a hydrolyzable group.
  • Each R 12 is independently a monovalent organic group, provided that R 12 does not include a hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • n1 is independently an integer of 0 to 3 for each (SiR 11 n1 R 12 3-n1 ) unit, provided that in formula (S1), there are at least two (SiR 11 n1 R 12 3-n1 ) units in which n1 is 1 to 3. In other words, in formula (S1), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded.
  • n1 is preferably an integer of 1 to 3, more preferably 2 to 3, and further preferably 3, independently for each (SiR 11 n1 R 12 3-n1 ) unit.
  • each X 11 is independently a single bond or a divalent organic group.
  • a divalent organic group is preferably -R 28 -O x -R 29 - (wherein R 28 and R 29 are independently a single bond or a C 1-20 alkylene group, and x is 0 or 1).
  • Such a C 1-20 alkylene group may be linear or branched, but is preferably linear.
  • Such a C 1-20 alkylene group is preferably a C 1-10 alkylene group, more preferably a C 1-6 alkylene group, and even more preferably a C 1-3 alkylene group.
  • each X 11 is independently —C 1-6 alkylene-O—C 1-6 alkylene- or —O—C 1-6 alkylene-.
  • each X 11 is independently a single bond or a straight-chain C 1-6 alkylene group, preferably a single bond or a straight-chain C 1-3 alkylene group, more preferably a single bond or a straight-chain C 1-2 alkylene group, and even more preferably a straight-chain C 1-2 alkylene group.
  • Each R 13 is independently a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is preferably a C 1-20 alkyl group.
  • Each R 15 is independently a single bond, an oxygen atom, a C 1-6 alkylene group, or a C 1-6 alkyleneoxy group.
  • each R 15 is independently an oxygen atom, a C 1-6 alkylene group, or a C 1-6 alkyleneoxy group.
  • Each t is independently an integer of 2 or greater.
  • each t is independently an integer from 2 to 10, preferably an integer from 2 to 6.
  • Each R 14 is independently a hydrogen atom, a halogen atom, or -X 11 -SiR 11 n1 R 12 3-n1 .
  • the halogen atom is preferably an iodine atom, a chlorine atom, or a fluorine atom, and more preferably a fluorine atom.
  • R 14 is a hydrogen atom.
  • formula (S1) is formula (S1-a) below.
  • R 11 , R 12 , R 13 , X 11 and n1 are as defined above in formula (S1); t1 and t2 each independently represent an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 2 to 10, for example, an integer of 1 to 5 or an integer of 2 to 5;
  • the order of occurrence of each repeating unit enclosed in parentheses with t1 and t2 is arbitrary in the formula.
  • formula (S1) is the following formula (S1-b): [In the formula, R 11 , R 12 , R 13 , X 11 , n1 and t are the same as defined in the above formula (S1)]
  • the Si atom of --SiR 11 n1 R 12 3-n1 does not form a siloxane bond.
  • Each R a1 is independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 .
  • Z1 's are each independently an oxygen atom or a divalent organic group .
  • the right side is bonded to ( SiR21p1R22q1R23r1 ) .
  • Z 1 does not include any that forms a siloxane bond with the Si atom to which Z 1 is bonded.
  • (Si-Z 1 -Si) does not include a siloxane bond.
  • the above Z 1 is preferably a C 1-6 alkylene group, -(CH 2 ) z1 -O-(CH 2 ) z2 - (wherein z1 is an integer of 0 to 6, for example an integer of 1 to 6, and z2 is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 - (wherein z3 is an integer of 0 to 6, for example an integer of 1 to 6, and z4 is an integer of 0 to 6, for example an integer of 1 to 6).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but are preferably unsubstituted.
  • Z 1 is a C 1-6 alkylene group or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 -, preferably -phenylene-(CH 2 ) z4 -.
  • Z 1 is a C 1-3 alkylene group. In one embodiment, Z 1 can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 1 can be -CH 2 CH 2 -.
  • Each R 21 is independently -Z 1' -SiR 21' p1' R 22' q1' R 23' r1' .
  • Each Z 1' is independently an oxygen atom or a divalent organic group.
  • the right side is bonded to (SiR 21' p1' R 22' q1' R 23' r1' ).
  • Z 1 ' does not include any that forms a siloxane bond with the Si atom to which Z 1 ' is bonded.
  • Z 1 ' does not include any that forms a siloxane bond with the Si atom to which Z 1 ' is bonded.
  • Si-Z 1 ' -Si does not include a siloxane bond.
  • the above Z 1' is preferably a C 1-6 alkylene group, -(CH 2 ) z1' -O-(CH 2 ) z2' - (wherein z1' is an integer of 0 to 6, for example an integer of 1 to 6, and z2' is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH 2 ) z3' -phenylene-(CH 2 ) z4' - (wherein z3' is an integer of 0 to 6, for example an integer of 1 to 6, and z4' is an integer of 0 to 6, for example an integer of 1 to 6).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but are preferably unsubstituted.
  • Z 1' is a C 1-3 alkylene group. In one embodiment, Z 1' can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 1' can be -CH 2 CH 2 -.
  • Each R 21' is independently -Z 1'' -SiR 22'' q1'' R 23'' r1'' .
  • Z 1′′ is each independently an oxygen atom or a divalent organic group.
  • the right side is bonded to (SiR 22′′ q1′′ R 23′′ r1′′ ).
  • Z 1′′ is a divalent organic group.
  • Z 1′′ does not include any that forms a siloxane bond with the Si atom to which Z 1′′ is bonded.
  • Z 1′′ does not include any that forms a siloxane bond with the Si atom to which Z 1′′ is bonded.
  • Si—Z 1′′ —Si does not include a siloxane bond.
  • Z1 " is preferably a C 1-6 alkylene group, -(CH 2 ) z1" -O-(CH 2 ) z2" - (wherein z1" is an integer of 0 to 6, for example an integer of 1 to 6, and z2" is an integer of 0 to 6, for example an integer of 1 to 6) or -(CH 2 ) z3" -phenylene-(CH 2 ) z4" - (wherein z3" is an integer of 0 to 6, for example an integer of 1 to 6, and z4" is an integer of 0 to 6, for example an integer of 1 to 6).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • These groups may be substituted, but are preferably unsubstituted, by one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group.
  • Z 1" is a C 1-6 alkylene group or --(CH 2 ) z3" -phenylene-(CH 2 ) z4" --, preferably -phenylene-(CH 2 ) z4" --.
  • Z 1" is such a group, light resistance, particularly ultraviolet resistance, may be improved.
  • Z 1" above is a C 1-3 alkylene group.
  • Z 1" can be -CH 2 CH 2 CH 2 -.
  • Z 1" can be -CH 2 CH 2 -.
  • Each R 22 ′′ is independently a hydroxyl group or a hydrolyzable group.
  • each R 22 ′′ is independently a hydrolyzable group.
  • Each R 23 ′′ is independently a monovalent organic group.
  • Such a monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • Each q1" is independently an integer of 0 to 3, and each r1" is independently an integer of 0 to 3.
  • the sum of q1" and r1" is 3 in the (SiR 22" q1" R 23" r1" ) unit.
  • q1′′ is preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3, independently for each (SiR 22′′ q1′′ R 23′′ r1′′ ) unit.
  • Each R 22' is independently a hydroxyl group or a hydrolyzable group.
  • each R 22′ is independently a hydrolyzable group.
  • Each R 23′ is independently a monovalent organic group.
  • Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • Each p1' is independently an integer of 0 to 3
  • each q1' is independently an integer of 0 to 3
  • each r1' is independently an integer of 0 to 3.
  • the sum of p', q1' and r1' is 3 in the (SiR 21' p1' R 22' q1' R 23' r1' ) unit.
  • p1' is 0.
  • p1' may be, independently for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit, an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1' is 3.
  • q1' is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit.
  • p1' is 0, and q1' is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit.
  • Each R 22 independently represents a hydroxyl group or a hydrolyzable group.
  • each R 22 is independently a hydrolyzable group.
  • Each R23 is independently a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • Each p1 is independently an integer of 0 to 3
  • each q1 is independently an integer of 0 to 3
  • each r1 is independently an integer of 0 to 3.
  • the sum of p1, q1 and r1 is 3 in the (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
  • p1 is 0.
  • p1 may be, independently for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit, an integer from 1 to 3, an integer from 2 to 3, or 3.
  • q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
  • p1 is 0, and q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3, for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
  • Each R b1 independently represents a hydroxyl group or a hydrolyzable group.
  • each R b1 is independently a hydrolyzable group.
  • Each R c1 is independently a monovalent organic group.
  • Such a monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • Each k1 is independently an integer of 0 to 3
  • each l1 is independently an integer of 0 to 3
  • each m1 is independently an integer of 0 to 3.
  • the sum of k1, l1 and m1 is 3 in the (SiR a1 k1 R b1 l1 R c1 m1 ) unit.
  • k1 is independently for each (SiR a1 k1 R b1 l1 R c1 m1 ) unit an integer from 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.
  • At least two Si atoms having hydroxyl groups or hydrolyzable groups bonded thereto are present in the terminal portion of formula (S3).
  • the group represented by formula (S3) has any one of -Z 1 -SiR 22 q1 R 23 r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer of 0 to 2); -Z 1' -SiR 22' q1' R 23' r1' (wherein q1' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer of 0 to 2); or -Z 1" -SiR 22" q1" R 23" r1" (wherein q1" is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1" is an integer of 0 to 2).
  • Z 1 , Z 1' , Z 1" , R 22 , R 23 , R 22' , R 23' , R 22'' , and R 23'' are as defined above.
  • q1′′ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, in at least one, and preferably all, R 21′ .
  • p1' is 0 and q1' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, in at least one, preferably all, R 21 .
  • k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.
  • Each R d1 is independently -Z 2 -CR 31 p2 R 32 q2 R 33 r2 .
  • Z2 's each independently represent a single bond, an oxygen atom or a divalent organic group .
  • the right side is bonded to ( CR31p2R32q2R33r2 ) .
  • Z2 is a divalent organic group.
  • Z2 does not contain a siloxane bond.
  • Z 2 is preferably a C 1-6 alkylene group, -(CH 2 ) z5 -O-(CH 2 ) z6 - (wherein z5 is an integer of 0 to 6, for example an integer of 1 to 6, and z6 is an integer of 0 to 6, for example an integer of 1 to 6) or -(CH 2 ) z7 -phenylene-(CH 2 ) z8 - (wherein z7 is an integer of 0 to 6, for example an integer of 1 to 6, and z8 is an integer of 0 to 6, for example an integer of 1 to 6).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • These groups may be substituted by one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but are preferably unsubstituted.
  • Z 2 is a C 1-6 alkylene group or —(CH 2 ) z7 -phenylene-(CH 2 ) z8 —, preferably -phenylene-(CH 2 ) z8 —.
  • Z 2 is such a group, light resistance, particularly ultraviolet resistance, may be improved.
  • Z 2 is a C 1-3 alkylene group. In one embodiment, Z 2 can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 2 can be -CH 2 CH 2 -.
  • Each R 31 is independently -Z 2' -CR 32' q2' R 33' r2' .
  • Z 2' are each independently a single bond, an oxygen atom or a divalent organic group.
  • the right side is bonded to (CR 32' q2' R 33' r2' ).
  • Z 2′ does not contain a siloxane bond.
  • Z 2' is preferably a C 1-6 alkylene group, -(CH 2 ) z5' -O-(CH 2 ) z6' - (wherein z5' is an integer of 0 to 6, for example an integer of 1 to 6, and z6' is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH 2 ) z7' -phenylene-(CH 2 ) z8' - (wherein z7' is an integer of 0 to 6, for example an integer of 1 to 6, and z8' is an integer of 0 to 6, for example an integer of 1 to 6).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but are preferably unsubstituted.
  • Z 2' is a C 1-6 alkylene group or -(CH 2 ) z7' -phenylene-(CH 2 ) z8' -, preferably -phenylene-(CH 2 ) z8' -.
  • Z 2' is such a group, light resistance, particularly ultraviolet resistance, may be improved.
  • Z 2' is a C 1-3 alkylene group. In one embodiment, Z 2' can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 2' can be -CH 2 CH 2 -.
  • Each R 32' is independently -Z 3 -SiR 34 n2 R 35 3-n2 .
  • Z3 's are each independently a single bond, an oxygen atom or a divalent organic group.
  • the right side is bonded to (SiR 34 n2 R 35 3-n2 ).
  • Z3 is an oxygen atom.
  • Z3 is a divalent organic group.
  • Z3 does not contain a siloxane bond.
  • Z3 is preferably a C 1-6 alkylene group, -(CH 2 ) z5" -O-(CH 2 ) z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 6, and z6" is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH 2 ) z7" -phenylene-(CH 2 ) z8" - (wherein z7" is an integer of 0 to 6, for example an integer of 1 to 6, and z8" is an integer of 0 to 6, for example an integer of 1 to 6).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but are preferably unsubstituted.
  • Z 3 is a C 1-6 alkylene group or --(CH 2 ) z7 " -phenylene-(CH 2 ) z8" --, preferably -phenylene-(CH 2 ) z8" --.
  • Z 3 is such a group, light resistance, particularly ultraviolet resistance, may be improved.
  • Z 3 is a C 1-3 alkylene group. In one embodiment, Z 3 can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 3 can be -CH 2 CH 2 -.
  • Each R 34 is independently a hydroxyl group or a hydrolyzable group.
  • each R 34 is independently a hydrolyzable group.
  • Each R 35 is independently a monovalent organic group.
  • Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • n2 is independently an integer of 0 to 3 for each (SiR n2 R 35 3-n2 ) unit, provided that in the terminal portion of formula (S4), there are at least two (SiR n2 R 35 3-n2 ) units in which n2 is 1 to 3. In other words, in the terminal portion of formula (S4), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded.
  • n2 is preferably an integer of 1 to 3, more preferably 2 or 3, and further preferably 3, independently for each (SiR 34 n2 R 35 3-n2 ) unit.
  • Each R 33′ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group, the monovalent organic group being a monovalent organic group other than the hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
  • R 33' is a hydroxyl group.
  • R 33' is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • the above q2' are each independently an integer of 0 to 3, and the above r2' are each independently an integer of 0 to 3.
  • the sum of q2' and r2' is 3 in the (CR 32' q2' R 33' r2' ) unit.
  • q2' is preferably an integer of 1 to 3, more preferably 2 to 3, and further preferably 3, independently for each (CR 32' q2' R 33' r2' ) unit.
  • Each R 32 is independently -Z 3 -SiR 34 n2 R 35 3-n2 , which has the same meaning as described above for R 32' .
  • Each R 33 independently represents a hydrogen atom, a hydroxyl group, or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 -H (wherein each s is independently an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
  • R 33 is a hydroxyl group.
  • R 33 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • Each p2 is independently an integer of 0 to 3
  • each q2 is independently an integer of 0 to 3
  • each r2 is independently an integer of 0 to 3.
  • the sum of p2, q2 and r2 is 3 in the (CR 31 p2 R 32 q2 R 33 r2 ) unit.
  • p2 is 0.
  • p2 may be, independently at each (CR 31 p2 R 32 q2 R 33 r2 ) unit, an integer from 1 to 3, an integer from 2 to 3, or 3.
  • q2 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (CR 31 p2 R 32 q2 R 33 r2 ) unit.
  • p2 is 0, and q2 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3, for each (CR 31 p2 R 32 q2 R 33 r2 ) unit.
  • the R e1 's are each independently -Z 3 -SiR 34 n2 R 35 3-n2 , which has the same meaning as that described above for R 32' .
  • Each R f1 is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 -H (wherein each s is independently an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
  • R f1 is a hydroxyl group.
  • R f1 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • Each k2 is independently an integer of 0 to 3
  • each l2 is independently an integer of 0 to 3
  • each m2 is independently an integer of 0 to 3.
  • the sum of k2, l2, and m2 is 3 in the (CR d1 k2 R e1 l2 R f1 m2 ) unit.
  • the (SiR 34 n2 R 35 3-n2 ) units where n2 is 1 to 3, preferably 2 or 3, more preferably 3, are present at each terminal portion of formula (S4) in an amount of 2 or more, for example 2 to 27, preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 3, and particularly preferably 3.
  • n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, in at least one, and preferably all, R 32′ .
  • n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, in at least one, and preferably all, R 32 .
  • n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, in at least one, preferably all, R a1 .
  • k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.
  • R g1 and R h1 are each independently -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , and -Z 4 -CR d1 k2 R e1 l2 R f1 m2 , where R 11 , R 12 , R a1 , R b2 , R c1 , R d1 , R e1 , R f1 , n1, k1, l1, m1, k2, l2, and m2 are the same as defined above.
  • R g1 and R h1 are each independently --Z 4 --SiR 11 n1 R 12 3-n1 .
  • Z4s are each independently a single bond, an oxygen atom or a divalent organic group.
  • the right side is bonded to (SiR 11 n1 R 12 3-n1 ).
  • Z4 is an oxygen atom.
  • Z4 is a divalent organic group.
  • Z4 does not contain a siloxane bond.
  • Z 4 above is preferably a C 1-6 alkylene group, -(CH 2 ) z5" -O-(CH 2 ) z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 6, and z6" is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH 2 ) z7" -phenylene-(CH 2 ) z8" - (wherein z7" is an integer of 0 to 6, for example an integer of 1 to 6, and z8" is an integer of 0 to 6, for example an integer of 1 to 6).
  • Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but are preferably unsubstituted.
  • Z 4 is a C 1-6 alkylene group or --(CH 2 ) z7 " -phenylene-(CH 2 ) z8" --, preferably -phenylene-(CH 2 ) z8" --.
  • Z 4 is such a group, light resistance, particularly ultraviolet resistance, may be improved.
  • Z 4 is a C 1-3 alkylene group. In one embodiment, Z 4 can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 4 can be -CH 2 CH 2 -.
  • formulas (S1), (S2), (S3), (S4) and (S5) do not contain a siloxane bond.
  • R 3 Si is a group represented by formula (S3), (S4) or (S5).
  • R 3 Si is a group represented by formula (S3) or (S4).
  • R 3 Si is a group represented by formula (S4) or (S5).
  • R Si is a group represented by formula (S1).
  • formula (S1) is a group represented by formula (S1-b).
  • R 13 is a hydrogen atom
  • X 11 is a single bond
  • -R 28 -O x -R 29 - in the formula, R 28 and R 29 are each independently a single bond or a C 1-20 alkylene group, and x is 0 or 1)
  • n1 is 1 to 3, preferably 2 to 3, and more preferably 3.
  • R 1 Si is a group represented by formula (S2): In a preferred embodiment, formula (S2) is -SiR 11 2 R 12 or -SiR 11 3 .
  • R 3 Si is a group represented by formula (S3).
  • formula (S3) is -SiR a1 2 R c1 or -SiR a1 3
  • R a1 is -Z 1 -SiR 22 q1 R 23 r1
  • Z 1 is a C 1-6 alkylene group, -(CH 2 ) z1 -O-(CH 2 ) z2 - (wherein z1 is an integer of 0 to 6, for example an integer of 1 to 6, and z2 is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 - (wherein z3 is an integer of 0 to 6, for example an integer of 1 to 6, and z4 is an integer of 0 to 6, for example an integer of 1 to 6), preferably a C 1-6 alkylene group, and q1 is 1 to 3, preferably 2 to 3, more
  • R Si is a group represented by formula (S4).
  • formula (S4) is -CR e1 2 R f1 or -CR e1 3
  • R e1 is -Z 3 -SiR 34 n2 R 35 3-n2
  • Z 3 is a C 1-6 alkylene group, -(CH 2 ) z5" -O-(CH 2 ) z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 6, and z6" is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH 2 ) z7" -phenylene-(CH 2 ) z8" - (wherein z7" is an integer of 0 to 6, for example an integer of 1 to 6, and z8" is an integer of 0 to 6, for example an integer of 1 to 6), preferably C It is a 1-6 alkylene group, and n2 is 1 to 3, preferably 2
  • R Si is a group represented by formula (S5).
  • R g1 and R h1 are -Z 4 -SiR 11 n1 R 12 3-n1
  • Z 4 is a C 1-6 alkylene group, -(CH 2 ) z5" -O-(CH 2 ) z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 6, and z6" is an integer of 0 to 6, for example an integer of 1 to 6) or -(CH 2 ) z7" -phenylene-(CH 2 ) z8" - (wherein z7" is an integer of 0 to 6, for example an integer of 1 to 6, and z8" is an integer of 0 to 6, for example an integer of 1 to 6), preferably a C 1-6 alkylene group, and n1 is 1 to 3, preferably 2 to 3, and more preferably 3.
  • m is an integer from 1 to 100, preferably from 5 to 80, more preferably from 10 to 50, for example, from 20 to 50 or from 20 to 40.
  • o is an integer from 0 to 200, preferably from 5 to 100, more preferably from 10 to 80, and even more preferably from 15 to 50, for example, from 20 to 50, 20 to 40, or 30 to 50.
  • the fluorosilicone compound represented by the above formula (I) may have a number average molecular weight of, but is not particularly limited to, 1 x 10 2 to 1 x 10 6.
  • the fluorosilicone compound represented by the above formula (I) may have a number average molecular weight of preferably 1000 to 100,000, more preferably 2000 to 50,000.
  • the "number average molecular weight" may be measured using GPC.
  • Fluorosilicone of formula (I) is, for example, the following formula (II):
  • each symbol has the same meaning as defined in formula (I)]
  • X′′ and Y′ are each a divalent group, preferably a divalent group having 1 to 18 carbon atoms, or a direct bond
  • R A and R Si are as defined above in formula (I)] and a compound represented by the formula (I) in the presence of a hydrosilylation catalyst.
  • the present disclosure provides a release composition containing a fluorosilicone compound represented by formula (I) of the present disclosure, wherein the release composition may be only one product or may be a mixture of at least two products.
  • the fluorosilicone release composition of the present disclosure may contain a curing-accelerating catalyst.
  • This catalyst is for accelerating the dehydration condensation reaction of silanol groups.
  • curing-accelerating catalysts are organic metal salts (preferably having 1 to 30 carbon atoms), such as dibutyltin dilaurate, dibutyltin diacetate, tetrabutyl titanate (butoxytitanium), tetraisopropyl titanate (isopropoxytitanium), bis-(acetylacetonyl)-diisopropyl titanate, bis(ethylacetoacetate)diisopropyl titanate ⁇ bis(ethylacetoacetate)diisopropoxytitanium ⁇ and other chelates of titanium and zirconium disclosed in WO2001-49774 (the disclosure of which is incorporated herein by reference), acids (particularly organic acids having 1 to 10 carbon atoms), such as acetic acid or propionic acid,
  • the fluorosilicone release composition of the present disclosure is preferably used in the form of a solution in a solvent such as an organic solvent.
  • the solvent dissolves the fluorosilicone release composition and evaporates to deposit the fluorosilicone release agent.
  • solvents include aliphatic solvents such as hexane, cyclohexane, heptane, octane, isooctane, industrial gasoline, aromatic solvents such as benzene, toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as isopropyl alcohol and ethanol, chlorine solvents such as trichloroethylene, chloroform and m-xylene hexachloride, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether, diisopropyl ether and tetrahydrofuran
  • the fluorosilicone release composition of the present disclosure may be in the form of an aerosol in which a solution of the fluorosilicone compound is filled together with a propellant such as LPG.
  • the fluorosilicone release composition of the present disclosure may be a solution containing a fluorosilicone compound and an organic solvent, or an aqueous emulsion containing water.
  • the release composition is an aqueous emulsion
  • it preferably contains at least one emulsifier selected from the group consisting of nonionic emulsifiers, anionic emulsifiers, and cationic emulsifiers.
  • the nonionic emulsifier may be any that can emulsify the fluoropolymer of the present disclosure and disperse it in an aqueous emulsion, and examples of such an emulsifier include polyoxyethylene alkyl ethers, sorbitan alkylates, and sorbitan alkyl esters. Examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether.
  • Anionic emulsifiers include alkyl sulfates, alkyl sulfonates, and alkyl phosphates.
  • Alkyl sulfates include sodium alkyl sulfate.
  • Cationic emulsifiers include quaternary ammonium salts and alkylamine salts. Quaternary ammonium salts include lauryltrimethylammonium chloride.
  • the amount of emulsifier is usually 0.5 to 25 parts by weight, preferably 1.0 to 20 parts by weight, and more preferably 2.0 to 15 parts by weight, per 100 parts by weight of the fluoropolymer.
  • the fluorosilicone release composition of the present disclosure can be applied by well-known methods.
  • the mold can be immersed in a diluted solution of the release composition, sprayed with the diluted solution, or brushed with the diluted solution, followed by evaporation of the solvent.
  • the mold can then be heated to hydrolyze and condense with the silyl moieties to form a cured film, thereby improving durability. Heating is preferably performed at 50-200°C for about 10-60 minutes.
  • the fluorosilicone release composition of the present disclosure can be used in a form mixed with other release components.
  • other release components include natural waxes such as carnauba wax and beeswax; synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and hydrogenated castor oil; various silicone oils and silicone resins; fluoro oils such as CTFE oil and PFPE oil; and fluoro resins such as PTFE and PCTFE.
  • the amount of the other release components may be 1 part by weight to 1000 parts by weight based on 100 parts by weight of the fluorosilicone compound (I).
  • the release composition When the release composition is an aerosol, it can be filled into an aerosol can using a propellant.
  • propellants include LPG, dimethyl ether, and carbon dioxide.
  • the amount of propellant is usually 10 to 95% by weight, preferably 20 to 90% by weight, and more preferably 30 to 90% by weight, based on the total amount of the release composition and the propellant. If the amount of propellant is 10% by weight or more, the spraying can be performed better and a more uniform coating tends to be obtained. Also, if the amount of propellant is 95% by weight or less, the coating does not tend to become too thin and the release properties do not tend to decrease too much.
  • the release composition can be used as an internal or external release agent. It is preferred to use it as an external release agent.
  • the release composition is usually used as follows: the release composition is applied to the inner surface of a mold, the solvent and dispersant are dried and removed, and then a release agent coating (a fluoropolymer coating) is formed on the mold. The mold is filled with the molding composition to form a molding material, and the molding material is then removed from the mold.
  • a release agent coating a fluoropolymer coating
  • the present disclosure further provides a method for forming the coating.
  • the method for forming the coating of the present disclosure includes the steps of: (i) applying the release composition of the present disclosure to the inner surface of a mold to form a coating of the release composition.
  • the present disclosure further provides a method for producing a molded article using the release composition of the present disclosure.
  • the method for producing a molded article of the present disclosure includes the steps of: (i) applying the release composition of the present disclosure to the inner surface of a mold to form a coating of the release composition; (ii) filling the mold having the coating of the mold release composition with the molding composition to obtain a molded article; and (iii) removing the molded article from the mold.
  • molds for which the release composition can be used include metal molds such as aluminum, SUS, and iron, epoxy resin and wooden molds, and nickel electroformed or chrome plated molds.
  • rubbers such as urethane rubber, H-NBR, NBR, silicone rubber, EPDM, CR, NR, fluororubber, SBR, BR, IIR and IR, urethane foam
  • thermosetting resins such as epoxy resin, phenolic resin and FRP (e.g., CFRP and GFRP)
  • thermoplastic resins such as ABS, polycarbonate and PBT.
  • the present disclosure provides a coating obtained from a release composition containing a fluorosilicone compound represented by formula (I) of the present disclosure.
  • raw materials for molded articles to be demolded include polyurethane, butyl rubber, styrene butadiene rubber, chloroprene rubber, EPDM, NBR, ACM, urethane rubber, silicone rubber, fluororubber, polycarbonate, epoxy resin, phenolic resin, unsaturated polyester, melamine, FRP, PVC, ABS, EVA and PP.
  • Applications of this disclosure include keypads, o-rings, packing, belts, panels and hoses.
  • fluorosilicone compound and release composition of the present disclosure will be described below in the following examples, but the present disclosure is not limited to the following examples. Note that in the present examples, the order of the repeating units that make up the siloxane portion is arbitrary, and the chemical formula shown below shows the average composition.
  • Synthesis Example 2 A 250 mL, 4-neck round bottom flask was equipped with a mechanical stirrer, thermometer/controller, heating mantle, and a water-cooled reflux condenser with a drying tube packed with CaSO4 , and an addition funnel.
  • Siloxane (2.0 g) having the structure Me 3 SiO-(Me 2 SiO) n -(MeHSiO) m -SiMe 3 (Me is a methyl group, n is 38, and m is 36) was added to a flask and heated to 60° C., followed by CF 3 O(C 6 H 4 )OCH 2 CHCH 2 (compound 1, 2.24 g) containing Pt (17 mg) as a complex with 1,2-divinyltetramethyldisiloxane. Vinyltrimethoxysilane (0.4 g) was then added dropwise. Excess olefin was then removed by heating under vacuum. Finally, filtration was performed to obtain compound 2.
  • Synthesis Example 3 Compound 3 was produced by the same procedure as in Synthesis Example 2, except that the amount of CF 3 O(C 6 H 4 )OCH 2 CHCH 2 (Compound 1) used was 2.51 g.
  • Synthesis Example 4 Compound 4 was produced by the same procedure as in Synthesis Example 2, except that the amount of CF 3 O(C 6 H 4 )OCH 2 CHCH 2 (Compound 1) was changed to 2.67 g and the amount of vinyltrimethoxysilane was changed to 0.2 g.
  • Examples A release test was carried out using the above compounds 2 to 4, control compounds 1 and 2, a compound synthesized according to the method described in Synthesis Example 1 of Japanese Patent No. 5,184,382 (control compound 3), and a commercially available release agent (DAIFREE GF-700, manufactured by Daikin Industries, Ltd.) (control compound 4).
  • the prepared test sample was sandwiched between a press machine, and the CFRP prepreg was cured and molded at a pressure of 10 MPa while being heated at 150°C for 10 minutes. After the test sample was cooled, the aluminum plate that had been covered was removed, and the test sample was set in a push-pull gauge. A push-pull gauge was attached to the hole in the packing tape in the test sample, and the packing tape was pulled up at a constant rhythm to release the CFRP prepreg molded from the coated plate. The force required to pull up the tape was measured as the release force. In addition, the same mold was used to continuously release the article, and the number of continuous releases (i.e., the number of releases) until release was no longer possible was measured.
  • Non-transferability evaluation The release surface of the CFRP prepreg after the release test was observed with a SEM (JCM-7000, manufactured by JEOL). The components derived from the release agent on the surface were identified by SEM-EDX and their amounts were compared. The less the components derived from the release agent, the better the non-transferability. The comparison results were classified as follows: ⁇ : Almost no residual components derived from the release agent (very good non-transferability) ⁇ : Residual components from release agent remain, but only slightly (good non-transferability) ⁇ : Release agent-derived components remain, and the amount is large (poor non-transferability)
  • the remaining rate of the coating film was calculated from the grids remaining on the prepreg, and the results were classified as follows: ⁇ : Residual rate of coating film is 80% or more (very good adhesion) ⁇ : Residual rate of coating film is 60-80% or more (good non-transferability) ⁇ : Residual rate of coating film is 20-60% or more (non-transferability is poor) ⁇ : Residual rate of coating film is less than 20% (non-transferability is very poor)
  • the fluorosilicone compounds disclosed herein can be usefully used as release agents.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne un composé de fluorosilicone représenté par la formule (1) [dans la formule, chaque symbole est tel que défini dans la description].
PCT/JP2024/020382 2023-06-09 2024-06-04 Composé de fluorosilicone Pending WO2024253093A1 (fr)

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JP2023095642A JP2024176822A (ja) 2023-06-09 2023-06-09 フルオロシリコーン化合物

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