WO2016178429A1 - Composition d'agent hydrofuge/oléofuge et procédé de production d'un produit textile hydrofuge/oléofuge - Google Patents

Composition d'agent hydrofuge/oléofuge et procédé de production d'un produit textile hydrofuge/oléofuge Download PDF

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Publication number
WO2016178429A1
WO2016178429A1 PCT/JP2016/063612 JP2016063612W WO2016178429A1 WO 2016178429 A1 WO2016178429 A1 WO 2016178429A1 JP 2016063612 W JP2016063612 W JP 2016063612W WO 2016178429 A1 WO2016178429 A1 WO 2016178429A1
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Prior art keywords
group
water
carbon atoms
monomer
oil repellent
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PCT/JP2016/063612
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English (en)
Japanese (ja)
Inventor
吉野　豪
西川　誠
旻時 鄭
恵媛 ▲裴▼
智赫 任
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Nicca Chemical Co Ltd
Nicca Korea Co ltd
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Nicca Chemical Co Ltd
Nicca Korea Co ltd
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Priority to KR1020177034154A priority Critical patent/KR102652086B1/ko
Priority to CN201680025066.3A priority patent/CN107532069A/zh
Priority to JP2017516620A priority patent/JPWO2016178429A1/ja
Publication of WO2016178429A1 publication Critical patent/WO2016178429A1/fr
Anticipated expiration legal-status Critical
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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • 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
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine

Definitions

  • the present invention relates to a water / oil repellent composition capable of imparting water / oil repellency to a fiber product and a method for producing a water / oil repellent fiber product.
  • PFOS perfluorooctane sulfonic acid
  • PFOA perfluorooctanoic acid
  • Patent Documents 1 and 2 contain (meth) acrylate having a perfluoroalkyl group having 6 or less carbon atoms as a copolymer component.
  • a water / oil repellent composition comprising a copolymer is disclosed.
  • the water / oil repellency component having a perfluoroalkyl group having 6 or less carbon atoms tends to be inferior in water / oil repellency and durability compared to those having 8 or more carbon atoms.
  • Patent Documents 1 and 2 a specific monomer containing a polyfluoroalkyl group and a specific monomer not containing a polyfluoroalkyl group are used in order to improve the durability of the water and oil repellency and the texture of the workpiece. Copolymerization with monomers is described.
  • the present invention has been made in view of the above circumstances, and has a water / oil repellent composition capable of giving good water / oil repellency, durability and texture thereof, and a water / oil repellent fiber product using the same. It aims at providing the manufacturing method of.
  • the present inventors have obtained a water / oil repellent containing a copolymer obtained by copolymerizing a specific monomer composition as a water / oil repellent component. Based on this finding, it was found that the composition can provide better water / oil repellency, durability and texture compared to conventional water / oil repellency components having a perfluoroalkyl group having 6 or less carbon atoms.
  • the present invention has been completed.
  • the water / oil repellent composition of the present invention comprises a monomer (A) represented by the following general formula (1), a monomer represented by the following general formula (2), and the following general formula (3). And a copolymer obtained by copolymerizing a monomer composition containing at least one monomer (B) selected from the group consisting of the monomers represented.
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom or a methyl group
  • R 3 and R 4 each independently represent at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.
  • a monovalent fluorine-containing hydrocarbon group which may contain a kind of group or a fluorine atom which may contain at least one kind of group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group
  • R 3 and R 4 contains at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.
  • It may be a monovalent fluorine-containing hydrocarbon group
  • X 1 and X 2 each independently represent a divalent organic group or a single bond.
  • R 5 and R 6 each independently represent a hydrogen atom, a halogen atom or a methyl group, and R 7 contains at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.
  • R 1 represents a monovalent hydrocarbon group having 1 to 30 carbon atoms or a monovalent fluorine-containing hydrocarbon group
  • R 8 represents a hydrogen atom, a halogen atom or a methyl group
  • X 3 represents a divalent organic group. Or it represents a single bond.
  • R 9 and R 10 each independently represent a hydrogen atom, a halogen atom or a methyl group
  • R 11 and R 12 each independently represent at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.
  • X 4 and X 5 each independently represents a divalent organic group or a single bond.
  • the water / oil repellent composition of the present invention it is possible to impart good water / oil repellency and durability and texture to textiles and the like by including the copolymer having the above-described configuration.
  • R 3 and R 4 in the general formula (1) are selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group. It is preferably a monovalent fluorine-containing hydrocarbon group that may contain at least one kind of group.
  • R 3 and R 4 in the general formula (1) are a C 2-18 perfluoroalkyl group, a group represented by the following general formula (4), or A group represented by the following general formula (5) is preferable.
  • m is 2 to 18, p is 0 or 1 to 5
  • R 13 represents a perfluoroalkylene group having 2 to 5 carbon atoms
  • n is a perfluoroalkylene represented by (R 13 O) It represents the average number of moles of oxy group added and is from 1 to 10.
  • R 7 in the general formula (2), and R 11 and R 12 in the general formula (3) are linear alkyl groups having 8 to 30 carbon atoms, A branched alkyl group having 8 to 30 carbon atoms or a cyclic alkyl group having 8 to 30 carbon atoms is preferable.
  • the monomer composition may further contain at least one monomer (C) selected from the group consisting of vinyl chloride and vinylidene chloride.
  • the present invention also provides a method for producing a water / oil repellent fiber product comprising a step of treating a fiber product with a treatment liquid containing the water / oil repellent composition according to the present invention.
  • the present invention it is possible to provide a water / oil repellent composition capable of giving good water / oil repellency, durability and texture thereof, and a method for producing a water / oil repellent fiber product using the composition.
  • the water / oil repellent composition of the present invention has good water / oil repellency and durability and texture compared to conventional water / oil repellent components having a perfluoroalkyl group having 6 or less carbon atoms. Can be given.
  • the durability of the water / oil repellency imparted by the water / oil repellent composition of the present invention is excellent in washing resistance and abrasion resistance. That is, the water / oil repellency imparted to the fiber product or the like by the water / oil repellent composition of the present invention can hardly be lowered by washing or friction.
  • alkyl (meth) acrylate means both alkyl acrylate and alkyl methacrylate.
  • the water / oil repellent composition of the present embodiment includes a monomer (A) represented by the following general formula (1), a monomer represented by the following general formula (2), and the following general formula (3). And a copolymer obtained by copolymerizing a monomer composition containing at least one monomer (B) selected from the group consisting of monomers represented by the formula:
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom or a methyl group
  • R 3 and R 4 each independently represent at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.
  • a monovalent fluorine-containing hydrocarbon group which may contain a kind of group or a fluorine atom which may contain at least one kind of group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group
  • R 3 and R 4 contains at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.
  • It may be a monovalent fluorine-containing hydrocarbon group
  • X 1 and X 2 each independently represent a divalent organic group or a single bond.
  • R 5 and R 6 each independently represent a hydrogen atom, a halogen atom or a methyl group, and R 7 contains at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.
  • R 1 represents a monovalent hydrocarbon group having 1 to 30 carbon atoms or a monovalent fluorine-containing hydrocarbon group
  • R 8 represents a hydrogen atom, a halogen atom or a methyl group
  • X 3 represents a divalent organic group. Or it represents a single bond.
  • R 9 and R 10 each independently represent a hydrogen atom, a halogen atom or a methyl group
  • R 11 and R 12 each independently represent at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.
  • X 4 and X 5 each independently represents a divalent organic group or a single bond.
  • the monomer (A) represented by the general formula (1) is a monomer in which R 1 and R 2 are hydrogen atoms from the viewpoint of versatility of raw materials and high safety of the product after decomposition. Is preferred.
  • the monomer (A) represented by the general formula (1) is both R 3 and R 4 from the viewpoint of water / oil repellency and durability (particularly washing resistance and wear resistance).
  • a group represented by the general formula (4) or a group represented by the following general formula (5) is more preferable.
  • the monomer (A) represented by the general formula (1) is a perfluoroalkyl group in which both R 3 and R 4 are a C 2-6 perfluoroalkyl group from the viewpoint of environmental burden (does not emit PFOA).
  • m is 2 to 6
  • p is 2 to 4 (preferably 2 to 3, more preferably 2)
  • n is 1 to 10, or the general formula
  • s in (5) is a group having 1 to 10.
  • both R 3 and R 4 are C 2-6 perfluoroalkyl groups.
  • a perfluoroalkyl group having 6 carbon atoms is more preferable.
  • both of R 3 and R 4 are such that m in the general formula (4) is 2 to 6 and p is 2 to 4 (preferably 2 to 3, more preferably 2). It is even more preferable that n is a group having 1 to 5 or a group having s of 1 to 5 in the general formula (5).
  • examples of the divalent organic group include —O—R 15 —, —NH—R 16 —, —R 17. — (Wherein R 15 , R 16 and R 17 represent a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms), —O—R 18 —N (R 19 ) —SO 2 —, —O —R 20 —SO 2 —R 21 —, —O—R 22 —S—R 23 —, and —O—R 24 —N (H) C (O) — (where R 18 , R 20 , R 21 , R 22 , R 23 and R 24 each represent a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, and R 19 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).
  • X 1 and X 2 are preferably —O—R 15 — from the viewpoint of ease of production and functionality (particularly durable water repellency).
  • R 15 , R 16 , R 17 , R 18 , R 20 , R 21 , R 22 , R 23, and R 24 are each from 2 to 4 is preferably a divalent hydrocarbon group, more preferably a divalent hydrocarbon group having 2 to 3 carbon atoms (even more preferably an ethylene group).
  • the water / oil repellent composition containing a copolymer obtained by copolymerizing the monomer composition containing the monomer (A) and the monomer (B) according to this embodiment is a monomer.
  • R 5 and R 6 are preferably hydrogen atoms from the viewpoint of versatility of raw materials.
  • R 7 in the general formula (2) is a 1 to 30 carbon atom which does not contain a fluorine atom and may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.
  • a monovalent fluorine-containing hydrocarbon group having 1 to 30 carbon atoms which may contain at least one group selected from the group consisting of a valent hydrocarbon group or an oxy group, a carbonyl group and a hydroxy group.
  • R 7 may contain at least one group selected from the group consisting of an oxy group, a carbonyl group, and a hydroxy group, and may contain no fluorine atom.
  • R 7 has 8 to 8 carbon atoms from the viewpoint of water / oil repellency, durability (particularly washing resistance and wear resistance) and versatility of raw materials.
  • a linear alkyl group having 30, a branched alkyl group having 8 to 30 carbon atoms, or a cyclic alkyl group having 8 to 30 carbon atoms is preferable.
  • R 7 may contain at least one group selected from the group consisting of an oxy group, a carbonyl group and a hydroxy group.
  • R 7 is a perfluoroalkyl group having 2 to 18 carbon atoms from the viewpoint of water / oil repellency and durability (particularly washing resistance and wear resistance).
  • the group represented by the general formula (4) or the group represented by the general formula (5) is preferable.
  • R 8 is preferably a hydrogen atom from the viewpoint of good reactivity and flexibility of the resulting fiber product.
  • R 8 is preferably a methyl group or a halogen atom (particularly a chlorine group).
  • a methyl group is preferable from the viewpoint of flexibility and cost.
  • examples of the divalent organic group include —O—R 25 —, —SO 3 N—, —NH—R 26 —, And —R 27 — (wherein R 25 , R 26 and R 27 represent a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms), —O—R 28 —N (R 29 ) —SO 2 —, —O—R 30 —SO 2 —R 31 —, —O—R 32 —S—R 33 —, and —O—R 34 —N (H) C (O) — (where R 28 , R 30 , R 31 , R 32 , R 33 and R 34 represent a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, and R 29 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) And so on.
  • X 3 is preferably —O—R 25 — or —NH—R 26 —, and —O—R 25 —, from the viewpoint of ease of production and functionality (particularly durable water repellency). It is more preferable. Further, R 25 , R 26 , R 27 , R 28 , R 30 , R 31 , R 32 , R 33 and R 34 have 2 to 2 carbon atoms from the viewpoint of ease of production and functionality (particularly durable water repellency). 4 is preferably a divalent hydrocarbon group, more preferably a divalent hydrocarbon group having 2 to 3 carbon atoms (even more preferably an ethylene group).
  • the monomer represented by the general formula (3) as the monomer (B) is such that R 9 and R 10 are hydrogen atoms from the viewpoint of ease of production and functionality (particularly durable water repellency). Is preferred.
  • the monomer represented by the general formula (3) is such that R 11 and R 12 are carbon from the viewpoint of water / oil repellency and durability (particularly washing resistance and wear resistance) and texture. It is preferably a linear alkyl group having 8 to 30 carbon atoms, a branched alkyl group having 8 to 30 carbon atoms, or a cyclic alkyl group having 8 to 30 carbon atoms, and is linear or branched having 16 to 22 carbon atoms. It is more preferably a chain alkyl group.
  • the divalent organic groups include —O—R 35 —, —SO 3 N—, —NH—R. 36 -, and -R 37 - (where represents a divalent hydrocarbon group of R 35, R 36 and R 37 is a single bond or a C 1 ⁇ 10), - O- R 38 -N (R 39) —SO 2 —, —O—R 40 —SO 2 —R 41 —, —O—R 42 —S—R 43 —, and —O—R 44 —N (H) C (O) — (where R 38 , R 40 , R 41 , R 42 , R 43 and R 44 each represents a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, and R 39 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • X 4 and X 5 are preferably —O—R 35 — or —NH—R 36 —, from the viewpoint of ease of production and functionality (particularly durable water repellency), and —O—R 35 -Is more preferable.
  • R 35 , R 36 , R 37 , R 38 , R 40 , R 41 , R 42 , R 43, and R 44 have two or more carbon atoms from the viewpoint of ease of production and functionality (particularly durable water repellency).
  • 4 is preferably a divalent hydrocarbon group, more preferably a divalent hydrocarbon group having 2 to 3 carbon atoms (even more preferably an ethylene group).
  • the monomer (B) is represented by the general formula (2) from the viewpoint of water / oil repellency, durability (particularly washing resistance and abrasion resistance) and texture. It is preferable that it is at least one of the monomers to be used.
  • the monomer (B) is represented by the following general formula (B-1) from the viewpoint of water / oil repellency, durability (particularly washing resistance and wear resistance) and texture. It is preferable to use a monomer.
  • CH 2 C (R 8 ) (COOR 7 ) (B-1)
  • R 7 and R 8 are as defined above, and from the viewpoints of water / oil repellency and texture, preferably, R 8 is a hydrogen atom and R 7 is a linear alkyl group having 8 to 30 carbon atoms.
  • R 8 is a hydrogen atom from the viewpoint of water / oil repellency, durability (particularly washing resistance and abrasion resistance) and texture.
  • R 7 is a linear alkyl group having 12 to 22 carbon atoms (even more preferably 16 to 22 carbon atoms).
  • R 8 is a hydrogen atom and R 7 is A monomer which is a linear alkyl group having 12 to 22 carbon atoms (even more preferably 16 to 22 carbon atoms), and a monomer having R 8 is a hydrogen atom and R 7 is a perfluoroalkyl group having 2 to 18 carbon atoms. It is even more preferable to use the polymer in combination.
  • the copolymer according to the present embodiment includes the monomer (A) and the monomer (B) as a copolymer component, thereby forming a copolymer of the monomer (A) and acrylic acid.
  • the water repellency and its durability tend to be improved
  • the monomer (A) and the short chain vinyl alkyl ether or short chain vinyl carboxylate Compared with these copolymers, the water repellency and its durability (especially washing resistance and abrasion resistance) and the texture tend to be improved.
  • the copolymer according to this embodiment has an advantage that it can be obtained in a shorter reaction time than when the monomer (A) is reacted with vinyl alkyl ether or vinyl carboxylate. Yes.
  • the blending ratio (mass ratio) of the monomer (A) and the monomer (B) is water / oil repellency and durability (particularly washing resistance and resistance).
  • (A) :( B) 10: 90 to 90:10 is preferable, and 20:80 to 80:20 is more preferable, from the viewpoints of wear and texture.
  • the monomer composition according to this embodiment is at least one monomer (C) selected from the group consisting of vinyl chloride and vinylidene chloride from the viewpoint of durability (particularly washing resistance and wear resistance). It is preferable that it is further included.
  • the blending amount of the monomer (C) is selected from the viewpoints of water and oil repellency, durability (particularly washing resistance and wear resistance) and texture (monomer (A) and monomer (The mass ratio [(A) + (B)] :( C) of the total mass of B) and the mass of monomer (C) is preferably 95: 5 to 70:30, and 90:10 to 80:20 is more preferable.
  • the monomer composition according to this embodiment is a monomer (A), a single monomer, for the purpose of imparting functionality such as adhesion to a substrate, adhesion, and abrasion resistance to the obtained copolymer.
  • Other monomers (D) capable of copolymerization other than the monomer (B) and the monomer (C) may be included.
  • Other monomers (D) include vinyl acetate, styrene, ⁇ -methylstyrene, p-methylstyrene, glycidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) ) Acrylamide, methylolated diacetone (meth) acrylamide, N-methylol (meth) acrylamide, 3-chloro-2-hydroxypropyl (meth) acrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene Aziridinylethyl (meth) acrylate, aziridinyl (meth) acrylate, polyoxyalkylene (meth) acrylate, methyl polyoxyalkylene (meth) acrylate, 2-ethylhexyl poly Oxyalkylene (meth
  • 1: 1: 1.2 to 2.5 is more preferred, and 1: 1: 2.3 is even more preferred.
  • the copolymer according to this embodiment is not particularly limited in the arrangement of monomers (structural units), and may be a random copolymer, a block copolymer, or an alternating copolymer.
  • the copolymer according to this embodiment preferably has a melt viscosity at 105 ° C. of 5 to 20000 Pa ⁇ s, and more preferably 10 to 10,000 Pa ⁇ s.
  • a melt viscosity at 105 ° C. of 5 to 20000 Pa ⁇ s, and more preferably 10 to 10,000 Pa ⁇ s.
  • the melt viscosity is within the above range, water repellency and its durability (particularly washing resistance and abrasion resistance), texture and processing stability can be easily obtained at a high level.
  • the melt viscosity is less than 5 Pa ⁇ s, the water repellency and its durability (especially washing resistance and wear resistance) tend to decrease.
  • it exceeds 20000 Pa ⁇ s the water repellency and its durability ( In particular, there is a tendency for washing resistance and wear resistance) to decrease, texture hardening, or processing stability to decrease.
  • the melt viscosity can be measured at a measurement temperature of 105 ° C. using a flow tester CFT-500D (manufactured by SHIMADZU).
  • the copolymer according to the present embodiment can be obtained by applying a conventionally known copolymerization method.
  • a conventionally known copolymerization method examples thereof include a solution polymerization method using an organic solvent as a solvent, and an emulsion polymerization method using water as a solvent and containing an organic solvent and various surfactants.
  • organic solvent examples include aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, isopropanol, n-butanol, 2-butanol, t-butanol, n-hexanol, 2-ethylhexanol, glycerin; ethylene glycol, diethylene glycol , Glycols such as triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether , Glycol ethers such as triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-meth
  • glycols and glycol ethers from the viewpoint of water / oil repellency, product stability, treatment liquid stability, and permeability of the treatment liquid into the fiber product.
  • Dipropylene glycol, tripropylene glycol, polypropylene glycol (average molecular weight 200 to 4000) and dipropylene glycol monomethyl ether are more preferable.
  • Such solvents can be used singly or in combination of two or more. When using in combination of 2 or more types, it is preferable to mix and use with water. Use of a mixed solvent is preferable because the solubility and emulsification dispersibility of the copolymer can be easily controlled, and the permeability to the fiber product can be easily controlled during processing.
  • the surfactant it is preferable to use a cationic surfactant, a nonionic surfactant, an amphoteric surfactant or the like.
  • Examples of cationic surfactants include monoalkyltrimethylammonium salts having 8 to 24 carbon atoms, dialkyldimethylammonium salts having 8 to 24 carbon atoms, monoalkylamine acetates having 8 to 24 carbon atoms, and dialkylamines having 8 to 24 carbon atoms. Examples thereof include acetates and alkyl imidazoline quaternary salts having 8 to 24 carbon atoms. Of these, monoalkyltrimethylammonium salts having 12 to 18 carbon atoms and dialkyldimethylammonium salts having 12 to 18 carbon atoms are preferable from the viewpoints of emulsifiability and processing stability.
  • cationic surfactants may be used alone or in combination of two or more.
  • nonionic surfactants include alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, oils and fats, and alkylene oxide adducts of polypropylene glycol.
  • Examples of the alcohol include linear or branched alcohol having 8 to 24 carbon atoms, alkenol, and acetylene alcohol represented by the following general formula (6).
  • R 45 and R 46 each independently represents an alkyl group having a linear or branched chain having 1 to 8 carbon atoms or an alkenyl group having a linear or branched chain having 2 to 8 carbon atoms.
  • polycyclic phenols monohydric phenols such as phenol and naphthol which may have a hydrocarbon group having 1 to 12 carbon atoms or styrenes thereof (styrene, ⁇ -methylstyrene, vinyltoluene) are added. Or their benzyl chloride reactants.
  • amines include linear or branched aliphatic amines having 8 to 44 carbon atoms.
  • amides include linear or branched fatty acid amides having 8 to 44 carbon atoms.
  • fatty acids examples include linear or branched fatty acids having 8 to 24 carbon atoms.
  • polyhydric alcohol fatty acid esters include condensation reaction products of polyhydric alcohols and linear or branched fatty acids having 8 to 24 carbon atoms.
  • fats and oils examples include vegetable oils, animal fats, vegetable waxes, animal waxes, mineral waxes, and hardened oils.
  • linear or branched alcohol having 8 to 24 carbon atoms or Alkenol and acetylene alcohol represented by the above general formula (6) are preferable, linear or branched alcohol having 8 to 24 carbon atoms, and acetylene alcohol represented by the above general formula (6) are more preferable.
  • alkylene oxide examples include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, epichlorohydrin and the like. From the viewpoint of little influence on water and oil repellency and good emulsifiability of the copolymer, the alkylene oxide is preferably ethylene oxide or 1,2-propylene oxide, and more preferably ethylene oxide.
  • the number of added moles of alkylene oxide is preferably 1 to 200, more preferably 3 to 100, and even more preferably 5 to 50.
  • the added mole number of alkylene oxide is within the above range, water and oil repellency and product stability can be easily obtained at a high level.
  • the added mole number of alkylene oxide is less than 1 mole, the product stability tends to be lowered and the water / oil repellency tends to be lowered, and when it exceeds 200 moles, the water / oil repellency tends to be lowered.
  • the HLB is based on the HLB of Griffin, and the expression of Griffin is changed to the following expression.
  • nonionic surfactants may be used alone or in combination of two or more. When two or more kinds are used in combination, a better aqueous dispersion can be obtained when a nonionic surfactant is used so that the weighted average HLB is 8-16.
  • various surfactants may be used alone or in combination of two or more, but the emulsifying dispersibility of the monomer during copolymerization, the emulsifying dispersibility of the copolymer From the viewpoints of the stability of the treatment liquid and the water / oil repellency, it is preferable to use a cationic surfactant and a nonionic surfactant in combination.
  • Such a surfactant is preferably contained in an amount of 1 to 20% by mass based on the copolymer, and preferably 3 to 16% by mass based on the copolymer.
  • the processing stability, water / oil repellency and durability thereof can be easily obtained at a high level.
  • the processing stability tends to decrease.
  • it exceeds 20% by mass the water and oil repellency and the durability thereof (particularly washing resistance and wear resistance) tend to be lowered.
  • copolymer it is preferable to produce a copolymer by emulsion polymerization in a solvent containing water.
  • the copolymer solution and emulsion dispersion thus obtained may be used as they are, or may be used after dilution. Further, after separating the copolymer, it may be used after being dissolved or emulsified and dispersed in a solvent.
  • a high-pressure emulsifier or the like it is preferable to mix and disperse a mixture comprising a monomer, a surfactant, an organic solvent, water and the like with a homomixer or a high-pressure emulsifier. It is preferable to mix and disperse the raw material mixture in advance before the start of polymerization because the water / oil / oil repellent component stability of the finally obtained water / oil repellent composition is improved.
  • a radical polymerization initiator In starting the polymerization reaction, heat, light, radiation, a radical polymerization initiator, an ionic polymerization initiator, or the like is preferably used.
  • a water-soluble or oil-soluble radical polymerization initiator is preferable, and general-purpose initiators such as an azo polymerization initiator, a peroxide polymerization initiator, and a redox initiator can be used depending on the polymerization temperature.
  • an azo compound is particularly preferable, and when polymerization is performed in a solvent using water, a salt of an azo compound is more preferable.
  • the polymerization temperature is not particularly limited, but is preferably 20 to 150 ° C, more preferably 40 to 90 ° C.
  • a molecular weight modifier may be used.
  • aromatic compounds or mercaptans are preferable, and alkyl mercaptans are more preferable.
  • the copolymer is preferably dispersed as particles in a solvent.
  • the average particle size is preferably 10 to 1000 nm, more preferably 50 to 300 nm, and even more preferably 80 to 200 nm from the viewpoints of water / oil repellency and product stability.
  • a laser diffraction type / scattering type particle size distribution analyzer LA-920 manufactured by Horiba, Ltd.
  • the percentage integrated value of the particle size of the ultraviolet absorber for fibers is 50% from the small particle size side. It can be measured by setting the diameter to the average particle diameter.
  • the water / oil repellent composition of the present embodiment preferably contains a solvent from the viewpoint of easy handling.
  • a solvent a solvent equivalent to the solvent that can be used to obtain the above copolymer can be used.
  • the content of the solvent in the water / oil repellent composition is preferably 50 to 90 mass%, more preferably 55 to 75 mass%, based on the total amount of the composition.
  • the content of the organic solvent is preferably 1 to 20% by mass, more preferably 5 to 15% by mass based on the total amount of the composition.
  • a water / oil repellent fiber product can be obtained by treating the fiber product with a treatment liquid containing the water / oil repellent composition of the present embodiment.
  • the water / oil repellent composition of the present embodiment can be used as a treatment liquid as it is, or can be diluted with water or an organic solvent to obtain a treatment liquid.
  • the treatment liquid according to the present embodiment contains 0.3 to 5% by mass of the water / oil repellent composition of the present embodiment from the viewpoint that the amount of the water / oil repellent composition applied to the fiber product can be easily controlled. It is preferable that
  • the treatment liquid according to this embodiment preferably contains an organic solvent.
  • an organic solvent the organic solvent equivalent to the organic solvent which can be used in order to obtain the said copolymer can be used.
  • isopropyl alcohol and diethylene glycol monobutyl ether can be preferably used from the viewpoint of processing stability and permeability to textile products.
  • Such an organic solvent is preferably contained in the treatment liquid in an amount of 0.3 to 3% by mass, more preferably 0.5 to 1.5% by mass, based on the total amount of the treatment liquid. .
  • the water / oil repellent composition of the present embodiment preferably has a pH of 2.0 to 6.0 from the viewpoint of water / oil repellency, texture and processing stability.
  • the treatment liquid according to this embodiment preferably has a pH of 3.0 to 7.0, preferably 4.0 to 6.0, from the viewpoint of water / oil repellency, texture, and processing stability. Is more preferable.
  • the pH adjustment of the water / oil repellent composition of the present embodiment and the treatment liquid according to the present embodiment can be adjusted to an arbitrary pH by using a pH adjuster.
  • a pH adjuster acids such as formic acid, acetic acid, malic acid and citric acid; alkalis such as caustic soda, sodium carbonate and aqueous ammonia can be used.
  • alkalis such as caustic soda, sodium carbonate and aqueous ammonia
  • a penetrant When treating a textile product with the treatment liquid according to the present embodiment, a penetrant, an antifoaming agent, an antistatic agent, a texture adjusting agent, a melamine resin, an isocyanate compound, a glyoxal resin, a catalyst, A known water / oil repellent may be used in combination.
  • a compound having a melamine skeleton can be used as the melamine resin.
  • a polymethylol melamine such as trimethylol melamine or hexamethylol melamine; a part or all of the methylol groups of the polymethylol melamine have 1 to 6 carbon atoms.
  • acyloxymethyl melamine in which a part or all of the methylol group of polymethylolmelamine is an acyloxymethyl group having an acyl group having 2 to 6 carbon atoms, etc.
  • melamine resins may be either a monomer or a dimer or higher multimer, or a mixture thereof. Furthermore, what co-condensed urea etc. to a part of melamine can also be used. Examples of such melamine resins include Becamine APM, Becamine M-3, Becamine M-3 (60), Becamine MA-S, Becamine J-101, and Becamine J-101LF manufactured by DIC Corporation, Union Chemical Industries, Ltd. Examples include UNIKA RESIN 380K manufactured by Riken Resin MM series manufactured by Miki Riken Kogyo Co., Ltd.
  • the isocyanate compound is not particularly limited as long as it has at least two isocyanate groups in the molecule, and a known polyisocyanate compound can be used.
  • a known polyisocyanate compound can be used.
  • diisocyanate compounds such as alkylene (preferably having 1 to 12 carbon atoms) diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers or trimers of these diisocyanate compounds.
  • the modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups.
  • biuret structure, isocyanurate structure, urethane structure, uretdione structure, allophanate structure examples thereof include polyisocyanates having a trimer structure and the like, and adducts of trimethylolpropane aliphatic isocyanate.
  • the isocyanate group may or may not be blocked with a blocking agent.
  • polyisocyanate compound A commercially available product can be used as the polyisocyanate compound.
  • Commercially available polyisocyanate compounds include, for example, “Basonate” series manufactured by BASF, “Baihijoule” series, “SBU Isocyanate” series, “Desmodur” series, and “Sumijoule” series manufactured by Covestro, Asahi Kasei Chemicals Corporation "Duranate” series made by company, “Coronate” series made by Tosoh Corporation, “Aquanate” series made by Nippon Polyurethane, etc., “Cosmonate” series made by Mitsui Chemicals, etc., made by DIC Corporation “Burnock” series, etc., NK Assist FU, NK Assist IS-100, NK Assist IS-80, NK Assist V, NK Assist NY, NK Assist NY-27, NK Assist NY-30, and Such as NK Assist NY-50 Such as
  • glyoxal resin conventionally known ones can be used, and examples thereof include 1,3-dimethylglyoxal urea resin, dimethylol dihydroxyethylene urea resin, dimethylol dihydroxypropylene urea resin, and the like.
  • the functional groups of these resins may be substituted with other functional groups.
  • examples of such glyoxal resins include, for example, Becamine N-80, Becamine NS-11, Becamine LF-K, Becamine NS-19, Becamine LF-55P Conch, Becamine NS-210L, Becamine NS-200 manufactured by DIC Corporation.
  • Becamine NF-3 Union Resin GS-20E manufactured by Union Chemical Industries, Ltd., Riken Resin RG series, Riken Resin MS series manufactured by Miki Riken Kogyo Co., Ltd., and the like.
  • a catalyst for the melamine resin and the glyoxal resin from the viewpoint of promoting the reaction.
  • a catalyst is not particularly limited as long as it is a commonly used catalyst.
  • borofluorinated compounds such as ammonium borofluoride and borofluoride sub-salt, and neutral metal salt catalysts such as magnesium chloride and magnesium sulfate.
  • neutral metal salt catalysts such as magnesium chloride and magnesium sulfate.
  • inorganic acids such as phosphoric acid, hydrochloric acid and boric acid. If necessary, these catalysts may be used in combination with an organic acid such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid.
  • Such a catalyst examples include a catalyst ACX, a catalyst 376, a catalyst O, a catalyst M, a catalyst G (GT), a catalyst X-110, a catalyst GT-3, and a catalyst manufactured by DIC Corporation.
  • Catalyst NFC-1, Unika Catalyst 3-P from Union Chemical Industry Co., Ltd., and Unica Catalyst MC-109, Riken Fixer RC Series, Riken Fixer MX Series, and Riken Fixer RZ- from Miki Riken Kogyo Co., Ltd. 5 etc. are mentioned.
  • the water / oil repellent composition of the present embodiment contains at least one selected from the group consisting of a melamine resin, an isocyanate compound and a glyoxal resin, the water / oil repellency and its durability (especially washing resistance and abrasion resistance) Properties), texture, tear strength, etc.
  • the total of those masses (active ingredients) is preferably 0.4 to 3000 parts by mass with respect to 100 parts by mass of the copolymer according to this embodiment. .
  • the water / oil repellent composition of the present embodiment is used for a fiber product containing 40% by mass or more of synthetic fiber, the water / oil repellency and its durability (especially washing resistance and abrasion resistance).
  • the blending amount (active ingredient) of the melamine resin and / or isocyanate compound is preferably 0.4 to 300 parts by mass with respect to 100 parts by mass of the copolymer according to the present embodiment. More preferably, it is part by mass. If it is said compounding quantity, it will become easy to obtain the improvement effect of water-and-oil repellency corresponding to the usage-amount, and its durability (especially washing resistance and abrasion resistance).
  • the water / oil repellent composition of the present embodiment is used for a fiber product having a synthetic fiber content of less than 40% by mass, the water / oil repellency and its durability (especially washing and abrasion resistance) From the viewpoint of properties, it is preferable to use a glyoxal resin and / or an isocyanate compound.
  • the blending amount (active ingredient) of the glyoxal resin and / or isocyanate compound is preferably 10 to 3000 parts by weight with respect to 100 parts by weight of the copolymer according to the present embodiment. It is more preferable that If it is said compounding quantity, it will become easy to obtain the improvement effect of water-and-oil repellency corresponding to the usage-amount, and its durability (especially washing resistance and abrasion resistance).
  • the treatment liquid according to the present embodiment can be produced, for example, by mixing water, an organic solvent, and the water / oil repellent composition of the present invention.
  • the order of mixing is not particularly limited, but from the viewpoint of processing stability, a method of mixing the organic solvent diluted with water and the water / oil repellent composition of the present embodiment diluted with water, or organic A method of diluting one of the solvent or the water / oil repellent composition of the present embodiment with water and then mixing the other is preferred.
  • the method for producing a water / oil repellent fiber product of this embodiment includes a step of treating the fiber product with a treatment liquid containing the water / oil repellent composition of this embodiment.
  • a conventionally performed method can be used without limitation.
  • the fiber product is treated with the treatment liquid by a pad method, a dipping method, a spraying method, a foaming method, a coating method, and the like, and then dried. Further, after drying, a curing (heat treatment) step may be incorporated as necessary.
  • a drying method a conventionally used method can be used without limitation, and either a dry heat method or a wet heat method may be used.
  • the material of the textile product to which the manufacturing method according to this embodiment can be applied is not particularly limited, and natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, nylon, polyester, polyurethane, and polypropylene. And synthetic fibers such as these, composite fibers of these, and blended fibers.
  • the form of the textile product may be any form such as a woven fabric, a knitted fabric, a yarn, a nonwoven fabric, and paper.
  • Example 1 [Preparation of water / oil repellent composition]
  • monomer (A) 18 g of stearyl acrylate (hereinafter abbreviated as SA) as monomer (B), 5 g of polyoxyethylene alkyl ether (hereinafter abbreviated as POA)
  • SA 18 g of stearyl acrylate
  • POA polyoxyethylene alkyl ether
  • STMAC stearyltrimethylammonium chloride
  • PPG propylene glycol
  • ion-exchanged water 261.7 g of ion-exchanged water
  • V-50 manufactured by Wako Pure Chemical Industries, Ltd.
  • the obtained water / oil repellent composition had a non-volatile content of 31.5%.
  • the melt viscosity at 105 ° C. of the copolymer contained in the water / oil repellent composition was about 5800 Pa ⁇ s.
  • the melt viscosity of the copolymer is determined by measuring the flow tester CFT- for a sample obtained by adding an organic solvent such as methanol or acetone to the water / oil repellent composition and drying the solid content that has been emulsified and separated.
  • 500D manufactured by SHIMADZU was used and measured at a measurement temperature of 105 ° C.
  • treatment liquid A and production of water and oil repellent fiber product A The water / oil repellent composition obtained above was diluted with ion-exchanged water to prepare treatment solutions A containing the water / oil repellent composition at concentrations of 2 g / l, 4 g / l, and 6 g / l, respectively. .
  • a dyed polyester woven fabric (120 g / m 2 ) and a nylon woven fabric (120 g / m 2 ) were immersed in this treatment liquid A, and each was squeezed with a mangle. At this time, the wet pickup rate of the polyester woven fabric was 60%, and the wet pickup rate of the nylon woven fabric was 40%.
  • Examples 2 to 9, Comparative Examples 1 to 8 Except that the types and amounts used of the monomers (the values in the table indicate the ratio (mass%) in 90 g of the total amount of monomers) are changed as shown in Tables 5 and 6 and Tables 9 and 10. In the same manner as in No. 1, the water / oil repellent compositions and the water / oil repellent fiber products A to C of Examples 2 to 9 and Comparative Examples 1 to 8 were obtained.
  • Examples 10 to 15 The types and amounts used of the monomers were changed as shown in Tables 7 and 8, and the same operation as in Example 1 was performed to prepare a water / oil repellent composition. Using the amount (g) of the isocyanate compound, melamine resin / catalyst, or glyoxal resin / catalyst shown in 7 and 8, the same operation as in Example 1 was performed to obtain water and oil repellent fiber products B, respectively.
  • the water and oil repellent fiber product B obtained above was evaluated for durable water repellency and abrasion resistance in the same manner as in Example 1. The results are shown in Tables 7 and 8.
  • the water and oil repellent fiber product B obtained above was evaluated for durable water repellency and abrasion resistance in the same manner as in Example 1. The results are shown in Table 11.
  • C6FIA Compound 1 of Synthesis Example 1
  • C6FMA Perfluorohexyl ethyl methacrylate SA: Stearyl acrylate
  • VA Behenyl acrylate
  • VCM Vinyl chloride monomer
  • St Styrene
  • BA Butyl acrylate
  • NK assist IS-100 Isocyanate-based cross-linking agent (Nikka Chemical Co., Ltd.) Made by company, product name)
  • UNIKA RESIN 380K Melamine resin (trade name, manufactured by Union Chemical Industries, Ltd.)
  • Unica Catalyst 3-P Melamine resin catalyst (trade name, manufactured by Union Chemical Industries, Ltd.)
  • UNIRESIN GS-20E Glyoxal resin (trade name, manufactured by Union Chemical Industry Co., Ltd.)
  • Unica Catalyst MC-109 Glyoxal resin catalyst (trade name, manufactured by Union Chemical Industries, Ltd.)
  • the water / oil repellent compositions of Examples 1 to 15 containing the monomer (A) and the copolymer containing the monomer (B) as a copolymerization component have sufficient water / oil repellency and processing stability.
  • the desired water / oil repellency and durability (particularly washing resistance and abrasion resistance) and texture can be imparted.
  • the present invention it is possible to provide a water / oil repellent composition capable of giving good water / oil repellency, durability and texture thereof, and a method for producing a water / oil repellent fiber product using the composition.
  • the water / oil repellent composition of the present invention has good water / oil repellency and durability and texture compared to conventional water / oil repellent components having a perfluoroalkyl group having 6 or less carbon atoms. Can be given.
  • the durability of the water / oil repellency imparted by the water / oil repellent composition of the present invention is excellent in washing resistance and abrasion resistance. That is, the water / oil repellency imparted to the fiber product or the like by the water / oil repellent composition of the present invention can hardly be lowered by washing or friction.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

La présente invention concerne une composition d'agent hydrofuge/oléofuge qui contient un copolymère obtenu par la copolymérisation d'une composition monomère contenant un monomère (A) représenté par la formule générale (1) et au moins un monomère (B) sélectionné dans le groupe constitué par les monomères représentés par la formule générale (2) et les monomères représentés par la formule générale (3). [Formule 1] [Dans la formule, R1 et R2 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène, ou un groupe méthyle, R3 et R4 représentent chacun indépendamment un groupe hydrocarbure contenant du fluor monovalent incluant éventuellement au moins un groupe sélectionné dans le groupe constitué par un groupe oxy, un groupe carbonyle, et un groupe hydroxyle, ou un groupe hydrocarbure monovalent qui possède de 1 à 30 atomes de carbone, qui n'inclut pas d'atome de fluor, et qui inclut éventuellement au moins un groupe sélectionné dans le groupe constitué par un groupe oxy, un groupe carbonyle, et un groupe hydroxyle, au moins l'un de R3 et R4 est un groupe hydrocarbure contenant du fluor monovalent qui inclut éventuellement au moins un groupe sélectionné dans le groupe constitué par un groupe oxy, un groupe carbonyle, et un groupe hydroxyle, et X1 et X2 représentent chacun indépendamment un groupe organique divalent ou une simple liaison.[Formule 2] [Dans la formule, R5 et R6 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène, ou un groupe méthyle, R7 représente un groupe hydrocarbure monovalent ou un groupe hydrocarbure contenant du fluor monovalent qui présente de 1 à 30 atomes de carbone et qui inclut éventuellement au moins un groupe sélectionné dans le groupe constitué par un groupe oxy, un groupe carbonyle, et un groupe hydroxyle, R8 représente un atome d'hydrogène, un atome d'halogène, ou un groupe méthyle, et X3 représente un groupe organique divalent ou une simple liaison.[Formule 3] [Dans la formule, R9 et R10 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène, ou un groupe méthyle, R11 et R12 représentent chacun indépendamment un groupe hydrocarbure monovalent qui possède de 1 à 30 atomes de carbone, qui n'inclut pas d'atome de fluor, et qui inclut éventuellement au moins un groupe sélectionné dans le groupe constitué par un groupe oxy, un groupe carbonyle, et un groupe hydroxyle, et X4 et X5 représentent chacun indépendamment un groupe organique divalent ou une simple liaison.
PCT/JP2016/063612 2015-05-07 2016-05-02 Composition d'agent hydrofuge/oléofuge et procédé de production d'un produit textile hydrofuge/oléofuge Ceased WO2016178429A1 (fr)

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WO2023234060A1 (fr) 2022-06-02 2023-12-07 明成化学工業株式会社 Composition d'agent résistant à l'huile et produit résistant à l'huile

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WO2021246475A1 (fr) 2020-06-03 2021-12-09 明成化学工業株式会社 Composition hydrofuge, kit, produit fibreux hydrofuge et procédé de fabrication associé
WO2023234060A1 (fr) 2022-06-02 2023-12-07 明成化学工業株式会社 Composition d'agent résistant à l'huile et produit résistant à l'huile

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