TW201710464A - Water repellent/oil repellent agent composition and method for producing water repellent/oil repellent textile product - Google Patents

Abstract

The water repellent/oil repellent agent composition according to the present invention contains a copolymer obtained through copolymerization of a monomer composition containing a monomer (A) represented by general formula (1) and at least one monomer (B) selected from the group consisting of monomers represented by general formula (2) and monomers represented by general formula (3). [Formula 1] [In the formula, R1 and R2 each independently represent a hydrogen atom, a halogen atom, or a methyl group, R3 and R4 each independently represent a monovalent fluorine-containing hydrocarbon group optionally including at least one group selected from the group consisting of an oxy group, a carbonyl group, and a hydroxy group, or a monovalent hydrocarbon group that has 1-30 carbon atoms, that does not include a fluorine atom, and that optionally includes at least one group selected from the group consisting of an oxy group, a carbonyl group, and a hydroxy group, at least one of R3 and R4 is a monovalent fluorine-containing hydrocarbon group that optionally includes at least one group selected from the group consisting of an oxy group, a carbonyl group, and a hydroxy group, and X1 and X2 each independently represent a divalent organic group or a single bond.] [Formula 2] [In the formula, R5 and R6 each independently represent a hydrogen atom, a halogen atom, or a methyl group, R7 represents a monovalent hydrocarbon group or monovalent fluorine-containing hydrocarbon group that has 1-30 carbon atoms and that optionally includes at least one group selected from the group consisting of an oxy group, a carbonyl group, and a hydroxy group, R8 represents a hydrogen atom, a halogen atom, or a methyl group, and X3 represents a divalent organic group or a single bond.] [Formula 3] [In the formula, R9 and R10 each independently represent a hydrogen atom, a halogen atom, or a methyl group, R11 and R12 each independently represent a monovalent hydrocarbon group that has 1-30 carbon atoms, that does not include a fluorine atom, and that optionally includes at least one group selected from the group consisting of an oxy group, a carbonyl group, and a hydroxy group, and X4 and X5 each independently represent a divalent organic group or a single bond.].

Description

Water-repellent oil-repellent composition and method for producing water-repellent oil-containing fiber product

The present invention relates to a water- and oil-repellent composition and a water- and oil-repellent fiber product which can impart water repellency to a fiber product.

In order to impart water repellency to fiber products, various water-repellent oil-repellent components having a fluorine-containing alkyl group have been proposed.

In recent years, when a water-repellent component having a perfluoroalkyl group having a carbon number of 8 is discharged into the environment, it may decompose PFOS (C ₈ H ₁₇ SO ₂ F, hereinafter referred to as PFOS) which may affect the environment. Or perfluorooctanoic acid (C ₇ H ₁₅ COOH, hereinafter referred to as PFOA) is subject to human disease. Moreover, when the carbon number of the perfluoroalkyl group is more than 8, the environmental impact may be increased, so that the perfluoroalkanesulfonic acid or perfluoroalkanoic acid having a carbon number of more than 8 such as PFOS and PFOA does not occur, and carbon is present. A water-repellent component of a perfluoroalkyl group having a number of 6 or less.

The water-repellent oil-repellent component having a perfluoroalkyl group having 6 or less carbon atoms, as disclosed in Patent Documents 1 and 2 below, contains a (meth) acrylate having a perfluoroalkyl group having 6 or less carbon atoms as a copolymerization. A water-repellent and oil-repellent composition of a copolymer of components.

Prior technical literature Patent literature

Patent Document 1: JP-A-2010-001499

Patent Document 2: Special Table 2012-503028

When the water-repellent oil-repellent component having a perfluoroalkyl group having 6 or less carbon atoms is compared with a carbon number of 8 or more, the water repellency and the durability thereof are deteriorated. In the above Patent Documents 1 and 2, in order to improve the durability of the water repellency and the feel of the processed product, it has been described that a specific monomer containing a polyfluoroalkyl group is copolymerized with a specific monomer not containing a polyfluoroalkyl group.

However, even with the water- and oil-repellent components described in Patent Documents 1 and 2, it is difficult to simultaneously improve the water-repellent oil-repellent property, the durability, and the feel of the processed product.

In view of the above circumstances, an object of the present invention is to provide a water- and oil-repellent composition which can impart good water- and oil-repellency and durability and feel, and a method for producing a water- and oil-repellent fiber product using the same.

In order to solve the above problems, the inventors of the present invention have intensively studied and found that a water-repellent and oil-repellent composition containing a copolymer obtained by copolymerizing a specific monomer composition used as a water-repellent component is compared with the previous carbon. When the water-repellent component of the perfluoroalkyl group of 6 or less is used, the water repellency and the durability and the feeling of touch can be imparted, and the present invention is completed based on the findings.

The water-repellent oil-repellent composition of the present invention contains 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) A copolymer obtained by copolymerizing a monomer composition of at least one monomer (B) selected from the group of monomers indicated.

Wherein R ¹ and R ² represent each independently a hydrogen atom, a halogen atom or a methyl group, and R ³ and R ⁴ each independently may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group. a monovalent fluorine-containing hydrocarbon group, or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group but not a fluorine atom, and at least R ³ and R ⁴ One of them is a monovalent fluorine-containing hydrocarbon group which may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group, and X ¹ and X ² each independently represent a divalent organic group or a single bond].

Wherein R ⁵ and R ⁶ represent each independently a hydrogen atom, a halogen atom or a methyl group, and R ⁷ represents a carbon number of from 1 to 30 which may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group; A monovalent hydrocarbon group or a monovalent fluorine-containing hydrocarbon group, R ⁸ represents a hydrogen atom, a halogen atom or a methyl group, and X ³ represents a divalent organic group or a single bond].

Wherein R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom or a methyl group, and R ¹¹ and R ¹² each independently may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group. However, the fluorine-free atom has a carbon number of from 1 to 30, and X ⁴ and X ⁵ each independently represent a divalent organic group or a single bond].

The water-repellent oil-repellent composition of the present invention can impart good water-repellent oil repellency, durability, and touch to a fiber product by containing a copolymer having the above-described constitution.

In view of water repellency and durability, in the water repellent composition of the present invention, R ³ and R ^{4 of the} above general formula (1) preferably contain an oxy group, a carbonyl group and a hydroxyl group. A monovalent fluorine-containing hydrocarbon group selected from at least one group of the group.

Further, in view of water repellency and durability, R ³ and R ^{4 of the} above general formula (1) are each a perfluoroalkyl group having 2 to 18 carbon atoms and a group represented by the following general formula (4). Or the base represented by the following general formula (5) is preferred.

C _m F _(2m+1) (CH ₂ ) _p O(R ¹³ O) _n -...(4)

Wherein m is 2 to 18, p is 0 or 1 to 5, R ¹³ represents a perfluoroalkylene group having 2 to 5 carbon atoms, and n represents a perfluoroalkylalkyloxy group represented by (R ¹³ O). The average number of additional moles is 1~10].

F(R ¹⁴ O) _s -...(5)

[wherein, R ¹⁴ represents a perfluoroalkylene group having 1 to 5 carbon atoms, and s represents an average additional molar number of the perfluoroalkylalkyloxy group represented by (R ¹⁴ O), which is 1 to 10].

Further, in the water-repellent oil-repellent composition of the present invention, R ⁷ of the above general formula (2) and R ¹¹ and R ^{12 of the} above general formula (3) are 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.

Further, in the water- and oil-repellent composition of the present invention, the monomer composition further contains at least one monomer (C) selected from the group consisting of vinyl chloride and vinylidene chloride.

Further, the present invention provides a method for producing a water- and oil-repellent fibrous product comprising the step of treating a fibrous product with a treatment liquid containing the water-repellent and oil-repellent composition of the present invention.

The present invention can provide a water- and oil-repellent composition which can impart good water-repellent oil-repellency and durability and feel, and a method for producing the water- and oil-repellent fiber product using the same. Comparison of the composition of the water-repellent and oil-repellent agent of the present invention In the case of a water-repellent oil-repellent component having a perfluoroalkyl group having 6 or less carbon atoms, it is possible to impart good water-repellent oil repellency, durability, and feel to a fiber product. Moreover, the durability of water repellency imparted by the water-repellent oil-repellent composition of the present invention is excellent in washing durability and abrasion resistance. In other words, the water-repellent property of the fiber product or the like by the water- and oil-repellent composition of the present invention is such that it is less likely to be deteriorated by washing or rubbing.

Form of implementing the invention

The invention will be described in detail below. In the present specification, an alkyl (meth)propane ester means both an alkyl acrylate and an alkyl methacrylate.

The water-repellent and oil-repellent composition of the present embodiment contains a monomer (A) represented by the following general formula (1), a monomer represented by the following general formula (2), and the following general The copolymer obtained by copolymerizing the monomer composition of at least one monomer (B) selected from the group represented by the formula (3).

Wherein R ¹ and R ² represent each independently a hydrogen atom, a halogen atom or a methyl group, and R ³ and R ⁴ each independently may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group. a monovalent fluorine-containing hydrocarbon group, or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group but not a fluorine atom, and at least R ³ and R ⁴ One of them is a monovalent fluorine-containing hydrocarbon group which may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group, and X ¹ and X ² each independently represent a divalent organic group or a single bond].

Wherein R ⁵ and R ⁶ represent each independently a hydrogen atom, a halogen atom or a methyl group, and R ⁷ represents a carbon number of from 1 to 30 which may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group; A monovalent hydrocarbon group or a monovalent fluorine-containing hydrocarbon group, R ⁸ represents a hydrogen atom, a halogen atom or a methyl group, and X ³ represents a divalent organic group or a single bond].

Wherein R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom or a methyl group, and R ¹¹ and R ¹² each independently may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group. However, the fluorine-free atom has a carbon number of from 1 to 30, and X ⁴ and X ⁵ each independently represent a divalent organic group or a single bond].

The monomer (A) represented by the above general formula (1) is preferably a monomer in which R ¹ and R ² are a hydrogen atom from the viewpoint of improving the versatility of the raw material and the safety of the product after decomposition.

Further, the monomer (A) represented by the above general formula (1) is preferably both R ³ and R ^{4 in} terms of water repellency and durability (especially washing resistance and abrasion resistance). a monovalent fluorine-containing hydrocarbon group containing at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group, more preferably a perfluoroalkyl group having 2 to 18 carbon atoms, or a group represented by the following general formula (4). Or the base represented by the following general formula (5).

C _m F _(2m+1) (CH ₂ ) _p O(R ¹³ O) _n -...(4)

Wherein m is 2 to 18, p is 0 or 1 to 5, R ¹³ represents a perfluoroalkylene group having 2 to 5 carbon atoms, and n represents a perfluoroalkylalkyloxy group represented by (R ¹³ O). The average number of additional moles is 1~10].

F(R ¹⁴ O) _s -...(5)

[wherein, R ¹⁴ represents a perfluoroalkylene group having 1 to 5 carbon atoms, and s represents an average additional molar number of the perfluoroalkylalkyloxy group represented by (R ¹⁴ O), which is 1 to 10].

Further, in view of the environmental load (the PFOA is not discharged), the monomer (A) represented by the above general formula (1) is preferably a perfluoroalkyl group having 2 to 6 carbon atoms, or both of the above, and R ³ and R ⁴ . In the general formula (4), m is 2 to 6, p is 2 to 4 (preferably 2 to 3, more preferably 2), n is a group of 1 to 10, or s in the above general formula (5) It is the base of 1~10. Among them, in terms of water repellency and durability (especially washing resistance and abrasion resistance), both R ³ and R ⁴ are preferably a perfluoroalkyl group having a carbon number of 2 to 6, and a carbon number of 6 The perfluoroalkyl group is more preferred. From the viewpoint of environmental load, both R ³ and R ⁴ are more preferably in the above general formula (4), m is 2 to 6, p is 2 to 4 (preferably 2 to 3, more preferably 2), and n is The base of 1 to 5, or the s in the above general formula (5) is a base of 1 to 5.

Further, when X ¹ and X ² in the above general formula (1) are a divalent organic group, the divalent organic group is, for example, -OR 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), -OR ¹⁸ -N(R ¹⁹ )-SO ₂ -, -OR ²⁰ -SO ₂ -R ²¹ -, -OR ²² -SR ²³ -, and -OR ²⁴ -N(H)C(O)- (wherein R ¹⁸ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ represent a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms; R ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). Among these, it is easy to manufacture and functional (especially durable water repellency), and X ¹ and X ^{2 are} preferably -OR ¹⁵ -. Further, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are easy to manufacture and functional (especially durable water repellency), preferably carbon number 2 The divalent hydrocarbon group of ~4 is more preferably a divalent hydrocarbon group having 2 to 3 carbon atoms (more preferably an ethyl group).

The water-repellent and oil-repellent composition containing the copolymer obtained by copolymerizing the monomer composition containing the monomer (A) and the monomer (B) in the embodiment is a combination of the monomer (A) and the single The body (B) is a water-repellent and oil-repellent composition containing a polymer obtained by polymerizing a monomer composition containing only the monomer (A), and tends to improve water repellency and durability (especially resistance) Washability and abrasion resistance). As a monomer represented by the above general formula (2) used as the monomer (B), R ⁵ and R ^{6 are} preferably a hydrogen atom from the viewpoint of general versatility of the raw material. Further, R ^{7 of the} general formula (2) may contain, for example, a hydrocarbon having 1 to 30 carbon atoms which is at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group but does not have a fluorine atom, or may contain A one-valent fluorine-containing hydrocarbon group having 1 to 30 carbon atoms of at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group.

The monomer represented by the above general formula (2) is such that the R ⁷ system may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group, but a fluorine atom having 1 to 30 carbon atoms. When it is water-repellent and its durability (especially washing resistance and abrasion resistance) and the general versatility of raw materials, R ^{7 is} preferably a linear alkyl group having a carbon number of 8 to 30 and a carbon number of 8. a branched alkyl group of ~30 or a cyclic alkyl group of 8 to 30 carbon atoms. Among them, the viewpoint of water repellency and durability (especially washability and abrasion resistance) and touch is more preferably a linear or branched alkyl group having a carbon number of 16-22. Further, the monomer represented by the above general formula (2) is such that the R ⁷ system may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group, and a monovalent fluorine-containing hydrocarbon group having 1 to 30 carbon atoms; From the viewpoint of water repellency and durability (especially washing resistance and abrasion resistance), R ^{7 is} preferably a perfluoroalkyl group having 2 to 18 carbon atoms, represented by the above general formula (4). A group or a group represented by the above general formula (5).

Further, the monomer represented by the above general formula (2) is excellent in reactivity and the flexibility of the obtained fiber product, and R ^{8 is} preferably a hydrogen atom, and the water repellency and durability (especially washing resistance and abrasion resistance) From the viewpoint of consumption, R ^{8 is} preferably a methyl group or a halogen atom (particularly a chlorine group). The methyl group or the halogen atom is preferably a methyl group from the viewpoint of flexibility and price.

Further, when X ³ in the above general formula (2) is a divalent organic group, a divalent organic group such as -OR 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), -OR ²⁸ -N(R ²⁹ )-SO ₂ -, -OR ³⁰ -SO ₂ -R ³¹ -, -OR ³² -SR ³³ -, and -OR ³⁴ -N(H)C(O)- (wherein R ²⁸ , R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ represent a single bond or a carbon number of 1 to 10 The valent hydrocarbon group, R ²⁹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the like. Among these, it is easy to manufacture and functional (especially durable water repellency), and X ^{3 is} preferably -OR ²⁵ - or -NH-R ²⁶ -, more preferably -OR ²⁵ -. Further, R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are easy to manufacture and functional (especially durable water repellency), preferably carbon number 2~ The divalent hydrocarbon group of 4 is more preferably a divalent hydrocarbon group having 2 to 3 carbon atoms (more preferably an ethyl group).

The monomer represented by the above general formula (3) used as the monomer (B) is easy to produce and functional (especially, durable water repellency), and R ⁹ and R ^{10 are} preferably a hydrogen atom.

Further, the monomer represented by the above general formula (3) is preferably a carbon number of 8 and R ¹¹ and R ^{12 in} terms of water repellency and durability (especially washability and abrasion resistance) and tactile sensation. a linear alkyl group of ~30, a branched alkyl group having 8 to 30 carbon atoms, or a cyclic alkyl group having 8 to 30 carbon atoms, more preferably a linear or branched chain having a carbon number of 16 to 22. alkyl.

Further, when X ⁴ and X ⁵ in the above general formula (3) are a divalent organic group, the divalent organic groups such as -OR ³⁵ -, -SO ₃ N-, -NH-R ³⁶ -, and -R ³⁷ - (wherein R ³⁵ , R ³⁶ and R ³⁷ represent a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms), -OR ³⁸ -N(R ³⁹ )-SO ₂ -, -OR ⁴⁰ -SO ₂ -R ⁴¹ -, -OR ⁴² -SR ⁴³ -, and -OR ⁴⁴ -N(H)C(O)- (wherein R ³⁸ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ represent a single bond or a carbon number of 1 to 10 The divalent hydrocarbon group, R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the like. Among these, it is easy to manufacture and functional (especially durable water repellency), and X ⁴ and X ^{5 are} preferably -OR ³⁵ - or -NH-R ³⁶ -, more preferably -OR ³⁵ -. Further, R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are easy to manufacture and functional (especially durable water repellency), and preferably have a carbon number of 2~ The divalent hydrocarbon group of 4 is more preferably a divalent hydrocarbon group having 2 to 3 carbon atoms (more preferably an ethyl group).

Among the above monomers, the monomer (B) is preferably a single one represented by the above general formula (2) in terms of water repellency and durability (especially washing resistance and abrasion resistance) and tactile sensation. At least one of the bodies.

In the present embodiment, the monomer (B) is preferably used in the following general formula (B-1) in terms of water repellency and durability (especially washing resistance and abrasion resistance) and touch. Represents the monomer.

CH ₂ =C(R ⁸ )(COOR ⁷ ) (B-1)

In the formula, R ⁷ and R ^{8 are} synonymous with the above, and are preferably a R ⁸ -based hydrogen atom and a R ⁷ -based linear alkyl group having a carbon number of 8 to 30 or a carbon number 2 from the viewpoint of water repellency and touch. ~18 perfluoroalkyl group, in terms of water repellency and durability (especially washability and abrasion resistance) and tactile sensation, more preferably R ⁸ hydrogen atom and R ⁷ carbon number 12 a linear alkyl group of ~22 (also preferably 16-22). In the present embodiment, the monomer (B) is preferably a combination of an R ⁸ -based hydrogen atom and an R ⁷ -based carbon in terms of water repellency and durability (especially washing resistance and abrasion resistance) and tactile sensation. A monomer having a linear alkyl group of 12 to 22 (more preferably 16 to 22), a monomer having a R ⁸ -based hydrogen atom and a R ⁷ -based perfluoroalkyl group having 2 to 18 carbon atoms.

The copolymer of the present embodiment is contained by a copolymerization component There is the above monomer (A) and the above monomer (B), so that the copolymer of the above monomer (A) and acrylic acid is compared, and the water repellency and durability (especially washing resistance and abrasion resistance) tend to be improved. Further, comparing the copolymer of the above monomer (A) with a short-chain vinyl alkyl ether or a short-chain vinyl carboxylate, tends to improve water repellency and durability (especially washability and abrasion resistance) With a touch. Further, in the copolymer of the present embodiment, when the monomer (A) is reacted with a vinyl alkyl ether or a vinyl carboxylate, the reaction time is short.

In the monomer composition of the present embodiment, the addition ratio (mass ratio) of the monomer (A) to the monomer (B) is in terms of water repellency and durability (especially washability and abrasion resistance). The point of tactile sensation is preferably (A): (B) = 10:90 to 90:10, more preferably 20:80 to 80:20.

The monomer composition of the present embodiment further contains at least one monomer selected from the group consisting of vinyl chloride and vinylidene chloride in terms of durability (especially washing resistance and abrasion resistance). ) is better.

At this time, the addition amount of the monomer (C) is water-repellent and its durability (especially the viewpoints of washing resistance, abrasion resistance and touch, and the total mass of the monomer (A) and the monomer (B). The mass ratio to the mass of the monomer (C) [(A) + (B)]: (C) is preferably 95: 5 to 70: 30, more preferably 90: 10 to 80: 20.

The monomer composition of the present embodiment may contain the monomer (A) and the monomer (B) in order to impart a property such as adhesion to the substrate, adhesion, abrasion resistance and the like to the obtained copolymer. Other than monomer (C) Other monomers (D) copolymerized.

Other monomers (D) such as vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, glycidyl (meth) acrylate, (meth) acrylamide, N, N- Dimethyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, 3- Chloro-2-hydroxypropyl (meth) acrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, aziridine Ethyl ethyl (meth) acrylate, azacyclopropyl (meth) acrylate, polyoxyalkylene (meth) acrylate, methyl polyoxyalkylene (meth) acrylate, 2- Ethylhexyl polyoxyalkylene (meth) acrylate, polyoxyalkylene di(meth) acrylate, triallyl isocyanurate, allyl glycidyl ether, allyl acetate, N- Vinyl carbazole, maleimide, N-methylmaleimide, (2-dimethylamino)ethyl (meth) acrylate, glycerol (meth) acrylate, alkylene Di(meth)acrylate, vinyl decane, trimethoxy Branches of a decyl (meth) acrylate or the like having a poly(oxy)oxy (meth) acrylate, a polyoxyalkylene (meth) acrylate, and a blocked isocyanate group (meth) acrylate A (meth) acrylate having a urethane bond or the like. Among the above monomers, a monomer having a reactive group reactive with a melamine resin, an isocyanate compound or a glyoxal resin is preferred.

The other monomer (D) may be used alone or in combination of two or more.

Further, the monomer (B) is a butyl (meth) acrylate. When the monomer (B) is used in combination with the styrene of the monomer (D), a relatively good performance can be obtained by using the alkyl (meth) acrylate having a carbon number of 8 to 30 in comparison with the monomer (B). At this time, the ratio of addition of the monomer (A) to butyl (meth) acrylate to styrene (mol ratio) is preferably monomer (A): butyl (meth) acrylate: styrene = 1: 1:1~3, preferably 1:1:1.2~2.5, more preferably 1:1:2.3.

The copolymer of the present embodiment is not particularly limited as long as the monomer (structural unit) is arranged, and may be a random copolymer, a block copolymer or an interactive copolymer.

When the copolymer of the present embodiment is a monomer remaining after the polymerization reaction described later, it is preferred to remove the monomer by distillation or the like as necessary.

The melt viscosity of the copolymer of the present embodiment at 105 ° C is preferably 5 to 20000 Pa. s, more preferably 10~10000Pa. s. When the melt viscosity is within the above range, water repellency and durability (especially washability and abrasion resistance), touch and processing stability are easily obtained at a high level. Also, the melt viscosity is less than 5Pa. s, tend to reduce water repellency and its durability (especially washability and abrasion resistance), more than 20,000Pa. In the case of s, the water repellency and durability (especially washing resistance and abrasion resistance) tend to be lowered, and the touch is hardened or the processing stability is lowered.

The melt viscosity can be measured using a flow rate tester CFT-500D (manufactured by SHIMADZU Co., Ltd.) at a measurement temperature of 105 °C.

The copolymer of the present embodiment is obtained by using a copolymer known in the prior art. For example, a solution polymerization method using an organic solvent as a solvent, an emulsion polymerization method containing an organic solvent or various surfactants using water as a solvent Wait.

Organic solvents such as methanol, ethanol, isopropanol, n-butanol, 2-butanol, t-butanol, n-hexanol, 2-ethylhexanol, glycerol, etc., aliphatic groups having 1 to 8 carbon atoms Alcohols; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, etc.; 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, three Glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, and the like, glycol ethers; ethylene glycol monomethyl a glycol ester such as ether acetate, propylene glycol monomethyl ether acetate or diethylene glycol monoethyl ether acetate; n-hexane, isohexane, cyclohexane, methylcyclohexane , n-butane, isooctane, n-decane, mineral turpentine, turpentine, isoparaffin, toluene, xylene, solvent oil, etc.; acetone, methyl ethyl ketone, methyl isobutyl a ketone such as a ketone, diisobutyl ketone, cyclohexanone or diacetone alcohol; An ester of ethyl ester, methyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc.; diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, Ethers such as dioxane, methyl tert-butyl ether, butyl carbitol, tetrahydrofuran, etc.; acetonitrile, n-methylpyrrolidone, dimethylformamide, DMSO, propylene carbonate, dimethyl carbonate, A halogen compound, a nitrogen compound, a sulfur compound, an inorganic solvent, an organic acid or the like. Among these, the water-repellent property, the product stability, the stability of the treatment liquid, and the permeability of the treatment liquid phase to the fibrous product are preferably selected from the group consisting of glycols and glycol ethers. At least one, more preferably dipropylene glycol, tripropylene glycol, polypropylene Glycol (average molecular weight 200~4000), dipropylene glycol monomethyl ether.

These solvents may be used alone or in combination of two or more. When two or more types are used in combination, it is preferred to use water in combination. By using a mixed solvent, it is easy to control the solubility and emulsifying dispersibility of the copolymer, and it is preferable to control the permeability to the fiber product during the treatment.

The surfactant is preferably a cationic surfactant, a nonionic surfactant, an amphoteric surfactant or the like.

a cationic surfactant such as a monoalkyltrimethylammonium salt having 8 to 24 carbon atoms, a dialkyldimethylammonium salt having 8 to 24 carbon atoms, a monoalkylamine acetate having a carbon number of 8 to 24, and carbon The number of dialkylamine acetates of 8 to 24, the alkyl imidazoline quaternary salts of 8 to 24 carbon atoms, and the like. Among these, from the viewpoints of emulsifying property and processing stability, a monoalkyltrimethylammonium salt having 12 to 18 carbon atoms and a dialkyldimethylammonium salt having 12 to 18 carbon atoms are preferable.

These cationic surfactants may be used alone or in combination of two or more.

Nonionic surfactants such as alcohols, polycyclic phenols, amines, guanamines, fatty acids, polyvalent alcohol fatty acid esters, oils and fats, and epoxide adducts of polypropylene glycol.

The alcohol is, for example, a linear or branched alcohol having 8 to 24 carbons or an enol, or an alkynol represented by the following general formula (6).

[wherein R ⁴⁵ and R ⁴⁶ represent independently a straight or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms].

Polycyclic phenols such as phenols such as phenol or naphthol which may have a hydrocarbon group of 1 to 12 carbon atoms, or addition of such styrenes (styrene, α-methylstyrene, vinyl toluene) Or such benzyl chloride reactants, and the like. The amines are, for example, a linear or branched aliphatic amine having 8 to 44 carbon atoms.

Amidoxime, for example, a linear or branched fatty acid decylamine having a carbon number of 8 to 44.

Fatty acids such as linear or branched fatty acids having 8 to 24 carbon atoms.

A polyvalent alcohol fatty acid ester such as a condensation reaction of a polyvalent alcohol with a linear or branched fatty acid having 8 to 24 carbon atoms.

Examples of oils and fats include vegetable oils, animal oils, vegetable waxes, animal waxes, mineral waxes, and hardened oils.

Among these, the influence on the oil repellency is less, the influence on the light resistance is less, and the emulsification viewpoint of obtaining a good copolymer is preferably a linear or branched carbon number of 8 to 24 The alcohol or the enol, the alkynol represented by the above general formula (6), more preferably a linear or branched alcohol having 8 to 24 carbon atoms, or an alkynol represented by the above general formula (6).

Epoxides such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, rings Oxychloropropane, etc. The epoxide is preferably ethylene oxide or 1,2-propylene oxide, more preferably ethylene oxide, from the viewpoint of less influence on water repellency and good emulsifying properties of the copolymer.

The number of additional moles of the epoxide is preferably from 1 to 200, more preferably from 3 to 100, still more preferably from 5 to 50. When the number of additional moles of the epoxide is within the above range, it is easy to obtain water repellency and product stability at a high level. Further, when the number of additional moles of the epoxide is less than 1 mol, the product tends to lower the stability of the product and the water repellency, and when it exceeds 200 m, the water repellency tends to be lowered.

In the copolymer of the present embodiment, when a nonionic surfactant having an HLB of 6 to 20 is used as the nonionic surfactant, a more excellent aqueous dispersion can be obtained. At this time, HLB refers to the substance according to the HLB of Greifen, and the Griffin type is changed to the following formula. Wherein the hydrophilic group means an oxiranyl group.

HLB = (hydrophilic group × 20) / molecular weight

These nonionic surfactants may be used alone or in combination of two or more. When two or more types are used in combination, a more excellent aqueous dispersion can be obtained by using a weight-averaged HLB of 8 to 16 as a nonionic surfactant.

The above various surfactants may be used singly or in combination of two or more kinds, but in terms of emulsification dispersibility of the monomer during copolymerization, emulsification dispersibility of the copolymer, stability of the treatment liquid, and water repellency, Preferably, a cationic surfactant and a nonionic active agent are used in combination.

The surfactant is preferably contained in an amount of from 1 to 20% by mass based on the copolymer, and more preferably from 3 to 16% by mass based on the copolymer. When the amount of the surfactant added is within the above range, it is easy to obtain processing stability, water repellency and durability (especially washing resistance and abrasion resistance) at a high level. Further, when the amount is less than 1% by mass, the processing stability tends to be lowered, and when it exceeds 20% by mass, the water repellency and the durability (especially the washing resistance and the abrasion resistance) tend to be lowered.

In the present embodiment, it is preferred to produce a copolymer by emulsion polymerization in a solvent containing water. The solution of the copolymer thus obtained and the emulsified dispersion can be used as they are or after dilution. Further, after separating the copolymer, it is dissolved in a solvent or emulsified and dispersed for use.

Further, in the present embodiment, it is preferred to carry out pre-emulsification using a high-pressure emulsifier or the like before the start of the polymerization reaction. For example, a mixture of a mixed monomer such as a homomixer or a high-pressure emulsifier, a surfactant, an organic solvent, water, or the like is preferably used. It is preferable to pre-mix and disperse the raw material mixture before the start of the polymerization to improve the stability of the water- and oil-repellent component of the water-repellent and oil-repellent composition finally obtained.

The polymerization reaction is preferably carried out using heat, light, radiation, a radical polymerization initiator, an ionic polymerization initiator, or the like. In particular, a water-soluble or oil-soluble radical polymerization initiator is used, and an initiator such as an azo polymerization initiator, a peroxide polymerization initiator, or a redox initiator can be used depending on the polymerization temperature. The polymerization initiator is particularly preferably an azo compound, and is more preferably a salt of an azo compound when it is polymerized in a solvent using water. The polymerization temperature is not particularly limited, and is preferably 20 to 150 ° C, more preferably 40 to 90 ° C.

A molecular weight modifier can be used for the polymerization. The molecular weight modifier is preferably an aromatic compound or a mercaptan, more preferably an alkyl mercaptan.

In the water-repellent and oil-repellent composition of the present embodiment, it is preferred that the copolymer is dispersed in a solvent in a particulate form. The average particle diameter at this time is preferably from 10 to 1000 nm, preferably from 50 to 300 nm, more preferably from 80 to 200 nm, from the viewpoint of water repellency and product stability.

The average particle diameter can be determined by using a laser diffraction type/scattering type, particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.), and measuring the percentage value of the particle diameter of the ultraviolet absorber for fibers, and then the small particle diameter side. A particle size of 50% is obtained as an average particle diameter.

The water-repellent and oil-repellent composition of the present embodiment preferably contains a solvent from the viewpoint of ease of handling. As the solvent, a solvent equivalent to the solvent which can be used in the production of the above copolymer can be used.

Further, among these, the same as in the case of the above copolymer, it is preferred to use the same solvent as described above.

The content of the solvent in the water-repellent composition is preferably from 50 to 90% by mass, more preferably from 55 to 75% by mass, based on the total amount of the composition.

When the water-repellent oil-repellent composition contains an organic solvent, the content of the organic solvent is preferably from 1 to 20% by mass, more preferably from 5 to 15% by mass, based on the total amount of the composition.

In this embodiment, the present embodiment can be used by using the present embodiment. The treatment liquid for the water-repellent agent composition treats the fiber product to obtain a water-repellent oil fiber product. The water-repellent and 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 and used as a treatment liquid.

The treatment liquid of the present embodiment preferably contains 0.3 to 5% by mass of the water- and oil-repellent composition of the present embodiment from the viewpoint of easily controlling the amount of the water- and oil-repellent composition to be imparted to the fiber product.

The treatment liquid of the present embodiment preferably contains an organic solvent. As such an organic solvent, an organic solvent equivalent to the organic solvent which can be used for the above copolymer can be used. Among them, isopropyl alcohol and diethylene glycol monobutyl ether are preferably used from the viewpoint of processing stability and permeability to a fibrous product.

The 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-repellent and oil-repellent composition of the present embodiment has a pH of preferably 2.0 to 6.0 from the viewpoints of water repellency, touch, and processing stability. Further, the treatment liquid of the present embodiment has a pH of preferably 3.0 to 7.0, more preferably 4.0 to 6.0, from the viewpoints of water repellency, feel, and processing stability.

In the water-repellent and oil-repellent composition of the present embodiment and the treatment liquid of the present embodiment, in order to adjust the pH, the pH can be arbitrarily adjusted using a pH adjuster. As the pH adjuster, an acid such as formic acid, acetic acid, malic acid or citric acid; a base such as caustic alkali, carbonic acid base or ammonia water can be used. Among these, it is preferred to adjust the pH using acetic acid or malic acid.

When the liquid fiber product is treated by the embodiment, A immersion agent, an antifoaming agent, an antistatic agent, a tactile modulating agent, a melamine resin, an isocyanate compound, a glyoxal resin, a catalyst, a previously known water-repellent oil-repellent agent, and the like can be used in combination in the chemical solution.

The melamine resin may be a compound having a melamine skeleton, such as polymethylol melamine such as trimethylol melamine or hexamethylol melamine; or some or all of the methylol groups of polymethylol melamine may have a carbon number of 1 to 6. Alkoxymethyl alkoxymethyl melamine of an alkyl group; part or all of the methylol group of polymethylol melamine becomes a methoxymethyl group of a decyloxymethyl group having a fluorenyl group having 2 to 6 carbon atoms Melamine and the like. The melamine resin may be a monomer or a polymer of a dimer or more, or a mixture of these may be used. Further, a substance in which a part of melamine is co-condensed with urea or the like can be used. Such melamine resins such as Becamin APM, Bekamin M-3, Bekamin M-3 (60), Bekamin MA-S, Bekamin J-101, and shellfish made by DIC Corporation Kamin J-101LF, Unicorn Resin 380K made by Unin Chemical Industry Co., Ltd., Rikenlei MM series made by Sanmu Riken Industrial Co., Ltd., etc.

The isocyanate compound is not particularly limited as long as it has at least two or more isocyanate groups in the molecule, and a known polyisocyanate compound can be used. For example, a diisocyanate compound such as an alkylene group (preferably having a carbon number of 1 to 12) diisocyanate, an aryl diisocyanate or a cycloalkyl diisocyanate, or a dimer or a trimer of the diisocyanate compound or the like Modification of the polyisocyanate compound.

Also, the modified polyisotropy derived from the diisocyanate compound The cyanate compound may be one having two or more isocyanate groups, and is not particularly limited, and has, for example, a biuret structure, a trimeric isocyanate structure, a urethane structure, a uretdione structure, an allophanate structure, A polyisocyanate such as a trimer structure or an adduct of an aliphatic isocyanate of trimethylolpropane. Further, as the polyisocyanate compound, MDI of a polymer (MDI = diphenylmethane diisocyanate) can be used. The isocyanate compounds block the isocyanate groups without or with a blocker.

Commercially available products can be used as the polyisocyanate compound. Commercially available polyisocyanate compounds such as "Bassona" series by BASF, "Bai Xiqiu" series by Kebesi, "SBU isocyanate" series, "Dansmore" series, and "Smith" The "Dan Lana" series made by Asahi Kasei Chemicals Co., Ltd., the "Klona" series made by Tosoh Corporation, and the "Yakuya" series made by Japan Polyurethane Co., Ltd. KK Isis FU, NK Assis IS-100, manufactured by Mitsui Chemicals Co., Ltd. NK Yasisi IS-80, NK Assis V, NK Assis NY, NK Assis NY-27, NK Assis NY-30, and NK Assis NY-50, etc. The Sith series and so on.

As the glyoxal resin, previously known materials such as 1,3-dimethylglyoxal urea resin, dimethylol dihydroxyethylidene resin, and dimethylol dihydroxypropyl propyl urea may be used. Resin, etc. The functional groups of the resins may be substituted by other functional groups. Such glyoxal resins such as Becamin N-80, Bekamin NS-11, Bekamin LF-made by DIC Corporation K, Bekamin NS-19, Bekamin LF-55P conc., Bekamin NS-210L, Bekamin N-200, and Bekamin NF-3, made by Union Chemical Industry Co., Ltd. Uniri GS-20E, Rikenlei RG series made by Sanmu Liyan Industrial Co., Ltd., and Rikenley MS series.

From the viewpoint of promoting the reaction of the melamine resin and the glyoxal resin, it is preferred to use a catalyst. The catalyst used in the above-mentioned catalyst is not particularly limited, and examples thereof include a fluoroboric acid compound such as ammonium fluoroborate or a fluoroboric acid sulfite, a neutral metal salt catalyst such as magnesium chloride or magnesium sulfate, phosphoric acid, hydrochloric acid, and boric acid. Inorganic acid and the like. When necessary, these catalysts may be used together as an organic acid such as citric acid, tartaric acid, malic acid, maleic acid or lactic acid for use as a catalyst. Such catalysts are, for example, Cadali ACX, Caldari 376, Caldari O, Caldari M, Caldari G (GT), Caldari X-110, Caldari GT-3, and Caldari NFC-1, Unicorn Chemicals Co., Ltd., Unicorn 3-P, and Unicomcast MC-109, Sanmu Riken Industrial Co., Ltd. Kenfei RC series, Riken flying MX series, and the Ricken flying RZ-5.

When the water-repellent and oil-repellent composition of the present embodiment contains at least one selected from the group consisting of melamine resin, isocyanate compound and glyoxal resin, water repellency and durability (especially washing resistance) The mass (active ingredient) is preferably from 0.4 to 3,000 parts by mass based on 100 parts by mass of the copolymer of the present embodiment, from the viewpoint of the abrasion resistance and the tensile strength.

When the water-repellent and oil-repellent composition of the present embodiment is used for a fiber product containing 40% by mass or more of synthetic fibers, water and oil repellency and From the viewpoint of durability (especially washing resistance and abrasion resistance), it is preferred to use a melamine resin and/or an isocyanate compound, and it is more preferred to use a melamine resin and an isocyanate compound in combination. In this case, the amount of the melamine resin and/or the isocyanate compound (active ingredient) is preferably 0.4 to 300 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of the copolymer of the present embodiment. When it is the above-mentioned addition amount, it is easy to obtain the effect of improving the water repellency and the durability (especially the washing resistance and the abrasion resistance) in accordance with the usage amount.

When the water-repellent and 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-repellent property and durability (especially washing resistance and abrasion resistance) are considered. It is preferred to use a glyoxal resin and/or an isocyanate compound. In this case, the amount of the addition of the glyoxal resin and/or the isocyanate compound (active ingredient) is preferably from 10 to 3,000 parts by mass, more preferably from 10 to 2,000 parts by mass, per 100 parts by mass of the copolymer of the present embodiment. When it is the above-mentioned addition amount, it is easy to obtain the effect of improving the water repellency and the durability (especially the washing resistance and the abrasion resistance) in accordance with the usage amount.

The treatment liquid of the present embodiment can be obtained, for example, by mixing water and an organic solvent with the water-repellent oil-repellent composition of the present invention. In this case, the order of mixing is not particularly limited, but in view of processing stability, a method of mixing an organic solvent diluted with water with a water-repellent composition of the present embodiment diluted with water, or The method of diluting one of the organic solvent or the water-repellent oil-repellent composition of the present embodiment and mixing the other one.

The manufacturer of the water-repellent oil-repellent fiber product of the present embodiment The method comprises the steps of treating the fibrous product with a treatment liquid containing the water-repellent and oil-repellent composition of the present embodiment.

The method of treating the fibrous product with the above treatment liquid is not limited, and the method previously used can be used. The fibrous product is treated with a treatment liquid by, for example, a pad dyeing method, a dipping method, a spray method, a bubble processing method, a coating method, or the like, and then dried. Further, a curing (heat treatment) step may be used in combination after drying. The drying method is not limited, and the method previously used may be used, and it may be a dry heat method or a damp heat method.

The material of the fiber product to which the production method of the present embodiment is applied is not particularly limited, and is, for example, a natural fiber such as cotton, hemp, ray, wool or the like, a semi-synthetic fiber such as rayon or acetate, nylon, polyester, or polyurethane. , synthetic fibers such as polypropylene, composite fibers, blended fibers, and the like. Further, the form of the fibrous product may be any form of woven fabric, knitted fabric, silk, non-woven fabric, paper, or the like.

Example

The invention will now be described in more detail by way of examples, but the invention is not limited to the examples.

[Synthetic monomer (A)] (Synthesis Example 1)

380 g of perfluorohexylethyl alcohol, 150 g of cyclohexane, 10 g of p-toluenesulfonic acid and 32 g of itaconic acid were placed in a 1000 ml flask. After heating it, The mixture was refluxed at about 85 ° C for 10 hours. Thereafter, cyclohexane was distilled off, and 400 g of ion-exchanged water and 5 g of sodium carbonate were added for neutralization. After removing the aqueous phase, it was washed twice with ion-exchanged water. Subsequently, after distillation under reduced pressure, a compound represented by the following formula (7) (hereinafter referred to as C6FIA) which is used as the monomer (A) is obtained. When the GC measurement was carried out, the purity was 99.9%.

(Example 1) [Modulating water and oil repellency composition]

72 g of C6FIA obtained in Synthesis Example 1 as the monomer (A), 18 g of stearic acid acrylate (hereinafter abbreviated as SA) used as the monomer (B), and polyethylene oxide alkyl ether (hereinafter abbreviated as POA) 5 g, stearin trimethylammonium chloride (hereinafter referred to as STMAC) 1 g, propylene glycol (hereinafter abbreviated as PPG) 30 g, and ion-exchanged water 261.7 g were placed in a 500 ml flask, and stirred at 40 ° C. After emulsifying and dispersing with an ultrasonic emulsifier, it was cooled to 30 ° C or lower, and then transferred to a 500 ml stainless steel high-pressure vessel. Next, 0.3 g of dodecyl mercaptan was added, and nitrogen substitution was carried out for 10 minutes. Thereafter, 0.3 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated to 60 ° C for 6 hours to obtain a water-repellent composition.

The non-volatile component of the obtained water-repellent oil composition is 31.5%. Moreover, the copolymer contained in the water-repellent composition has a melt viscosity of about 5800 Pa at 105 ° C. s.

Further, the melt viscosity of the copolymer was measured by using a flow rate tester CFT-500D (manufactured by SHIMADZU Co., Ltd.) at a measurement temperature of 105 ° C, and an organic solvent such as methanol or acetone was added to the water-repellent and oil-repellent composition to be emulsified and broken. The solid component is obtained by drying the obtained sample.

[1. Adjusting treatment liquid A and manufacturing water- and oil-repellent fiber products A]

The water-repellent oil-repellent composition obtained above was diluted with ion-exchanged water, and the treatment liquid A containing the water-repellent oil-repellent composition at a concentration of 2 g/l, 4 g/l, and 6 g/l was prepared. The dyed polyester woven fabric (120 g/m ² ) and nylon woven fabric (120 g/m ² ) were immersed in the treatment liquid A, and then stranded by a rolling mill. At this time, the wet absorbing rate of the polyester woven fabric was 60%, and the wet absorbing ratio of the nylon woven fabric was 40%. Thereafter, the treated cloth was dried in the order of 60 seconds at 120 ° C and then 60 seconds at 180 ° C, and each of the water-repellent fibrous products A was dispensed. The water repellency of the water-repellent oil-containing fibrous product A was evaluated by the method described later. The results are shown in Table 5.

[2. Modulation of treatment liquid B and manufacture of water- and oil-repellent fiber products B]

The water-repellent and oil-repellent composition obtained above was diluted with ion-exchanged water and NK Assis FU (trade name, manufactured by Rihua Chemical Co., Ltd., blocked isocyanate-based crosslinking agent), and prepared to contain 40 g/l. The water-repellent composition was treated with 8 g/l of NK Assis-FU treatment liquid B. The dyed polyester woven fabric (120 g/m ² ) was immersed in the treatment liquid B, and then twisted to a wet extraction rate of 60% by a rolling mill, followed by 120 ° C for 60 seconds and then at 180 ° C. Drying is carried out under conditions of 60 seconds to obtain a water-repellent fibrous product B. The durable water repellency of the water-repellent oil-containing fibrous product B was evaluated by the method described later. The results are shown in Table 5.

[3. Preparation of treatment liquid C and manufacture of water- and oil-repellent fiber products C]

The water-repellent and oil-repellent composition obtained above was diluted with ion-exchanged water to prepare a treatment liquid C containing 30 g/l of a water-repellent oil-repellent composition. The dyed polyester woven fabric (120 g/m ² ) was immersed in the treatment liquid C, and then dried by a rolling mill to a wet extraction rate of 60%, followed by 120 ° C for 60 seconds and then at 180 ° C. Drying under the conditions of 60 seconds is carried out to obtain a water-repellent fibrous product C. The oil repellency and feel of the water-repellent oil-containing fibrous product C were evaluated by the method described later. The results are shown in Table 5.

[evaluating water repellency]

Table 1 below shows the water repellency of the water-repellent oil-repellent fiber product A having the water-repellent No. obtained by the spray method of JIS L-1092.

Also, the water-repellent No. attached + printed system indicates a slightly better performance. The good thing, the attached-printed system means something inferior.

[Evaluation of Durable Water Repellent]

According to JIS L 0217 (1995), the water repellency of the initial stage of the water-repellent oil-containing fibrous product B, the washing after 5 times, the washing after 10 times, and the washing after 20 times were evaluated.

[evaluating oil repellency]

According to AATCC-TM-118 (1966), the test solution shown in the following Table 2 was placed on five places of the test cloth (water-repellent oil-containing fibrous product C), and the oil-repellency was judged by the state of penetration after 30 seconds.

[Evaluation of wear resistance]

According to ISO5470-1 (2002), the water-repellent oil fiber product B is worn. The wear machine uses 5135 ABRASER (Rotary Platform) Abraser (manufactured by TABERINDUSTRIES), the wear wheel system uses CS-10 (manufactured by TABER INDUSTRIES). Thereafter, according to AATCC TM-118 (2002), the test solution of the oil-repellent No. 4 was visually observed to be dropped on the cloth, and then evaluated on the following basis (refer to Figure 1 of AATCC Tecnical Manual/2006, p. 192). ).

A: Clear well-rounded drop with high contact angle

B: rounding drop with partial darkening with partial darkness

C: wicking with loss of contact angle

D: complete wetting

[evaluation of touch]

The touch of the water-repellent oil-containing fibrous product C was judged based on the judgment criteria shown in Table 3 below to evaluate the touch.

[Processing stability]

The composition of the water-repellent oil-repellent agent obtained by diluting the above-mentioned water-repellent oil-repellent composition with a concentration of 10 g/L of the water-repellent oil-repellent composition was prepared. The test solution heated to 40 ± 3 ° C was stirred at 6000 rpm for 10 minutes using a homomixer, and then filtered through a black cotton cloth. The amount of residue remaining on the cotton cloth was visually observed, and the stability was evaluated according to the judgment criteria of Table 4 below.

(Examples 2 to 9, Comparative Examples 1 to 8)

The same operation as in Example 1 was carried out except that the monomer type and the amount of use were changed according to Tables 5 and 6 and Tables 6 and 10 (the values in the table are the total amount of monomer (90% by mass)), and Example 2 was obtained. ~9, Comparative Example 1~8 water-repellent oil-repellent composition and water- and oil-repellent fiber products A~C.

The water-repellent oil-repellent composition and the water-repellent oil-removing fiber products A to C were evaluated in the same manner as in the first embodiment. The results are shown in Tables 5 and 6 and Tables 9 and 10.

(Examples 10 to 15)

Except that the monomer type and the amount of use were changed as shown in Tables 7 and 8, the same operation as in Example 1 was carried out, and after the water-repellent and oil-repellent composition was prepared, the relative 40 g of the water-repellent oil-repellent composition 40 g of the isocyanate compound, the melamine resin/catalyst or the glyoxal resin/catalyst of the content (g) shown in Tables 7 and 8 was used, and the same operation as in Example 1 was carried out. Water-oiled fibrous product B.

The water repellency and abrasion resistance of the water-repellent oil-containing fibrous product B obtained above were evaluated in the same manner as in Example 1. The results are shown in Tables 7 and 8.

(Comparative examples 9 to 10)

Except that the monomer type and the amount of use were changed as shown in Table 11, the same operation as in Example 1 was carried out, and after the water-repellent and oil-repellent composition was prepared, NK Assis FU was not added except the water- and oil-repellent composition. Further, the same operation as in Example 1 was carried out, and each of the water-repellent fibrous products B was obtained.

The water repellency and abrasion resistance of the water-repellent oil-containing fibrous product B obtained above were evaluated in the same manner as in Example 1. The results are shown in Table 11.

The symbols in the table indicate the following compounds.

C6FIA: Compound of Synthesis Example 1

C6FMA: perfluorohexylethyl methacrylate

SA: stearin acrylate

VA: behenyl acrylate

VCM: vinyl chloride monomer

St: Styrene

BA: butyl acrylate

NK Assis IS-100: Isocyanate crosslinker (made by Rihua Chemical Co., Ltd., trade name)

UNIKA resin 380K: melamine resin (manufactured by Unionon Chemical Industry Co., Ltd., trade name)

Unicaster 3-P: Catalyst for melamine resin (manufactured by Unionon Chemical Industry Co., Ltd., trade name)

Uniri GS-20E: Glyoxal resin (manufactured by Unionon Chemical Industry Co., Ltd., trade name)

Unicaster MC-109: Catalyst for Glyoxal Resin (Unique Chemical Industry Co., Ltd., trade name)

The water-repellent oil-repellent composition of Examples 1 to 15 containing a copolymer of a monomer (A) and a monomer (B) as a copolymerization component has sufficient water-repellent oil-repellent property and processing stability, and thus is treated The fiber product imparts desired water repellency and durability (especially washability and abrasion resistance) and feel.

Industrial use possibility

The present invention can provide a water- and oil-repellent composition which can impart good water-repellent oil-repellency and durability and feel, and a method for producing the water- and oil-repellent fiber product using the same. When the water-repellent oil-repellent composition of the present invention has a water-repellent component having a perfluoroalkyl group having a carbon number of 6 or less, it is possible to impart good water-repellent oil-repellent property, durability, and touch to a fiber product. Further, the durability of the water repellency imparted by the water-repellent and oil-repellent composition of the present invention is excellent in washing resistance and abrasion resistance. In other words, the water-repellent oil-repellent property imparted to the fiber product or the like by the water- and oil-repellent composition of the present invention is such that it is less likely to be lowered by washing or rubbing.

Claims (6)

A water- and oil-repellent composition comprising 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) a copolymer obtained by copolymerizing a monomer composition of at least one monomer (B) selected from the group of monomers indicated, Wherein R ¹ and R ² represent each independently a hydrogen atom, a halogen atom or a methyl group, and R ³ and R ⁴ each independently may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group. a monovalent fluorine-containing hydrocarbon group, or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group but not a fluorine atom, and at least R ³ and R ⁴ One of them is a monovalent fluorine-containing hydrocarbon group which may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group, and X ¹ and X ² each independently represent a divalent organic group or a single bond] Wherein R ⁵ and R ⁶ represent each independently a hydrogen atom, a halogen atom or a methyl group, and R ⁷ represents a carbon number of from 1 to 30 which may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group; a monovalent hydrocarbon group or a monovalent fluorine-containing hydrocarbon group, R ⁸ represents a hydrogen atom, a halogen atom or a methyl group, and X ³ represents a divalent organic group or a single bond] Wherein R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom or a methyl group, and R ¹¹ and R ¹² each independently may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group. However, the fluorine-free atom has a carbon number of from 1 to 30, and X ⁴ and X ⁵ each independently represent a divalent organic group or a single bond]. The water-repellent oil-repellent composition of claim 1, wherein R ³ and R ⁴ of the above general formula (1) are monovalents which may contain at least one selected from the group consisting of an oxy group, a carbonyl group and a hydroxyl group. Fluorinated hydrocarbon group. The water-repellent oil-repellent composition of claim 1 or 2, wherein R ³ and R ^{4 of the} above general formula (1) represent independent perfluoroalkyl groups having 2 to 18 carbon atoms, and the following general formula (4) The group represented, or the group represented by the following general formula (5), C _m F _(2m+1) (CH ₂ ) _p O(R ¹³ O) _n - (4) [wherein, m 2 to 18, p is 0 or 1 to 5, R ¹³ represents a perfluoroalkylene group having 2 to 5 carbon atoms, and n represents an average addition of a perfluoroalkyloxy group represented by (R ¹³ O). The number is 1~10]F(R ¹⁴ O) _s -...(5) [wherein, R ¹⁴ represents a perfluoroalkyl group having a carbon number of 1 to 5, and s represents a representation of (R ¹⁴ O). The average number of moles of perfluoroalkyleneoxy groups is 1 to 10]. The water-repellent oil-repellent composition according to any one of claims 1 to 3, wherein R ⁷ of the above general formula (2) and R ¹¹ and R ¹² of the above general formula (3) are a carbon number of 8 to 30 A chain alkyl group, a branched alkyl group having 8 to 30 carbon atoms, or a cyclic alkyl group having 8 to 30 carbon atoms. The water-repellent oil-repellent composition according to any one of claims 1 to 4, wherein the monomer composition further comprises at least one monomer selected from the group consisting of vinyl fluoride and vinylidene chloride (C) . A method for producing a water-repellent oil-repellent fiber product, which comprises the step of treating a fiber product with a treatment liquid containing the water- and oil-repellent composition of any one of claims 1 to 5.