JP-7856088-B2 - Water-repellent and oil-repellent compositions, fiber treatment agents, fiber treatment methods, fiber processed products, and coating agents

JP7856088B2JP 7856088 B2JP7856088 B2JP 7856088B2JP-7856088-B2

Inventors

村田直樹

Assignees

株式会社レゾナック

Dates

Publication Date: 20260511
Application Date: 20211117
Priority Date: 20210217

Claims (15)

A copolymer (A) that does not contain structural units having siloxane bonds, A copolymer (B) containing structural units having siloxane bonds, Polyether-modified polydimethylsiloxane (C) and Aqueous medium (D) is included, The copolymer (A) is A structural unit (a1) derived from a compound having ethylenically unsaturated bonds and ester bonds, and lacking a carboxyl group, It has a structural unit (a2) derived from a compound having an ethylenically unsaturated bond and a carboxyl group, The copolymer (B) is A structural unit (b1) derived from a compound having ethylenically unsaturated bonds and ester bonds, and lacking a carboxyl group, Structural units (b2) derived from compounds having ethylenically unsaturated bonds and carboxyl groups, It has a structural unit (b3) derived from polydimethylsiloxane having an ethylenically unsaturated bond, represented by the following formula (1), A water-repellent and oil-repellent composition in which the mass ratio (A/B) of copolymer (A) to copolymer (B) is 10/90 or more and 80/20 or less . (In formula (1), R1 represents a hydrogen atom or a methyl group. R2 represents a divalent aliphatic group having 1 to 6 carbon atoms, which may contain an ether bond. R3 represents an aliphatic group, aromatic group, or hydroxyl group having 1 to 30 carbon atoms. h is 0, 1, or 2. j is an integer from 0 to 500.)
The water-repellent and oil-repellent composition according to claim 1, wherein the structural unit (a1) and the structural unit (b1) are structural units derived from a compound having a (meth)acryloyl group.
The water-repellent and oil-repellent composition according to claim 1 or 2, wherein the structural unit (a2) and the structural unit (b2) are structural units derived from (meth)acrylic acid.
The water-repellent and oil-repellent composition according to any one of claims 1 to 3 , wherein the copolymer (A) contains 0.10% by mass or more and 20% by mass or less of the structural unit (a2).
The water-repellent and oil-repellent composition according to any one of claims 1 to 4 , wherein the copolymer (B) contains 0.10% by mass or more and 20% by mass or less of the structural unit (b2).
The water-repellent and oil-repellent composition according to any one of claims 1 to 5 , wherein the copolymer (B) contains 3.0% by mass or more and 50% by mass or less of the structural unit (b3).
The water-repellent and oil-repellent composition according to any one of claims 1 to 6 , wherein the polyether-modified polydimethylsiloxane (C) has a hydroxyl group at the end of the polyether chain.
The water-repellent and oil-repellent composition according to any one of claims 1 to 7, wherein the polyether-modified polydimethylsiloxane (C) is contained in an amount of 0.10 parts by mass or more and 20 parts by mass or less with respect to a total of 100 parts by mass of the copolymer (A) and the copolymer (B).
Furthermore, the water-repellent and oil-repellent composition according to any one of claims 1 to 8 , further comprising a surfactant (E).
The water-repellent and oil-repellent composition according to claim 9 , wherein the surfactant (E) is an anionic surfactant.
A textile treatment agent comprising the water-repellent and oil-repellent composition according to any one of claims 1 to 10 .
A method for treating fibers using the fiber treatment agent of claim 11 .
A coating agent comprising the water-repellent and oil-repellent composition according to any one of claims 1 to 10 .
A textile product in which the solid components contained in the textile treatment agent of claim 11 are attached to the fibers.
The structural unit (a1) and the structural unit (b1) are at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. The structural unit (a2) and the structural unit (b2) are at least one selected from the group consisting of acrylic acid and methacrylic acid. The content of the structural unit (a1) in the copolymer (A) is 85% by mass or more and 99% by mass or less. The content of the structural unit (a2) in the copolymer (A) is 0.5% by mass or more and 5.0% by mass or less. The content of the structural unit (b1) in the copolymer (B) is 50% by mass or more and 93% by mass or less. The content of the structural unit (b2) in the copolymer (B) is 0.5% by mass or more and 5.0% by mass or less. The content of the structural unit (b3) in the copolymer (B) is 7.0% by mass or more and 50% by mass or less. The content of the structural unit (b3) in the total amount of copolymer (A) and copolymer (B) is 1.5% by mass or more and 30% by mass or less. The ratio of the mass of copolymer (A) to the mass of copolymer (B) is 10/90 to 90/10. The water-repellent and oil-repellent composition according to claim 1, wherein the weight-average molecular weight of the polyether-modified polydimethylsiloxane (C) is 7,000 or more and 14,000 or less.

Description

The present invention relates to a water-repellent and oil-repellent composition, a fiber treatment agent, a fiber treatment method, a fiber processed product, and a coating agent. This application claims priority based on Japanese Patent Application No. 2021-023556, filed in Japan on February 17, 2021, and the contents of that application are incorporated herein by reference. Conventionally, a method for imparting water- and oil-repellent properties to substrates such as fibers and paper has been performed using water- and oil-repellent agent compositions. Some water- and oil-repellent agent compositions contain compounds having perfluoroalkyl groups with eight or more carbon atoms. However, compounds containing perfluoroalkyl groups with eight or more carbon atoms may produce perfluorooctanoic acid (PFOA) through decomposition or metabolism. The U.S. Environmental Protection Agency has requested a reduction in the amount of perfluorooctanoic acid produced. Therefore, water- and oil-repellent compositions containing compounds with short-chain perfluoroalkyl groups have been proposed. For example, Patent Document 1 describes a water-repellent and oil-repellent composition comprising a pyrazole-block hydrophobic polyisocyanate aqueous dispersion containing a pyrazole-block hydrophobic polyisocyanate and a nonionic surfactant, and a water-repellent and oil-repellent component having a perfluoroalkyl group with six or fewer carbon atoms. Patent Document 2 describes a water- and oil-repellent composition comprising a fluorine-containing polymer having a structural unit having a polyfluoroalkyl group with 1 to 6 carbon atoms, a fluorine-containing polymer having a structural unit based on a fluoroolefin, and an aqueous medium. Furthermore, in recent years, there has been research into reducing the use of compounds containing short-chain perfluoroalkyl groups. For this reason, water- and oil-repellent compositions that do not contain fluorine compounds have been proposed. For example, Patent Document 3 describes an oil-repellent composition comprising an aqueous emulsion in which a copolymer (A) containing constituent units based on ethylenically unsaturated carboxylic acid monomers is dispersed in an aqueous medium (B), and a polyether-modified polydimethylsiloxane (C). Patent Document 4 describes a fiber treatment oil repellent containing a silicone-acrylic copolymer obtained by polymerizing a monomer containing a (meth)acrylate having a quaternary ammonium group, a (meth)acrylic-modified silicone oil at both ends, and a nonionic hydrophobic ethylenically unsaturated monomer. Japanese Patent Publication No. 2012-031285International Publication No. 2012/020806International Publication No. 2018/163911Japanese Patent Publication No. 2016-102272 The water-repellent and oil-repellent compositions, fiber treatment agents, paper treatment agents, and coating agents of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below. The configurations described below can be modified as appropriate without departing from the scope of the present invention. For example, the present invention is not limited to the following examples, and additions, omissions, substitutions, or changes can be made to the number, quantity, ratio, composition, type, position, material, configuration, etc., without departing from the spirit of the present invention. In the following explanation, "monomer" refers to a compound having a radically polymerizable ethylene unsaturated bond. "Ethylene unsaturated bond" refers to a double bond between carbon atoms, excluding the carbon atoms forming the aromatic ring. Unless otherwise specified, in the following explanation, "ethylenically unsaturated bond" refers to an ethylenically unsaturated bond that is radically polymerizable. "(Meth)acrylic" means "acrylic" or "methacrylic.""(Meth)acrylate" means "acrylate" or "methacrylate." "Non-volatile content" refers to components in a composition, etc., whose boiling point at 1 atmosphere (1013 hPa) is 130°C or higher. The term "active ingredient" refers to the components within a mixture that belong to a specific category, such as a solution, when those components are used in a mixture. For example, in a propylene glycol 1-monomethyl ether solution of polyether-modified polydimethylsiloxane, the active ingredient refers to all compounds in that solution that correspond to polyether-modified polydimethylsiloxane. The number-average molecular weight and weight-average molecular weight are polystyrene-converted values measured using gel permeation chromatography (GPC). In polymers of compounds having ethylenically unsaturated bonds, a structural unit derived from a compound having an ethylenically unsaturated bond is defined as having the same chemical structure in the polymer as the chemical structure in the portion of the compound other than the ethylenically unsaturated bond. For exam