US-12617884-B2 - Organic fine particle

US12617884B2US 12617884 B2US12617884 B2US 12617884B2US-12617884-B2

Abstract

An organic fine particle capable of adhering to a substrate under a state having a particle shape, wherein the organic fine particle, when adhered to a substrate, exhibits water-repellency on the substrate, and the organic fine particle is formed of a fluorine-free polymer. Also disclosed is an organic fine particle containing: (1) a hydrophobic monomer which has one ethylenically unsaturated double bond and at least one hydrocarbon group having 3-40 carbon atoms; or (2) a polymer which has a repeating unit formed from a (meth)acrylic monomer having a polydimethylsiloxane group. Also disclosed is a method for producing the organic fine particle and a water-repellent composition which is an aqueous dispersion of the organic fine particle. Also disclosed is a textile product and method for treating the same which includes applying a treatment liquid containing the water-repellent composition to the textile product.

Inventors

Yuko Shiotani
Shouta Shibutani
Rena Inamasu
Yoshito Tanaka
Ryou Akuta
Mayumi Iida
Marina NAKANO
Masahiro Higashi
Tomohiro Yoshida

Assignees

DAIKIN INDUSTRIES, LTD.

Dates

Publication Date: 20260505
Application Date: 20220329
Priority Date: 20190930

Claims (20)

1 . A water-repellent composition which is an aqueous dispersion, the composition comprising an organic fine particle (A) which is: (A1) an organic fine particle capable of adhering to a substrate under a state having a particle shape, wherein the organic fine particle, when adhered to a substrate, exhibits water-repellency on the substrate, and the organic fine particle (A1) is formed of a fluorine-free polymer wherein the fluorine-free polymer does not comprise a repeating unit formed from styrene; or (A2) an organic fine particle comprising a polymer comprising a repeating unit formed from: (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms; or (2) a (meth)acrylic monomer having a polydimethylsiloxane group, wherein the polymer further comprises a repeating unit formed from: (4) a crosslinkable monomer having at least two ethylenically unsaturated double bonds; and (3) a reactive or hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and/or hydrophilic group, and wherein the polymer does not comprise a repeating unit formed from styrene; and (B) an aqueous medium, wherein an average particle size of the organic fine particle (A) is 30 to 1000 nm.
2 . The water-repellent composition according to claim 1 , further comprising any one or more of (C) a binder resin, (D) a surfactant, and (E) a cross-linking agent.
3 . The water-repellent composition according to claim 2 , wherein the binder resin (C) is at least one polymer selected from a fluorine-free polymer having a hydrocarbon group having 3 to 40 carbon atoms in a side chain and a fluorine-containing polymer having a fluoroalkyl group having 1 to 20 carbon atoms in a side chain.
4 . A method for producing the water-repellent composition according to claim 1 , the method comprising: polymerizing a monomer in an aqueous medium in the presence of a surfactant in an amount of 15 parts by weight or less, based on 100 parts by weight of the monomer, to obtain the aqueous dispersion.
5 . The production method according to claim 4 , further comprising: adding an aqueous dispersion of the binder resin (C) to an aqueous dispersion of the organic fine particle (A), or polymerizing a monomer for the binder resin in the aqueous dispersion of the organic fine particle (A) to obtain the binder resin (C), or polymerizing a monomer for the organic fine particle (A) in the aqueous dispersion of the binder resin to obtain the aqueous dispersion in which the organic fine particle (A) and the binder resin (C) are dispersed.
6 . A method for treating a textile product comprising: applying a treatment liquid containing the water-repellent composition according to claim 1 to the textile product.
7 . A textile product comprising the organic fine particle (A) in the water-repellent composition according to claim 1 adhered a surface thereof.
8 . A textile product comprising the organic fine particle (A) in the water-repellent composition according to claim 1 adhered a surface thereof, wherein the textile product satisfies at least one of a static contact angle of water on a fabric of 120 degrees or more, or a falling speed of water on the fabric of 200 mm/sec or more.
9 . The water-repellent composition according to claim 1 , wherein the organic fine particle (A) is the organic fine particle (A2) comprising the polymer comprising a repeating unit formed from: (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms; or (2) a (meth)acrylic monomer having a polydimethylsiloxane group, wherein the polymer further comprises a repeating unit formed from: (4) a crosslinkable monomer having at least two ethylenically unsaturated double bonds.
10 . The water-repellent composition according to claim 1 , wherein each of the fluorine-free polymer and the polymer comprises a repeating unit formed from at least one monomer selected from the group consisting of a monomer having a t-butyl group and a high glass transition point monomer of which a homopolymer has a glass transition point of 50° C. or more (excluding styrene).
11 . The water-repellent composition according to claim 1 , satisfying at least any one of: (i) when the organic fine particle (A) is adhered to a glass substrate, a static contact angle of water on the glass substrate is 100 degrees or more; (ii) when the organic fine particle (A) is adhered to a fabric, a static contact angle of water on the fabric is 120 degrees or more; and (iii) when the organic fine particle (A) is adhered to a fabric, a falling speed of water on the fabric is 100 mm/s or more.
12 . The water-repellent composition according to claim 1 , wherein when a heat treatment is performed at 170° C. for 1 minute after the organic fine particle (A) is adhered to a substrate, an average diameter of the organic fine particle (A) after the heat treatment is 50% or more of an average diameter of the organic fine particle (A) before the heat treatment, or an average diameter of the organic fine particle (A) observable on the fabric is 50 to 700 nm.
13 . The water-repellent composition according to claim 1 , wherein each of the fluorine-free polymer and the polymer comprises a repeating unit formed from at least one monomer selected from the group consisting of: (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one t-butyl group and (5) a high glass transition point monomer of which a homopolymer has a glass transition point of 50° C. or more (excluding styrene); and further a repeating unit formed from: (4) the crosslinkable monomer.
14 . The water-repellent composition according to claim 13 , wherein each of the fluorine-free polymer and the polymer comprises a repeating unit formed from (3) the reactive or hydrophilic monomer, and wherein each of the fluorine-free polymer and the polymer optionally comprises a repeating unit formed from (2) the (meth)acrylic monomer having a polydimethylsiloxane group, wherein the homopolymer of the monomer (5) has a glass transition point of 100° C. or more.
15 . The water-repellent composition according to claim 1 , which is obtained by polymerizing a monomer containing the crosslinkable monomer (4) and then polymerizing a monomer free from the crosslinkable monomer (4), and in which a part of the particle is meltable.
16 . The water-repellent composition according to claim 1 , wherein a static contact angle of water on a silicon substrate treated with a homopolymer of the hydrophobic monomer (1) is 70 to 120 degrees.
17 . The water-repellent composition according to claim 13 , wherein the hydrophobic monomer (1) is a monomer represented by the formula: CH 2 ═C(—R 12 )—C(═O)—Y 11 (R 11 ) k or CH 2 ═C(—R 22 )—Y 21 (H) 5-l (R 21 ) l wherein R 11 and R 21 are each independently a hydrocarbon group having 3 to 40 carbon atoms; R 12 and R 22 are a hydrogen atom, a monovalent organic group, or a halogen atom; Y 11 is a divalent to tetravalent group composed of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom, —C 6 H 4 —, —O—, —C(═O)—, —S(═O) 2 —, or —NR′—, wherein R′ is H or a hydrocarbon group having 1 to 4 carbon atoms, provided that the case of only a divalent hydrocarbon group is excluded; Y 21 is a benzene ring; H is a hydrogen atom; H and R 21 are each directly bonded to Y 21 ; and k and l are each 1 to 3, the (meth)acrylic monomer (2) is a monomer represented by the formula: CH 2 ═C(—R 92 )—C(═O)—Y 91 —R 91 wherein R 91 is a group having a polydimethylsiloxane group; R 92 is a hydrogen atom, a monovalent organic group, or a halogen atom; and Y 91 is a divalent to tetravalent group composed of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom, —C 6 H 4 —, —O—, —C(═O)—, —S(═O) 2 —, or —NR′—, wherein R′ is H or a hydrocarbon group having 1 to 4 carbon atoms, the reactive or hydrophilic monomer (3) is a monomer represented by the formula: CH 2 ═C(—R 32 )—C(═O)—Y 31 —(R 33 ) o (R 31 ) m or CH 2 ═C(—R 42 )—Y 41 (H) 5-n (R 41 ) n wherein R 31 and R 41 are each independently a reactive group or a hydrophilic group; R 32 and R 42 are a hydrogen atom, a monovalent organic group, or a halogen atom; Y 31 is a direct bond, —O—, or —NR′—, wherein R′ is H or a hydrocarbon group having 1 to 4 carbon atoms; R 33 is a divalent to tetravalent hydrocarbon group having 1 to 10 carbon atoms; Y 41 is a benzene ring; H is a hydrogen atom; H and R 41 are each directly bonded to Y 41 ; m and n are each 1 to 3; and o is 0 or 1, the crosslinkable monomer (4) is a monomer represented by the formula: wherein R 51 and R 61 are each independently a direct bond or a divalent to tetravalent group composed of at least one selected from a hydrocarbon group having 1 to 20 carbon atoms, (CH 2 CH 2 O) r —, wherein r is an integer of 1 to 10, —C 6 H 4 —, —O—, or —NR′—, wherein R′ is H or a hydrocarbon group having 1 to 4 carbon atoms; R 52 and R 62 are each independently a hydrogen atom, a monovalent organic group, or a halogen atom; Y 51 is —O—, or —NR′—, wherein R′ is H or a hydrocarbon group having 1 to 4 carbon atoms; p is 2 to 4; and q is 1 to 5, and the high glass transition point monomer (5) is a monomer represented by the formula: wherein R 71 and R 81 are a group composed of at least one selected from a hydrocarbon group having 1 to 30 carbon atoms, —C 6 H 4 —, —O—, or —NR′—, wherein R′ is H or a hydrocarbon group having 1 to 4 carbon atoms; R 72 and R 82 are a hydrogen atom, a monovalent organic group, or a halogen atom; and Y 71 is —O—, or —NR′—, wherein R′ is H or a hydrocarbon group having 1 to 4 carbon atoms.
18 . The water-repellent composition according to claim 1 , wherein the organic fine particle (A) has a falling speed of 150 mm/second or more, when treated on a fabric.
19 . A method for producing the water-repellent composition according to claim 1 , the method comprising obtaining the organic fine particle (A) by polymerizing a monomer containing the crosslinkable monomer (4) and then polymerizing a monomer free from the crosslinkable monomer (4).
20 . The water-repellent composition according to claim 1 , wherein the fluorine-free polymer comprises a repeating unit formed from the crosslinkable monomer (4).

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a Rule 53(b) Continuation of International Application No. PCT/JP2020/037266 filed Sep. 30, 2020, which claims priority based on Japanese Patent Application No. 2019-180579 filed Sep. 30, 2019 and Japanese Patent Application No. 2020-118767 filed Jul. 9, 2020, the respective disclosures of which are incorporated herein by reference in their entireties. TECHNICAL FIELD The present disclosure relates to an organic fine particle and more particularly to a fluorine-free organic fine particle. BACKGROUND ART Conventionally, water-repellency is imparted to the surface of a substrate such as metal, glass, paper, fabric, and plastic by a chemical treatment in which coating is performed using a fluororesin, a silicone resin, or the like. For example, it is known that a water-repellent substrate surface having a water contact angle of about 1200 can be obtained by coating with a fluororesin. In addition, by a method of forming a fine uneven structure on a surface of a substrate or a method of combining the formation of such a fine uneven structure on a surface of a substrate and the coating treatment, ultra-water-repellency is imparted to the surface of the substrate such that the water contact angle becomes 150° or more. The fine uneven structure can be formed mainly by a method using fine particles or a patterning method such as etching. Patterning methods such as etching are limited in the range and substrates that can be used. When hydrophobic inorganic fine particles are used as the fine particles, a large amount of a dispersant such as an emulsifier is required to obtain an aqueous dispersion of the hydrophobic inorganic fine particles. When the degree of hydrophobicity of the hydrophobic inorganic fine particles is reduced, that is, hydrophobic inorganic fine particles having hydrophilic groups are used, the dispersion in water becomes a little easier, but the hydrophobicity of the fine particles themselves is reduced, and the performance as a water-repellent is reduced. On the other hand, there are soap-free polymerization and an organic fine particle synthesis method using a small amount of an emulsifier. Since these are dispersed in water without an emulsifier or with a small amount of emulsifier, a hydrophilic monomer is generally used, and most of the fine particles thereof also exhibit hydrophilicity. Since it is difficult to use a monomer having high hydrophobicity, it has been difficult to synthesize organic fine particles exhibiting water-repellency by using soap-free polymerization or an organic fine particle synthesis method using a small amount of emulsifier. Previous publications (particularly patent publications) have disclosed imparting water-repellency with organic fine particles, but examples have been limited to inorganic fine particles. Patent Literature 1 discloses a method for producing a water-repellent coating film comprising a first step of forming a friction-resistant base film using fine particles (A) having an average particle size of 15 to 500 μm, a resin composition (B) and a solvent (C), and a second step of forming an ultra-water-repellent finishing film using fine particles (a) having an average particle size of 5 to 500 nm and being hydrophobic, a resin composition (b), and a solvent (c). The fine particles (a) used for forming the ultra-water-repellent finishing film in the examples of Patent Literature 1 are silica and inorganic fine particles. Patent Literature 2 discloses a fluorine-free polymer containing a constituent unit derived from a (meth)acrylate monomer and a constituent unit derived from a silicone oil having a (meth)acryloyl group. Conventionally, there has been a problem of color deepening. In general, among textile products, synthetic fibers, particularly polyester fibers, are widely used in various applications, but they are inferior to natural fibers such as wool and silk in characteristics such as color density, depth, and clearness in dyed products, and therefore tend to be evaluated as having a low commercial value in the market. In order to solve these problems, various proposals have been made for improving characteristics such as color density, depth, and clearness of dyed products obtained from synthetic fibers such as polyester fibers. For example, there has been proposed a color deepening agent comprising an aqueous dispersion of a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a cationic surfactant, and comprising a polymer having a refractive index of 1.50 or less and a glass transition point of more than 110° C. and a polymer having a refractive index of 1.50 or less and a glass transition point of less than 20° C. (see, for example, Patent Literature 3), and such a color deepening agent is said to provide a good color deepening effect to a textile product. However, in a fiber requiring water-repellency, a color deepening agent tends to lower the