Granted Patent B2

US 12,617,884 · App. 17/707,001 · Granted May 5, 2026

Inventors: Yuko Shiotani (Osaka, JP); Shouta Shibutani (Osaka, JP); Rena Inamasu (Osaka, JP); Yoshito Tanaka (Osaka, JP); Ryou Akuta (Osaka, JP); Mayumi Iida (Osaka, JP); Marina Nakano (Osaka, JP); Masahiro Higashi (Osaka, JP); Tomohiro Yoshida (Osaka, JP)

Assignee: DAIKIN INDUSTRIES, LTD.

C08F212/12D06N3/045D06N2209/142

Abstract

Claims (94)

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).

21 . The water-repellent composition according to claim 1 , wherein each of the fluorine-free polymer and the polymer is a random polymer.

22 . The water-repellent composition according to claim 1 , wherein each of the fluorine-free polymer and the polymer comprises a repeating unit formed from a monomer having a t-butyl group.

23 . The water-repellent composition according to claim 1 , wherein each of the fluorine-free polymer and the polymer comprises a repeating unit formed from the hydrophobic monomer (1).

Assignments (2)

Priority Claims (2)

Continuity (2)

References Cited (25)