organic microparticles

Abstract

This organic fine particle can adhere, in the form of a particle, to a substrate, and exhibits water repellency on the substrate when adhering to the substrate. Provided 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. The organic fine particle can impart excellent water repellency to a substrate.

Description

[Technical Field]

[0001] The present disclosure relates to organic fine particles, and in particular to fluorine-free organic fine particles. [Background technology]

[0002] Conventionally, water repellency has been imparted to the surface of substrates such as metals, glass, paper, cloth, and plastics by chemical treatment of coating with fluororesin or silicone resin, etc. For example, it is known that coating with fluororesin can provide a water-repellent substrate surface with a water contact angle of approximately 120°.

[0003] In addition, by forming a fine uneven structure on the surface of a substrate, or by combining the formation of such a fine uneven structure on the surface of a substrate with the above-mentioned coating treatment, the substrate surface is imparted with superhydrophobicity, with a water contact angle of 150° or more. Methods for creating uneven structures include the use of fine particles and patterning methods such as etching. Patterning methods such as etching are limited in the range of materials and substrates that can be used.

[0004] 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. If the hydrophobicity of the hydrophobic inorganic fine particles is reduced, that is, if hydrophobic inorganic fine particles with hydrophilic groups are used, dispersion in water becomes somewhat easier, but the hydrophobicity of the fine particles themselves decreases, and therefore the performance as a water repellent decreases.

[0005] On the other hand, there are methods such as soap-free polymerization and organic particle synthesis using small amounts of emulsifiers. These generally use hydrophilic monomers to disperse in water without emulsifiers or with only small amounts of emulsifiers, and most of the resulting particles are also hydrophilic. Because it is difficult to use highly hydrophobic monomers, it has been difficult to synthesize organic particles that exhibit water-repellent properties using soap-free polymerization or organic particle synthesis methods using small amounts of emulsifiers.

[0006] Previous literature (particularly patent publications) has disclosed that organic fine particles can be used to impart water repellency, but the examples have been limited to inorganic fine particles.

[0007] Patent Document 1 discloses a method for producing a water-repellent coating film, which includes a first step of forming an abrasion-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 finish 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). In the examples of Patent Document 1, the fine particles (a) used to form the ultra-water-repellent finish film are silica, which are inorganic fine particles. Patent Document 2 discloses a non-fluorine-containing polymer containing a structural unit derived from a (meth)acrylic acid ester monomer and a structural unit derived from a silicone oil having a (meth)acryloyl group.

[0008] In the past, synthetic fibers, especially polyester fibers, have been used widely in a variety of applications among textile products, but compared to natural fibers such as wool and silk, they are inferior in color density, depth, and clarity when dyed, and therefore tend to be evaluated as having low commercial value in the market.

[0009] To address these problems, various proposals have been made to improve the color strength, depth, vividness, and other properties of dyed products obtained from synthetic fibers such as polyester fibers. For example, a darkening agent has been proposed, which is composed of an aqueous dispersion of a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a cationic surfactant, and which comprises a polymer having a refractive index of 1.50 or less and a glass transition temperature exceeding 110°C, and a polymer having a refractive index of 1.50 or less and a glass transition temperature below 20°C (see, for example, Patent Document 3). Such a darkening agent is said to provide a good darkening effect on textile products. However, in fibers that require water repellency, the darkening agent tends to reduce the water repellency. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-20248 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-199712 [Patent Document 3] Japanese Patent Application Publication No. 9-3774 Summary of the Invention [Problem to be solved by the invention]

[0011] The present disclosure provides organic fine particles that can impart excellent water repellency to a substrate. [Means for solving the problem]

[0012] The present disclosure relates to organic fine particles that exhibit water repellency on a substrate when attached to the substrate. The organic fine particles can be attached to the substrate in a particulate form. In the present disclosure, the water repellency exhibited is (i) When attached to a glass substrate, the contact angle of water is 100 degrees or more; (ii) When applied to a fabric, the contact angle of water is 120 degrees or more; or (iii) When attached to a cloth, the falling speed is 100 mm / s or more. means at least one of the above.

[0013] The polymer constituting the organic fine particles is (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms, and / or (2) (Meth)acrylic monomer having a polydimethylsiloxane group It is preferred that the repeating unit be formed from:

[0014] The present disclosure provides: (A) organic particulates, and (B) Aqueous medium The present invention relates to a water repellent composition comprising: In addition, the present disclosure provides: (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms, and / or (2) (Meth)acrylic monomer having a polydimethylsiloxane group The present invention relates to organic fine particles comprising a polymer having repeating units formed from Furthermore, the present disclosure provides (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms; (3) a reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group; and (4) a crosslinking monomer having at least two ethylenically unsaturated double bonds; The present invention relates to organic fine particles comprising a polymer having repeating units formed from

[0015] Preferred aspects of the present disclosure are as follows. Aspect 1: Organic fine particles that can be attached to a substrate in a particulate state, and that exhibit water repellency on the substrate when attached to the substrate. Aspect 2: The organic microparticles according to embodiment 1 satisfy at least one of the following: (i) when the organic microparticles are attached to a glass substrate, the static contact angle of water on the glass substrate is 100 degrees or more; (ii) when the organic microparticles are attached to a cloth, the static contact angle of water on the cloth is 120 degrees or more; or (iii) when the organic microparticles are attached to a cloth, the rolling speed of water on the cloth is 100 mm / s or more. Aspect 3: The organic microparticles according to aspect 1 or 2, wherein when the organic microparticles are attached to a substrate and then heat-treated at 170°C for 1 minute, the average diameter of the organic microparticles after the heat treatment is at least 50% of the average diameter of the organic microparticles before the heat treatment, or the average particle size of the microparticles observable on the cloth is 50 to 700 nm. Aspect 4: (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms, or (2) (Meth)acrylic monomer having a polydimethylsiloxane group 1. Organic fine particles comprising a polymer having a repeating unit formed from: Aspect 5: The polymer is (4) a crosslinking monomer having at least two ethylenically unsaturated double bonds; The organic fine particles according to embodiment 4, further comprising a repeating unit formed from Aspect 6: The polymer further comprises: (3) a reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group; and (5) A high glass transition point monomer whose homopolymer has a glass transition point of 100°C or higher. 6. The organic fine particles according to embodiment 4 or 5, having a repeating unit formed from at least one monomer selected from the group consisting of: Aspect 7: The organic fine particles according to any one of aspects 4 to 6, wherein a combination of a (meth)acrylic monomer having a hydrocarbon group having 12 to 24 carbon atoms in a side chain among the hydrophobic monomers (1) and the (meth)acrylic monomer (2) is used in an amount in which the total weight of both monomers is less than 80% by weight of the total amount of the monomer components. Aspect 8: The organic fine particles according to any one of aspects 4 to 7, which are obtained by polymerizing a monomer containing the monomer (4) and then polymerizing a monomer not containing the monomer (4), and which are partly meltable. Aspect 9: 9. The organic fine particles according to any one of aspects 4 to 8, wherein the static contact angle of water on a silicon substrate treated with a homopolymer of the hydrophobic monomer (1) is 70 to 120 degrees. Aspect 10: The hydrophobic monomer (1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 (R 11 ) k or CH2=C(-R 22 )-Y 21 (H)5-l (R 21 ) l [In the formula, R 11 and R 21 are each independently a hydrocarbon group having 3 to 40 carbon atoms, R 12 and R 22 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 is a divalent to tetravalent group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom, -CH-, -O-, -C(=O)-, -S(=O)-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms) (excluding the case where it consists only of a divalent hydrocarbon group), Y 21 is a benzene ring, H is a hydrogen atom, H and R 21 is Y 21 are directly bonded to k and l are 1 to 3. is a monomer represented by The (meth)acrylic monomer (2) is a compound represented by the formula: CH2=C(-R 92 )-C(=O)-Y 91 -R 91 [In the formula, R 91 is a group having a polydimethylsiloxane group, R 92 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 91 is a divalent to tetravalent group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, and -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms). is a monomer represented by The reactive / hydrophilic monomer (3) has the formula: CH2=C(-R 32 )-C(=O)-Y 31 -(R 33 ) o (R31 ) m or CH2=C(-R 42 )-Y 41 -(H) 5-n (R 41 ) n [In the formula, R 31 and R 41 are each independently a reactive group or a hydrophilic group, R 32 and R 42 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 31 is a direct bond, -O-, or -NR'- (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 is Y 41 are directly bonded to m and n are 1 to 3; o is 0 or 1.] is a monomer represented by The crosslinking monomer (4) has the formula: TIFF0007759808000001.tif3825 TIFF0007759808000002.tif3331 or TIFF0007759808000003.tif3842[where, R 51 and R 61 are each independently a divalent to tetravalent group consisting of at least one selected from a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -(CHCHO)r- (r is an integer of 1 to 10), -CH-, -O-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R 52 and R 62are each independently a hydrogen atom, a monovalent organic group, or a halogen atom, Y 51 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), p is 2 to 4; q is 1 to 5. is a monomer represented by The high glass transition temperature monomer (5) has the formula: TIFF0007759808000004.tif3322 or TIFF0007759808000005.tif3433 [In the formula, R 71 and R 81 is a group consisting of at least one selected from a hydrocarbon group having 1 to 30 carbon atoms, —C6H4—, —O—, or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), R 72 and R 82 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 71 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms). 10. The organic fine particles according to any one of aspects 4 to 9, wherein the organic fine particles are a monomer represented by the formula: Aspect 11: The organic fine particles according to any one of aspects 4 to 10, wherein in the reactive monomer (3), the reactive group is an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group, or a blocked isocyanate group, and the hydrophilic group is at least one group selected from the group consisting of a hydroxyl group, an amino group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an alkali metal or alkaline earth metal salt of a carboxylic acid, a sulfonic acid, or a phosphoric acid, or an ammonium salt having a counter anion of a chlorine, bromine, or iodine ion. Aspect 12: The hydrophobic monomer (1) is t-butyl (meth)acrylate, Nt-butyl (meth)acrylamide, t-butylstyrene, stearyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, stearamidoethyl (meth)acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 and at least one monomer selected from the group consisting of: The (meth)acrylic monomer (2) is a compound represented by the formula: TIFF0007759808000006.tif5732 TIFF0007759808000007.tif5731 TIFF0007759808000008.tif6136 TIFF0007759808000009.tif6136 or TIFF0007759808000010.tif5132 [In the formula, n is a number from 1 to 500.] and at least one monomer selected from the group consisting of: The reactive / hydrophilic monomer (3) is glycidyl (meth)acrylate, glycerol (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, dimethylaminoethyl methacrylate At least one monomer selected from the group consisting of quaternized compounds, tetrahydrofurfuryl (meth)acrylate, The crosslinkable monomer (4) is selected from the group consisting of divinylbenzene, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, methylene glycol di(meth)acrylate, polytetramethyl at least one monomer selected from the group consisting of ethylene glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, trimethylol propane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and 5-hydroxy-1,3-adamantane di(meth)acrylate; The organic fine particles according to any one of aspects 4 to 11, wherein the high glass transition point monomer (5) is at least one monomer selected from the group consisting of isobornyl (meth)acrylate, bornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, phenyl (meth)acrylate, naphthyl acrylate, and benzyl acrylate. Aspect 13: 13. The organic fine particles according to any one of aspects 3 to 12, wherein the molar ratio of the hydrophobic monomer (1) or (meth)acrylic monomer (2) / the reactive hydrophilic monomer (3) / the high glass transition point monomer (5) is 20 to 100 / 0 to 50 / 0 to 70, the crosslinkable monomer (4) is 0.1 to 30 molar parts per 100 molar parts of the total of the hydrophobic monomer (1) and the reactive hydrophilic monomer (3), and the (meth)acrylic monomer (2) is 0 to 30 molar parts per 100 molar parts of the total of the hydrophobic monomer (1), the (meth)acrylic monomer (2), and the reactive hydrophilic monomer (3). Aspect 14: 14. The organic fine particles according to any one of aspects 1 to 13, which have a falling speed of 150 mm / sec or more when applied to a cloth. Aspect 15: 15. The organic fine particles according to any one of aspects 1 to 14, having an average particle size of 30 nm to 1000 nm. Aspect 16: The method for producing organic fine particles according to any one of aspects 3 to 14, wherein the organic fine particles are obtained by polymerizing a monomer containing the monomer (4) and then polymerizing a monomer not containing the monomer (4). Aspect 17: (A) the organic fine particles according to any one of aspects 1 to 15, and (B) Aqueous medium A water repellent composition which is an aqueous dispersion of organic fine particles comprising: Aspect 18: The water repellent composition according to embodiment 17, further comprising one or more of (C) a binder resin, (D) a surfactant, and (E) a crosslinking agent. Aspect 19: A water repellent composition according to embodiment 18, wherein the binder resin (C) is at least one polymer selected from the group consisting of a non-fluorinated polymer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain and a fluorinated polymer having a fluoroalkyl group having 1 to 20 carbon atoms in the side chain. Aspect 20: Aspect 20. The water repellent composition according to aspect 18 or 19, wherein the amount of the surfactant (D) is 15 parts by weight or less per 100 parts by weight of the organic fine particles (A). Aspect 21: A water repellent composition according to any one of Aspects 18 to 20, wherein the binder resin (C) is an acrylic polymer, a urethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, a polystyrene, a silicone polymer, or a combination thereof. Aspect 22: A water repellent composition according to any one of aspects 17 to 21, which is capable of preventing frost formation. Aspect 23: a step of polymerizing the monomer in an aqueous medium in the presence of a surfactant in an amount of 15 parts by weight or less relative to 100 parts by weight of the monomer to obtain an aqueous dispersion of organic fine particles (A); A method for producing a water repellent composition according to any one of aspects 17 to 22, comprising: Aspect 24: moreover, A process for obtaining an aqueous dispersion in which organic fine particles (A) and binder resin (C) are dispersed by adding an aqueous dispersion of binder resin (C) to an aqueous dispersion of organic fine particles (A), or by polymerizing a monomer for binder resin in the aqueous dispersion of organic fine particles (A) to obtain binder resin (C), or by polymerizing a monomer for organic fine particles in the aqueous dispersion of binder resin. 24. The method of claim 23, comprising: Aspect 25: A method for treating textile products, comprising applying a treatment liquid containing the water repellent composition according to any one of aspects 17 to 22 to the textile products. Aspect 26: A textile product having organic fine particles and / or a binder resin in the water repellent composition according to any one of aspects 17 to 22 adhered to its surface. Aspect 27: the organic fine particles and / or the binder resin in the water repellent composition according to any one of Aspects 17 to 22 are attached to a surface; A textile product that satisfies at least one of the following: the static contact angle of water on the fabric is 120 degrees or more, or the rolling speed of water on the fabric is 200 mm / sec or more. [Effects of the Invention]

[0016] The organic fine particles and water repellent composition of the present disclosure can impart excellent water repellency (particularly, high water repellency) to substrates such as textiles. Textiles treated with the water repellent composition of the present disclosure exhibit excellent water droplet rolling off properties. Furthermore, since the rolling off speed is particularly high, the composition is suitable for applications requiring high water repellency. Compared to inorganic particles, organic particles have a more flexible main chain, which allows the particles themselves to become mobile when heated. Therefore, in water, the hydrophilic groups are localized on the outermost surface, allowing for stable dispersion. After application to a substrate and drying, the hydrophobic portions, which have low surface free energy, can be localized on the outermost surface. Even with hydrophilic particles, the hydrophobic portions segregate on the surface after application, resulting in highly water-repellent particles. While color-enhancing agents tend to reduce water repellency, the organic fine particles of the present disclosure can exert a color-enhancing effect without impairing water repellency. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a scanning electron microscope (SEM) photograph of a PET cloth (Example 1) to which organic fine particles of Synthesis Example 1 are attached. [Figure 2] 1 is a scanning electron microscope (SEM) photograph of a PET fabric (Example 157) to which organic fine particles of Synthesis Example 93, Binder B8, and Crosslinking Agent 1 are attached. DETAILED DESCRIPTION OF THE INVENTION

[0018] The water repellent composition comprises (A) organic particulates, and (B) Aqueous medium The compound comprises: The water repellent composition further comprises: (C) a binder resin, and / or (D) Surfactant By including the binder resin (C), higher water repellency can be obtained.

[0019] In a preferred embodiment, the water repellent composition contains the following components: Organic fine particles (A), Organic fine particles (A) + aqueous medium (B), Organic fine particles (A) + aqueous medium (B) + binder resin (C), Organic fine particles (A) + aqueous medium (B) + surfactant (D), Organic fine particles (A) + aqueous medium (B) + binder resin (C) + surfactant (D) Organic fine particles (A) + aqueous medium (B) + binder resin (C) + crosslinking agent (E), or Organic fine particles (A) + aqueous medium (B) + binder resin (C) + surfactant (D) + crosslinking agent (E)

[0020] (A) Organic fine particles The organic fine particles act as an active ingredient for exerting water repellency, and are preferably formed from a non-fluorinated polymer. The average particle size of the organic fine particles may be 30 to 1000 nm, preferably 50 to 700 nm or 200 to 600 nm, from the viewpoint of water repellency and stability of the aqueous dispersion. The average particle size means the average particle size of the particles measured by dynamic light scattering (DLS).

[0021] The organic fine particles remain in particle form on the substrate and exhibit water repellency. The water repellency that is exhibited is (i) When attached to a glass substrate, the contact angle of water is 100 degrees or more; (ii) When applied to a fabric, the contact angle of water is 120 degrees or more; or (iii) When attached to a cloth, the falling speed is 100 mm / s or more. means.

[0022] The contact angle of water on a glass substrate having a composition containing organic fine particles attached thereto (i.e., the contact angle of water on a glass substrate having organic fine particles attached thereto, or the contact angle of water on a glass substrate having organic fine particles and a binder (and other components) attached thereto) may be 100 degrees or more, for example, 110 degrees or more, particularly 118 degrees or more and 180 degrees or less. Specifically, the contact angle of water on a glass substrate having a composition containing organic fine particles attached thereto is determined by drop-casting the composition containing organic fine particles onto a glass substrate (a glass slide made of soda-lime glass) and heating it at 150°C for 3 minutes to prepare a substrate having organic fine particles attached thereto, dropping 2 μL of water onto the glass substrate having the organic fine particles attached thereto, and measuring the static contact angle 1 second after the drop has landed using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.).

[0023] The contact angle of water on a cloth to which a composition containing organic fine particles is applied (the contact angle of water on a cloth to which organic fine particles are applied or the contact angle of water on a cloth to which organic fine particles and a binder (and other components) are applied) is preferably 120 degrees or more, more preferably 130 degrees or more, and even more preferably 140 degrees or more. Specifically, the contact angle of water on a cloth is measured by applying a composition containing organic fine particles to a PET cloth (basis weight: 88 g / m 2 After immersing the PET cloth (70 denier, gray), it is passed through a mangle and then a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. 2 μL of water is dropped onto the PET cloth, and the static contact angle is measured 1 second after the drop has landed using a fully automatic contact angle meter (DropMaster 701, manufactured by Kyowa Interface Science).

[0024] In the case of a cloth (PET cloth), the water sliding speed is preferably 100 mm / s or more, for example, 130 mm / s or more, and further preferably 150 mm / s or more or 200 mm / s or more. The sliding speed is the average sliding speed over a distance of about 40 mm when 20 μL of water is dropped from a microsyringe onto a substrate tilted at 30 degrees. Specifically, a composition containing organic fine particles is applied to a PET cloth (basis weight: 88 g / m 2After soaking the PET cloth (70 denier, gray), it was passed through a mangle and then passed through a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. Using a fully automatic contact angle meter (DropMaster701 manufactured by Kyowa Interface Science), 20 μL of water was dropped from a microsyringe onto the PET cloth tilted at 30 degrees, and the way the dropped water fell was measured using a high-speed camera (VW-9000 manufactured by Keyence Corporation). The average falling speed over a distance of approximately 40 mm was recorded as the falling speed.

[0025] The unevenness of the microparticles on the substrate can be observed using a laser microscope or a scanning electron microscope. After applying the particles to the substrate and heating at 170°C for 1 minute, the average diameter (average particle size) of the particles after heating is preferably 50% or more, more preferably 60% or more, of the average diameter before heating. Alternatively, the average particle size of the microparticles observable on the fabric is preferably 30 to 1000 nm, more preferably 50 to 700 nm or 40 to 500 nm. This average particle size is generally preferably the average particle size after applying the particles to the substrate and heating at 170°C for 1 minute.

[0026] In some embodiments, the organic particulate comprises: (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms, and / or (2) (Meth)acrylic monomer having a polydimethylsiloxane group The polymer comprises a repeating unit formed from:

[0027] In some embodiments, the organic particulate comprises: (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms; (3) a reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group; and (4) a crosslinking monomer having at least two ethylenically unsaturated double bonds; The polymer comprises a repeating unit formed from: The polymer constituting the organic fine particles is preferably a non-fluorinated polymer.

[0028] (1) Hydrophobic monomer The hydrophobic monomer (1) has at least one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms. The static water contact angle of the homopolymer of hydrophobic monomer (1) is preferably 70 to 120 degrees, for example, 75 to 115 degrees. For example, when the glass transition temperature of the homopolymer of hydrophobic monomer (1) is 80°C or higher, the static water contact angle of the homopolymer is preferably 90 degrees or higher, more preferably 97 degrees or higher. Furthermore, when the hydrophobic monomer (1) has a branched hydrocarbon group (for example, a branched alkyl group), particularly a t-butyl group or an isopropyl group, or a group with a multi-branched structure as shown in the following formula, the static water contact angle of the homopolymer is preferably 75 to 115 degrees. TIFF0007759808000011.tif3561

[0029] The static contact angle of a homopolymer is the static contact angle measured with a 2 μL water droplet after applying a solution of the homopolymer dissolved in a good solvent (especially chloroform) to a silicon substrate and heating it at 80°C. Specifically, a chloroform solution of the homopolymer (solids concentration 1.0%) is spin-coated onto a silicon wafer substrate (high-purity silicon wafer for research, AS ONE 2-960-55) and heated at 80°C for 15 minutes to form a coating. 2 μL of water is then dropped onto this coating, and the static contact angle is measured 1 second after the drop has landed using a fully automatic contact angle meter (DropMaster 701, manufactured by Kyowa Interface Science).

[0030] The hydrophobic monomer (1) is preferably an acrylate compound, an acrylamide compound, or a styrene compound containing a hydrocarbon group having 3 to 40 carbon atoms. That is, the hydrophobic monomer (1) is preferably an acrylate compound containing a hydrocarbon group having 3 to 40 carbon atoms, an acrylamide compound containing a hydrocarbon group having 3 to 40 carbon atoms, or a styrene compound containing a hydrocarbon group having 3 to 40 carbon atoms (excluding a benzene ring). The hydrophobic monomer (1) is preferably a non-fluorine-containing monomer.

[0031] The hydrophobic monomer (1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 (R 11 ) k or CH2=C(-R 22 )-Y 21 (H) 5-l (R 21 ) l [In the formula, R 11 and R 21 are each independently a hydrocarbon group having 3 to 40 carbon atoms, R 12 and R 22 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 is a divalent to tetravalent group (excluding the case where it consists only of divalent hydrocarbon groups) consisting of at least one or more selected from divalent to tetravalent hydrocarbon groups having 1 carbon atom (particularly, -CH-, -CH=, and -C≡), -CH-, -O-, -C(=O)-, -S(=O)-, and -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), Y 21 is a benzene ring, H is a hydrogen atom, H and R 21 is Y 21 are directly bonded to k and l are 1 to 3. It is preferable that the monomer is a monomer represented by the following formula:

[0032] R 11 and R 21 is preferably a branched or long-chain (or long-chain linear) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and especially an alkyl group. The -CH3 group has a lower surface free energy than -CH2- and is more likely to exhibit water repellency. For this reason, a structure with many branches and many -CH3 groups is preferred. In a branched hydrocarbon group, the number of -CH3 groups is preferably 2 to 15, for example, 3 to 10 or 4 to 9. On the other hand, a long-chain alkyl group of a certain length (preferably 16 to 40 carbon atoms) exhibits high water repellency due to its crystallinity. Therefore, branched hydrocarbon groups (for example, branched alkyl groups), particularly t-butyl groups and isopropyl groups, or multi-branched hydrocarbon groups having 5 to 30 carbon atoms, for example, multi-branched groups represented by the following formula, or long-chain hydrocarbon groups (or long-chain linear hydrocarbon groups), for example, alkyl groups having 16 to 40 or 16 to 26 carbon atoms, particularly 18 to 22 carbon atoms, are preferred. The long-chain hydrocarbon group is preferably a stearyl group, an icosyl group, or a behenyl group. TIFF0007759808000012.tif3561

[0033] k is 1, 2 or 3. However, Y 11 In the case where Y has a tetravalent hydrocarbon group having one carbon atom (specifically, a -C≡ having a branched structure), k=3. 11 In the case where Y has a trivalent hydrocarbon group having one carbon atom (for example, a -CH= group having a branched structure), k=2. 11 does not have a trivalent or tetravalent hydrocarbon group having one carbon atom (for example, Y 11 has (for example, 1 to 6) divalent hydrocarbon groups (-CH2-) having one carbon atom, then k=1.

[0034] R 12 and R 22 R may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Alternatively, R may be a -CF group. 12and R 22 Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a -CF3 group, and a cyano group. 12 and R 22 is preferably a hydrogen atom, a methyl group, or a chlorine atom. 12 More preferably, R is a methyl group. 12 The methyl group in R provides higher water repellency. 22 is preferably a hydrogen atom, particularly from the viewpoint of reactivity.

[0035] Y 11 is preferably a divalent group or a trivalent group, particularly preferably a divalent group. Examples of divalent to tetravalent hydrocarbon groups having one carbon atom include -CH2-, -CH= having a branched structure, and -C≡ having a branched structure. Y 11 When Y is a divalent group, it may or may not have a -CH2-. 11 When is a trivalent group, it preferably has a branched structure -CH=, -CH2-(-H(C-)-)-CH2-, That is, It is particularly preferred to have TIFF0007759808000013.tif2040.

[0036] Y 11 -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-X'-, -Y'-X'-Y'-, -Y'-X'-Y'-C(=O)-, -Y'-X'-C(=O)-Y'-, -Y'-X'-Y'-C(=O)-Y'-, or -Y'-X'-Y'-X'- [In the formula, each Y' independently represents a direct bond, -O-, -NR'- (R' represents H or a hydrocarbon group having 1 to 4 carbon atoms), or -S(=O)2-, X' is -(CH2) m-(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure having 1 to 5 or 3 to 5 carbon atoms, or -(CH2) l -C6H4-(CH2) l - (each l is independently an integer of 0 to 5, and -C6H4- is a phenylene group). It may be. The hydrocarbon group having a branched structure and having 3 to 5 carbon atoms may be divalent, trivalent, or tetravalent. Specific examples of the hydrocarbon group having a branched structure and having 3 to 5 carbon atoms include: -CH(CH3)-CH2- (divalent), TIFF0007759808000014.tif1539(2-valent), -CH2-(-H(C-)-)-CH2- (trivalent), That is, TIFF0007759808000015.tif2040 is.

[0037] Divalent group Y 11 Specific examples are -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m-NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2-, -NH-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4- or -NH-(CH2) m -NH-C6H4- (wherein m is an integer of 1 to 5, particularly 2 or 4).

[0038] Divalent group Y 11 -O-, -NH-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is preferable that:

[0039] Divalent group Y 11 is -O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, or -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, especially -O-(CH2) m -NH-C(=O)- [In the formula, m is an integer of 1 to 5, particularly 2 or 4.] It is more preferable that:

[0040] The trivalent group Y 11 teeth, TIFF0007759808000016.tif1553 It is preferable that:

[0041] Y 21 is a benzene ring. Y 21 The monomer having Y has a styryl group. 21 In the monomer having 21 A group and 2 to 4 hydrogen atoms are attached to the benzene ring.

[0042] Specific examples of hydrophobic monomers are as follows: The compound of the following chemical formula is an acrylic compound having a hydrogen atom at the α-position, but specific examples may be a methacrylic compound having a methyl group at the α-position and an α-chloroacrylic compound having a chlorine atom at the α-position, with a methacrylic compound having a methyl group at the α-position being preferred. Also, among styrene derivatives, the compound of the following chemical formula is an acrylic compound having a hydrogen atom at the α-position, but specific examples may be an α-methylstyrene compound having a methyl group at the α-position and an α-chlorostyrene compound having a chlorine atom at the α-position, with a styrene compound having a hydrogen atom at the α-position being preferred. TIFF0007759808000017.tif2351

[0043] TIFF0007759808000018.tif2152 TIFF0007759808000019.tif2253 TIFF0007759808000020.tif2153

[0044] TIFF0007759808000021.tif2357 TIFF0007759808000022.tif2357 TIFF0007759808000023.tif2361

[0045] TIFF0007759808000024.tif2563 TIFF0007759808000025.tif2363 TIFF0007759808000026.tif2966

[0046] TIFF0007759808000027.tif3069 TIFF0007759808000028.tif2354 TIFF0007759808000029.tif2045 [In the above formula, n is a number from 3 to 40, and m is a number from 1 to 5.]

[0047] TIFF0007759808000030.tif2019 TIFF0007759808000031.tif3023

[0048] TIFF0007759808000032.tif3548 TIFF0007759808000033.tif3038 TIFF0007759808000034.tif20116 TIFF0007759808000035.tif2525

[0049] TIFF0007759808000036.tif3027 TIFF0007759808000037.tif2028

[0050] TIFF0007759808000038.tif2529 TIFF0007759808000039.tif3038 TIFF0007759808000040.tif4127 TIFF0007759808000041.tif4132 TIFF0007759808000042.tif4133 [Wherein, tBu is t-butyl.]

[0051] Preferred specific examples of the hydrophobic monomer (1) include t-butyl (meth)acrylate, Nt-butyl (meth)acrylamide, t-butylstyrene, stearyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, stearamidoethyl (meth)acrylate, CH═CHC(═O)OC═H═NHSO═C 18 H 37、 4-t-butylphenyl (meth)acrylate, 2,3,4-methylphenyl (meth)acrylate.

[0052] (2) (Meth)acrylic monomer having a polydimethylsiloxane group The (meth)acrylic monomer (2) has a polydimethylsiloxane group on the side chain. The (meth)acrylic monomer (2) is a compound represented by the formula: CH2=C(-R 92 )-C(=O)-Y 91 -R 91 [In the formula, R 91 is a group having a polydimethylsiloxane group, R 92 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 91 is a divalent to tetravalent group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, and -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms). It is preferable that the monomer is a monomer represented by the following formula:

[0053] R 91 is a group having a polydimethylsiloxane group and has the average formula: -(SiR2O) a SiR3 [In the formula, a represents 2 to 4,000, for example, 3 to 400, Each R is independently a monovalent alkyl group having 1 to 12 carbon atoms, and at least two R are methyl groups. It is preferable that the group is a group represented by the following formula: R 92 is preferably a hydrogen atom, a methyl group or a chlorine atom. Y 91 represents a hydrocarbon group having 1 to 8 carbon atoms (for example, an alkylene group having 1 to 8 or 2 to 4 carbon atoms, particularly -C3H6-), -O-(CH2) p -, -O-(CH2) p -NHC(=O)-(CH2) q - or -NH-(CH2) q - (p is a number from 1 to 5, and q is a number from 1 to 5).

[0054] Specific examples of the (meth)acrylic monomer (2) include: TIFF0007759808000043.tif5732 TIFF0007759808000044.tif5731 TIFF0007759808000045.tif6136 TIFF0007759808000046.tif6136 TIFF0007759808000047.tif5132 [In the formula, n is a number from 1 to 500.] is.

[0055] When the (meth)acrylic monomer (2) is used together with a (meth)acrylic monomer (or any of the hydrophobic monomers (1)) having a hydrocarbon group containing 3 to 40 or 3 to 30 carbon atoms (particularly 12 to 24 carbon atoms), the combined weight of the (meth)acrylic monomer (2) and the hydrophobic monomer (1) is preferably less than 80% by weight, particularly less than 50% by weight or less than 40% by weight of the total weight of the monomer components. That is, the combined weight of the repeating unit formed from the (meth)acrylic monomer (1) having a hydrocarbon group containing 3 to 40 or 12 to 24 carbon atoms and the repeating unit formed from the (meth)acrylic monomer (2) is preferably less than 80% by weight, particularly less than 50% by weight or less than 40% by weight of the total weight of the monomer components. In some embodiments, the constituent monomers do not consist solely of a combination of hydrophobic monomer (1) and (meth)acrylic monomer (2), which are (meth)acrylic monomers having a hydrocarbon group with 3 to 40 or 3 to 30 (particularly 12 to 24) carbon atoms. In some embodiments, the combination of hydrophobic monomer (1) and (meth)acrylic monomer (2), which are (meth)acrylic monomers having a hydrocarbon group with 3 to 40 or 3 to 30 (particularly 12 to 24) carbon atoms, may not be used.

[0056] (3) Reactive / hydrophilic monomers The reactive / hydrophilic monomer (3) has one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group. Examples of reactive groups are epoxy groups (for example, glycidyl groups), chloromethyl groups, bromomethyl groups, iodomethyl groups, and blocked isocyanate groups. Examples of hydrophilic groups are hydroxyl groups, amino groups, carboxylic acid groups, sulfonic acid groups, phosphate groups, alkali metal or alkaline earth metal salt groups of carboxylic, sulfonic or phosphate groups, and ammonium salt groups with chloride, bromide or iodide ions as counter anions. The reactive / hydrophilic monomer (3) is preferably a non-fluorine-containing monomer.

[0057] The reactive / hydrophilic monomer (3) has the formula: CH2=C(-R 32 )-C(=O)-Y 31 -(R 33 ) o (R 31 ) m or CH2=C(-R 42 )-Y 41 -(H) 5-n (R 41 ) n [In the formula, R 31 and R 41 are each independently a reactive group or a hydrophilic group, R 32 and R 42 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 31 is a direct bond, -O-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R 33 is a direct bond or a group having 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 is Y 41 are directly bonded to m and n are 1 to 3; o is 0 or 1.] It is preferable that the monomer is a monomer represented by the following formula:

[0058] R 31 and R 41 is a monovalent group. 31 and R 41 In the above, examples of the reactive group or hydrophilic group are as described above.

[0059] R 32 and R 42R may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Alternatively, R may be a -CF group. 32 and R 42 Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a -CF3 group, and a cyano group. 32 and R 42 is preferably a hydrogen atom, a methyl group, or a chlorine atom. 32 More preferably, R is a methyl group. 32 The methyl group in R provides higher water repellency. 42 is preferably a hydrogen atom, particularly from the viewpoint of reactivity. Y 31 is preferably —O— or —NH—.

[0060] R 33 is preferably a divalent to tetravalent hydrocarbon group having 1 to 10 carbon atoms. Examples of divalent to tetravalent hydrocarbon groups having 1 carbon atom include -CH2-, -CH= having a branched structure, and -C≡ having a branched structure. 33 is a divalent alkylene group, for example, -(CH2) r - (where r is a number from 1 to 5), or a divalent, trivalent or tetravalent alkyl group, such as -(CH2) r -(CH-) s -H (r is a number from 1 to 5, and s is 1, 2, or 3. The positions of the CH2 groups and CH- groups do not have to be in the order shown).

[0061] Y 41 is a benzene ring. Y 41 The monomer having Y has a styryl group. 41 In the monomer having 41 A group and 2 to 4 hydrogen atoms are attached to the benzene ring.

[0062] Specific examples of the reactive / hydrophilic monomer (3) include glycidyl (meth)acrylate, glycerol (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, and dimethylaminoethyl methacrylate. Quaternized, tetrahydrofurfuryl (meth)acrylate; and These are 4-hydroxymethylstyrene, 4-hydroxyethylstyrene, 4-aminomethylstyrene, 4-aminoethylstyrene, 2-(4-vinylphenyl)oxirane, and 2-(4-vinylbenzoyl)oxirane.

[0063] (4) Crosslinkable monomer The crosslinkable monomer (4) is a compound having at least two (particularly, two, three, or four) ethylenically unsaturated double bonds. The crosslinkable monomer (4) is preferably a non-fluorine-containing monomer.

[0064] The crosslinking monomer (4) has the formula: TIFF0007759808000048.tif3623 TIFF0007759808000049.tif3028 or TIFF0007759808000050.tif3539[where, R 51 and R 61 are each independently a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -(CH2CH2O) ra divalent to tetravalent group consisting of at least one selected from - (r is an integer of 1 to 10), -CH-, -O-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R 52 and R 62 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 51 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), p is 2 to 4; q is 1 to 5. It is preferable that the monomer is a monomer represented by the following formula:

[0065] R 51 and R 61 Examples of R are a direct bond, a divalent to tetravalent (e.g., divalent to trivalent) hydrocarbon group having 1 to 20 (or 2 to 10) carbon atoms which may be interrupted by an oxygen atom and / or in which a hydrogen atom may be substituted with an OH group, an ethylene glycol group, a propylene glycol group, a glycerol group, a cyclohexyl group, a dicyclopentanyl group, an adamantyl group, an isobornyl group, a naphthalene group, a bornyl group, a tricyclodecanyl group, and a phenyl group, or a group containing any of these groups. 51 and R 61 may be a polymer group, and the structural unit constituting the polymer group may be any of the groups exemplified above (for example, an ethylene glycol group).

[0066] R 52 and R 62 R may each independently represent a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Alternatively, R may represent a -CF group. 52 and R 62 Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a -CF3 group, and a cyano group. 52 and R 62 is preferably a hydrogen atom, a methyl group, or a chlorine atom. 52 More preferably, R is a methyl group.52 The methyl group in R provides higher water repellency. 62 is preferably a hydrogen atom from the viewpoint of reactivity, but is preferably a methyl group from the viewpoint of water repellency. 62 It is preferable to select The crosslinkable monomer (4) is preferably a di(meth)acrylate or divinylbenzene.

[0067] Specific examples of the crosslinkable monomer (4) include divinylbenzene, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, and methylene glycol di(meth). ) acrylate, polytetramethylene glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, 5-hydroxy-1,3-adamantane di(meth)acrylate.

[0068] (5) High glass transition point monomer The polymer may have repeat units formed from high glass transition temperature monomers. The glass transition temperature of the homopolymer of the high glass transition temperature monomer (5) is 50° C. or higher, preferably 100° C. or higher. The glass transition temperature of the homopolymer may be, for example, 120° C. or higher, particularly 150° C. or higher, and may be 250° C. or lower. The glass transition temperature (Tg) of the homopolymer was calculated by differential scanning calorimetry (DSC). A DSC curve was obtained by heating 10 mg of a sample at a rate of 10 °C / min, and the Tg was calculated as the midpoint between the intersection of the extensions of the baselines before and after the second-order transition of the DSC curve and the tangent to the inflection point of the DSC curve. The high glass transition point monomer (5) is preferably a non-fluorine-containing monomer.

[0069] The high glass transition temperature monomer (5) has the formula: TIFF0007759808000051.tif3020 or TIFF0007759808000052.tif3030[where, R 71 and R 81 is a group consisting of at least one selected from a hydrocarbon group having 1 to 30 carbon atoms, —C6H4—, —O—, or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), R 72 and R 82 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 71 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms). It is a monomer represented by

[0070] R 71 and R 81 Examples of the aryl group include a cyclohexyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, an isobornyl group, a naphthalene group, a bornyl group, a tricyclodecanyl group, and a phenyl group.

[0071] R 72 and R 82 R may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Alternatively, R may be a -CF group. 72 and R 82 Examples of R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a -CF3 group, and a cyano group.72 and R 82 is preferably a hydrogen atom, a methyl group, or a chlorine atom. 72 More preferably, R is a methyl group. 72 The methyl group in R provides higher water repellency. 82 is preferably a hydrogen atom from the viewpoint of reactivity, but is preferably a methyl group from the viewpoint of water repellency. 82 It is preferable to select Y 71 is preferably —O— or —NH—.

[0072] Specific examples of the high glass transition temperature monomer (5) include: Acrylate esters such as cyclohexyl acrylate, isobornyl acrylate, bornyl acrylate, adamantyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, phenyl acrylate, naphthyl acrylate, benzyl acrylate, 2-t-butylphenyl acrylate, and naphthyl acrylate; Methacrylate esters such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, bornyl methacrylate, adamantyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, tricyclodecanyl methacrylate, phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, (2-dimethylamino)ethyl methacrylate, aziridinyl methacrylate, aziridinylethyl methacrylate, and dicyclopentenyl methacrylate; chloroacrylate esters such as methyl chloroacrylate; t-butyl(meth)acrylamide, butyl(meth)acrylamide, phenyl(meth)acrylamide, isopropyl(meth)acrylamide, stearyl(meth)acrylamide, cyclohexyl(meth)acrylamide, isobornyl(meth)acrylamide, bornyl(meth)acrylamide, adamantyl(meth)acrylamide, dicyclopentanyl(meth)acrylamide, dicyclopentenyl(meth)acrylamide, tricyclodecanyl(meth)acrylamide, benzyl(meth)acrylamide, naphthyl(meth)acrylamide, and 2-t-butylphenyl(meth)acrylamide.

[0073] The high glass transition point monomer (5) is preferably isobornyl (meth)acrylate, bornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, phenyl (meth)acrylate, naphthyl acrylate, or benzyl acrylate, and isobornyl (meth)acrylate is particularly preferred.

[0074] (6) Other monomers A monomer (6) other than the monomers (1) and (2) may also be used. Examples of the other monomer (6) include, for example, ethylene, vinyl acetate, acrylonitrile, vinyl chloride, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and vinyl alkyl ether. The other monomer (6) is preferably a non-fluorine monomer. The other monomer is not limited to these examples.

[0075] As used herein, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylamide" means acrylamide or methacrylamide.

[0076] Each of the monomers (1) to (6) may be a single type or a mixture of two or more types.

[0077] In the present disclosure, preferred combinations of monomers in the polymer are as follows: Monomer (1) + Monomer (4) Monomer (1) + Monomer (5) Monomer (1) + Monomer (3) + Monomer (4) Monomer (1) + Monomer (3) + Monomer (5) Monomer (1) + Monomer (4) + Monomer (5) Monomer (1) + Monomer (3) + Monomer (4) + Monomer (5) Monomer (2) + Monomer (4) Monomer (4) + Monomer (5) Monomer (2) + Monomer (5) Monomer (2) + Monomer (3) + Monomer (4) Monomer (2) + Monomer (3) + Monomer (5) Monomer (2) + Monomer (4) + Monomer (5) Monomer (2) + Monomer (3) + Monomer (4) + Monomer (5) Monomer (1) + Monomer (2) + Monomer (3) + Monomer (4) Monomer (1) + Monomer (2) + Monomer (4) + Monomer (5) Monomer (1) + Monomer (2) + Monomer (3) + Monomer (4) + Monomer (5) Monomer (1) + Monomer (2) + Monomer (3) + Monomer (4) + Monomer (5) + Monomer (6)

[0078] Particularly preferred combinations are as follows: Monomer (1) + Monomer (3) + Monomer (4) Monomer (1) + Monomer (4) + Monomer (5) Monomer (2) + Monomer (3) + Monomer (4) Monomer (2) + Monomer (3) + Monomer (5) Monomer (1) + Monomer (2) + Monomer (3) + Monomer (4) Monomer (1) + Monomer (2) + Monomer (4) + Monomer (5) Monomer (1) + Monomer (3) + Monomer (4) + Monomer (5) Monomer (1) + Monomer (2) + Monomer (3) + Monomer (4) + Monomer (5)

[0079] In the polymer, the molar ratio of hydrophobic monomer (1) or (meth)acrylic monomer (2) / reactive hydrophilic monomer (3) / high glass transition point monomer (5) may be 20-100 / 0-50 / 0-70. Alternatively, the molar ratio of hydrophobic monomer (1) or (meth)acrylic monomer (2) / reactive hydrophilic monomer (3) / high glass transition point monomer (5) may be 20-99.9 / 0.1-50 / 0-70, preferably 20-99.5 / 0.5-50 / 0-68. The molar ratio of hydrophobic monomer (1) or (meth)acrylic monomer (2) / reactive hydrophilic monomer (3) may be 50-99 / 1-50, preferably 55-98 / 2-45. The molar ratio of the hydrophobic monomer (1) or (meth)acrylic monomer (2) to the high glass transition point monomer (5) may be 50 to 99 / 1 to 50, preferably 55 to 98 / 2 to 45. The crosslinkable monomer (4) may be 0.1 to 30 molar parts, for example 0.1 to 25 molar parts, per 100 molar parts in total of the hydrophobic monomer (1), the (meth)acrylic monomer (2), the high glass transition point monomer (5), and the reactive hydrophilic monomer (3).

[0080] Alternatively, the molar ratio of one or both of the hydrophobic monomer (1) and the (meth)acrylic monomer (2) to the reactive hydrophilic monomer (3) to the high glass transition point monomer (5) may be 50-95 / 0-30 / 0-30, 60-95 / 0-30, or 1-20 / 0-30, or 1-20, or 80-95 / 0-15, or 1-10 / 0-15, or 1-10, or 85-95 / 0-15, or 1-10 / 0-15, or 1-10. The amount of the crosslinkable monomer (4) may be 0-20 parts by weight, 1-15 parts by weight, or 2-10 parts by weight per 100 parts by weight of the polymer.

[0081] The amount of the other monomer (6) may be 0 to 10% by weight, for example 0.1 to 5% by weight, based on the polymer.

[0082] The water-repellent polymer may be a random polymer or a block copolymer, but is preferably a random polymer.

[0083] (B) Aqueous medium The water repellent composition contains an aqueous medium, which is water or a mixture of water and an organic solvent. The water repellent composition is generally an aqueous dispersion in which a polymer is dispersed in an aqueous medium (water or a mixture of water and an organic solvent). The aqueous medium may be water alone or a mixture of water and a (water-miscible) organic solvent. The amount of the organic solvent may be 30% by weight or less, for example 10% by weight or less, based on the liquid medium. The aqueous medium is preferably water alone. The amount of the aqueous medium may be 50 to 99.5 parts by weight, particularly 70 to 99.5 parts by weight, when the total of the water-repellent polymer and the aqueous medium is 100 parts by weight.

[0084] (C) Binder resin The binder resin functions as a binder that binds organic fine particles to the substrate. A water-repellent resin is preferred as the binder resin. The water-repellent resin also functions as an active ingredient that exhibits water repellency. Examples of binder resins include acrylic polymers, urethane polymers, polyolefins, polyesters, polyethers, polyamides, polyimides, polystyrenes, and silicone polymers. The water-repellent resin is a non-fluorine-containing polymer having a hydrocarbon group with 3 to 40 carbon atoms in the side chain, or a fluorine-containing polymer having a fluoroalkyl group with 1 to 20 carbon atoms in the side chain. The water-repellent resin is preferably a non-fluorine-containing polymer. In non-fluorine-containing polymers having a hydrocarbon group having 3 to 40 carbon atoms, the hydrocarbon group is preferably a branched hydrocarbon group or a long-chain (or long-chain linear) hydrocarbon group. The -CH3 group has a lower surface free energy than -CH2-, resulting in water repellency. Therefore, branched hydrocarbon groups (e.g., branched alkyl groups) are preferred, particularly structures with many branches and many -CH3 groups, such as t-butyl, isopropyl, and 2,6,8-trimethylnonan-4-yl groups. In the branched hydrocarbon group, the number of -CH3 groups is preferably 2 to 15, for example, 3 to 10, or 4 to 8. The carbon number of the long-chain hydrocarbon group (or long-chain linear hydrocarbon group) may be 7 to 40 or 12 to 30, for example, 16 to 26, and particularly 18 to 22. Examples of the water-repellent resin include urethane polymers, silicone polymers, acrylic polymers, and polystyrene. Examples of non-fluorinated polymers include amidoamine dendrimers with long hydrocarbon chains, which are described in U.S. Patent No. 8,703,894, the disclosure of which is incorporated herein by reference.

[0085] A urethane polymer having a hydrocarbon group having 3 to 40 carbon atoms in its side chain can be produced, for example, by reacting an isocyanate group-containing compound (e.g., a monoisocyanate or polyisocyanate, specifically a diisocyanate or triisocyanate) with a hydroxyl group-containing compound having a hydrocarbon group having 3 to 40 carbon atoms. Polyurethanes having a branched structure such as t-butyl groups, isopropyl groups, or 2,6,8-trimethylnonan-4-yl groups in their side chains can be produced, for example, by reacting an isocyanate group-containing compound (e.g., a monoisocyanate or polyisocyanate, specifically a diisocyanate or triisocyanate) with a hydroxyl group-containing compound having a branched structure such as t-butyl groups, isopropyl groups, or 2,6,8-trimethylnonan-4-yl groups. Examples of urethane polymers include urethane compounds having long-chain hydrocarbon groups, such as sorbitan tristearate, sorbitan monostearate, and polyfunctional isocyanurates, as described in U.S. Patent Publication No. 2014 / 0295724, the disclosure of which is incorporated herein by reference. Examples of urethane polymers include polyurethanes having long-chain hydrocarbon groups, as described in Japanese Patent Publication No. 2019-519653 (International Publication No. 2018 / 007549), the disclosure of which is incorporated herein by reference.

[0086] A silicone polymer having a hydrocarbon group having 3 to 40 carbon atoms in its side chain can be produced, for example, by reacting a dichlorosilane compound containing a dichlorosilane having a hydrocarbon group having 3 to 40 carbon atoms. Polysilicones having a branched structure such as t-butyl groups, isopropyl groups, or 2,6,8-trimethylnonan-4-yl groups in their side chains can be produced, for example, by reacting a dichlorosilane compound containing a dichlorosilane having a branched structure such as t-butyl groups, isopropyl groups, or 2,6,8-trimethylnonan-4-yl groups. An example of a silicone polymer is long-chain alkyl-modified polydimethylsiloxane.

[0087] An acrylic polymer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain can be produced by polymerizing a monomer including an acrylic monomer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain. Examples of the acrylic monomer are the same as those explained above for the hydrophobic monomer (1). Specific examples of the acrylic monomer include, for example: Stearyl (meth)acrylate, behenyl (meth)acrylate, TIFF0007759808000053.tif2351 (especially stearamidoethyl (meth)acrylate) [In the above formula, n is a number from 7 to 40, and m is a number from 1 to 5.] is.

[0088] An acrylic polymer having a branched structure such as a t-butyl group, an isopropyl group, or a 2,6,8-trimethylnonan-4-yl group in the side chain can be produced by polymerizing a monomer containing an acrylic monomer having a branched structure such as a t-butyl group, an isopropyl group, or a 2,6,8-trimethylnonan-4-yl group in the side chain. Examples of the acrylic monomer are the same as those described above for the hydrophobic monomer (1). Specific examples of the acrylic monomer include t-butyl (meth)acrylate, isopropyl (meth)acrylate, and 2,6,8-trimethylnonan-4-yl acrylate.

[0089] Examples of acrylic polymers include polymers containing repeating units derived from acrylic monomers having long-chain hydrocarbon groups, such as behenyl (meth)acrylate and stearyl (meth)acrylate, and repeating units derived from vinylidene chloride and / or vinyl chloride. Examples of acrylic polymers include polymers containing repeating units derived from an acrylic monomer having a long-chain hydrocarbon group, such as behenyl (meth)acrylate or stearyl (meth)acrylate, repeating units derived from vinylidene chloride and / or vinyl chloride, and repeating units derived from styrene or α-methylstyrene. These acrylic polymers may be used in combination with paraffin wax. Examples of such polymers are described in JP 2012-522062 (WO 2010 / 115496), the disclosure of which is incorporated herein by reference. Examples of acrylic polymers include polymers containing repeating units derived from an acrylic monomer having a long-chain hydrocarbon group such as stearyl (meth)acrylate, repeating units derived from vinylidene chloride and / or vinyl chloride, and repeating units derived from a reactive emulsifier such as polyoxyalkylene alkenyl ether, and are described in JP 2017-25440 (WO 2017 / 014131), the disclosure of which is incorporated herein by reference.

[0090] In the fluorine-containing polymer having a fluoroalkyl group having 1 to 20 carbon atoms in the side chain, the fluoroalkyl group is preferably a perfluoroalkyl group. Examples of fluorine-containing water-repellent resins include fluorine-containing acrylic polymers containing repeating units formed from a (meth)acrylate having a perfluoroalkyl group having 4 to 8 carbon atoms in the side chain and a long-chain alkyl (meth)acrylate such as behenyl (meth)acrylate or stearyl (meth)acrylate. Other monomers may be used in the non-fluorine-containing polymers and fluorine-containing polymers such as urethane polymers, silicone polymers, acrylic polymers and polystyrene. Examples of the other monomers include, but are not limited to, ethylene, vinyl acetate, acrylonitrile, vinyl chloride, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, (meth)acrylate having polydimethylsiloxane on the side chain, and vinyl alkyl ether.

[0091] (D) Surfactant The water repellent composition may or may not contain a surfactant (emulsifier). Generally, to stabilize the particles during polymerization and the aqueous dispersion after polymerization, a small amount of surfactant (for example, 0.01 to 15 parts by weight per 100 parts by weight of the monomer) may be added during polymerization, or the surfactant may be added after polymerization. In particular, when the object to be treated is a textile product, the surfactant in the water repellent composition preferably contains a nonionic surfactant. Furthermore, the surfactant preferably contains one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

[0092] The nonionic surfactant, cationic surfactant, and amphoteric surfactant may each be one type or a combination of two or more types. The amount of surfactant may be 15 parts by weight or less (for example, 0 to 15 parts by weight or 0.01 to 15 parts by weight), preferably 8 parts by weight or less, per 100 parts by weight of organic fine particles (A). Generally, the addition of a surfactant improves the stability of the aqueous dispersion and the permeability into fabrics, but reduces water repellency. It is preferable to select the type and amount of surfactant so as to achieve both of these effects.

[0093] (E) Crosslinking agent The crosslinking agent (E) is preferably one that crosslinks when heated after the aqueous dispersion of organic fine particles is applied to the fabric, and is preferably one that is dispersed in water.

[0094] A preferred example of the crosslinking agent (E) is a blocked isocyanate compound. [A(NCO) m (wherein A is a group remaining after removal of the isocyanate group from the polyisocyanate, and m is an integer of 2 to 8). [R H (wherein R may be a hydrocarbon group which may be substituted with a heteroatom such as a nitrogen atom or an oxygen atom, and H is a hydrogen atom)].

[0095] A(NCO) m Examples of the isocyanate include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate (HDI). Examples of blocking agents that form R groups are oximes, phenols, alcohols, mercaptans, amides, imidazoles, ureas, amines, imines, pyrazoles and active methylene compounds.

[0096] The crosslinking agent (E) is preferably a blocked isocyanate such as oxime-blocked toluene diisocyanate, blocked hexamethylene diisocyanate, or blocked diphenylmethane diisocyanate. The amount of the crosslinking agent (E) may be 0 to 30 parts by weight or 0.01 to 20 parts by weight, for example, 0.1 to 15 parts by weight, relative to 100 parts by weight of the total of the organic fine particles (A) and the binder resin (C).

[0097] (F) Additives The water repellent composition may contain an additive (F) in addition to the organic fine particles (A) and the aqueous medium (B), and, if necessary, the binder resin (C), the surfactant (D) and / or the crosslinking agent (E). Examples of additives include other water repellents, oil repellents, drying speed regulators, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, defoamers, texture modifiers, slippage modifiers, antistatic agents, hydrophilizing agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants, etc. The amount of the additive may be 0 to 20 parts by weight, or 0.05 to 20 parts by weight, for example 0.1 to 10 parts by weight, relative to 100 parts by weight of the total of the organic fine particles (A) and the binder resin (C).

[0098] The polymers (polymers constituting the organic fine particles and polymers constituting the binder resin) can be produced by any of the usual polymerization methods, and the polymerization reaction conditions can be selected arbitrarily. Such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. Emulsion polymerization is preferred.

[0099] As long as a water repellent composition in the form of an aqueous dispersion can be obtained, the method for producing the polymer is not limited. For example, a polymer (organic fine particles) can be produced by polymerizing a monomer for organic fine particles in an aqueous medium in the presence or absence of a surfactant. Alternatively, an aqueous dispersion can be obtained by producing a polymer by solution polymerization, followed by adding a surfactant and water and removing the solvent.

[0100] When the water repellent composition contains organic fine particles and a binder resin, the production of an aqueous dispersion of organic fine particles and the production of an aqueous dispersion of the binder resin are carried out separately, and the aqueous dispersion of organic fine particles and the aqueous dispersion of the binder resin are mixed to produce a water repellent composition containing organic fine particles and a binder resin. Alternatively, the water repellent composition containing organic fine particles and a binder resin can be produced by polymerizing a monomer for the binder resin in an aqueous dispersion of organic fine particles. Furthermore, the water repellent composition containing organic fine particles and a binder resin can be produced by polymerizing a monomer for the organic fine particles in an aqueous dispersion of the binder resin.

[0101] In emulsion polymerization without using a surfactant, it is preferable to polymerize the monomer in an aqueous medium at a low concentration (for example, a monomer concentration of 1 to 30% by weight, particularly 1 to 15% by weight).

[0102] In emulsion polymerization using a surfactant or a reactive emulsifier, it is preferable to add a small amount (30 parts by mole or less, for example, 0.1 to 20 parts by mole per 100 parts by mole of the total monomers) of monomer (1) or monomer (2) whose homopolymer has a static water contact angle of 95 degrees or more. This allows polymerization at a high concentration and improves the water repellency of the polymer. Examples of the additional monomers include t-butylstyrene, stearyl (meth)acrylate, behenyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, stearamidoethyl (meth)acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37、 4-t-butylphenyl (meth)acrylate, 2,3,4-methylphenyl (meth)acrylate, and A (meth)acrylic monomer having a polydimethylsiloxane group. CH2=C(-R 92 )-C(=O)-Y 91 -R 91 [In the formula, R 91is a group having a polydimethylsiloxane group, R 92 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 91 is a divalent to tetravalent group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, and -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms). It is a monomer represented by the formula: When the ratio of the monomer (5) and the monomer (3) to the total monomers constituting the organic fine particles is 35 parts by mole or more, the monomer (1) having a static water contact angle of 95 degrees or more is preferably 1 to 70 parts by mole, for example 1 to 60 parts by mole.

[0103] In solution polymerization, a method is employed in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by mole, for example, 0.01 to 10 parts by mole, per 100 parts by mole of the monomer.

[0104] The organic solvent is inert to the monomers and dissolves or uniformly disperses them, and may be, for example, an ester (e.g., an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 30 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol, ethanol, or methanol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 50 to 99.5 parts by weight, for example, 70 to 99 parts by weight, assuming that the total of the monomer and the organic solvent is 100 parts by weight.

[0105] In emulsion polymerization, the monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the mixture is stirred at a temperature of 30 to 80°C for 1 to 10 hours to polymerize. Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[2- Examples of suitable initiators include water-soluble initiators such as 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], sodium peroxide, potassium persulfate, and ammonium persulfate, and oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 10 moles per 100 moles of monomer. If necessary, a reducing agent such as Rongalit, ascorbic acid, tartaric acid, sodium disulfite, isoascorbic acid, or ferrous sulfate may be used in combination.

[0106] As the emulsifier, various anionic, cationic, or nonionic emulsifiers can be used, and are used in the range of 0.5 to 20 parts by weight per 100 parts by weight of the monomer. It is preferable to use an anionic and / or nonionic and / or cationic emulsifier. If the monomers are not completely compatible with each other, it is also preferable to add a compatibilizer, such as a water-soluble organic solvent, that can fully compatibilize these monomers. Addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0107] Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, and methanol, and these may be used in an amount of 0.1 to 50 parts by weight, for example, 1 to 40 parts by weight, per 100 parts by weight of water.

[0108] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0109] The water repellent composition is generally preferably an aqueous dispersion. The water repellent composition comprises a polymer (the active ingredient of the water repellent composition) and an aqueous medium. The amount of the aqueous medium may be, for example, 50 to 99.9 wt %, particularly 70 to 99.5 wt %, based on the water repellent composition. In the water repellent composition, the concentration of the polymer may be 0.1 to 50% by weight, for example, 0.5 to 40% by weight.

[0110] The water repellent composition (and the aqueous dispersion of organic fine particles) can be used as an external treatment agent (surface treatment agent) or an internal treatment agent. The water repellent composition (and the aqueous dispersion of organic fine particles) can be used as an oil repellent, an antifouling agent, a soil release agent, a stripping agent, or a mold release agent.

[0111] When the water repellent composition is an external treatment agent, it can be applied to the substrate by a conventionally known method. Typically, the water repellent composition is dispersed and diluted in an organic solvent or water, and then applied to the surface of the substrate by a known method such as dip coating, spray coating, or foam coating, followed by drying. If necessary, the water repellent composition may be applied together with an appropriate crosslinking agent (e.g., blocked isocyanate) and cured. Furthermore, the water repellent composition may be used in combination with an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixative, or an anti-wrinkle agent. The polymer concentration in the treatment solution to be brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example, 0.05 to 10% by weight.

[0112] Examples of materials to be treated with the water repellent composition (and the aqueous dispersion of organic fine particles) include textiles, stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Examples of textiles include natural fibers of animal and plant origin, such as cotton, hemp, wool, and silk; synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers, such as rayon and acetate; inorganic fibers, such as glass fiber, carbon fiber, and asbestos fiber; and mixtures of these fibers.

[0113] The textile product may be in the form of fiber, cloth, or the like. The water repellent composition can also be used as a stain repellent, release agent, or mold release agent (e.g., internal or external mold release agent), for example, to easily release the surface of a substrate from another surface (another surface of the substrate or a surface of another substrate).

[0114] The organic microparticles can be applied to a fibrous substrate (e.g., a textile) by any of the known methods for treating textiles with a liquid. When the textile is a fabric, the fabric may be immersed in the solution, or the solution may be applied or sprayed onto the fabric. The treated textile is dried and preferably heated, for example, at 100°C to 200°C, to develop water repellency.

[0115] Alternatively, the organic microparticles may be applied to the textile by a cleaning process, such as in a laundry application or a dry cleaning process.

[0116] When the organic fine particles are attached to a substrate and then heat-treated at 170°C for 1 minute, the average diameter of the organic fine particles after the heat treatment is preferably 50% or more of the average diameter of the organic fine particles before the heat treatment.The average diameter (average particle size) of the organic fine particles after the heat treatment is preferably 60% or more, for example, 70% or more of the average diameter (average particle size) of the organic fine particles before the heat treatment.Alternatively, after the particles are applied to a substrate (including cloth), the average particle size of the fine particles observable on the substrate is preferably 50 to 700 nm. The average diameter of organic fine particles before heat treatment is the particle size of the fine particles measured by dynamic light scattering (DLS) from an aqueous dispersion of organic fine particles (if two or more peaks are observed in the DLS measurement, the average particle size calculated from only the smaller peak is used, rather than the average particle size of all peaks), or the average diameter of organic fine particles attached to a substrate before heat treatment. If the two values ​​differ, the smaller one is used.

[0117] The average diameter of organic microparticles on a substrate refers to the average diameter of 10 randomly selected, independent, smallest particle size observed under a scanning electron microscope (SEM) after the organic microparticles have been attached to the substrate. Generally, the average diameter of organic microparticles after heat treatment refers to the average diameter of 10 randomly selected, independent, smallest particle size observed on the substrate under a scanning electron microscope (SEM) after a dispersion of organic microparticles has been applied to a substrate (e.g., cloth) and heat-treated at 170°C for 1 minute. For example, when the substrate is cloth, a cloth with organic microparticles attached can be produced by immersing the cloth in an aqueous dispersion containing organic microparticles, passing it through a mangle, and then passing it through a pin tenter at 170°C for 1 minute. The average diameter of organic microparticles before heat treatment refers to the average diameter of 10 randomly selected, independent, smallest particle size observed on the substrate under a scanning electron microscope (SEM) after the dispersion of organic microparticles has been applied to a substrate (e.g., cloth) and air-dried for at least 1 hour.

[0118] The textiles to be treated are typically fabrics, including woven, knitted and nonwoven fabrics, textiles in the form of apparel and carpets, but may also be fibres or yarns or intermediate textile products (such as slivers or rovings). The textile material may be natural fibres (such as cotton or wool), man-made fibres (such as viscose rayon or leocell), or synthetic fibres (such as polyester, polyamide or acrylic fibres), or may be a mixture of fibres (such as a mixture of natural and synthetic fibres).

[0119] Alternatively, the fibrous substrate may be leather. The organic microparticles may be applied to the leather from an aqueous solution or emulsion at various stages of leather processing, for example, during wet processing of the leather or during finishing of the leather, to render the leather hydrophobic and oleophobic. Alternatively, the fibrous substrate may be paper. The organic particulates may be applied to preformed paper or may be applied at various stages of papermaking, for example, during the drying period of the paper.

[0120] "Treatment" means applying a treatment agent to an object to be treated by immersion, spraying, coating, etc. Through treatment, organic fine particles, which are the active ingredients of the treatment agent, penetrate into the interior of the object to be treated and / or adhere to the surface of the object to be treated.

[0121] It is preferred that the treated substrate (particularly textile products) has a water rolling speed of 100 mm / s or more, for example 130 mm / s or more, or even 150 mm / s or more or 200 mm / s or more. The treated substrate exhibits the effect of preventing frost formation.

[0122] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims. [Example]

[0123] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples. In the following, parts, % or ratios represent parts by weight, % by weight or ratios by weight unless otherwise specified. The test procedure is as follows:

[0124] [Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)] The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent and Shodex KF-606M, KF-601, and KF-800D columns, and the molecular weights were calculated in terms of polystyrene.

[0125] [Measurement of thermal properties by differential scanning calorimetry (DSC)] The melting point of the polymer was calculated by differential scanning calorimetry (DSC). The DSC measurement was performed by cooling to -20°C under a nitrogen atmosphere, then heating to 200°C at 10°C / min, cooling again to -20°C, and measuring the melting point observed during the subsequent heating process to 200°C at 10°C / min. For polymers exhibiting multiple melting peaks, the peak with the greatest heat of fusion resulting from the melting of the long-chain alkyl was taken as the melting point. The glass transition temperature was determined as the midpoint between the intersection of the extensions of the baselines before and after the second-order transition of the DSC curve and the tangent to the inflection point of the DSC curve.

[0126] [Measurement of particle size of dispersion] Dynamic light scattering (DLS) measurements were performed using a Malvern ZEN1600 to determine the average particle diameter in the dispersion. The aqueous dispersion of organic fine particles was diluted with pure water to a solids concentration of 0.1% and measurements were performed at 25°C. Analysis of particle size distribution was performed based on scattering intensity.

[0127] [Static contact angle measurement] (Synthesis examples L1~L5) A chloroform solution of the polymer (solids concentration 1.0%) was spin-coated onto a silicon wafer substrate (high-purity silicon wafer for research, AS ONE 2-960-55) and heated at 80°C for 15 minutes to produce a coating. 2 μL of water was dropped onto this coating, and the static contact angle 1 second after the drop landed was measured using a fully automatic contact angle meter (DropMaster 701, manufactured by Kyowa Interface Science).

[0128] (Organic fine particles) The contact angle of the organic fine particles was measured by drop-casting an aqueous dispersion of the organic fine particles onto a glass substrate (soda-lime glass slide) and heating it at 150°C for 3 minutes to prepare a substrate with organic fine particles attached, dropping 2 μL of water onto the glass substrate with the organic fine particles attached, and measuring the static contact angle 1 second after the drop landed using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of the organic fine particles on the glass substrate is preferably 100° or more, more preferably 110° or more, and even more preferably 118° or more.

[0129] The static contact angle of water on a cloth (PET cloth) treated with an aqueous dispersion of organic fine particles or a composition containing organic fine particles and a binder resin was 88 g / m2. 2 PET cloth (70 denier, gray) was immersed in an aqueous dispersion of organic fine particles or a composition containing organic fine particles and a binder resin, then passed through a mangle and a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. 2 μL of water was dropped onto the PET cloth, and the static contact angle 1 second after the drop was measured using a fully automatic contact angle meter (DropMaster 701, manufactured by Kyowa Interface Science). The contact angle of the organic fine particles on the cloth (PET cloth) is preferably 120° or more, more preferably 130° or more, and even more preferably 140° or more. The contact angle of the aqueous dispersion of the binder resin was measured by drop-casting the aqueous dispersion of the binder resin onto a glass substrate (soda-lime glass slide), heating it at 150°C for 3 minutes to form a coating film, dropping 2 μL of water onto this coating film, and measuring the static contact angle 1 second after the drop had landed using a fully automatic contact angle meter (DropMaster 701, manufactured by Kyowa Interface Science).

[0130] [Fall speed test] In the falling speed test, PET cloth (basis weight: 88 g / m 2 PET cloth (70 denier, gray) was immersed in an aqueous dispersion of organic fine particles or a composition containing organic fine particles and a binder resin, and then passed through a mangle and a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. Using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science), 20 μL of water was dropped from a microsyringe onto the PET cloth tilted at 30°, and the way the dropped water fell was measured using a high-speed camera (VW-9000 manufactured by Keyence Corporation). The average falling speed over a distance of approximately 40 mm was recorded as the falling speed.

[0131] [Solid content measurement] 1 g of the obtained aqueous dispersion of organic fine particles was placed in an aluminum cup and dried for 1 hour at 150° C. The solid content was calculated from the weight before and after drying. Solid content % = (weight before drying - weight after drying) / weight before drying x 100

[0132] [Water repellency test] An aqueous dispersion of organic fine particles was prepared to a predetermined concentration, and a cloth was immersed in the test solution and then passed through a mangle. The water repellency of the heat-treated test cloth was evaluated. The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). The water repellency is expressed by a water repellency number as shown in the table below. The higher the number, the better the water repellency. A "+" next to a number means that the cloth is better than that number, and a "-" means that the cloth is worse than that number. Polyester cloth (PET) (basis weight: 88 g / m 2 The evaluation was carried out using a 70 denier, gray fabric.

[0133] TIFF0007759808000054.tif47146

[0134] [Strong water repellency test] When testing using the spray method of JIS-L-1092 (AATCC-22), the ease with which water splashes onto the fabric and the speed at which it flows off the fabric were visually evaluated. The higher the score, the better the water repellency.

[0135] TIFF0007759808000055.tif73160

[0136] [Washing durability of water repellency and strong water repellency (water repellency (after washing) and strong water repellency (after washing))] Washing is repeated 20 times according to JIS L-0217-103, and the water repellency and strong water repellency are evaluated afterwards. After washing, the water repellency is preferably 80 points or more, and the strong water repellency is preferably 2 points or more.

[0137] [Scanning electron microscope (SEM) observation (particle size)] SEM observations were performed using an ERA9000 manufactured by ELONIX at an accelerating voltage of 3.5 kV with Pt vapor deposition at a working distance of 5.0 mm, and an SU8020 manufactured by Hitachi High-Technologies at an accelerating voltage of 3.0 kV with Pt vapor deposition. The particle size determined by both instruments was the same. A cloth was immersed in a composition containing organic fine particles, and then passed through a mangle and a pin tenter at 170°C for 1 minute to create a cloth with the organic fine particles attached. The average particle diameter of 10 independent smallest units randomly selected from the cloth was then determined using a scanning electron microscope (SEM). The particle diameter retention rate (%) before and after heating was calculated using the average particle diameter of the organic microparticles on the substrate after heating determined by SEM observation (the average diameter of the particles on the cloth heated at 170°C for 1 minute) and the average particle diameter of the organic microparticles before heating (the smaller of the average particle diameter of the microparticle dispersion determined by DLS measurement or the average particle diameter on the substrate before heating determined by SEM observation) according to the following formula. Retention rate of average particle diameter before and after heating (%) = (average particle diameter after heating) / (average particle diameter before heating) x 100

[0138] [Dark color measurement] L was measured at three points on each treated fabric using a color difference meter (Minolta Co., Ltd., color difference meter CR-200, detection area is a circle with a diameter of 8 mm). The color difference (ΔL) was calculated from the L of the fabric before and after treatment with the treatment solution using the following formula. ΔL = (L value after fabric treatment) - (L value before fabric treatment)

[0139] In the examples and comparative examples, the abbreviations have the following meanings. tBuSty: 4-t-butylstyrene tBuMA: t-butyl methacrylate StMA: stearyl methacrylate Sty: Styrene MeSty: 4-methylstyrene C17AEA: CH2=CHCO2-CH2CH2-NH-C(=O)-C 17 H 35 iBMA: isobornyl methacrylate GMA: glycidyl methacrylate DHMA: 2,3-dihydroxypropyl methacrylate HEMA: Hydroxyethyl methacrylate HBA: 4-hydroxybutyl acrylate DQ: Dimethylaminoethyl methacrylate quaternary BCPMA: dicyclopentanyl methacrylate CHMA: cyclohexyl methacrylate DVB: Divinylbenzene NP-A: Neopentyl glycol diacrylate NP-MA: Neopentyl glycol dimethacrylate DMS-MA: Polydimethylsiloxyethyl methacrylate DMS-MA1: Polydimethylsiloxyethyl methacrylate (molecular weight 1000) DMS-MA2: Polydimethylsiloxyethyl methacrylate (molecular weight 500) DMS-MA3: Polydimethylsiloxyethyl methacrylate (molecular weight 12,000) DCP: dicyclopentanyl diacrylate DCP-M: Dicyclopentanyl dimethacrylate ADDA: Adamantyl diacrylate HADDM: 5-hydroxy-1,3-adamantane dimethacrylate EGDMA: Ethylene glycol dimethacrylate tBuA: t-butyl acrylate MMA: methyl methacrylate VAc: vinyl acetate tBuAAm: t-butylacrylamide StA: Stearyl acrylate

[0140] Emulsifier 1: Polyethylene glycol monooleyl ether (liquid) Emulsifier 2: Polyethylene glycol monooleyl ether (solid) Emulsifier 3: Glyceryl stearate Emulsifier 4: Lauryltrimonium chloride Emulsifier 5: Cetrimonium chloride Emulsifier 6: Stearyltrimonium chloride Emulsifier 7: Polyoxyalkylene alkenyl ether (HLB16) Emulsifier 8: Polyoxyalkylene alkenyl ether (HLB14) Emulsifier 9: Polyoxyalkylene alkenyl ether (HLB13) Emulsifier 10: Tetraglyceryl monostearate Emulsifier 11: Lauric acid diethanolamide Emulsifier 12: Sorbitan tristearate Crosslinker 1: Oxime-blocked toluene diisocyanate Crosslinker 2: Oxime-blocked hexamethylene diisocyanate PDMS-A: Long-chain alkyl-modified dimethylsiloxane StOH: Stearyl alcohol

[0141] <Synthesis Example 1> In a nitrogen-purged reaction vessel, 0.66 g of t-butylstyrene (tBuSty), 0.39 g of glycidyl methacrylate (GMA), 0.018 g of divinylbenzene (DVB), and 33 ml of pure water were added and dispersed. After nitrogen substitution, 18.6 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content was 2.85%. The particle size (average particle size) of the aqueous dispersion was 250 nm. The contact angle of water on a glass substrate of organic fine particles was 120°. PET (fabric) (basis weight: 88 g / m) treated with the aqueous dispersion of organic fine particles was 2The static contact angle of water for a glass substrate (70 denier, gray) was 143.1° and the sliding speed was 265 mm / s. An aqueous dispersion of organic fine particles was cast onto a glass substrate, air-dried, and then left in a -30°C environment for two days. When the substrate was then removed to a 25°C environment, frost formed on the glass, but no frost was observed on the organic fine particles. The particle diameter was retained at 80% before and after heating at 170°C for one minute.

[0142] <Synthesis Examples 2 to 44> The same procedure as in Synthesis Example 1 was repeated, except that the monomers shown in Table 1 were used. The results are shown in Table 1. In Synthesis Examples 25 to 28, in addition to the monomers shown in the table, a cationic emulsifier (lauryltrimonium chloride) was added in the specified amount shown in the table relative to the total monomer amount, and polymerization was carried out. In Synthesis Example 29, in addition to the monomers shown in the table, a cationic emulsifier (lauryltrimonium chloride) and polyethylene glycol monooleyl ether were added in an amount of 0.5% relative to the total monomer amount, and polymerization was carried out. The aqueous dispersion of organic fine particles synthesized in Synthesis Example 13 was cast onto a glass substrate, air-dried, and then left in an environment at -30°C for 2 days. When the substrate was then removed to an environment at 25°C, frost formed on the glass, but no frost was observed on the organic fine particle coating. In Synthesis Examples 2 to 44, the particle diameter retention rate before and after heating at 170°C for 1 minute was 80%.

[0143] <Comparative Synthesis Examples 1-3> The same procedure as in Synthesis Example 1 was repeated, except that the monomers shown in Table 1 were used. The results are shown in Table 1. In Comparative Synthesis Example 1, the emulsion after polymerization was unstable, and it was not possible to apply it uniformly to the cloth. In Comparative Synthesis Examples 2 and 3, in the falling speed test, water droplets adhered to the cloth and did not fall.

[0144] [Table 1]

[0145] <Synthesis Example L1> A nitrogen-purged reaction vessel was charged with 1.50 g of tBuSty, 0.015 g of azobisisobutyronitrile, and 10 ml of toluene. The mixture was heated and stirred at 65°C for 8 hours, and then reprecipitated in methanol to obtain PtBuSty. The molecular weight (Mw) was 21,000, and the molecular weight distribution (Mw / Mn) was 2.0. The water contact angle of the resulting polymer was 100°. The glass transition temperature (Tg) was 125°C.

[0146] <Synthesis example L2> A nitrogen-purged reaction vessel was charged with 1.50 g of MeSty, 0.021 g of azobisisobutyronitrile, and 10 ml of toluene. The mixture was heated and stirred at 65°C for 8 hours, and then reprecipitated in methanol to obtain PMeSty. The molecular weight (Mw) was 15,000, and the molecular weight distribution (Mw / Mn) was 2.0. The water contact angle of the resulting polymer was 95°. The glass transition temperature (Tg) was 107°C.

[0147] <Synthesis example L3> In a nitrogen-purged reaction vessel, 1.00 g of Sty, 0.015 g of azobisisobutyronitrile, and 3.4 ml of toluene were added, and the mixture was heated and stirred at 65°C for 8 hours. After this, PSty was reprecipitated in methanol. The molecular weight (Mw) was 15,000, and the molecular weight distribution (Mw / Mn) was 2.1. The water contact angle of the resulting polymer was 89°. The glass transition temperature (Tg) was 100°C.

[0148] <Synthesis example L4> 2.00 g of tBuMA, 0.023 g of azobisisobutyronitrile, and 20 ml of toluene were added to a nitrogen-purged reaction vessel, and the mixture was heated and stirred at 65°C for 8 hours. After this, PtBuMA was reprecipitated in a mixed solution of methanol and water to obtain PtBuMA. The molecular weight (Mw) was 18,000, and the molecular weight distribution (Mw / Mn) was 2.0. The water contact angle of the resulting polymer was 89°. The glass transition temperature (Tg) was 107°C.

[0149] <Synthesis example L5> 2.00 g of StMA, 0.0097 g of azobisisobutyronitrile, and 20 ml of toluene were added to a nitrogen-purged reaction vessel, and the mixture was heated and stirred at 65°C for 8 hours. After this, PStMA was reprecipitated in methanol to obtain PStMA. The molecular weight (Mw) was 35,000, and the molecular weight distribution (Mw / Mn) was 2.1. The water contact angle of the resulting polymer was 109°. The melting point (Tm) was 50°C.

[0150] <Synthesis Example B1> A nitrogen-purged reaction vessel was charged with 3.00 g of StA, 0.149 g of polyethylene glycol monooleyl ether, 0.020 g of sorbitan tristearate, and 60 ml of purified water, and emulsified. 25 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of PStA. The solids content was 4.6%. The water contact angle of the emulsion dispersion applied to a glass substrate was 110°.

[0151] <Synthesis example B2> A nitrogen-purged reaction vessel was charged with 3.00 g of StA, 0.262 g of polyethylene glycol monooleyl ether, 0.037 g of sorbitan tristearate, and 60 ml of purified water, and emulsified. 25 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of PStA. The solids content was 4.7%. The water contact angle of the emulsion dispersion applied to a glass substrate was 110°.

[0152] <Synthesis Example B3> A nitrogen-purged reaction vessel was charged with 3.00 g of StA, 0.131 g of polyethylene glycol monooleyl ether, 0.018 g of sorbitan tristearate, 40 mg of 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, and 60 ml of purified water, and emulsified. 3 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65°C for 4 hours. 0.296 g of HBA was then added, and the mixture was heated and stirred for 4 hours, yielding an aqueous dispersion of StA / HBA block polymer. The water contact angle of the emulsion dispersion when applied to a glass substrate was 109°.

[0153] <Synthesis example B4> A nitrogen-purged reaction vessel was charged with 2.00 g of StA, 0.098 g of HBA, 0.087 g of polyethylene glycol monooleyl ether, 0.013 g of sorbitan tristearate, 24 mg of 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, and 18 mL of purified water, and emulsified. 3 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of a random polymer of StA / HBA. The water contact angle of the emulsion dispersion when applied to a glass substrate was 107°.

[0154] <Synthesis Example B5> In a nitrogen-purged reaction vessel, 0.5 g of StA, CH2=CHCO2-CH2CH2-NH-C(=O)-C 17 H 35 0.59 g of (C17AEA), 0.049 g of HBA, 0.096 g of polyethylene glycol monooleyl ether, 0.014 g of sorbitan tristearate, 12 mg of 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, and 10 mL of purified water were mixed and emulsified. 3 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of a random polymer of StA / C17AEA / HBA. The water contact angle of a film formed by applying the emulsified dispersion to a glass substrate was 108°.

[0155] <Synthesis example B6> A nitrogen-purged reaction vessel was emulsified with 0.5 g of StA, 0.59 g of C17AEA, 0.048 g of polyethylene glycol monooleyl ether, 0.007 g of sorbitan tristearate, 12 mg of 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, and 10 ml of purified water. 1 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and the mixture was heated and stirred at 65°C for 4 hours. 0.049 g of HBA was then added and heated and stirred for another 4 hours to obtain an aqueous dispersion of the StA·C17AEA / HBA block polymer. The water contact angle of the emulsion dispersion when applied to a glass substrate was 109°.

[0156] <Synthesis Example B7> A 200ml plastic container was charged with 10g of tripropylene glycol, 20g of StA, 0.05g of trialkylammonium chloride, 2.0g of sorbitan monoalkylate, 1.0g of polyoxyethylene alkyl ether, and 60g of pure water. The mixture was stirred at 2000 rpm with a homomixer for 1 minute and then ultrasonically dispersed for 15 minutes. The emulsion was transferred to an autoclave, purged with nitrogen, and then 0.05g of alkyl mercaptan, 8.6g of vinyl chloride, and 0.5g of azo initiator were added. The mixture was heated and stirred at 60°C for 20 hours to obtain an aqueous dispersion of the polymer. The water contact angle of the emulsion dispersion applied to a glass substrate was 108°.

[0157] <Synthesis example B8> A 500 ml plastic container was charged with 30 g of tripropylene glycol, 45 g of C17AEA, 34 g of StA, 1 g of N-alkylol acrylamide, 2 g of trialkylammonium chloride, 2 g of sorbitan monoalkylate, 2.5 g of polyoxyethylene trialkyl ether, 3.5 g of polyoxyethylene alkyl ether, and 180 g of pure water, and the mixture was stirred at 2000 rpm for 1 minute at 80°C using a homomixer, and then dispersed ultrasonically for 15 minutes. The emulsified dispersion was transferred to an autoclave, and after nitrogen substitution, 0.2 g of alkyl mercaptan and 20 g of vinyl chloride were added. An aqueous dispersion of the polymer was obtained by adding 1 g of an azo-based initiator and stirring the mixture for 20 hours at 60°C. The water contact angle of the film formed by applying the emulsion dispersion to a glass substrate was 109°.

[0158] <Synthesis Example B9> A nitrogen-purged reactor was charged with 28.9 g of sorbitan tristearate, 0.31 g of sorbitan monostearate, 7.5 g of hexamethylene triisocyanate (biuret), 37.5 g of methyl isobutyl ketone, and 0.03 g of dibutyltin laurate, and the mixture was heated and stirred at 80°C. To this solution, 9 g of tripropylene glycol, 1.8 g of sorbitan tristearate, 0.75 g of polyethylene glycol monooleyl ether, 0.6 g of trimethyloctadecylammonium chloride, and 40 g of purified water were added and stirred. The methyl isobutyl ketone was removed using an evaporator, yielding an aqueous dispersion of the reaction product of sorbitan stearate and isocyanate. The water contact angle of the film formed by applying the dispersion to a glass substrate was 105°.

[0159] <Synthesis Example S1> In a reaction vessel purged with nitrogen, 0.5 g of tBuSty, 0.30 g of GMA, 0.014 g of DVB, and 25 ml of purified water were added, followed by 22.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and the mixture was heated and stirred at 65°C for 8 hours. Further, 0.24 g of VAc and 11.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride were added, and the mixture was heated for an additional 3 hours. The solid content was 3.0%. The particle diameter retention rate before and after heating at 170°C for 1 minute was 70%.

[0160] <Synthesis example S2> In a reaction vessel purged with nitrogen, 0.5 g of tBuSty, 0.30 g of GMA, 0.014 g of DVB, and 25 ml of purified water were added, followed by 22.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and the mixture was heated and stirred at 65°C for 8 hours. Further, 0.24 g of MMA and 9.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride were added, and the mixture was heated for an additional 3 hours. The solid content was 2.9%. The particle diameter retention rate before and after heating at 170°C for 1 minute was 70%.

[0161] <Synthesis Example S3> In a reaction vessel purged with nitrogen, 0.5 g of tBuSty, 0.30 g of GMA, 0.014 g of DVB, and 25 ml of purified water were added, followed by 22.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and the mixture was heated and stirred at 65°C for 8 hours. Further, 0.06 g of tBuAAm, 0.183 g of tBuA, and 7.7 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride were added, and the mixture was heated for an additional 3 hours. The solid content was 2.5%. The particle diameter retention rate before and after heating at 170°C for 1 minute was 70%.

[0162] <Synthesis Example S4> In a reaction vessel purged with nitrogen, 0.5 g of tBuSty, 0.30 g of GMA, 0.014 g of DVB, and 25 ml of purified water were added, followed by 22.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and the mixture was heated and stirred at 65°C for 8 hours. Further, 0.12 g of StA, 0.12 g of tBuA, and 5.4 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride were added, and the mixture was heated for an additional 3 hours. The solid content was 2.5%. The particle diameter retention rate before and after heating at 170°C for 1 minute was 75%. <Synthesis Example S5> A nitrogen-purged reaction vessel was charged with 0.24 g of VAc, 25 ml of purified water, and 11.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and the mixture was heated and stirred for 3 hours. Furthermore, 0.50 g of tBuSty, 0.30 g of GMA, 0.014 g of DVB, and 22.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride were added, and the mixture was heated and stirred at 65°C for 8 hours. The solid content was 2.8%. The particle diameter retention rate before and after heating at 170°C for 1 minute was 70%.

[0163] <Examples 1 to 117> The aqueous dispersions of organic fine particles synthesized in Synthesis Examples 1 to 44 and the binder resins and emulsifiers synthesized in Synthesis Examples B1 to B9 were mixed in the proportions shown in Table 2 to prepare treatment solutions. 2 The emulsion was applied to a sheet of polyester (70 denier, gray) and various measurements (sliding speed test, contact angle measurement, water repellency test, strong water repellency test, and washing durability test) were carried out. The results are shown in Table 2. However, with the exception of Synthesis Examples 1 to 44, the proportions (g) shown in Table 2 only show the weight of the solid content, not the weight of the entire emulsion dispersion. For emulsifiers, crosslinking agents, etc., which were added in small amounts, a 3 wt % diluted aqueous solution was prepared separately and added. A scanning electron microscope (SEM) photograph of the PET fabric (Example 1) to which the organic fine particles of Synthesis Example 1 were attached is shown in FIG.

[0164] [Table 2-1]

[0165] [Table 2-2]

[0166] [Table 2-3]

[0167] [Table 2-4]

[0168] [Table 2-5]

[0169] [Table 2-6]

[0170] [Table 2-7]

[0171] [Table 2-8]

[0172] <Synthesis Examples 45-82> The same procedure as in Synthesis Example 1 was repeated, except that the monomers shown in Table 3 were used and the emulsifiers shown in Table 3 were added in the amounts shown in the table relative to the total amount of monomers for polymerization. <Examples 118 to 155> The particles obtained in Synthesis Examples 45 to 82 were mixed with 25 wt% solids of Binder B3 to adjust the treatment solution so that the particle concentration was 2.25%. The treatment solution was applied to PET cloth, and the sliding speed was measured. The results are shown in Table 3 as the sliding speed for each Synthesis Example. 1.1 g of an aqueous solution of Crosslinker 1 was added to 1 g of binder resin to the treatment solution. In Synthesis Examples 45 to 82, the particle diameter retention rate before and after heating at 170°C for 1 minute was 85% or more. In Synthesis Example 46, the particle diameter on the cloth was 198 nm.

[0173] <Synthesis Example 83> A 10 ml aqueous dispersion of 300 nm diameter crosslinked polymethyl methacrylate (PMMA) microparticles with a solids concentration of 20 wt% was added to a nitrogen-purged reaction vessel, along with 400 mg of polyethylene glycol monooleyl ether, 100 mg of sorbitan stearate, and 1 g of StA. After 3 hours, 16 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of PMMA / StA microparticles. The resulting aqueous dispersion was applied to a glass substrate, and the water contact angle measured after 1 minute of heating at 150°C was 105°. The particle diameter retention before and after 1 minute of heating at 170°C was 90%.

[0174] <Synthesis Example 84> Polymerization was carried out in the same manner as in Synthesis Example 83, except that the amount of StA added was 100 wt% relative to the solid content of PMMA, and 16 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added after 25 hours, to obtain an aqueous dispersion of PMMA / StA microparticles. The resulting aqueous dispersion was applied to a glass substrate, and the water contact angle measured after heating at 150°C for 1 minute was 111°. The particle diameter retention before and after heating at 170°C for 1 minute was 90%.

[0175] <Synthesis Example 85> Polymerization was carried out in the same manner as in Synthesis Example 83, except that the amount of StA added was 30 wt% relative to the solid content of PMMA, and 16 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added after 25 hours, to obtain an aqueous dispersion of PMMA / StA microparticles. The resulting aqueous dispersion was applied to a glass substrate, and after heating at 150°C for 1 minute, the water contact angle measured was 111°. The particle diameter retention before and after heating at 170°C for 1 minute was 90%.

[0176] <Synthesis Example 86> Polymerization was performed in the same manner as in Synthesis Example 83, except that the amount of StA added was 10 wt% relative to the solid content of PMMA, the total amount of emulsifier used was 1 / 5, and 16 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added after 18 hours, yielding an aqueous dispersion of PMMA / StA microparticles. The resulting aqueous dispersion was applied to a glass substrate, and after heating at 150°C for 1 minute, the water contact angle measured was 126°. The particle diameter retention before and after heating at 170°C for 1 minute was 90%.

[0177] <Synthesis Example 87> Polymerization was carried out in the same manner as in Synthesis Example 86, except that an aqueous dispersion of PMMA crosslinked microparticles with a diameter of 70 nm was used, to obtain an aqueous dispersion of PMMA / StA microparticles. The obtained aqueous dispersion was applied to a glass substrate, and after heating at 150°C for 1 minute, the water contact angle measured was 142°. The particle diameter retention rate before and after heating at 170°C for 1 minute was 90%.

[0178] <Synthesis Example 88> A nitrogen-purged reaction vessel was charged with 1.5 g of Sty, 38 mg of DVB, 86 mg of glyceryl stearate, 219 mg of polyethylene glycol monooleyl ether, and 10 g of purified water. After emulsification, 40 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and heated and stirred at 65°C. After 28 hours, 0.2 g of StA was emulsified with 28 mg of glyceryl stearate, 95 mg of polyethylene glycol monooleyl ether, and 1 g of purified water. This mixture was then added and heated and stirred for another 8 hours to obtain an aqueous dispersion of PSty / StA crosslinked microparticles. The resulting aqueous dispersion was applied to a glass substrate and heated at 150°C for 1 minute. The water contact angle measured after heating was 115°. The particle diameter retention before and after heating at 170°C for 1 minute was 85%.

[0179] <Synthesis Example 89> Polymerization was carried out in the same manner as in Synthesis Example 88, except that the initial emulsifiers were changed to 56 mg of glyceryl stearate and 144 mg of polyethylene glycol monooleyl ether, to obtain an aqueous dispersion of PSty / StA crosslinked microparticles. The resulting aqueous dispersion was applied to a glass substrate, and the water contact angle measured after heating at 150°C for 1 minute was 118°. The particle diameter retention before and after heating at 170°C for 1 minute was 90%.

[0180] <Synthesis Example 90> Polymerization was carried out in the same manner as in Synthesis Example 88, except that the initial emulsifiers were changed to 56 mg of glyceryl stearate and 144 mg of polyethylene glycol monooleyl ether, to obtain an aqueous dispersion of PSty / StA crosslinked microparticles. The resulting aqueous dispersion was applied to a glass substrate, and the water contact angle measured after heating at 150°C for 1 minute was 118°. The particle diameter retention before and after heating at 170°C for 1 minute was 90%.

[0181] <Synthesis Example 91> A nitrogen-purged reaction vessel was charged with 0.32 g of tBuSty (initial monomers), 0.38 g of GMA, 17 mg of DVB, 0.015 g of stearyltrimonium chloride, and 19 g of purified water. After emulsification, 18 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and the mixture was heated and stirred at 65°C. Thirty minutes after the addition of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 0.32 g of tBuSty and 17 mg of DVB were added as additional monomers. The mixture was heated and stirred for 8 hours to obtain an aqueous dispersion of crosslinked microparticles. Binder B8 was added at a solids content of 25 wt% to the particles in the resulting aqueous dispersion, resulting in a treatment solution with a particle concentration of 2.25%. The treatment solution was applied to PET fabric and evaluated for water repellency, scoring 90 points. The contact angle of the fabric was 140°. The particle diameter was maintained at 90% before and after heating at 170°C for 1 minute.

[0182] <Synthesis Examples 92-110> The same procedure as in Synthesis Example 91 was repeated, except that the monomers and amounts used as the initial monomer and additional monomer, and the emulsifier and amount used were those shown in Table 4. In Synthesis Example 109, the additional monomer was emulsified with 1.5% emulsifier relative to the monomer and added. In Synthesis Example 110, instead of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, tBu hydroperoxide and L-ascorbic acid were added in amounts of 1 mol % each relative to the monomer synthesis, and the synthesis was carried out at a temperature of 75°C.

[0183] <Examples 156 to 174> For Synthesis Examples 92 to 110, the water dispersions of the obtained particles were applied to a glass substrate, heated at 150° C. for 1 minute, and the water contact angles measured were shown in Table 4. For Synthesis Examples 92 to 96, 25 wt% of binder B8 was mixed with the resulting particles to adjust the particle concentration to 2.25%. For Synthesis Examples 97 to 110, 25 wt% of binder B3 was mixed with the resulting particles to adjust the particle concentration to 2.25%. The treatment solution was applied to PET cloth, and measurements of the sliding speed, water repellency, and strong water repellency were performed. The results are shown in Table 4 as the sliding speed, water repellency, and strong water repellency for each synthesis example. To the treatment solution, 1.1 g of an aqueous solution of crosslinker 1 was added per 1 g of binder resin. For Synthesis Examples 92 to 110, the particle diameter retention rate before and after heating at 170°C for 1 minute was 85% or more. FIG. 2 shows a scanning electron microscope (SEM) photograph of the PET fabric (Example 157) to which the organic fine particles of Synthesis Example 93, Binder B8, and Crosslinking Agent 1 were attached.

[0184] [Table 3]

[0185] [Table 4]

[0186] <Synthesis Example 111> A reaction vessel was charged with 1.00 g of t-butylstyrene (tBuSty), 0.049 g of divinylbenzene (DVB), 52 mg of emulsifier 1, and 19 ml of pure water and dispersed. After nitrogen substitution, 16.9 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of organic fine particles. The solids content was 4.54%. The particle size (average particle size) of the aqueous dispersion was 234 nm. This organic fine particles and the aqueous dispersion of Synthesis Example B8 were diluted with pure water to solids contents of 0.6% and 0.4%, respectively, for a total of 1 wt%, to obtain a treatment solution. PET fabric was immersed in this treatment solution and passed through a mangle. The heat-treated test fabric was evaluated for water repellency. The sliding speed was 209 mm / s, the water repellency rating was 100 points, and the strong water repellency rating was 3++ points. Moreover, the retention of particle diameter before and after heating at 170°C for 1 minute was 80%.

[0187] <Synthesis Example 112> A reaction vessel was charged with 0.39 g of tBuMA, 0.37 g of iBMA, 0.16 g of GMA, 0.072 g of DVB, 55 mg of emulsifier 1, and 19 ml of pure water and dispersed. After nitrogen substitution, 15.1 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of organic fine particles. The solids content was 4.80%. The particle size (average particle size) of the aqueous dispersion was 302 nm. This organic fine particles and the aqueous dispersion of Synthesis Example B8 were diluted with pure water to solids contents of 0.8% and 0.2%, respectively, for a total of 1 wt%, to obtain a treatment solution. PET fabric was immersed in this treatment solution and passed through a mangle. The heat-treated test fabric was evaluated for water repellency. The sliding speed was 179 mm / s, with a water repellency rating of 100 and a strong water repellency rating of 3. The particle diameter was maintained at 85% before and after heating at 170°C for 1 minute.

[0188] <Synthesis Example 113> A reaction vessel was charged with 0.90 g of iBMA, 0.052 g of DVB, 0.083 g of StA, 22 mg of emulsifier 1, 65 mg of a 23% aqueous solution of emulsifier 6, and 19 ml of pure water and dispersed. After nitrogen substitution, 12.1 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of organic fine particles. The solids content was 3.28%. The particle size (average particle size) of the aqueous dispersion was 137 nm. This organic fine particles and the aqueous dispersion of Synthesis Example B8 were diluted with pure water to solids contents of 0.8% and 0.2%, respectively, for a total of 1 wt%, to obtain a treatment solution. PET fabric was immersed in this treatment solution and passed through a mangle. The heat-treated test fabric was evaluated for water repellency. The sliding speed was 183 mm / s, the water repellency rating was 95 points, and the strong water repellency rating was 3 points. The particle diameter was maintained at 85% before and after heating at 170°C for 1 minute.

[0189] <Examples 175 to 178> The treatment solution was adjusted according to the ratio in Table 5, and PET Q15 (basis weight: 88 g / m 2 , 70 denier, gray) and PET R964 (basis weight 40g / m 2 The coating was applied to black and white cloth, and various measurements (water repellency test, dark color ΔL value measurement) were carried out. The results are shown in Table 5.

[0190] [Table 5]

[0191] Conventional color-enhancing agents tend to reduce water repellency, but Table 5 shows that the particles of the present disclosure can achieve a color-enhancing effect without impairing water repellency. [Industrial Applicability]

[0192] The organic microparticles of the present disclosure can be used as oil repellents, antifouling agents, soil release agents, stripping agents or mold release agents.

[0193] Another aspect of the present disclosure is as follows. [1] (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 30 carbon atoms; (3) a reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group; and (4) a crosslinking monomer having at least two ethylenically unsaturated double bonds; 1. Organic fine particles comprising a polymer having a repeating unit formed from: [2] The polymer further comprises: (5) A high glass transition point monomer whose homopolymer has a glass transition point of 100°C or higher The organic fine particles according to [1], having a repeating unit formed from [3] The organic fine particles according to [1] or [2], wherein the contact angle of the homopolymer of the hydrophobic monomer (1) is 70 to 120 degrees.

[0194] [4] The hydrophobic monomer (1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 (R 11 ) k or CH2=C(-R 22 )-Y 21 (H) 5-l (R 21 ) l [In the formula, R 11 and R 21 are each independently a hydrocarbon group having 3 to 40 carbon atoms, R 12 and R 22 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 is a divalent to tetravalent group consisting of at least one selected from a divalent to tetravalent hydrocarbon group having 1 carbon atom, -CH-, -O-, -C(=O)-, -S(=O)-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms) (excluding the case where it consists only of a divalent hydrocarbon group), Y 21 is a benzene ring, H is a hydrogen atom, H and R 21 is Y 21 are directly bonded to k and l are 1 to 3. is a monomer represented by The reactive / hydrophilic monomer (3) has the formula: CH2=C(-R 32 )-C(=O)-Y 31 -(R 33 ) o (R 31 ) m or CH2=C(-R 42 )-Y 41 -(H) 5-n (R 41 ) n [In the formula, R 31 and R 41 are each independently a reactive group or a hydrophilic group, R 32 and R 42 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 31 is a direct bond, -O-, or -NR'- (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 is Y 41 are directly bonded to m and n are 1 to 3; o is 0 or 1.] is a monomer represented by The crosslinking monomer (4) has the formula: TIFF0007759808000068.tif3825 TIFF0007759808000069.tif3331 or TIFF0007759808000070.tif3842[where, R 51 and R 61 are each independently a divalent to tetravalent group consisting of at least one selected from a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -(CHCHO)r- (r is an integer of 1 to 10), -CH-, -O-, or -NR'- (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'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), p is 2 to 4; q is 1 to 5. is a monomer represented by The high glass transition temperature monomer (5) has the formula: TIFF0007759808000071.tif3322 or TIFF0007759808000072.tif3433 [In the formula, R 71 and R 81 is a group consisting of at least one selected from a hydrocarbon group having 1 to 30 carbon atoms, —C6H4—, —O—, or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), R 72 and R 82 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 71 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms). The organic fine particles according to [2] or [3], wherein the monomer is a monomer represented by the formula:

[0195] [5] The organic fine particles according to any one of [1] to [4], wherein in the reactive monomer (3), the reactive group is an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group, or a blocked isocyanate group, and the hydrophilic group is at least one group selected from the group consisting of a hydroxyl group, an amino group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an alkali metal or alkaline earth metal salt of a carboxylic acid, a sulfonic acid, or a phosphoric acid, or an ammonium salt having a counter anion of a chlorine, bromine, or iodine ion.

[0196] [6] The hydrophobic monomer (1) is t-butyl (meth)acrylate, Nt-butyl (meth)acrylamide, t-butylstyrene, stearyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, stearamidoethyl (meth)acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 and at least one monomer selected from the group consisting of: The reactive / hydrophilic monomer (3) is glycidyl (meth)acrylate, glycerol (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, dimethylaminoethyl methacrylate At least one monomer selected from the group consisting of quaternized compounds, tetrahydrofurfuryl (meth)acrylate, The crosslinkable monomer (4) is selected from the group consisting of divinylbenzene, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, methylene glycol di(meth)acrylate, polytetramethyl at least one monomer selected from the group consisting of ethylene glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, trimethylol propane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and 5-hydroxy-1,3-adamantane di(meth)acrylate; The organic fine particles according to any one of [1] to [5], wherein the high glass transition point monomer (5) is at least one monomer selected from the group consisting of isobornyl (meth)acrylate, bornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, phenyl (meth)acrylate, naphthyl acrylate, and benzyl acrylate.

[0197] [7] The organic fine particles according to any one of [2] to [6], wherein the molar ratio of the hydrophobic monomer (1) / reactive and hydrophilic monomer (3) / high glass transition point monomer (5) is 20 to 99.9 / 0.1 to 50 / 0 to 70, and the crosslinkable monomer (4) is 0.1 to 30 molar parts per 100 molar parts in total of the hydrophobic monomer (1) and the reactive and hydrophilic monomer (3). [8] The organic fine particles according to any one of [1] to [7], which have a falling speed of 150 mm / sec or more when applied to a cloth. [9] The organic fine particles according to any one of [1] to [8], which have an average particle size of 30 nm to 1000 nm.

[0198]

[10] (A) Organic fine particles according to any one of [1] to [9], and (B) Aqueous medium A water repellent composition which is an aqueous dispersion of organic fine particles comprising:

[11] The water repellent composition according to

[11] , further comprising one or both of (C) a binder resin and (D) a surfactant.

[0199]

[12] The water repellent composition according to

[11] , wherein the binder resin (C) is at least one polymer selected from the group consisting of a non-fluorinated polymer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain and a fluorinated polymer having a fluoroalkyl group having 1 to 20 carbon atoms in the side chain.

[13] The water repellent composition according to

[12] or

[13] , wherein the amount of the surfactant (D) is 15 parts by weight or less per 100 parts by weight of the organic fine particles (A).

[0200]

[14] The water repellent composition according to any one of

[11] to

[13] , wherein the binder resin (C) is an acrylic polymer, a urethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, a polystyrene, a silicone polymer, or a combination thereof.

[15] The water repellent composition according to any one of

[10] to

[14] , which can prevent frost formation.

[16] a step of polymerizing the monomers (1) to (4) and, if necessary, the monomer (5) in an aqueous medium in the presence of a surfactant in an amount of 15 parts by weight or less per 100 parts by weight of the monomers to obtain an aqueous dispersion of organic fine particles (A); The method for producing a water repellent composition according to any one of

[10] to

[15] , comprising:

[0201]

[17] moreover, A process for obtaining an aqueous dispersion in which organic fine particles (A) and binder resin (C) are dispersed by adding an aqueous dispersion of binder resin (C) to an aqueous dispersion of organic fine particles (A), or by polymerizing a monomer for binder resin in the aqueous dispersion of organic fine particles (A) to obtain binder resin (C), or by polymerizing a monomer for organic fine particles in the aqueous dispersion of binder resin.

[16] The method for producing the present invention.

[18] A method for treating textile products, which comprises applying a treatment liquid containing the water repellent composition according to any one of

[10] to

[15] to the textile products.

[19] A textile product having organic fine particles and / or a binder resin in the water repellent composition according to any one of

[10] to

[15] attached to its surface.

[20] A textile product having a surface to which organic fine particles and / or a binder resin in the water repellent composition according to any one of

[10] to

[15] adheres, and having a falling speed of 200 mm / sec or more.

Claims

1. A water repellent composition containing organic fine particles, the organic fine particles can be attached to a substrate in a particulate state, and when attached to the substrate, exhibit water repellency on the substrate; The organic fine particles are (1) a monomer having a t-butyl group, and (4) a crosslinkable monomer having at least two ethylenically unsaturated double bonds; The polymer is formed from a non-fluorinated polymer having a repeating unit formed from The monomer having a t-butyl group has 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 [In the formula, R １１ and R ２１ are each independently a hydrocarbon group having 3 to 40 carbon atoms, R １１ and at least one of R ２１ at least one of is a t-butyl group, R １２ and R ２２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y １１ represents a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms) (excluding cases where the group is only a divalent hydrocarbon group), Y ２１ is a benzene ring, H is a hydrogen atom, H and R ２１ Is Y ２１ are directly bonded to k and l are 1 to 3. (1) a hydrophobic monomer represented by The water repellency When the organic fine particles are attached to a glass substrate, the water contact angle (i) is 100 degrees or more; The water contact angle (ii) when the organic fine particles are attached to a cloth is 120 degrees or more, or When organic fine particles are attached to a cloth, the falling speed (iii) is 100 mm / s or more. This means that The contact angle (i) is a static contact angle measured one second after the water repellent composition is drop-cast onto a glass substrate (a glass slide made of soda-lime glass) and heated at 150°C for 3 minutes to prepare a substrate having organic fine particles attached thereto, and 2 μL of water is dropped onto the glass substrate having the organic fine particles attached thereto. The contact angle (ii) was measured by applying a water repellent composition to a PET cloth (basis weight: 88 g / m ２ , 70 denier, gray) was immersed in the PET cloth, and then passed through a mangle and a pin tenter at 170°C for 1 minute to prepare a PET cloth having organic fine particles attached thereto. 2 μL of water was dropped onto the PET cloth, and the static contact angle after 1 second from the drop was measured. The sliding speed (iii) was measured by applying the water repellent composition to a PET cloth (basis weight: 88 g / m ２ , 70 denier, gray) was immersed in the PET cloth, and then passed through a mangle and a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. 20 μL of water was dropped from a microsyringe onto the PET cloth at an angle of 30 degrees, and the average falling speed of the dropped water over a distance of 40 mm was measured. Water repellent composition.

2. The contact angle (i) is 100 degrees or more, a contact angle (ii) of 120 degrees or more, or The water repellent composition according to claim 1, wherein the water repellent composition satisfies at least one of the following conditions: a falling speed (iii) of 100 mm / s or more;

3. When the organic fine particles are attached to a substrate and then heat-treated at 170°C for 1 minute, the average diameter of the organic fine particles after the heat treatment is 50% or more of the average diameter of the organic fine particles before the heat treatment, or 3. The water repellent composition according to claim 1, wherein the particle size of the fine particles observable on the fabric is 50 to 700 nm.

4. The non-fluorinated polymer (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one t-butyl group, and (5) High glass transition point monomers (excluding styrene) whose homopolymer has a glass transition point of 50°C or higher. A repeating unit formed from at least one monomer selected from The water repellent composition according to any one of claims 1 to 3, comprising:

5. 5. The water repellent composition according to claim 1, wherein the crosslinkable monomer is a compound having two ethylenically unsaturated double bonds.

6. The water repellent composition according to any one of claims 1 to 5, wherein the non-fluorinated polymer is a random polymer.

7. The non-fluorinated polymer further comprises (3) A reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group. and having a repeat unit formed from The water repellent composition according to any one of claims 4 to 6, wherein the glass transition temperature of the homopolymer of the monomer (5) is 100°C or higher.

8. The non-fluorinated polymer further comprises (2) (Meth)acrylic monomer having a polydimethylsiloxane group and having a repeat unit formed from The water repellent composition according to any one of claims 1 to 7, wherein a combination of a (meth)acrylic monomer having a hydrocarbon group having 12 to 24 carbon atoms in a side chain, among the hydrophobic monomers (1), and the (meth)acrylic monomer (2) is used in an amount such that the total weight of both monomers is less than 80 wt% of the total amount of the monomer components.

9. The water repellent composition according to any one of claims 1 to 8, wherein the organic fine particles are partly soluble organic fine particles obtained by polymerizing a monomer containing the monomer (4) and then polymerizing a monomer not containing the monomer (4).

10. 10. The water repellent composition according to claim 1, wherein the static contact angle of water on a silicon substrate treated with a homopolymer of the hydrophobic monomer (1) is 70 to 120 degrees.

11. The (meth)acrylic monomer (2) is represented by the formula: CH ２ =C(-R 9２ )-C(=O)-Y ９１ -R 9１ [In the formula, R 9１ is a group having a polydimethylsiloxane group, R ９２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y ９１ represents a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms) and is a divalent to tetravalent group. is a monomer represented by The reactive / hydrophilic monomer (3) has 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 [In the formula, R ３１ and R ４１ are each independently a reactive group or a hydrophilic group, R ３２ and R ４２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y ３１ is a direct bond, —O—, or —NR′— (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 Is Y ４１ are directly bonded to m and n are 1 to 3; o is 0 or 1. is a monomer represented by The crosslinkable monomer (4) is represented by the formula: or [In the formula, R ５１ and R ６１ each independently represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or —(CH ２ CH ２ O) r- (r is an integer of 1 to 10), -C ６ H ４ a divalent to tetravalent group consisting of at least one selected from -, -O-, and -NR'- (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′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), p is 2 to 4; q is 1 to 5. is a monomer represented by The high glass transition temperature monomer (5) is a compound represented by the formula: or [In the formula, R 7１ and R 8１ represents a hydrocarbon group having 1 to 30 carbon atoms, -C ６ H ４ a group consisting of at least one selected from -, -O-, and -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms); R ７２ and R ８２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y ７１ is —O— or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms). The water repellent composition according to any one of claims 1 to 10, wherein the monomer is represented by the formula:

12. The water repellent composition according to any one of claims 7 to 11, wherein in the reactive monomer (3), the reactive group is an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group, or a blocked isocyanate group, and the hydrophilic group is at least one group selected from the group consisting of a hydroxyl group, an amino group, a carboxylic acid group, a sulfonic acid group, a phosphate group, an alkali metal or alkaline earth metal salt of a carboxylic acid, a sulfonic acid, or a phosphate, or an ammonium salt having a counter anion of a chlorine, bromine, or iodine ion.

13. the hydrophobic monomer (1) is at least one monomer selected from the group consisting of t-butyl(meth)acrylate, N-t-butyl(meth)acrylamide, t-butylstyrene, and 2,4-di-t-butylstyrene; The (meth)acrylic monomer (2) is represented by the formula: or [In the formula, n is a number from 1 to 500.] and at least one monomer selected from the group consisting of: The reactive / hydrophilic monomer (3) is selected from the group consisting of glycidyl (meth)acrylate, glycerol (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, and dimethylaminoethyl methacrylate. at least one monomer selected from the group consisting of quaternized compounds, tetrahydrofurfuryl (meth)acrylate, The crosslinkable monomer (4) is selected from the group consisting of divinylbenzene, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, methylene glycol di(meth)acrylate, polytetramethyl at least one monomer selected from the group consisting of ethylene glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, trimethylol propane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and 5-hydroxy-1,3-adamantane di(meth)acrylate; The water repellent composition according to any one of claims 1 to 12, wherein the high glass transition point monomer (5) is at least one monomer selected from the group consisting of isobornyl (meth)acrylate, bornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, phenyl (meth)acrylate, naphthyl acrylate, and benzyl acrylate.

14. 14. The water repellent composition according to claim 1, wherein the molar ratio of the hydrophobic monomer (1) or (meth)acrylic monomer (2) to the reactive hydrophilic monomer (3) and the high glass transition point monomer (5) is 20 to 100 / 0 to 50 / 0 to 70, the crosslinkable monomer (4) is 0.1 to 30 molar parts per 100 molar parts in total of the hydrophobic monomer (1) and the reactive hydrophilic monomer (3), and the (meth)acrylic monomer (2) is 0 to 30 molar parts per 100 molar parts in total of the hydrophobic monomer (1), the (meth)acrylic monomer (2), and the reactive hydrophilic monomer (3).

15. The sliding speed (iii) of the organic fine particles when attached to a cloth is 150 mm / sec or more, The sliding speed (iii) was measured by applying the water repellent composition to a PET cloth (basis weight: 88 g / m ２ The water repellent composition according to any one of claims 1 to 14, wherein a PET fabric (70 denier, gray) is immersed in the water, passed through a mangle, and then passed through a pin tenter at 170°C for 1 minute to prepare a PET fabric having organic fine particles attached thereto, and 20 µL of water is dropped from a microsyringe onto the PET fabric at an angle of 30 degrees, and the average speed of the dropped water falling over a distance of 40 mm is 1.

16. 16. The water repellent composition according to claim 1, wherein the organic fine particles have an average particle size of 30 nm to 1000 nm.

17. A method for producing the water repellent composition according to any one of claims 1 to 16, comprising polymerizing a monomer containing the monomer (4) and then polymerizing a monomer not containing the monomer (4) to obtain organic fine particles.

18. A water repellent composition which is an aqueous dispersion of organic fine particles, the water repellent composition comprising: (A) Organic fine particles that can be attached to a substrate in a particulate state, and that exhibit water repellency on the substrate when attached to the substrate, and the organic fine particles are (1) a monomer having a t-butyl group, and (4) a crosslinkable monomer having at least two ethylenically unsaturated double bonds; The organic fine particles are formed of a non-fluorinated polymer having a repeating unit formed from The monomer having a t-butyl group has 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 [In the formula, R １１ and R ２１ are each independently a hydrocarbon group having 3 to 40 carbon atoms, at least one of R 11 and at least one of R 21 is a t-butyl group; R １２ and R ２２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y １１ represents a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms) (excluding cases where the group is only a divalent hydrocarbon group), Y ２１ is a benzene ring, H is a hydrogen atom, H and R ２１ Is Y ２１ are directly bonded to k and l are 1 to 3. (1) a hydrophobic monomer represented by and (B) Aqueous medium comprising The water repellency is When the organic fine particles are attached to a glass substrate, the water contact angle (i) is 100 degrees or more; The water contact angle (ii) when the organic fine particles are attached to a cloth is 120 degrees or more, or When organic fine particles are attached to a cloth, the falling speed (iii) is 100 mm / s or more. This means that The contact angle (i) is a static contact angle measured one second after the water repellent composition is drop-cast onto a glass substrate (a glass slide made of soda-lime glass) and heated at 150°C for 3 minutes to prepare a substrate having organic fine particles attached thereto, and 2 μL of water is dropped onto the glass substrate having the organic fine particles attached thereto. The contact angle (ii) was measured by applying a water repellent composition to a PET cloth (basis weight: 88 g / m ２ , 70 denier, gray) was immersed in the PET cloth, and then passed through a mangle and a pin tenter at 170°C for 1 minute to prepare a PET cloth having organic fine particles attached thereto. 2 μL of water was dropped onto the PET cloth, and the static contact angle after 1 second from the drop was measured. The sliding speed (iii) was measured by applying the water repellent composition to a PET cloth (basis weight: 88 g / m ２ A PET cloth (70 denier, gray) was immersed in the water repellent composition, and then passed through a mangle and a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. 20 μL of water was dropped from a microsyringe onto the PET cloth at an angle of 30 degrees, and the average speed at which the dropped water fell over a distance of 40 mm was measured.

19. The water repellent composition according to claim 18, further comprising one or more of (C) a binder resin, (D) a surfactant, and (E) a crosslinking agent.

20. The water repellent composition according to claim 19, wherein the binder resin (C) is at least one polymer selected from the group consisting of a non-fluorinated polymer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain and a fluorinated polymer having a fluoroalkyl group having 1 to 20 carbon atoms in the side chain.

21. 21. The water repellent composition according to claim 19 or 20, wherein the amount of the surfactant (D) is 15 parts by weight or less per 100 parts by weight of the organic fine particles (A).

22. The water repellent composition according to any one of claims 19 to 21, wherein the binder resin (C) is an acrylic polymer, a urethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, a polystyrene, a silicone polymer, or a combination thereof.

23. The water repellent composition according to any one of claims 18 to 22, which is capable of preventing frost formation.

24. The organic fine particles (A) (2) (Meth)acrylic monomer having a polydimethylsiloxane group The water repellent composition according to any one of claims 18 to 23, comprising a polymer having repeating units formed from

25. a step of polymerizing the monomer in an aqueous medium in the presence of a surfactant in an amount of 15 parts by weight or less relative to 100 parts by weight of the monomer to obtain an aqueous dispersion of organic fine particles (A); The method for producing the water repellent composition according to any one of claims 18 to 24, comprising:

26. moreover, A step of obtaining an aqueous dispersion in which organic fine particles (A) and binder resin (C) are dispersed by adding an aqueous dispersion of binder resin (C) to an aqueous dispersion of organic fine particles (A), or by polymerizing a monomer for binder resin in the aqueous dispersion of organic fine particles (A) to obtain binder resin (C), or by polymerizing a monomer for organic fine particles in the aqueous dispersion of binder resin. The method of claim 25, comprising:

27. A method for treating textile products, which comprises applying a treatment liquid containing the water repellent composition according to any one of claims 1 to 16 and 18 to 24 to the textile products.

28. A textile product having organic fine particles adhered to its surface, which has been treated with a treatment liquid containing the water repellent composition according to any one of claims 1 to 16 and 18 to 24.

29. At least one of the following is satisfied: when the organic fine particles are attached to a cloth, the water contact angle (ii) is 120 degrees or more; and when the organic fine particles are attached to a cloth, the sliding speed (iii) is 200 mm / sec or more. The contact angle (ii) was measured by applying a water repellent composition to a PET cloth (basis weight: 88 g / m ２ , 70 denier, gray) was immersed in the PET cloth, and then passed through a mangle and a pin tenter at 170°C for 1 minute to prepare a PET cloth having organic fine particles attached thereto. 2 μL of water was dropped onto the PET cloth, and the static contact angle after 1 second from the drop was measured. The sliding speed (iii) was measured by applying the water repellent composition to a PET cloth (basis weight: 88 g / m ２ The textile product according to claim 28, wherein a PET fabric having organic fine particles attached thereto is prepared by soaking the PET fabric in a PET cloth (70 denier, gray), passing the PET fabric through a mangle, and then passing the mangle through a pin tenter at 170°C for 1 minute, and then dropping 20 μL of water from a microsyringe onto the PET fabric at an incline of 30 degrees, and the average speed of the dropped water falling over a distance of 40 mm is 10 μL.

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