organic particles

Abstract

The present invention provides organic fine particles capable of adhering to a substrate in a particulate shape and exhibiting water repellency on the substrate when adhered to the substrate. There is provided an organic fine particle which is an organic fine particle containing a polymer having: (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms or (2) a repeating unit formed from a (meth)acrylic monomer having a polydimethylsiloxanyl group. The organic fine particles can impart excellent water repellency to the substrate.

Description

Technical Field

[0001] The present invention relates to organic fine particles, and more particularly to non-fluorinated organic fine particles. Background Art

[0002] Conventionally, by performing chemical treatment such as coating with a fluororesin or a silicone resin, water repellency is imparted to the surface of a substrate such as metal, glass, paper, cloth, or plastic. For example, by coating with a fluororesin, a water-repellent substrate surface having a water contact angle of about 120° can be obtained.

[0003] In addition, by a method of forming a fine concavo-convex structure on the substrate surface or a method of combining the formation of such a fine concavo-convex structure on the substrate surface with the above coating treatment, super water repellency with a water contact angle of 150° or more is imparted to the substrate surface. In the production of the concavo-convex structure, a method using fine particles or a method of patterning such as etching can be mainly cited. The range and substrates that can be used for patterning methods such as etching are limited.

[0004] When hydrophobic inorganic fine particles are used as 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 hydrophobic inorganic fine particles with a reduced hydrophobicity, that is, hydrophobic inorganic fine particles having hydrophilic groups remaining, are used, although the dispersion in water becomes slightly easier, the hydrophobicity of the fine particles themselves is reduced, and thus the performance as a water repellent is reduced.

[0005] On the other hand, there are also soap-free polymerization or organic fine particle synthesis methods with a small amount of emulsifier. In these methods, since there is no emulsifier or a small amount of emulsifier is dispersed in water, hydrophilic monomers are generally almost always used, and the fine particles also exhibit hydrophilicity. Since it is difficult to use monomers with high hydrophobicity, it is difficult to synthesize organic fine particles exhibiting water repellency using soap-free polymerization or organic fine particle synthesis methods with a small amount of emulsifier.

[0006] Past literature (especially patent gazettes) has disclosed imparting water repellency to organic fine particles, but the examples are limited to inorganic fine particles.

[0007] Patent Document 1 discloses a method for manufacturing a water-repellent coating film, which is characterized by including a first step of forming an abrasion-resistant base film using fine particles (A) having an average particle diameter of 15 to 500 μm, a resin composition (B), and a solvent (C); and a second step of forming a super water-repellent finishing film using fine particles (a) having an average particle diameter 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 super water-repellent finishing film are silica, which are inorganic fine particles.

[0008] Patent Document 2 discloses a non-fluorinated polymer containing a structural unit derived from a (meth)acrylate monomer and a structural unit derived from a silicone oil having a (meth)acryloyl group.

[0009] In the past, there has been a problem of dark coloration. Generally, in fiber products, synthetic fibers, especially polyester fibers, are widely used in various applications. However, compared with natural fibers such as wool or silk, they are inferior in terms of characteristics such as the shade, depth, and vividness of the color in dyed products. Therefore, there is a tendency for the commercial value of products on the market to be evaluated lower.

[0010] As a countermeasure against such problems, various proposals have been made to improve the characteristics such as the shade, depth, and vividness of the color 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 contains 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 (for example, refer to Patent Document 3). It is said that this darkening agent can impart a good darkening effect to fiber products. However, in fibers that require water repellency, the darkening agent tends to reduce the water repellency.

[0011] Prior Art Documents

[0012] Patent Documents

[0013] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2012 - 20248

[0014] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2016 - 199712

[0015] Patent Document 3: Japanese Unexamined Patent Application Publication No. 9 - 3774 Summary of the Invention

[0016] Technical Problem to be Solved by the Invention

[0017] The present invention provides organic fine particles capable of imparting excellent water repellency to a substrate.

[0018] Technical Solution for Solving the Technical Problem

[0019] The present invention 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 shape.

[0020] In the present invention, the exhibited water repellency means at least one of the following:

[0021] (i) When attached to a glass substrate, the contact angle of water is 100 degrees or more.

[0022] (ii) When attached to cloth, the contact angle of water is 120 degrees or more; or

[0023] (iii) When attached to cloth, the slipping speed is 100 mm / s or more.

[0024] The polymer constituting the organic fine particles preferably has a repeating unit formed from the following monomers:

[0025] (1) A hydrophobic monomer having 1 ethylenically unsaturated double bond and at least 1 hydrocarbon group having 3 to 40 carbon atoms, and / or

[0026] (2) A (meth)acrylic monomer having a polydimethylsiloxanyl group.

[0027] The present invention relates to a water-repellent composition containing (A) organic fine particles and (B) an aqueous medium.

[0028] Moreover, the present invention relates to organic fine particles containing the following polymer, the polymer having a repeating unit formed from the following (1) hydrophobic monomer and / or (2) (meth)acrylic monomer:

[0029] (1) A hydrophobic monomer having 1 ethylenically unsaturated double bond and at least 1 hydrocarbon group having 3 to 40 carbon atoms,

[0030] (2) A (meth)acrylic monomer having a polydimethylsiloxanyl group.

[0031] Furthermore, the present invention relates to organic fine particles containing a polymer having a repeating unit formed from the following monomers:

[0032] (1) A hydrophobic monomer having 1 ethylenically unsaturated double bond and at least 1 hydrocarbon group having 3 to 40 carbon atoms,

[0033] (3) A reactive / hydrophilic monomer having 1 ethylenically unsaturated double bond and at least 1 reactive group and / or hydrophilic group, and

[0034] (4) A crosslinkable monomer having at least 2 ethylenically unsaturated double bonds.

[0035] Preferred embodiments of the present invention are as follows.

[0036] Embodiment 1:

[0037] An organic fine particle which is an organic fine particle capable of attaching to a substrate in a particulate state and exhibits water repellency on the substrate when attached to the substrate.

[0038] Embodiment 2:

[0039] The organic fine particles as described in Method 1 satisfy at least any one of the following conditions:

[0040] (i) When attached to a glass substrate, the static contact angle of water on the glass substrate is 100 degrees or more; (ii) When attached to a cloth, the static contact angle of water on the cloth is 120 degrees or more; or (iii) When attached to a cloth, the sliding speed of water on the cloth is 100 mm / s or more.

[0041] Method 3:

[0042] The organic fine particles as described in Method 1 or 2, wherein when heat-treated at 170 °C for 1 minute after being attached to a substrate, the average diameter of the heat-treated organic fine particles is 50% or more of the average diameter of the organic fine particles before heat treatment, or the particle size of the fine particles observable on the cloth is 50 to 700 nm.

[0043] Method 4:

[0044] An organic fine particle comprising a polymer having a repeating unit formed from the following (1) hydrophobic monomer or (2) (meth)acrylic monomer,

[0045] (1) A hydrophobic monomer having 1 ethylenically unsaturated double bond and at least 1 hydrocarbon group having 3 to 40 carbon atoms;

[0046] (2) A (meth)acrylic monomer having a polydimethylsiloxanyl group.

[0047] Method 5:

[0048] The organic fine particles as described in Method 4, wherein the polymer further has a repeating unit formed from (4) a crosslinkable monomer having at least 2 ethylenically unsaturated double bonds.

[0049] Method 6:

[0050] The organic fine particles as described in Method 4 or 5, wherein the polymer further has a repeating unit formed from at least one monomer selected from the following (3) reactive / hydrophilic monomer and (5) high glass transition temperature monomer,

[0051] (3) A reactive / hydrophilic monomer having 1 ethylenically unsaturated double bond and at least 1 reactive group and / or hydrophilic group;

[0052] (5) A high glass transition temperature monomer having a glass transition temperature of 100 °C or more for the homopolymer.

[0053] Method 7:

[0054] The organic fine particles according to any one of Modes 4 to 6, wherein in the hydrophobic monomer (1), a combination of a (meth)acrylic acid monomer having a hydrocarbon group with 12 to 24 carbon atoms in the side chain and the (meth)acrylic acid monomer (2) is used in an amount such that the total weight of the two monomers is less than 80% by weight of the total monomer components.

[0055] Mode 8:

[0056] The organic fine particles according to any one of Modes 4 to 7, wherein after polymerizing the monomer containing the monomer (4), a part of the particles obtained by polymerizing the monomer not containing the monomer (4) can be melted.

[0057] Mode 9:

[0058] The organic fine particles according to any one of Modes 4 to 8, wherein the static contact angle of water on the silicon substrate treated with the homopolymer of the hydrophobic monomer (1) is 70 to 120 degrees.

[0059] Mode 10:

[0060] The organic fine particles according to any one of Modes 4 to 9, wherein the hydrophobic monomer (1) is a monomer represented by the following formula:

[0061] CH 2 =C(-R 12 )-C(=O)-Y 11 (R 11 ) k

[0062] or

[0063] CH 2 =C(-R 22 )-Y 21 (H) 5－l (R 21 ) l

[0064] [In the formula, R 11 and R 21 are each independently a hydrocarbon group having 3 to 40 carbon atoms,

[0065] R 12 and R 22 are a hydrogen atom, a monovalent organic group, or a halogen atom,

[0066] Y 11 is selected from a hydrocarbon group having 1 to 4 carbon atoms with a valence of 2 to 4, -C 6 H 4 -, -O-, -C(=O)-, -S(=O) 2a divalent to tetravalent group composed of at least one of — or —NR’— (wherein R’ is H or a hydrocarbon group having 1 to 4 carbon atoms) (however, the case of only a divalent hydrocarbon group is excluded),

[0067] Y 21 is a benzene ring,

[0068] H is a hydrogen atom,

[0069] H and R 21 are directly bonded to Y 21 respectively,

[0070] k and l are 1 to 3.];

[0071] (Meth)acrylic monomer (2) is a monomer represented by the following formula:

[0072] CH 2 =C(-R 92 )-C(=O)-Y 91 -R 91

[0073] [In the formula, R 91 is a group having a polydimethylsiloxanyl group,

[0074] R 92 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0075] Y 91 is a divalent to tetravalent group composed of at least one selected from a hydrocarbon group having 1 carbon atom, —C 6 H 4 —, —O—, —C(=O)—, —S(=O) 2 — or —NR’— (wherein R’ is H or a hydrocarbon group having 1 to 4 carbon atoms).];

[0076] Reactive / hydrophilic monomer (3) is a monomer represented by the following formula:

[0077] CH 2 =C(-R 32 )-C(=O)-Y 31 -(R 33 ) o (R 31 ) m

[0078] or

[0079] CH 2 =C(-R 42 )-Y 41 -(H) 5－n (R 41 ) n

[0080] [In the formula, R 31 and R 41 are each independently a reactive group or a hydrophilic group,

[0081] R 32 and R 42 are a hydrogen atom, a monovalent organic group or a halogen atom,

[0082] Y 31 is a valence bond, -O-, or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0083] R 33 is a hydrocarbon group having 1 to 10 carbon atoms with a valence of 2 to 4,

[0084] Y 41 is a benzene ring,

[0085] H is a hydrogen atom,

[0086] H and R 41 are directly bonded to Y 41 respectively,

[0087] m and n are 1 to 3,

[0088] o is 0 or 1.];

[0089] The crosslinkable monomer (4) is a monomer represented by the following formula:

[0090]

[0091] [In the formula, R 51 and R 61 are each independently a group having a valence of 2 to 4 composed of at least one selected from a valence bond, a hydrocarbon group having 1 to 20 carbon atoms, -(CH 2 CH 2 O)r-(r is an integer of 1 to 10), -C 6 H 4 -, -O-, or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0092] R 52 and R 62 are each independently a hydrogen atom, a monovalent organic group or a halogen atom,

[0093] Y 51 is -O- or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0094] p is 2 to 4,

[0095] q is 1 to 5.];

[0096] The monomer with a high glass transition temperature (5) is a monomer represented by the following formula:

[0097]

[0098] [In the formula, R 71 and R 81 are groups composed of at least one selected from hydrocarbon groups having 1 to 30 carbon atoms, -C 6 H 4 -, -O-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0099] R 72 and R 82 are hydrogen atoms, monovalent organic groups, or halogen atoms,

[0100] Y 71 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms).].

[0101] Mode 11:

[0102] The organic fine particles according to any one of Modes 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, a blocked isocyanate group, and the hydrophilic group is at least one group selected from 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 base of a carboxylic acid, a sulfonic acid, a phosphoric acid; an ammonium base in which a chloride ion, a bromide ion, or an iodide ion is a paired anion.

[0103] Mode 12:

[0104] The organic fine particles according to any one of Modes 4 to 11, wherein the hydrophobic monomer (1) is at least one monomer selected from tert-butyl (meth)acrylate, N-tert-butyl (meth)acrylamide, tert-butylstyrene, stearyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-tert-butylstyrene, 2,4,6-trimethylstyrene, stearic acid amide ethyl (meth)acrylate, CH 2 =CHC(=O)OC 2 H 4 NHSO 2 C 18 H 37 and the (meth)acrylic acid monomer (2) is at least one monomer selected from the following formulas:

[0105] (Meth)acrylic acid monomer (2) is at least one monomer selected from the following formulas:

[0106]

[0107]

[0108] [In the formula, n is a number from 1 to 500.];

[0109] The reactive / hydrophilic monomer (3) is at least one monomer selected from glycidyl (meth)acrylate, glycerol (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (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, glycidyl ether of 4-hydroxybutyl acrylate, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, quaternized dimethylaminoethyl methacrylate, tetrahydrofuryl (meth)acrylate;

[0110] The crosslinking monomer (4) is at least one monomer selected from 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, polytetramethylene glycol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentyl di(meth)acrylate, 5-hydroxy-1,3-adamantyl di(meth)acrylate;

[0111] The high glass transition temperature monomer (5) is at least one monomer selected from isobornyl (meth)acrylate, bornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, phenyl (meth)acrylate, naphthyl acrylate, benzyl acrylate.

[0112] Mode 13:

[0113] The organic fine particles according to any one of Modes 3 to 12, wherein the molar ratio of the hydrophobic monomer (1) or (meth)acrylic monomer (2) / reactive-hydrophilic monomer (3) / high glass transition temperature monomer (5) is 20 to 100 / 0 to 50 / 0 to 70, the crosslinkable monomer (4) is 0.1 to 30 mol parts with respect to 100 mol parts in total of the hydrophobic monomer (1) and the reactive-hydrophilic monomer (3), and the (meth)acrylic monomer (2) is 0 to 30 mol parts with respect to 100 mol parts in total of the hydrophobic monomer (1), the (meth)acrylic monomer (2), and the reactive-hydrophilic monomer (3).

[0114] Mode 14:

[0115] The organic fine particles according to any one of Modes 1 to 13, wherein, when treating cloth, it has a slipping speed of 150 mm / second or more.

[0116] Mode 15:

[0117] The organic fine particles according to any one of Modes 1 to 14, wherein the average particle diameter is 30 nm to 1000 nm.

[0118] Mode 16:

[0119] A method for producing organic fine particles, which is used to produce the organic fine particles according to any one of Modes 3 to 14. In this production method, after polymerizing the monomers containing the monomer (4), the monomers not containing the monomer (4) are polymerized to obtain the organic fine particles.

[0120] Mode 17:

[0121] A water repellent composition, which is an aqueous dispersion of organic fine particles containing (A) the organic fine particles according to any one of Modes 1 to 15 and (B) an aqueous medium.

[0122] Mode 18:

[0123] The water repellent composition according to Mode 17, which further contains any one or more of (C) an adhesive resin, (D) a surfactant, and (E) a crosslinking agent.

[0124] Mode 19:

[0125] The water repellent composition according to Mode 18, wherein the adhesive resin (C) is at least one polymer selected from a non-fluorine polymer having a hydrocarbon group with 3 to 40 carbon atoms in the side chain and a fluorine-containing polymer having a fluoroalkyl group with 1 to 20 carbon atoms in the side chain.

[0126] Mode 20:

[0127] The water repellent composition according to Mode 18 or 19, wherein

[0128] The amount of surfactant (D) is 15 parts by weight or less relative to 100 parts by weight of the organic fine particles (A).

[0129] Mode 21:

[0130] The water-repellent composition according to any one of Modes 18 to 20, wherein the binder resin (C) is an acrylic polymer, a polyurethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, a polystyrene, a silicone polymer, and combinations thereof.

[0131] Mode 22:

[0132] The water-repellent composition according to any one of Modes 17 to 21, which can prevent frosting.

[0133] Mode 23:

[0134] A method for producing a water-repellent composition for producing the water-repellent composition according to any one of Modes 17 to 22, the production method including: a step of polymerizing monomers in an aqueous medium in the presence of a surfactant that is 15 parts by weight or less relative to 100 parts by weight of the monomers to obtain an aqueous dispersion of organic fine particles (A).

[0135] Mode 24:

[0136] The production method according to Mode 23, which includes the following steps:

[0137] A step of obtaining an aqueous dispersion in which organic fine particles (A) and a binder resin (C) are dispersed by adding an aqueous dispersion of the binder resin (C) to the aqueous dispersion of the organic fine particles (A), or by polymerizing monomers for the binder resin in the aqueous dispersion of the organic fine particles (A), or by polymerizing monomers for the organic fine particles in the aqueous dispersion of the binder resin.

[0138] Mode 25:

[0139] A method for treating a fiber product, which applies a treatment liquid containing the water-repellent composition according to any one of Modes 17 to 22 to the fiber product.

[0140] Mode 26:

[0141] A fiber product, wherein organic fine particles and / or a binder resin in the water-repellent composition according to any one of Modes 17 to 22 are attached to the surface.

[0142] Mode 27:

[0143] A fiber product, wherein organic fine particles and / or a binder resin in the water-repellent composition according to any one of Modes 17 to 22 are attached to the surface,

[0144] And satisfy at least any one of the conditions that the static contact angle of water on the cloth is 120 degrees or more or the sliding speed of water on the cloth is 200 mm / second or more.

[0145] Effects of the Invention

[0146] The organic fine particles and water-repellent composition of the present invention can impart excellent water repellency (especially high strong water repellency) to substrates such as fiber products. In the case of fiber products treated with the water-repellent composition of the present invention, the slipperiness of water droplets is excellent. In addition, especially the sliding speed is high, so it is suitable for uses requiring high water repellency.

[0147] In the organic fine particles, by making the main chain softer than the inorganic fine particles, the particles themselves can have motility by heating. Therefore, when in water, by positioning the hydrophilic group on the outermost surface, they can be stably dispersed, and after being coated on the substrate and dried, the hydrophobic part with a small surface free energy can be positioned on the outermost surface. Even for the fine particles imparted with hydrophilicity, by the segregation of the hydrophobic part on the surface after coating, they can become fine particles showing high water repellency.

[0148] The colorant has a tendency to reduce the water repellency, but the organic fine particles of the present invention can exhibit a color intensifying effect without impairing the water repellency. Description of the Drawings

[0149] Figure 1 It is a scanning electron microscope (SEM) photograph of a PET cloth (Example 1) to which the organic fine particles of Synthesis Example 1 are attached.

[0150] Figure 2 It is a scanning electron microscope (SEM) photograph of a PET cloth (Example 157) to which the organic fine particles of Synthesis Example 93, binder B8, and crosslinking agent 1 are attached. Detailed Description of the Invention

[0151] The water-repellent composition comprises (A) organic fine particles and (B) an aqueous medium.

[0152] The water-repellent composition may further comprise (C) a binder resin and / or (D) a surfactant. By including the binder resin (C), higher water repellency can be obtained.

[0153] In a preferred embodiment, the water-repellent composition comprises the following components.

[0154] Organic fine particles (A),

[0155] Organic fine particles (A) + aqueous medium (B),

[0156] Organic fine particles (A) + aqueous medium (B) + binder resin (C),

[0157] Organic fine particles (A) + aqueous medium (B) + surfactant (D),

[0158] Organic fine particles (A) + aqueous medium (B) + binder resin (C) + surfactant (D)

[0159] Organic fine particles (A) + aqueous medium (B) + binder resin (C) + crosslinking agent (E) or

[0160] Organic fine particles (A) + aqueous medium (B) + binder resin (C) + surfactant (D) + crosslinking agent (E)

[0161] (A) Organic fine particles

[0162] The organic fine particles act as an effective component for imparting water repellency. The organic fine particles are preferably formed of a non-fluorine polymer.

[0163] From the viewpoints of water repellency and the stability of the aqueous dispersion, the average particle diameter of the organic fine particles can be 30 to 1000 nm, preferably 50 to 700 nm or 200 to 600 nm. The average particle diameter refers to the average particle diameter of the particles measured by the dynamic light scattering method (DLS).

[0164] The organic fine particles maintain their particle shape on the substrate and exhibit water repellency.

[0165] The exhibited water repellency means that:

[0166] (i) When attached to a glass substrate, the contact angle of water is 100 degrees or more;

[0167] (ii) When attached to cloth, the contact angle of water is 120 degrees or more; or

[0168] (iii) The sliding speed when attached to cloth is 100 mm / s or more.

[0169] On a glass substrate coated with a composition containing organic fine particles, the contact angle of water (i.e., the contact angle of water on the glass substrate coated with organic fine particles or the contact angle of water on the glass substrate coated with organic fine particles and an adhesive (and other components)) is 100 degrees or more, for example, it can be 110 degrees or more, and particularly can be 118 degrees or more and 180 degrees or less. Specifically, the contact angle of water on the glass substrate coated with the composition containing organic fine particles can be measured by the following operation: that is, the composition containing organic fine particles is drop-cast on a glass substrate (slide glass: made of soda-lime glass), heated at 150 °C for 3 minutes to prepare a substrate coated with organic fine particles, 2 μL of water is dropped on the glass substrate coated with organic fine particles, and the static contact angle 1 second after dropping is measured using a fully automatic contact angle meter (Drop Master 701 manufactured by Kyowa Interface Science).

[0170] On a cloth coated with a composition containing organic fine particles, the contact angle of water (the contact angle of water on the cloth coated with organic fine particles or the contact angle of water on the cloth coated with organic fine particles and an adhesive (and other components)) 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 the cloth is measured by the following operation: that is, a PET cloth (unit area weight: 88 g / m 2 2, 70 denier, gray) is impregnated with the composition containing organic fine particles, the cloth is tied with a cloth-tying machine, and passed through a pin tenter at 170 °C for 1 minute to prepare a PET cloth coated with organic fine particles. 2 μL of water is dropped on the PET cloth, and the static contact angle 1 second after dropping is measured using a fully automatic contact angle meter (Drop Master 701 manufactured by Kyowa Interface Science).

[0171] In a cloth (PET cloth), the sliding speed of water 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 when 20 μL of water is dropped using a microsyringe on a substrate inclined at 30 degrees and slides a distance of about 40 mm. Specifically, a PET cloth (unit area weight: 88 g / m 2 2, 70 denier, gray) is impregnated with the composition containing organic fine particles, the cloth is tied with a cloth-tying machine, and passed through a pin tenter at 170 °C for 1 minute to prepare a PET cloth coated with organic fine particles. Using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science), for a PET cloth inclined at 30 degrees, 20 μL of water is dropped using a microsyringe, and the manner in which the dropped water slides is measured using a high-speed camera (VW-9000 manufactured by Keyence Corporation), and the average sliding speed for a distance of about 40 mm is taken as the sliding speed.

[0172] The unevenness of fine particles on a substrate can be observed with a laser microscope or a scanning electron microscope. After coating the particles on the substrate, before and after heating at 170°C for 1 minute, preferably, the average diameter (average particle size) of the particles after heating is 50% or more, more preferably 60% or more, of that before heating. Alternatively, the average particle size of the fine particles observable on the cloth is preferably 30 to 1000 nm, more preferably 50 to 700 nm or 40 to 500 nm. This average particle size is preferably the average particle size after heating at 170°C for 1 minute usually after coating the particles on the substrate.

[0173] In some embodiments, the organic fine particles comprise a polymer having repeating units formed from (1) a hydrophobic monomer and / or (2) a (meth)acrylic monomer:

[0174] (1) A hydrophobic monomer having 1 ethylenically unsaturated double bond and at least 1 hydrocarbon group having 3 to 40 carbon atoms;

[0175] (2) A (meth)acrylic monomer having a polydimethylsiloxanyl group.

[0176] In some embodiments, the organic fine particles comprise a polymer having repeating units formed from (1) a hydrophobic monomer, (3) a reactive / hydrophilic monomer, and (4) a crosslinkable monomer:

[0177] (1) A hydrophobic monomer having 1 ethylenically unsaturated double bond and at least 1 hydrocarbon group having 3 to 40 carbon atoms;

[0178] (3) A reactive / hydrophilic monomer having 1 ethylenically unsaturated double bond and at least 1 reactive group and / or hydrophilic group;

[0179] (4) A crosslinkable monomer having at least 2 ethylenically unsaturated double bonds.

[0180] The polymer constituting the organic fine particles is preferably a non-fluoropolymer.

[0181] (1) Hydrophobic monomer

[0182] The hydrophobic monomer (1) has at least 1 ethylenically unsaturated double bond and at least 1 hydrocarbon group having 3 to 40 carbon atoms.

[0183] The static contact angle of water with the homopolymer of the 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 the hydrophobic monomer (1) is 80°C or higher, the static contact angle of water with the homopolymer is preferably 90 degrees or higher, more preferably 97 degrees or higher. Further, when the hydrophobic monomer (1) has a branched hydrocarbon group (for example, a branched alkyl group), particularly a tert-butyl group or an isopropyl group, or a group having a multi-branched structure as shown in the following formula, it is preferred that the static contact angle of water with the homopolymer is 75 to 115 degrees.

[0184]

[0185] The static contact angle of the homopolymer is the value of the static contact angle measured with a water droplet of 2 μl after a solution prepared by dissolving the homopolymer in a good solvent (especially chloroform) is coated on a silicon substrate and heated at 80°C. Specifically, a chloroform solution of the homopolymer (solid component concentration: 1.0%) is spin-coated on a silicon wafer substrate (high-purity silicon wafer for research AS ONE 2-960-55), heated at 80°C for 15 minutes to form a coating film, 2 μL of water is dropped onto this coating film, and the static contact angle 1 second after the drop is measured using a fully automatic contact angle meter (Drop Master 701 manufactured by Kyowa Interface Science Co., Ltd.).

[0186] 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 the benzene ring). The hydrophobic monomer (1) is preferably a non-fluorine monomer.

[0187] The hydrophobic monomer (1) is preferably a monomer represented by the following formula:

[0188] CH 2 =C(-R 12 )-C(=O)-Y 11 (R 11 ) k

[0189] or

[0190] CH 2 =C(-R 22 )-Y 21 (H) 5－l (R 21 ) l

[0191] [In the formula, R 11 and R 21 are each independently a hydrocarbon group having 3 to 40 carbon atoms,

[0192] R 12 and R 22 are a hydrogen atom, a monovalent organic group, or a halogen atom,

[0193] Y 11 is a hydrocarbon group having 1 carbon atom with a valence of 2 to 4 (especially selected from -CH 2 -, -CH=, and -C≡), -C 6 H4 —, —O—, —C(=O)—, —S(=O) 2 — or —NR’— (R’ is H or a hydrocarbon group having 1 to 4 carbon atoms), and at least one divalent to tetravalent group (excluding the case of only a divalent hydrocarbon group),

[0194] Y 21 is a benzene ring,

[0195] H is a hydrogen atom,

[0196] H and R 21 are directly bonded to Y 21 respectively,

[0197] k and l are 1 to 3.

[0198] R 11 and R 21 are preferably branched or long-chain (or long-chain straight-chain) hydrocarbon groups. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The —CH 3 group has a lower surface free energy than —CH 2 — and is prone to exhibit water repellency. Therefore, a structure with many branches and many —CH 3 groups is preferred. In the branched hydrocarbon group, the number of —CH 3 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 having 16 to 40 carbon atoms) exhibits high water repellency due to its crystallinity. Therefore, a branched hydrocarbon group (e.g., a branched alkyl group), particularly a tert-butyl group or an isopropyl group or a hydrocarbon group with a multi-branched structure having 5 to 30 carbon atoms, for example, a multi-branched structure group as shown in the following formula or a long-chain hydrocarbon group (or long-chain straight-chain hydrocarbon group), such as an alkyl group having 16 to 40 or 16 to 26 carbon atoms, particularly 18 to 22 carbon atoms. The long-chain hydrocarbon group is preferably a stearyl group, an eicosyl group or a docosyl group.

[0199]

[0200] k is 1, 2 or 3. However, in the case where Y 11 has a tetravalent hydrocarbon group having 1 carbon atom (specifically, a branched —C≡), etc., k = 3. In the case where Y 11 has a trivalent hydrocarbon group having 1 carbon atom (e.g., a branched —CH=), etc., k = 2. In the case where Y 11 does not have a trivalent and tetravalent hydrocarbon group having 1 carbon atom (e.g., in the case where Y 11 has a divalent hydrocarbon group having 1 carbon atom (—CH 2 —) (e.g., 1 to 6)), k = 1.

[0201] R 12 and R 22 may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group. Alternatively, it may be -CF 3 group. R 12 and R 22 examples are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, -CF 3 group, a cyano group. R 12 and R 22 are preferably a hydrogen atom, a methyl group or a chlorine atom. R 12 is more preferably a methyl group. By making R 12 a methyl group, higher water repellency can be obtained. Especially from the viewpoint of reactivity, R 22 is preferably a hydrogen atom.

[0202] Y 11 is preferably a divalent group or a trivalent group, and particularly preferably a divalent group.

[0203] Examples of the C1 hydrocarbon group having a valence of 2 to 4 are -CH 2 -, the branched -CH= and the branched -C≡.

[0204] When Y 11 is a divalent group, it may or may not have -CH 2 -. When Y 11 is a trivalent group, it preferably has a branched structure -CH=, and particularly preferably has

[0205] -CH 2 -( -H(C - ) - ) - CH 2 -,

[0206] i.e.,

[0207]

[0208] Y 11 may be -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'-

[0209] [wherein, Y' are each independently a valence bond, -O-,-NR'-(R' is H or a C1-C4 hydrocarbon group) or -S(=O) 2 -,

[0210] X' is -(CH 2 ) m -(where m is an integer from 1 to 5), a linear hydrocarbon group with an unsaturated bond and 1 to 5 carbon atoms, a branched hydrocarbon group with 1 to 5 or 3 to 5 carbon atoms, or -(CH 2 ) l -C 6 H 4 -(CH 2 ) l -(where l is independently an integer from 0 to 5, -C 6 H 4 - is a phenylene group).].

[0211] The branched hydrocarbon group with 3 to 5 carbon atoms can be divalent, trivalent or tetravalent. Specific examples of the branched hydrocarbon group with 3 to 5 carbon atoms are:

[0212] -CH(CH 3 )-CH 2 -(divalent),

[0213]

[0214] (divalent),

[0215] -CH 2 -(-H(C-)-)-CH 2 -(trivalent),

[0216] That is,

[0217]

[0218] Specific examples of Y 11 as a divalent group are -O-, -NH-, -O-C(=O)-, -NH-C(=O)-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C 6 H 4 -, -NH-C 6 H 4 -, -O-(CH 2 ) m -O-, -NH-(CH 2 ) m -NH-, -O-(CH 2 ) m -NH-, -NH-(CH 2 ) m -O-, -O-(CH 2 ) m -O-C(=O)-, -O-(CH2 ) m -C(=O)-O-, -NH-(CH 2 ) m -O-C(=O)-, -NH-(CH 2 ) m -C(=O)-O-, -O-(CH 2 ) m -O-C(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-O-, -O-(CH 2 ) m -C(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-, -O-(CH 2 ) m -NH-C(=O)-NH-, -O-(CH 2 ) m -O-C 6 H 4 -, -O-(CH 2 ) m -NH-S(=O) 2 -, -O-(CH 2 ) m -S(=O) 2 -NH-, -NH-(CH 2 ) m -NH-S(=O) 2 -, -NH-(CH 2 ) m -S(=O) 2 -NH-, -NH-(CH 2 ) m -O-C(=O)-NH-, -NH-(CH 2 ) m -NH-C(=O)-O-, -NH-(CH 2 ) m -C(=O)-NH-, -NH-(CH 2 ) m -NH-C(=O)-, -NH-(CH 2 ) m -NH-C(=O)-NH-, -NH-(CH 2 ) m -O-C 6 H 4 - or -NH-(CH 2 ) m -NH-C 6 H4 - [wherein, m is an integer from 1 to 5, particularly 2 or 4].

[0219] Y as a divalent group 11 is preferably -O-, -NH-, -O-(CH 2 ) m -O-C(=O)-, -O-(CH 2 ) m -NH-C(=O)-, -O-(CH 2 ) m -O-C(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-O-, -O-(CH 2 ) m -NH-C(=O)-NH-, -O-(CH 2 ) m -NH-S(=O) 2 - or -O-(CH 2 ) m -S(=O) 2 -NH-, -NH-(CH 2 ) m -O-C(=O)-, -NH-(CH 2 ) m -NH-C(=O)-, -NH-(CH 2 ) m -O-C(=O)-NH-, -NH-(CH 2 ) m -NH-C(=O)-O-, -NH-(CH 2 ) m -NH-C(=O)-NH-

[0220] [wherein, m is an integer from 1 to 5, particularly 2 or 4].

[0221] Y as a divalent group 11 is more preferably -O-, -O-(CH 2 ) m -O-C(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-O- or -O-(CH 2 ) m -NH-C(=O)-, -O-(CH 2 ) m -NH-S(=O) 2 - or -O-(CH 2 ) m -S(=O)2 -NH-, especially -O-(CH 2 ) m -NH-C(=O)

[0222] [wherein, m is an integer of 1 to 5, especially 2 or 4].

[0223] Y as a trivalent group 11 is preferably

[0224]

[0225] Y 21 is a benzene ring. The monomer having Y 21 has a styryl group. In the monomer having Y 21 , 1 to 3 R 21 groups and 2 to 4 hydrogen atoms are bonded to the benzene ring.

[0226] Specific examples of the hydrophobic monomer are as described below. The compounds of the following chemical formulas are acrylic compounds with a hydrogen atom at the α-position, but specific examples can be methacrylic compounds with a methyl group at the α-position and α-chloroacrylic compounds with a chlorine atom at the α-position, and preferably methacrylic compounds with a methyl group at the α-position. In addition, among styrene derivatives, the compounds of the following chemical formulas are also acrylic compounds with a hydrogen atom at the α-position, but specific examples can be α-methylstyrene compounds with a methyl group at the α-position and α-chlorostyrene compounds with a chlorine atom at the α-position, and preferably styrene compounds with a hydrogen atom at the α-position.

[0227]

[0228]

[0229] [In the above formula, n is a number from 3 to 40, and m is a number from 1 to 5.]

[0230]

[0231]

[0232]

[0233] [wherein, tBu is a tert-butyl group.]

[0234] Preferred specific examples of the hydrophobic monomer (1) are tert-butyl (meth)acrylate, N-tert-butyl (meth)acrylamide, tert-butylstyrene, stearyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-tert-butylstyrene, 2,4,6-trimethylstyrene, stearic acid amidoethyl (meth)acrylate, CH 2=CHC(=O)OC 2 H 4 NHSO 2 C 18 H37, 4-tert-butylphenyl (meth)acrylate, 2,3,4-trimethylphenyl (meth)acrylate.

[0235] (2) (Meth)acrylic monomers having a polydimethylsiloxanyl group

[0236] (Meth)acrylic monomer (2) has a polydimethylsiloxanyl group in the side chain.

[0237] (Meth)acrylic monomer (2) is preferably a monomer represented by the following formula:

[0238] CH 2 =C(-R 92 )-C(=O)-Y 91 -R 91

[0239] [In the formula, R 91 is a group having a polydimethylsiloxanyl group,

[0240] R 92 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0241] Y 91 is a 2- to 4-valent group composed of at least one selected from a hydrocarbon group having 1 carbon atom with 2 to 4 valences, -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).].

[0242] R 91 is a group having a polydimethylsiloxanyl group, preferably a group represented by the average formula:

[0243] -(SiR 2 O) a SiR 3

[0244] [In the formula, a is 2 to 4000, for example, 3 to 400,

[0245] each R is independently a monovalent alkyl group having 1 to 12 carbon atoms, and at least 2 Rs are methyl groups.].

[0246] R 92 is preferably a hydrogen atom, a methyl group or a chlorine atom.

[0247] Y 91Preferably 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 -C 3 H 6 -), -O-(CH 2 ) p -), -O-(CH 2 ) p -NHC(=O)-(CH 2 ) q - or -NH-(CH 2 ) q - (p is a number from 1 to 5, q is a number from 1 to 5.).

[0248] Specific examples of the (meth)acrylic acid monomer (2) are:

[0249]

[0250]

[0251] [In the formula, n is a number from 1 to 500.].

[0252] When the (meth)acrylic acid monomer (2) is used together with a (meth)acrylic acid monomer (or any hydrophobic monomer (1)) having a hydrocarbon group having 3 to 40 or 3 to 30 (particularly 12 to 24) carbon atoms in the hydrophobic monomer (1), the total weight of the (meth)acrylic acid monomer (2) and the hydrophobic monomer (1) is preferably used in an amount less than 80% by weight, particularly less than 50% by weight or less than 40% by weight, of the total amount of the monomer components. That is, it is preferably used in an amount less than 80% by weight, particularly less than 50% by weight or less than 40% by weight, of the total amount of the monomer components, a combination of a repeating unit formed from a (meth)acrylic acid monomer having a hydrocarbon group having 3 to 40 or 12 to 24 carbon atoms in the hydrophobic monomer (1) and a repeating unit formed from the (meth)acrylic acid monomer (2).

[0253] In some embodiments, the constituent monomers are not composed only of a combination of the hydrophobic monomer (1) which is a (meth)acrylic acid monomer having a hydrocarbon group having 3 to 40 or 3 to 30 (particularly 12 to 24) carbon atoms and the (meth)acrylic acid monomer (2). In some embodiments, the combination of the hydrophobic monomer (1) which is a (meth)acrylic acid monomer having a hydrocarbon group having 3 to 40 or 3 to 30 (particularly 12 to 24) carbon atoms and the (meth)acrylic acid monomer (2) may not be used.

[0254] (3) Reactive / Hydrophilic Monomer

[0255] The reactive / hydrophilic monomer (3) has 1 ethylenically unsaturated double bond and at least 1 reactive group and / or hydrophilic group.

[0256] Examples of the reactive group are epoxy groups (e.g., glycidyl groups), chloromethyl groups, bromomethyl groups, iodomethyl groups, and blocked isocyanate groups.

[0257] Examples of the hydrophilic group are hydroxyl groups, amino groups, carboxyl groups, sulfonic acid groups, and phosphoric acid groups; alkali metal or alkaline earth metal bases of carboxylic acids, sulfonic acids, and phosphoric acids; and ammonium bases with chloride ions, bromide ions, or iodide ions as counter anions.

[0258] The reactive / hydrophilic monomer (3) is preferably a non-fluorine monomer.

[0259] The reactive / hydrophilic monomer (3) is preferably a monomer represented by the following formula:

[0260] CH 2 =C(-R 32 )-C(=O)-Y 31 -(R 33 ) o (R 31 ) m

[0261] or

[0262] CH 2 =C(-R 42 )-Y 41 -(H) 5-n (R 41 ) n

[0263] [In the formula, R 31 and R 41 are each independently a reactive group or a hydrophilic group,

[0264] R 32 and R 42 are a hydrogen atom, a monovalent organic group, or a halogen atom,

[0265] Y 31 is a valence bond, -O-, or -NR’- (R’ is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0266] R 33 is a valence bond or a group of a hydrocarbon group having 2 to 4 valences and 1 to 10 carbon atoms,

[0267] Y 41 is a benzene ring,

[0268] H is a hydrogen atom,

[0269] H and R 41 are directly bonded to Y 41 respectively,

[0270] m and n are 1 to 3,

[0271] o is 0 or 1.

[0272] R 31 and R 41 are monovalent groups. Examples of reactive groups or hydrophilic groups in R 31 and R 41 are as described above.

[0273] R 32 and R 42 can be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group. Or it can be a -CF 3 group. Examples of R 32 and R 42 are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a -CF 3 group, a cyano group. R 32 and R 42 are preferably a hydrogen atom, a methyl group, a chlorine atom. R 32 is more preferably a methyl group. By making R 32 a methyl group, higher water repellency can be obtained. Especially from the viewpoint of reactivity, R 42 is preferably a hydrogen atom.

[0274] Y 31 is preferably -O- or -NH-.

[0275] R 33 is preferably a hydrocarbon group having 1 to 10 carbon atoms and 2 to 4 valences. Examples of hydrocarbon groups having 1 carbon atom and 2 to 4 valences are -CH 2 -, a branched -CH=, and a branched -C≡. R 33 is preferably a divalent alkylene group, for example, -(CH 2 ) r -(r is a number from 1 to 5.) Or a divalent or trivalent or tetravalent alkyl group, for example, -(CH 2 ) r -(CH-) s -H (r is a number from 1 to 5, s is 1, 2 or 3. The positions of the CH 2 group and the CH- group may not be in the order described.)

[0276] Y 41 is a benzene ring. The monomer having Y 41 has a styryl group. In the monomer having Y 41 , 1 to 3 R 41 groups and 2 to 4 hydrogen atoms are bonded to the benzene ring.

[0277] 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, glycidyl ether of 4-hydroxybutyl acrylate, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, quaternized dimethylaminoethyl methacrylate, tetrahydrofuranyl (meth)acrylate; and

[0278] 4-hydroxymethylstyrene, 4-hydroxyethylstyrene, 4-aminomethylstyrene, 4-aminoethylstyrene, 2-(4-vinylphenyl)oxirane, 2-(4-vinylbenzoyl)oxirane.

[0279] (4) Crosslinkable monomer

[0280] The crosslinkable monomer (4) is a compound having at least 2 (especially 2, 3 or 4) ethylenically unsaturated double bonds. The crosslinkable monomer (4) is preferably a non-fluorine monomer.

[0281] The crosslinkable monomer (4) is preferably a monomer represented by the following formula:

[0282]

[0283] [In the formula, R 51 and R 61 are each independently a divalent to tetravalent group composed of at least one selected from a valence bond or a hydrocarbon group having 1 to 20 carbon atoms, -(CH 2 CH 2 O) r -(r is an integer from 1 to 10), -C 6 H 4 -, -O- or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0284] R 52 and R 62 are a hydrogen atom, a monovalent organic group or a halogen atom,

[0285] Y 51 is -O- or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0286] p is from 2 to 4,

[0287] and q is from 1 to 5.

[0288] R 51 and R 61 Examples of R and R are valence bonds, hydrocarbon groups having 2 to 4 valences (e.g., 2 to 3 valences) with 1 to 20 carbon atoms (or 2 to 10 carbon atoms) that can be interrupted by oxygen atoms and / or in which hydrogen atoms can be replaced by OH groups, ethylene glycol groups, propylene glycol groups, glycerol groups, cyclohexyl groups, dicyclopentyl groups, adamantyl groups, isobornyl groups, naphthyl groups, borneol groups, tricyclodecyl groups, and phenyl groups, or groups containing any of these groups. R 51 and R 61 can be polymer groups, and the structural units constituting the polymer groups can be the exemplified groups above (e.g., ethylene glycol groups).

[0289] R 52 and R 62 can each independently be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group. Or it can be a -CF 3 group. R 52 and R 62 Examples of R and R are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a -CF 3 group, and a cyano group. R 52 and R 62 are preferably a hydrogen atom, a methyl group, or a chlorine atom. R 52 More preferably, it is a methyl group. By having R 52 as a methyl group, higher water repellency can be obtained. Especially from the viewpoint of reactivity, R 62 is preferably a hydrogen atom, but from the viewpoint of water repellency, it is preferably a methyl group. To balance its reactivity and water repellency, it is preferable to select R 62 .

[0290] The crosslinkable monomer (4) is preferably di(meth)acrylate or divinylbenzene.

[0291] Specific examples of the crosslinkable monomer (4) are 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, polytetramethylene glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentyl di(meth)acrylate, 5-hydroxy-1,3-adamantane di(meth)acrylate.

[0292] (5) Monomer with a high glass transition temperature

[0293] The polymer may have repeating units formed from monomers with a high glass transition temperature.

[0294] The glass transition temperature of the homopolymer of the monomer with a high glass transition temperature (5) is 50 °C or higher, preferably 100 °C or higher. The glass transition temperature of the homopolymer is, for example, 120 °C or higher, particularly may be 150 °C or higher, and may be 250 °C or lower.

[0295] The glass transition temperature (glass transition temperature) of the homopolymer is calculated by differential scanning calorimetry (DSC). By heating 10 mg of the sample at 10 °C / min, a DSC curve is obtained, and it can be determined as the temperature represented by the midpoint of the intersection of the extension lines of the respective baselines before and after the secondary transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[0296] The monomer with a high glass transition temperature (5) is preferably a non-fluorine monomer.

[0297] The monomer with a high glass transition temperature (5) is a monomer represented by the following formula:

[0298]

[0299]

[0300] [In the formula, R 71 and R 81 are groups composed of at least one or more selected from hydrocarbon groups having 1 to 30 carbon atoms, -C 6 H 4 -, -O-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0301] R 72 and R 82is a hydrogen atom, a monovalent organic group or a halogen atom,

[0302] Y 71 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms).

[0303] R 71 and R 81 Examples of R are cyclohexyl, dicyclopentyl, dicyclopentenyl, adamantyl, isobornyl, naphthyl, bornyl, tricyclodecyl, phenyl.

[0304] R 72 and R 82 can be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group. Or it can be -CF 3 group. R 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, -CF 3 group, a cyano group. R 72 and R 82 are preferably a hydrogen atom, a methyl group, a chlorine atom. R 72 is more preferably a methyl group. By making R 72 a methyl group, higher water repellency can be obtained. On the other hand, especially from the viewpoint of reactivity, R 82 is preferably a hydrogen atom, but is preferably a methyl group from the viewpoint of water repellency. In order to balance its reactivity and water repellency, it is preferable to select R 82 .

[0305] Y 71 is preferably -O- or -NH-.

[0306] Specific examples of the high glass transition temperature monomer (5) are:

[0307] Acrylic acid esters such as cyclohexyl acrylate, isobornyl acrylate, bornyl acrylate, adamantyl acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, tricyclodecyl acrylate, phenyl acrylate, naphthyl acrylate, benzyl acrylate, 2-tert-butylphenyl acrylate, naphthyl acrylate;

[0308] Methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid isopropyl ester, methacrylic acid tert-butyl ester, methacrylic acid cyclohexyl ester, methacrylic acid isobornyl ester, methacrylic acid bornyl ester, methacrylic acid adamantyl ester, methacrylic acid dicyclopentyl ester, methacrylic acid dicyclopentenyl ester, methacrylic acid tricyclodecyl ester, methacrylic acid phenyl ester, methacrylic acid naphthyl ester, methacrylic acid benzyl ester, methacrylic acid (2-dimethylamino)ethyl ester, methacrylic acid aziridinyl ester, methacrylic acid aziridinylethyl ester, methacrylic acid dicyclopentenyl ester, etc. methacrylic acid esters;

[0309] Chloroacrylic acid esters such as methyl chloroacrylate;

[0310] Tert-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, dicyclopentyl (meth)acrylamide, dicyclopentenyl (meth)acrylamide, tricyclodecyl (meth)acrylamide, benzyl (meth)acrylamide, naphthyl (meth)acrylamide, 2-tert-butylphenyl (meth)acrylamide.

[0311] The high glass transition temperature monomer (5) is preferably isobornyl (meth)acrylate, bornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, phenyl (meth)acrylate, naphthyl acrylate, benzyl acrylate, and particularly preferably isobornyl (meth)acrylate.

[0312] (6) Other monomers

[0313] Other monomers (6) other than monomers (1) to (2) may also be used.

[0314] Examples of other monomers (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. Other monomers (6) are preferably non-fluorine monomers. Other monomers are not limited to these examples.

[0315] In this specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylamide" means acrylamide or methacrylamide.

[0316] Each of monomers (1) to (6) may be a single kind alone, or may be a mixture of two or more kinds.

[0317] In the present invention, the preferred combinations of monomers in the polymer are as follows.

[0318] Monomer (1) + Monomer (4)

[0319] Monomer (1) + Monomer (5)

[0320] Monomer (1) + Monomer (3) + Monomer (4)

[0321] Monomer (1) + Monomer (3) + Monomer (5)

[0322] Monomer (1) + Monomer (4) + Monomer (5)

[0323] Monomer (1) + Monomer (3) + Monomer (4) + Monomer (5)

[0324] Monomer (2) + Monomer (4)

[0325] Monomer (4) + Monomer (5)

[0326] Monomer (2) + Monomer (5)

[0327] Monomer (2) + Monomer (3) + Monomer (4)

[0328] Monomer (2) + Monomer (3) + Monomer (5)

[0329] Monomer (2) + Monomer (4) + Monomer (5)

[0330] Monomer (2) + Monomer (3) + Monomer (4) + Monomer (5)

[0331] Monomer (1) + Monomer (2) + Monomer (3) + Monomer (4)

[0332] Monomer (1) + Monomer (2) + Monomer (4) + Monomer (5)

[0333] Monomer (1) + Monomer (2) + Monomer (3) + Monomer (4) + Monomer (5)

[0334] Monomer (1) + Monomer (2) + Monomer (3) + Monomer (4) + Monomer (5) + Monomer (6)

[0335] The particularly preferred combinations are as follows.

[0336] Monomer (1) + Monomer (3) + Monomer (4)

[0337] Monomer (1) + Monomer (4) + Monomer (5)

[0338] Monomer (2) + Monomer (3) + Monomer (4)

[0339] Monomer (2) + Monomer (3) + Monomer (5)

[0340] Monomer (1) + Monomer (2) + Monomer (3) + Monomer (4)

[0341] Monomer (1) + Monomer (2) + Monomer (4) + Monomer (5)

[0342] Monomer (1) + Monomer (3) + Monomer (4) + Monomer (5)

[0343] Monomer (1) + Monomer (2) + Monomer (3) + Monomer (4) + Monomer (5)

[0344] In the polymer, the molar ratio of the hydrophobic monomer (1) or (meth)acrylic acid monomer (2) / reactive-hydrophilic monomer (3) / high glass transition temperature monomer (5) can be 20 to 100 / 0 to 50 / 0 to 70. Alternatively, the molar ratio of the hydrophobic monomer (1) or (meth)acrylic acid monomer (2) / reactive-hydrophilic monomer (3) / high glass transition temperature monomer (5) can be 20 to 99.9 / 0.1 to 50 / 0 to 70, preferably 20 to 99.5 / 0.5 to 50 / 0 to 68. The molar ratio of the hydrophobic monomer (1) or (meth)acrylic acid monomer (2) / reactive-hydrophilic monomer (3) can be 50 to 99 / 1 to 50, preferably 55 to 98 / 2 to 45. The molar ratio of the hydrophobic monomer (1) or (meth)acrylic acid monomer (2) / high glass transition temperature monomer (5) can be 50 to 99 / 1 to 50, preferably 55 to 98 / 2 to 45. The crosslinkable monomer (4) can be 0.1 to 30 mol parts, for example 0.1 to 25 mol parts, based on the total 100 mol parts of the hydrophobic monomer (1), (meth)acrylic acid monomer (2), high glass transition temperature monomer (5) and reactive-hydrophilic monomer (3).

[0345] Alternatively, the molar ratio of one or both of the hydrophobic monomer (1) or (meth)acrylic acid monomer (2) / reactive-hydrophilic monomer (3) / high glass transition temperature monomer (5) can be 50 to 95 / 0 to 30 / 0 to 30, 60 to 95 / 0 to 30 or 1 to 20 / 0 to 30 or 1 to 20, 80 to 95 / 0 to 15 or 1 to 10 / 0 to 15 or 1 to 10, 85 to 95 / 0 to 15 or 1 to 10 / 0 to 15 or 1 to 10. The amount of the crosslinkable monomer (4) can be 0 to 20 parts by weight, 1 to 15 parts by weight or 2 to 10 parts by weight based on 100 parts by weight of the polymer.

[0346] The amount of the other monomer (6) can be 0 to 10% by weight, for example 0.1 to 5% by weight, based on the polymer.

[0347] The water-repellent polymer can be a random polymer or a block copolymer, preferably a random polymer.

[0348] (B) Aqueous medium

[0349] The water-repellent composition contains an aqueous medium. The aqueous medium is water or a mixture of water and an organic solvent.

[0350] The water-repellent composition is usually an aqueous dispersion in which a polymer is dispersed in an aqueous medium (water or a mixture of water and an organic solvent).

[0351] The aqueous medium can be water alone or a mixture of water and a (water-miscible) organic solvent. The amount of the organic solvent can be 30% by weight or less, for example 10% by weight or less, relative to the liquid medium. The aqueous medium is preferably water alone.

[0352] When the water-repellent polymer and the aqueous medium are set to a total of 100 parts by weight, the amount of the aqueous medium can be 50 to 99.5 parts by weight, particularly 70 to 99.5 parts by weight.

[0353] (C) Binder resin

[0354] The binder resin functions as a binder that binds the organic fine particles to the substrate. A water-repellent resin is preferably used as the binder resin. The water-repellent resin also functions as an active ingredient that exhibits water repellency. Examples of the binder resin are acrylic polymers, polyurethane polymers, polyolefins, polyesters, polyethers, polyamides, polyimides, polystyrenes, and silicone polymers.

[0355] The water-repellent resin is a non-fluorinated polymer having a hydrocarbon group with 3 to 40 carbon atoms in the side chain or a fluorinated polymer having a fluoroalkyl group with 1 to 20 carbon atoms in the side chain. The water-repellent resin is preferably a non-fluorinated polymer.

[0356] In the non-fluorinated polymer having a hydrocarbon group with 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 —CH 3 group has a lower surface free energy than —CH 2 — and exhibits water repellency. Therefore, a branched hydrocarbon group (e.g., a branched alkyl group), particularly a structure having more branched —CH 3 groups, such as a structure of tert-butyl, isopropyl, 2,6,8-trimethylnonan-4-yl, etc., is preferred. In the branched hydrocarbon group, the number of —CH 3 groups is preferably 2 to 15, for example 3 to 10 or 4 to 8. The number of carbon atoms of the long-chain hydrocarbon group (or long-chain linear hydrocarbon group) can be 7 to 40 or 12 to 30, for example 16 to 26, particularly 18 to 22.

[0357] Examples of the water-repellent resin are polyurethane polymers, silicone polymers, acrylic polymers, and polystyrenes.

[0358] Examples of non-fluoropolymers include amidoamine dendrimers having long-chain hydrocarbon groups, as described in US Patent No. 8,703,894. The disclosure of this document is incorporated herein by reference.

[0359] Polyurethane polymers having a hydrocarbon group with 3 to 40 carbon atoms in the 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 with 3 to 40 carbon atoms.

[0360] Polyurethanes having a branched structure such as a tert-butyl group, isopropyl group, 2,6,8-trimethylnonan-4-yl group, etc. in the 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 branched structure such as a tert-butyl group, isopropyl group, 2,6,8-trimethylnonan-4-yl group, etc.

[0361] Examples of polyurethane polymers include polyurethane compounds having long-chain hydrocarbon groups, which contain sorbitan tristearate, sorbitan monostearate, and polyfunctional isocyanurate, as described in US Patent Publication 2014 / 0295724. The disclosure of this document is incorporated herein by reference. Examples of polyurethane polymers include polyurethanes having long-chain hydrocarbon groups, as described in Japanese Patent Application Laid-Open No. 2019-519653 (International Publication No. 2018 / 007549). The disclosure of this document is incorporated herein by reference.

[0362] Organosilicon polymers having a hydrocarbon group with 3 to 40 carbon atoms in the side chain can be produced, for example, by reacting a dichlorosilane compound containing a dichlorosilane having a hydrocarbon group with 3 to 40 carbon atoms.

[0363] Polyorganosilicons having a branched structure such as a tert-butyl group, isopropyl group, 2,6,8-trimethylnonan-4-yl group, etc. in the side chain can be produced, for example, by reacting a dichlorosilane compound containing a dichlorosilane having a branched structure such as a tert-butyl group, isopropyl group, 2,6,8-trimethylnonan-4-yl group, etc.

[0364] An example of an organosilicon polymer is long-chain alkyl-modified polydimethylsiloxane.

[0365] Acrylic polymers having a hydrocarbon group with 3 to 40 carbon atoms in the side chain can be produced by polymerizing monomers containing acrylic monomers having a hydrocarbon group with 3 to 40 carbon atoms in the side chain. Examples of acrylic monomers are the same as those described in the above hydrophobic monomer (1). Specific examples of acrylic monomers are, for example:

[0366] (Meth)acrylic acid stearyl ester, (meth)acrylic acid docosyl ester,

[0367]

[0368] (especially (meth)acrylic acid stearic acid amide ethyl ester)

[0369] [In the above formula, n is a number from 7 to 40, and m is a number from 1 to 5.].

[0370] An acrylic polymer having a branched structure such as a tert-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 tert-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 in the above hydrophobic monomer (1). Specific examples of the acrylic monomer are, for example, (meth)acrylic acid tert-butyl ester, (meth)acrylic acid isopropyl ester, and 2,6,8-trimethylnonan-4-yl acrylate.

[0371] As an example of the acrylic polymer, there is a polymer containing a repeating unit derived from an acrylic monomer having a long-chain hydrocarbon group such as (meth)acrylic acid docosyl ester or (meth)acrylic acid stearyl ester, and a repeating unit derived from vinylidene chloride and / or vinyl chloride.

[0372] As an example of the acrylic polymer, there is a polymer containing a repeating unit derived from an acrylic monomer having a long-chain hydrocarbon group such as (meth)acrylic acid docosyl ester or (meth)acrylic acid stearyl ester, a repeating unit derived from vinylidene chloride and / or vinyl chloride, and a repeating unit derived from styrene or α-methylstyrene. This acrylic polymer can be used in admixture with paraffin. This example is described in Japanese Patent Application Laid-Open No. 2012-522062 (International Publication No. 2010 / 115496). The disclosure of this document is incorporated herein by reference.

[0373] As an example of the acrylic polymer, there is a polymer containing a repeating unit derived from an acrylic monomer having a long-chain hydrocarbon group such as (meth)acrylic acid stearyl ester, a repeating unit derived from vinylidene chloride and / or vinyl chloride, and a repeating unit derived from a reactive emulsifier such as polyoxyalkylene vinyl ether. This is described in Japanese Patent Application Laid-Open No. 2017-25440 (International Publication No. 2017 / 014131). The disclosure of this document is incorporated herein by reference.

[0374] In a fluoropolymer having a fluoroalkyl group having 1 to 20 carbon atoms in the side chain, the fluoroalkyl group is preferably a perfluoroalkyl group.

[0375] Examples of the fluorine-containing water-repellent resin include fluorine-containing acrylic polymers containing repeating units formed from (meth)acrylates having a perfluoroalkyl group with 4 to 8 carbon atoms in the side chain and long-chain alkyl (meth)acrylates such as docosyl (meth)acrylate or stearyl (meth)acrylate.

[0376] Other monomers can also be used in polyurethane polymers, silicone polymers, acrylic polymers, and polystyrene, which are non-fluorine polymers and fluorine-containing polymers.

[0377] Examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, vinyl chloride, poly(ethylene glycol) (meth)acrylate, poly(propylene glycol) (meth)acrylate, methoxypoly(ethylene glycol) (meth)acrylate, methoxypoly(propylene glycol) (meth)acrylate, (meth)acrylates having a polydimethylsiloxane in the side chain, and vinyl alkyl ethers. Other monomers are not limited to these examples.

[0378] (D) Surfactant

[0379] The water-repellent composition may or may not contain a surfactant (emulsifier). Usually, in order to stabilize the particles during polymerization and the aqueous dispersion after polymerization, a small amount (for example, 0.01 to 15 parts by weight relative to 100 parts by weight of the monomer) of a surfactant can be added during polymerization, or a surfactant can be added after polymerization.

[0380] When the object to be treated is a fiber product, particularly in the water-repellent composition, the surfactant preferably contains a nonionic surfactant. In addition, the surfactant preferably contains one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. A combination of a nonionic surfactant and a cationic surfactant is preferably used.

[0381] Each of the nonionic surfactant, cationic surfactant, and amphoteric surfactant can be one kind or a combination of two or more.

[0382] The amount of the surfactant can be 15 parts by weight or less (for example, 0 to 15 parts by weight or 0.01 to 15 parts by weight) relative to 100 parts by weight of the organic fine particles (A), and is preferably 8 parts by weight or less. Generally, if a surfactant is added, the stability of the aqueous dispersion and the permeability to the cloth are improved, but the water-repellent performance is reduced. In order to balance these effects, it is preferable to select the type and amount of the surfactant.

[0383] (E) Crosslinking agent

[0384] The crosslinking agent (E) is preferably a substance that undergoes crosslinking upon heating after treating the fabric with an aqueous dispersion of organic fine particles. Additionally, it is preferred that the crosslinking agent itself is also dispersed in water.

[0385] Preferred examples of the crosslinking agent (E) are blocked isocyanate compounds. Blocked isocyanate compounds can be produced by reacting

[0386] [which may be A(NCO) m (wherein A is the group remaining after removing the isocyanate group from the polyisocyanate, and m is an integer from 2 to 8).] isocyanate with

[0387] [which may be RH (wherein R may be a hydrocarbon group that can be substituted by a heteroatom such as a nitrogen atom or an oxygen atom, and H is a hydrogen atom)] blocking agent.

[0388] A(NCO) m For example, it is benzylidene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), etc.

[0389] Examples of the blocking agent that forms the R group are oxime, phenol, alcohol, thiol, amide, imide, imidazole, urea, amine, imine, pyrazole, and active methylene compounds.

[0390] As the crosslinking agent (E), blocked isocyanates such as oxime-blocked toluene diisocyanate, blocked hexamethylene diisocyanate, and blocked diphenylmethane diisocyanate are preferred.

[0391] The amount of the crosslinking agent (E) can 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 a total of 100 parts by weight of the organic fine particles (A) and the binder resin (C).

[0392] (F) Additive

[0393] In addition to containing the organic fine particles (A), the aqueous medium (B), and, if necessary, the binder resin (C), the surfactant (D), and / or the crosslinking agent (E), the water-repellent composition may further contain an additive (F).

[0394] Examples of the additive are: other water-repellent agents, oil-repellent agents, drying rate adjusters, film-forming aids, compatibilizers, anti-freezing agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, defoaming agents, texture adjusters, slipperiness adjusters, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants, and so on.

[0395] The amount of the additive can 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 a total of 100 parts by weight of the organic fine particles (A) and the binder resin (C).

[0396] The polymer (the polymer constituting the organic fine particles and the polymer constituting the binder resin) can be produced by any conventional polymerization method, and the conditions of the polymerization reaction can also be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. Emulsion polymerization is preferred.

[0397] The production method of the polymer is not limited as long as a water-repellent composition in the form of an aqueous dispersion can be obtained. For example, the polymer (organic fine particles) can be produced by polymerizing the monomers for the organic fine particles in an aqueous medium in the presence or absence of a surfactant. Alternatively, after producing the polymer by solution polymerization, a surfactant and water are added and the solvent is removed to obtain an aqueous dispersion.

[0398] When the water-repellent composition contains organic fine particles and a binder resin, the water-repellent composition containing organic fine particles and a binder resin can be produced by separately producing an aqueous dispersion of the organic fine particles and an aqueous dispersion of the binder resin and mixing the aqueous dispersion of the organic fine particles with the aqueous dispersion of the binder resin. Alternatively, in the aqueous dispersion of the organic fine particles, the monomers for the binder resin are polymerized to produce a water-repellent composition containing organic fine particles and a binder resin. In addition, in the aqueous dispersion of the binder resin, the monomers for the organic fine particles are polymerized to produce a water-repellent composition containing organic fine particles and a binder resin.

[0399] In emulsion polymerization without using a surfactant, in an aqueous medium, it is preferred to polymerize the monomers at a low concentration (for example, the monomer concentration is 1 to 30% by weight, especially 1 to 15% by weight).

[0400] In emulsion polymerization using a surfactant or a reactive emulsifier, it is preferred to add a small amount (30 mole parts or less, for example, 0.1 to 20 mole parts relative to 100 mole parts of the total monomers) of monomer (1) whose static contact angle of water of the homopolymer is 95 degrees or more or monomer (2). Thereby, polymerization can be carried out at a high concentration and the water repellency of the polymer is improved.

[0401] Examples of the additional monomers are tert-butylstyrene, stearyl (meth)acrylate, docosyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-tert-butylstyrene, 2,4,6-trimethylstyrene, stearic acid amidoethyl (meth)acrylate, CH 2 =CHC(=O)OC 2 H4 NHSO 2 C 18 H 37 , 4-tert-butylphenyl (meth)acrylate, 2,3,4-trimethylphenyl (meth)acrylate, and

[0402] (meth)acrylic monomers having a polydimethylsiloxanyl group,

[0403] CH 2 =C(−R 92 )−C(=O)−Y 91 −R 91 the monomers shown

[0404] [wherein, R 91 is a group having a polydimethylsiloxanyl group,

[0405] R 92 is a hydrogen atom, a monovalent organic group, or a halogen atom,

[0406] Y 91 is a 2- to 4-valent group composed of at least one selected from a C1 hydrocarbon group having 2 to 4 valences, −C 6 H 4 −, −O−, −C(=O)−, −S(=O) 2 − or −NR'− (R' is H or a C1-4 hydrocarbon group).].

[0407] When the ratio of monomer (5) and monomer (3) is 35 mol parts or more as all the monomers constituting the organic fine particles, the monomer (1) in which the static contact angle of water of the homopolymer is 95 degrees or more is preferably 1 to 70 mol parts, for example, 1 to 60 mol parts.

[0408] In solution polymerization, a method is adopted in which, in the presence of a polymerization initiator, monomers are dissolved in an organic solvent, and after nitrogen substitution, heating and stirring are carried out at 30 to 120 °C for 1 to 10 hours. As the polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxyneopentanoate, diisopropyl peroxydicarbonate, etc. can be cited. The polymerization initiator can be used in the range of 0.01 to 20 mol parts, for example, 0.01 to 10 mol parts, relative to 100 mol parts of the monomers.

[0409] An organic solvent is a substance that is inert to monomers and can dissolve or uniformly disperse them. For example, it can be an ester (such as an ester having 2 to 30 carbon atoms, specifically ethyl acetate, butyl acetate), a ketone (such as a ketone having 2 to 30 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone), an alcohol (such as an alcohol having 1 to 30 carbon atoms, specifically isopropyl alcohol, ethanol, 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, trichlorotrifluoroethane, etc. If the total of the monomer and the organic solvent is set to 100 parts by weight, the organic solvent can be used in the range of 50 to 99.5 parts by weight, for example, 70 to 99 parts by weight.

[0410] In the case of emulsion polymerization, a method is adopted in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen replacement, they are stirred for 1 to 10 hours in the range of 30 to 80 °C to effect polymerization. As the polymerization initiator, water-soluble substances such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, 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-(2 - imidazolin - 2 - yl)propane] dihydrochloride, 2,2'-azobis[2-(2 - imidazolin - 2 - yl)propane], sodium peroxide, potassium persulfate, ammonium persulfate, etc., or oil-soluble substances such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxyneopentanoate, diisopropyl peroxydicarbonate, etc. The polymerization initiator can be used in the range of 0.01 to 10 moles per 100 moles of the monomer. Reducing agents such as sodium formaldehyde sulfoxylate (Rongalit), ascorbic acid, tartaric acid, sodium dithionite, isoascorbic acid, ferrous sulfate, etc. can also be used together as needed.

[0411] As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and can be used in the range of 0.5 to 20 parts by weight relative to 100 parts by weight of the monomer. It is preferred to use anionic and / or nonionic and / or cationic emulsifiers. In the case where the monomers are completely immiscible, it is also preferred to add a compatibilizer that makes these monomers fully compatible, such as a water-soluble organic solvent. By adding the compatibilizer, the emulsifying property and copolymerizability can be improved.

[0412] 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, methanol, etc., and can be used in the range of 0.1 to 50 parts by weight, for example, 1 to 40 parts by weight relative to 100 parts by weight of water.

[0413] In the polymerization, a chain transfer agent can also be used. Depending on the amount of the chain transfer agent used, the molecular weight of the polymer can be changed. Examples of the chain transfer agent include thiol group-containing compounds such as lauryl mercaptan, mercaptoethanol, and thioglycerol (especially (for example, alkyl mercaptans having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of the chain transfer agent used can also be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight relative to 100 parts by weight of the total amount of the monomers.

[0414] The water-repellent composition is usually 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 can be, for example, 50 to 99.9% by weight, particularly 70 to 99.5% by weight relative to the water-repellent composition.

[0415] In the water-repellent composition, the concentration of the polymer can be 0.1 to 50% by weight, for example, 0.5 to 40% by weight.

[0416] 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 agent, an antifouling agent, a dirt release agent, a peeling agent or a mold release agent.

[0417] When the water-repellent composition is an external treatment agent, it can be applied to the object to be treated by known methods. Generally, the following method is adopted: the water-repellent composition is dispersed and diluted in an organic solvent or water, and is attached to the surface of the object to be treated by known methods such as dip coating, spraying, and dip coating, and then dried. Additionally, if necessary, it can also be applied together with a suitable crosslinking agent (e.g., blocked isocyanate) for curing. Furthermore, an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a coating fixing agent, a wrinkle-proof agent, etc. can be added to the water-repellent composition for use together. The concentration of the polymer in the treatment liquid in contact with the substrate can be 0.01 to 10% by weight (especially in the case of dip coating), for example, 0.05 to 10% by weight.

[0418] Examples of the object to be treated with the water-repellent composition (and the aqueous dispersion of organic fine particles) include: fiber products, stone, filters (e.g., electrostatic filters), dust masks, components of fuel cells (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and gypsum, etc. Various examples can be cited for fiber products. For example, animal and plant natural fibers 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 fiber, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or their mixed fibers can be cited.

[0419] The fiber product can be in any form such as fiber or cloth.

[0420] The water-repellent composition can also be used as an antifouling agent, a release agent, a mold release agent (e.g., an internal mold release agent or an external mold release agent). For example, the surface of the substrate can be easily peeled off from other surfaces (other surfaces of the substrate or surfaces of other substrates).

[0421] The organic fine particles can be applied to a fibrous substrate (e.g., fiber products, etc.) by any known method for treating fiber products with a liquid. When the fiber product is cloth, the cloth can be immersed in the solution, or the solution can be attached to or sprayed on the cloth. The treated fiber product is dried in order to exhibit water repellency, and is preferably heated at 100°C to 200°C, for example.

[0422] Alternatively, the organic fine particles can be applied to the fiber product by a cleaning method, for example, applied to the fiber product in a washing application or a dry cleaning method, etc.

[0423] When heat treatment is performed at 170°C for 1 minute after attachment to a substrate, it is preferable that the average diameter of the organic fine particles after heat treatment is 50% or more of the average diameter of the organic fine particles before heat treatment. It is preferable that the average diameter (average particle size) of the organic fine particles after heat treatment is 60% or more, for example, 70% or more of the average diameter (average particle size) of the organic fine particles before heat treatment. Alternatively, after coating the particles on a substrate (including cloth), the average particle size of the fine particles observable on the substrate is preferably 50 to 700 nm.

[0424] The average diameter of the organic fine particles before heat treatment is determined by the particle size of the fine particles measured by dynamic light scattering method (DLS) from the aqueous dispersion of the organic fine particles (when two or more peaks are observed in the DLS measurement, it is not the average particle size of all the peaks, but the average particle size calculated only from the peak with a smaller particle size) or the average diameter of the organic fine particles before heat treatment attached to the substrate. When the values of the two are different, the smaller one is used.

[0425] The average diameter of the organic fine particles on the substrate means the average of the particle diameters of 10 randomly selected independent minimum units observed by a scanning electron microscope (SEM) after attaching the organic fine particles to the substrate. Generally, the average diameter of the organic fine particles after heat treatment means the average of the particle diameters of 10 randomly selected independent minimum units observed by a scanning electron microscope (SEM) on the substrate after coating the dispersion liquid of the organic fine particles on the substrate (for example, cloth) and performing heat treatment at 170°C for 1 minute. For example, when the substrate is cloth, after immersing the cloth in the aqueous dispersion containing the organic fine particles, tying the cloth with a cloth-tying machine, and passing it through a pin tenter at 170°C for 1 minute, a cloth with attached organic fine particles can be produced. The average diameter of the organic fine particles before heat treatment means the average of the particle diameters of 10 randomly selected independent minimum units observed by a scanning electron microscope (SEM) on the substrate after coating the dispersion liquid of the organic fine particles on the substrate (for example, cloth) and air-drying for 1 hour or more.

[0426] The fiber products to be treated are typically cloth, including woven fabrics, knitted fabrics, and non-woven fabrics, cloth in the form of clothing and blankets, but can also be fibers or yarns or intermediate fiber products (for example, scraps or rovings, etc.). The fiber product material can be natural fibers (for example, cotton or wool, etc.), chemical fibers (for example, viscose rayon or lyocell, etc.) or synthetic fibers (for example, polyester, polyamide or acrylic fibers, etc.), or can be a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.).

[0427] Alternatively, the fibrous substrate can be leather. In order to make the leather hydrophobic and oleophobic, organic fine particles can be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, for example, during the wet processing of the leather or during the finishing of the leather.

[0428] Alternatively, the fibrous substrate may be paper. The organic fine particles may be applied to a pre-formed paper, or applied at various stages of papermaking, for example, during the drying of the paper.

[0429] "Treatment" means applying a treatment agent to an object to be treated by impregnation, spraying, coating, etc. Through treatment, the 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.

[0430] In the treated substrate (especially a fiber product), the slipping speed of water is preferably 100 mm / s or more, for example, 130 mm / s or more, further 150 mm / s or more or 200 mm / s or more.

[0431] The treated substrate exhibits an anti-frosting effect.

[0432] The above describes the embodiments, but it can be understood that various changes can be made to the embodiments and details without departing from the gist and scope of the claims of the patent.

[0433] Examples

[0434] Hereinafter, examples are listed to describe the present invention in detail, but the present invention is not limited to these examples.

[0435] Hereinafter, parts or % or ratio means parts by weight or % by weight or weight ratio unless otherwise specified.

[0436] The order of the tests is as follows.

[0437] 〔Number-average molecular weight (Mn), weight-average molecular weight (Mw), molecular weight distribution (Mw / Mn)〕

[0438] The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) are determined by gel permeation chromatography (GPC). For GPC, tetrahydrofuran is used as the eluent, and KF-606M, KF-601, and KF-800D manufactured by Shodex are used as the chromatographic columns. The molecular weight and the like are calculated in terms of polystyrene.

[0439] 〔Thermal property measurement by differential scanning calorimetry (DSC)〕

[0440] The melting point of the polymer was calculated by differential scanning calorimetry (DSC). The DSC measurement was carried out in a nitrogen atmosphere. After cooling to -20 °C, it was heated to 200 °C at a rate of 10 °C / min, then cooled again to -20 °C, and then heated to 200 °C at a rate of 10 °C / min. The melting point observed during this process was measured. In polymers showing multiple melting peaks, the peak with the largest heat of fusion originating from the melting of the long-chain alkyl group was taken as the melting point. The glass transition temperature (glass transition point) was determined as the temperature represented by the midpoint of the intersection of the extension lines of the respective baselines before and after the secondary transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[0441] [Measurement of the particle size of the dispersion]

[0442] For the dynamic light scattering (DLS) measurement, ZEN1600 manufactured by MALVERN was used to determine the average diameter of the particles in the dispersion. The aqueous dispersion of the organic fine particles was diluted with pure water to a solid content concentration of 0.1%, and the measurement was carried out at 25 °C. The analysis of the particle size distribution was based on the scattering intensity standard.

[0443] [Measurement of the static contact angle]

[0444] (Synthesis Examples L1 - L5)

[0445] A chloroform solution of the polymer (solid content concentration 1.0%) was spin-coated on 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 film. 2 μL of water was dropped onto this coating film, and the static contact angle 1 second after the drop was measured using a fully automatic contact angle meter (Drop Master 701 manufactured by Kyowa Interface Science).

[0446] (Organic fine particles)

[0447] The contact angle of the organic fine particles was measured as follows: The aqueous dispersion of the organic fine particles was drop-coated on a glass substrate (made of soda-lime glass for microscope slides), and heated at 150 °C for 3 minutes to form a substrate with the organic fine particles attached. 2 μL of water was dropped onto the glass substrate with the organic fine particles attached, and the static contact angle 1 second after the drop was measured using a fully automatic contact angle meter (Drop Master 701 manufactured by Kyowa Interface Science). 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.

[0448] In addition, the static contact angle of water on a cloth (PET cloth) treated with the aqueous dispersion of the organic fine particles or the composition containing the organic fine particles and the binder resin was measured as follows: The PET cloth (unit area weight: 88 g / m 2, 70 denier, gray) is immersed in an aqueous dispersion of organic particles or a composition containing organic particles and a binder resin, then cloth is woven using a loom, and it is passed through a pin tenter at 170 °C for 1 minute to prepare a PET cloth with organic particles attached thereto. 2 μL of water is dropped onto the PET cloth, and the static contact angle 1 second after the drop is measured using a fully automatic contact angle meter (Drop Master 701 manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of the organic particles on the cloth (PET cloth) is preferably 120° or more, more preferably 130° or more, and even more preferably 140° or more.

[0449] The contact angle of the aqueous dispersion of the binder resin is measured as follows: The aqueous dispersion of the binder resin is drop-coated on a glass substrate (made of soda-lime glass slide), heated at 150 °C for 3 minutes to form a coating film, 2 μL of water is dropped onto the coating film, and the static contact angle 1 second after the drop is measured using a fully automatic contact angle meter (Drop Master 701 manufactured by Kyowa Interface Science Co., Ltd.).

[0450] 〔Sliding speed test〕

[0451] In the sliding speed test, a PET cloth (unit area weight: 88 g / m 2 , 70 denier, gray) is immersed in an aqueous dispersion of organic particles or a composition containing organic particles and a binder resin, then cloth is woven using a loom, and it is passed through a pin tenter at 170 °C for 1 minute to prepare a PET cloth with organic particles attached thereto. Using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.), 20 μL of water is dropped from a microsyringe onto the PET cloth with a 30° inclination, and the manner in which the dropped water slides is measured using a high-speed camera (VW-9000 manufactured by Keyence Corporation). The average sliding speed over a distance of about 40 mm is taken as the sliding speed.

[0452] 〔Determination of solid content〕

[0453] 1 g of the obtained aqueous dispersion of organic particles is placed in an aluminum cup and dried at 150 °C for 1 hour. The solid content is calculated from the weights before and after drying.

[0454] Solid content % = (weight before drying - weight after drying) / weight before drying × 100

[0455] 〔Water repellency test〕

[0456] The aqueous dispersion of organic particles is adjusted to a specified concentration. After immersing the cloth in this test solution and tying the cloth with a cloth-tying machine, the test cloth after heat treatment is used to evaluate the water repellency. According to the spray method of JIS-L-1092 (AATCC-22), the water repellency of the treated cloth is evaluated. As shown in the table described below, it is indicated by Water Repellency No. The larger the score, the better the water repellency. The "+" of the marked number means better than that number, and "-" means worse than that number. Polyester cloth (PET) (unit area weight: 88 g / m 2 , 70 denier, gray) is used for evaluation.

[0457]

[0458] 〔Strong water repellency test〕

[0459] When testing by the spray method of JIS-L-1092 (AATCC-22), the ease of repelling water in contact with the cloth and the flow rate from the cloth are visually evaluated. The larger the score, the better the strong water repellency.

[0460]

[0461] 〔Water repellency and strong water repellency washing detergency (water repellency (after washing) and strong water repellency (after washing))〕

[0462] Washing is repeatedly carried out 20 times according to the JIS L-0217-103 method, and the water repellency and strong water repellency after that are evaluated. Preferably, after washing, the water repellency is 80 points or more and the strong water repellency is 2 points or more.

[0463] 〔Scanning electron microscope (SEM) observation (particle size)〕

[0464] SEM observation is carried out by ELONIX Corporation's ERA 9000 at an acceleration voltage of 3.5 kV, Pt evaporation coating and a W.D. of 5.0 mm, and by Hitachi High-Technologies Corporation's SU8020 at an acceleration voltage of 3.0 kV, Pt evaporation coating. The particle sizes obtained by the two devices are the same.

[0465] After immersing the cloth in the composition containing organic particles and tying the cloth with a cloth-tying machine, it is passed through a pin tenter at 170 °C for 1 minute, thereby producing a cloth with organic particles attached, and the average of the particle diameters of 10 randomly selected independent minimum units observed on the cloth with a scanning electron microscope (SEM) is obtained.

[0466] The retention rate (%) of the diameter of the particles before and after heating was determined according to the following formula using the average particle diameter of the organic fine particles on the substrate after heating (the average diameter of the particles on the cloth heated at 170 °C for 1 minute) determined by SEM observation and the average particle diameter of the organic fine particles before heating (the smaller of the average particle diameter of the fine particle dispersion determined by DLS measurement or the average particle diameter on the substrate before heating determined by SEM observation).

[0467] Retention rate (%) of the average diameter of the particles before and after heating = (Average particle diameter after heating) / (Average particle diameter before heating) × 100

[0468] 〔Measurement of dark color property〕

[0469] Using a color difference meter (manufactured by Minolta Co., Ltd., Color Difference Meter CR-200, the detection part is a circle with a diameter of 8 mm), L was measured at three positions on each treated cloth. The color difference (ΔL) was calculated from the L of the cloth before treatment with the treatment liquid and the L after treatment according to the following formula.

[0470] ΔL = (L value of the cloth after treatment) - (L value of the cloth before treatment)

[0471] In the examples and comparative examples, the meanings of the abbreviated symbols are as follows.

[0472] tBuSty: 4-tert-butylstyrene

[0473] tBuMA: tert-butyl methacrylate

[0474] StMA: stearyl methacrylate

[0475] Sty: styrene

[0476] MeSty: 4-methylstyrene

[0477] C17AEA: CH 2 =CHCO 2 -CH 2 CH 2 -NH-C(=O)-C 17 H 35

[0478] iBMA: isobornyl methacrylate

[0479] GMA: glycidyl methacrylate

[0480] DHMA: 2,3-dihydroxypropyl methacrylate

[0481] HEMA: 2-hydroxyethyl methacrylate

[0482] HBA: 4-hydroxybutyl acrylate

[0483] DQ: Dimethylaminoethyl methacrylate quaternary compound

[0484] BCPMA: Dicyclopentyl methacrylate

[0485] CHMA: Cyclohexyl methacrylate

[0486] DVB: Divinylbenzene

[0487] NP-A: Neopentyl glycol diacrylate

[0488] NP-MA: Neopentyl glycol dimethacrylate

[0489] DMS-MA: Polydimethylsiloxaneoxyethyl methacrylate

[0490] DMS-MA 1: Polydimethylsiloxaneoxyethyl methacrylate (molecular weight 1000)

[0491] DMS-MA2: Polydimethylsiloxaneoxyethyl methacrylate (molecular weight 500)

[0492] DMS-MA3: Polydimethylsiloxaneoxyethyl methacrylate (molecular weight 12000)

[0493] DCP: Dicyclopentyl diacrylate

[0494] DCP-M: Dicyclopentyl dimethacrylate

[0495] ADDA: Adamantyl diacrylate

[0496] HADDM: 5-Hydroxy-1,3-adamantane dimethacrylate

[0497] EGDMA: Ethylene glycol dimethacrylate

[0498] tBuA: tert-Butyl acrylate

[0499] MMA: Methyl methacrylate

[0500] VAc: Vinyl acetate

[0501] tBuAAm: tert-Butyl acrylamide

[0502] StA: Stearyl acrylate

[0503] Emulsifier 1: Polyethylene glycol monooleyl ether (liquid)

[0504] Emulsifier 2: Polyethylene glycol monooleyl ether (solid)

[0505] Emulsifier 3: Glyceryl stearate

[0506] Emulsifier 4: Lauryl trimethyl ammonium chloride

[0507] Emulsifier 5: Cetyl trimethyl ammonium chloride

[0508] Emulsifier 6: Stearyl trimethyl ammonium chloride

[0509] Emulsifier 7: Polyoxyalkylene alkenyl ether (HLB 16)

[0510] Emulsifier 8: Polyoxyalkylene alkenyl ether (HLB 14)

[0511] Emulsifier 9: Polyoxyalkylene alkenyl ether (HLB 13)

[0512] Emulsifier 10: Tetraglycerol monostearate

[0513] Emulsifier 11: Lauric acid diethanolamide

[0514] Emulsifier 12: Sorbitan tristearate

[0515] Crosslinking agent 1: Oxime-terminated toluene diisocyanate

[0516] Crosslinking agent 2: Oxime-terminated hexamethylene diisocyanate

[0517] PDMS-A: Long-chain alkyl-modified dimethyl silicone

[0518] StOH: Stearyl alcohol

[0519] <Synthesis Example 1>

[0520] Add 0.66 g of tert-butylstyrene (tBuSty), 0.39 g of glycidyl methacrylate (GMA), 0.018 g of divinylbenzene (DVB), and 33 ml of pure water to the reaction vessel after nitrogen replacement to disperse them. After nitrogen replacement, add 18.6 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride and heat and stir at 65 °C for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content is 2.85%. The particle size (average particle size) of the aqueous dispersion is 250 nm. The contact angle of water on the glass substrate of the organic fine particles is 120°. The static contact angle of water on the PET (cloth) (unit area weight: 88 g / m 2 、70 denier, gray) treated with the aqueous dispersion of organic fine particles is 143.1°, and the sliding speed is 265 mm / s. In addition, the aqueous dispersion of organic fine particles is cast on a glass substrate and air-dried, and then placed in an environment of -30 °C for 2 days. Then, the substrate is taken out in an environment of 25 °C. As a result, frost adheres to the glass, but no frosting is confirmed on the organic fine particles. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute is 80%.

[0521] <Synthesis Examples 2 - 44>

[0522] Except for using the monomers shown in Table 1 as monomers, the same steps as in Synthesis Example 1 were repeated. The results are shown in Table 1. In Synthesis Examples 25 - 28, in addition to the monomers shown in the table, a cationic emulsifier (lauryl trimethyl ammonium chloride) was added in a specified amount shown in the table relative to the total monomer amount and then polymerization was carried out. In Synthesis Example 29, in addition to the monomers shown in the table, 0.5% of a cationic emulsifier (lauryl trimethyl ammonium chloride) and polyethylene glycol monooleyl ether were added relative to the total monomer amount and polymerization was carried out. The aqueous dispersion of the organic fine particles synthesized in Synthesis Example 13 was cast onto a glass substrate and air-dried, and then placed in an environment at -30°C for 2 days. Then, the substrate was taken out in an environment at 25°C. As a result, frost adhered to the glass, but no frosting was confirmed on the coating film of the organic fine particles. In Synthesis Examples 2 - 44, the retention rate of the particle diameter before and after heating at 170°C for 1 minute was 80%.

[0523] <Comparative Synthesis Examples 1 - 3>

[0524] Except for using the monomers shown in Table 1 as monomers, the same steps as in Synthesis Example 1 were repeated. The results are shown in Table 1. The stability of the emulsion after polymerization in Comparative Synthesis Example 1 was poor, and the cloth could not be treated evenly. In Comparative Synthesis Examples 2 and 3 in the sliding speed test, water droplets adhered to the cloth and did not slide off.

[0525] [Table 1]

[0526]

[0527] * Poor emulsification state, polymerization could not proceed evenly

[0528] ** 0.5% of a nonionic emulsifier was also added in addition to the cationic emulsifier

[0529] - : Not measured

[0530] <Synthesis Example L1>

[0531] 1.50 g of tBuSty, 0.015 g of azobisisobutyronitrile, and 10 ml of toluene were added into a reaction vessel after nitrogen replacement, and after heating and stirring at 65°C for 8 hours, PtBuSty was obtained by reprecipitation in methanol. The molecular weight (Mw) was 21000, and the molecular weight distribution (Mw / Mn) was 2.0. The water contact angle of the obtained polymer was 100°. The glass transition temperature (Tg) was 125°C.

[0532] <Synthesis Example L2>

[0533] After nitrogen replacement, 1.50 g of MeSty, 0.021 g of azobisisobutyronitrile, and 10 ml of toluene were added to the reaction vessel. After heating and stirring at 65 °C for 8 hours, PMeSty was obtained by reprecipitation in methanol. The molecular weight (Mw) was 15,000, and the molecular weight distribution (Mw / Mn) was 2.0. The water contact angle of the obtained polymer was 95°. The glass transition temperature (Tg) was 107 °C.

[0534] <Synthesis Example L3>

[0535] After nitrogen replacement, 1.00 g of Sty, 0.015 g of azobisisobutyronitrile, and 3.4 ml of toluene were added to the reaction vessel. After heating and stirring at 65 °C for 8 hours, PSty was obtained by reprecipitation 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 obtained polymer was 89°. The glass transition temperature (Tg) was 100 °C.

[0536] <Synthesis Example L4>

[0537] After nitrogen replacement, 2.00 g of tBuMA, 0.023 g of azobisisobutyronitrile, and 20 ml of toluene were added to the reaction vessel. After heating and stirring at 65 °C for 8 hours, PtBuMA was obtained by reprecipitation in a mixed solution of methanol and water. The molecular weight (Mw) was 18,000, and the molecular weight distribution (Mw / Mn) was 2.0. The water contact angle of the obtained polymer was 89°. The glass transition temperature (Tg) was 107 °C.

[0538] <Synthesis Example L5>

[0539] After nitrogen replacement, 2.00 g of StMA, 0.0097 g of azobisisobutyronitrile, and 20 ml of toluene were added to the reaction vessel. After heating and stirring at 65 °C for 8 hours, PStMA was obtained by reprecipitation in methanol. The molecular weight (Mw) was 35,000, and the molecular weight distribution (Mw / Mn) was 2.1. The water contact angle of the obtained polymer was 109°. The melting point (Tm) was 50 °C.

[0540] <Synthesis Example B1>

[0541] After nitrogen replacement, 3.00 g of StA, 0.149 g of polyethylene glycol monooleyl ether, 0.020 g of sorbitan tristearate, and 60 ml of pure water were added to the reaction vessel to emulsify. 25 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and it was heated and stirred at 65 °C for 8 hours. Thus, an aqueous dispersion of PStA was obtained. The solid content was 4.6%. The water contact angle of the film obtained by coating the emulsified dispersion system on a glass substrate was 110°.

[0542] <Synthesis Example B2>

[0543] Add 3.00 g of StA, 0.262 g of polyethylene glycol monooleyl ether, 0.037 g of sorbitan tristearate, and 60 ml of pure water into the reaction vessel after nitrogen replacement, and emulsify them. Add 25 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and heat and stir at 65 °C for 8 hours to obtain an aqueous dispersion of PStA. The solid content is 4.7%. The water contact angle of the film obtained by coating the emulsified dispersion system on a glass substrate is 110°.

[0544] <Synthesis Example B3>

[0545] Add 3.00 g of StA, 0.131 g of polyethylene glycol monooleyl ether, 0.018 g of sorbitan tristearate, 40 mg of 2-[(dodecylphenylsulfonylthiocarbonyl)phenylsulfonyl]propionic acid, and 60 ml of pure water into the reaction vessel after nitrogen replacement, and emulsify them. Add 3 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and heat and stir at 65 °C for 4 hours. Further add 0.296 g of HBA, and heat and stir for 4 hours to obtain an aqueous dispersion of a block polymer of StA / HBA. The water contact angle of the film obtained by coating the emulsified dispersion system on a glass substrate is 109°.

[0546] <Synthesis Example B4>

[0547] Add 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-[(dodecylphenylsulfonylthiocarbonyl)phenylsulfonyl]propionic acid, and 18 ml of pure water into the reaction vessel after nitrogen replacement, and emulsify them. Add 3 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and heat and stir at 65 °C for 8 hours to obtain an aqueous dispersion of a random polymer of StA / HBA. The water contact angle of the film obtained by coating the emulsified dispersion system on a glass substrate is 107°.

[0548] <Synthesis Example B5>

[0549] Add 0.5 g of StA, CH 2 =CHCO 2 -CH 2 CH 2 -NH-C(=O)-C 17 H 350.59 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-[(dodecylsulfamoylthio-carbonyl)phenylsulfamoyl]propionic acid, and 10 ml of pure water were 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 the film obtained by coating the emulsified dispersion system on a glass substrate was 108°.

[0550] <Synthesis Example B6>

[0551] 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-[(dodecylsulfamoylthio-carbonyl)phenylsulfamoyl]propionic acid, and 10 ml of pure water were added to a reaction vessel after nitrogen replacement and emulsified. 1 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65 °C for 4 hours. Further, 0.049 g of HBA was added, and the mixture was heated and stirred for 4 hours to obtain an aqueous dispersion of a block polymer of StA·C17AEA / HBA. The water contact angle of the film obtained by coating the emulsified dispersion system on a glass substrate was 109°.

[0552] <Synthesis Example B7>

[0553] 10 g of tripropylene glycol, 20 g of StA, 0.05 g of trialkylammonium chloride, 2.0 g of sorbitan mono-chelate, 1.0 g of polyoxyethylene alkyl ether, and 60 g of pure water were added to a 200 ml plastic container, stirred with a homogenizer at 2000 rpm for 1 minute, and dispersed ultrasonically for 15 minutes. The emulsified dispersion system was transferred to an autoclave, 0.05 g of alkyl mercaptan and 8.6 g of vinyl chloride were added after nitrogen replacement, 0.5 g of an azo initiator was added, and the mixture was heated and stirred at 60 °C for 20 hours to obtain an aqueous dispersion of a polymer. The water contact angle of the film obtained by coating the emulsified dispersion system on a glass substrate was 108°.

[0554] <Synthesis Example B8>

[0555] Add 30 g of tripropylene glycol, 45 g of C17AEA, 34 g of StA, 1 g of N-alkyl alcohol acrylamide, 2 g of trialkyl ammonium chloride, 2 g of sorbitan mono chelate, 2.5 g of polyoxyethylene trialkyl ether, 3.5 g of polyoxyethylene alkyl ether, and 180 g of pure water into a 500-ml plastic container. Stir at 2000 rpm for 1 minute with a homogenizer at 80°C, and disperse ultrasonically for 15 minutes. Transfer the emulsified dispersion system to an autoclave. After nitrogen replacement, add 0.2 g of alkyl mercaptan and 20 g of vinyl chloride.

[0556] Add 1 g of an azo-based initiator, and heat and stir at 60°C for 20 hours to obtain an aqueous dispersion of the polymer. The water contact angle of the film obtained by coating the emulsified dispersion system on a glass substrate is 109°.

[0557] <Synthesis Example B9>

[0558] Add 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 dilaurate into a reaction vessel after nitrogen replacement, and heat and stir at 80°C. Add 9 g of tripropylene glycol, 1.8 g of sorbitan tristearate, 0.75 g of polyethylene glycol monooleyl ether, 0.6 g of trimethyl octadecyl ammonium chloride, and 40 g of pure water to this solution and stir. Remove methyl isobutyl ketone through an evaporator to obtain an aqueous dispersion of the reaction product of sorbitan stearate and isocyanate. The water contact angle of the film obtained by coating the dispersion system on a glass substrate is 105°.

[0559] <Synthesis Example S1>

[0560] Add 0.5 g of tBuSty, 0.30 g of GMA, 0.014 g of DVB, and 25 ml of pure water into a reaction vessel after nitrogen replacement. Add 22.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and heat and stir at 65°C for 8 hours.

[0561] Furthermore, add 0.24 g of VAc and 11.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and heat for another 3 hours. The solid content is 3.0%. The retention rate of the particle diameter before and after heating at 170°C for 1 minute is 70%.

[0562] <Synthesis Example S2>

[0563] Add 0.5 g of tBuSty, 0.30 g of GMA, 0.014 g of DVB, and 25 ml of pure water into a reaction vessel after nitrogen replacement. Add 22.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and heat and stir at 65°C for 8 hours.

[0564] Further add 0.24 g of MMA and 9.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and then heat for 3 hours. The solid component content is 2.9%. The retention rate of the particle diameter before and after heating at 170°C for 1 minute is 70%.

[0565] <Synthesis Example S3>

[0566] Add 0.5 g of tBuSty, 0.30 g of GMA, 0.014 g of DVB, and 25 ml of pure water into the reaction vessel after nitrogen replacement. Add 22.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and heat and stir at 65°C for 8 hours.

[0567] Further add 0.06 g of tBuAAm, 0.183 g of tBuA, and 7.7 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and then heat for 3 hours. The solid component content is 2.5%. The retention rate of the particle diameter before and after heating at 170°C for 1 minute is 70%.

[0568] <Synthesis Example S4>

[0569] Add 0.5 g of tBuSty, 0.30 g of GMA, 0.014 g of DVB, and 25 ml of pure water into the reaction vessel after nitrogen replacement. Add 22.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and heat and stir at 65°C for 8 hours.

[0570] Further add 0.12 g of StA, 0.12 g of tBuA, and 5.4 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, and then heat for 3 hours. The solid component content is 2.5%. The retention rate of the particle diameter before and after heating at 170°C for 1 minute is 75%.

[0571] <Synthesis Example S5>

[0572] Add 0.24 g of VAc, 25 ml of pure water, and 11.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride into the reaction vessel after nitrogen replacement, and heat and stir for 3 hours. Further add 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, and heat and stir at 65°C for 8 hours. The solid component content is 2.8%. The retention rate of the particle diameter before and after heating at 170°C for 1 minute is 70%.

[0573] <Examples 1 to 117>

[0574] The aqueous dispersions of the organic fine particles synthesized in Synthesis Examples 1 to 44, the binder resins synthesized in Synthesis Examples B1 to B9, and the emulsifier were mixed at the ratios shown in Table 2 to prepare a treatment solution. The treatment solution was coated on a PET cloth (basis weight: 88 g / m 2 , 70 denier, gray), and various measurements were carried out (sliding speed test, contact angle measurement, water repellency test, strong water repellency test, washing durability test). The results are shown in Table 2. However, in the ratios (g) shown in Table 2, for those other than Synthesis Examples 1 to 44, it represents not the weight of the entire emulsified dispersion system but only the weight of the solid components. In addition, emulsifiers, crosslinking agents, etc. with small addition amounts were added after separately preparing a 3 wt% diluted aqueous solution.

[0575] The scanning electron microscope (SEM) photograph of the PET cloth (Example 1) with the organic fine particles of Synthesis Example 1 attached is shown in Figure 1 .

[0576] [Table 2-1]

[0577]

[0578] [Table 2-2]

[0579]

[0580] [Table 2-3]

[0581]

[0582] [Table 2-4]

[0583]

[0584] [Table 2-5]

[0585]

[0586] [Table 2-6]

[0587]

[0588] [Table 2-7]

[0589]

[0590] [Table 2-8]

[0591]

[0592] <Synthesis Examples 45 to 82>

[0593] Use the monomers shown in Table 3 as monomers. In addition, polymerize by adding the emulsifier shown in Table 3 in a specified amount relative to the total monomer amount as shown in the table. Other than that, repeat the same steps as in Synthesis Example 1.

[0594] <Examples 118 - 155>

[0595] In Synthesis Examples 45 - 82, 25 wt% of the binder B3 with a solid content was mixed with the obtained particles, and the treatment liquid was adjusted so that the concentration of the particles became 2.25%. The treatment liquid was coated on a PET cloth, and the slipping speed was measured. The results are shown in Table 3 as the slipping speed for each synthesis example. In the treatment liquid, 1.1 g of an aqueous solution of crosslinking agent 1 was added per 1 g of the binder resin. In Synthesis Examples 45 - 82, the retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 85% or more. In Synthesis Example 46, the particle diameter of the particles on the cloth was 198 nm.

[0596] <Synthesis Example 83>

[0597] In a reaction vessel purged with nitrogen, 10 ml of an aqueous dispersion of crosslinked fine particles of polymethyl methacrylate (PMMA) with a particle diameter of 300 nm and a solid content concentration of 20 wt%, 400 mg of polyethylene glycol monooleyl ether, 100 mg of sorbitan monostearate, and 1 g of StA were added and stirred at 45 °C. 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 fine particles. The contact angle of water measured after coating the obtained aqueous dispersion on a glass substrate and heating at 150 °C for 1 minute was 105 degrees. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 90%.

[0598] <Synthesis Example 84>

[0599] The amount of StA added was set to 100 wt% relative to the solid content of PMMA, and 16 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added after 25 hours. Polymerization was carried out in the same manner as in Synthesis Example 83 to obtain an aqueous dispersion of PMMA / StA fine particles. The contact angle of water measured after coating the obtained aqueous dispersion on a glass substrate and heating at 150 °C for 1 minute was 111 degrees. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 90%.

[0600] <Synthesis Example 85>

[0601] The amount of added StA was set to 30 wt% relative to the solid content of PMMA, and 16 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added after 25 hours. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 83 to obtain an aqueous dispersion of PMMA / StA fine particles. The aqueous dispersion thus obtained was coated on a glass substrate, and the contact angle of water measured after heating at 150 °C for 1 minute was 111 degrees. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 90%.

[0602] <Synthesis Example 86>

[0603] The amount of added StA was set to 10 wt% relative to the solid content of PMMA, the total amount of emulsifiers used was set to 1 / 5, and 16 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added after 18 hours. Otherwise, polymerization was carried out in the same manner as in Synthesis Example 83 to obtain an aqueous dispersion of PMMA / StA fine particles. The aqueous dispersion thus obtained was coated on a glass substrate, and the contact angle of water measured after heating at 150 °C for 1 minute was 126 degrees. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 90%.

[0604] <Synthesis Example 87>

[0605] An aqueous dispersion of PMMA crosslinked fine particles with a diameter of 70 nm was used, and otherwise, polymerization was carried out in the same manner as in Synthesis Example 86 to obtain an aqueous dispersion of PMMA / StA fine particles. The aqueous dispersion thus obtained was coated on a glass substrate, and the contact angle of water measured after heating at 150 °C for 1 minute was 142 degrees. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 90%.

[0606] <Synthesis Example 88>

[0607] 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 pure water were added to a nitrogen-substituted reaction vessel, emulsified, and then 40 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, followed by heating and stirring at 65 °C. After 28 hours, an emulsion obtained by emulsifying 0.2 g of StA with 28 mg of glyceryl stearate, 95 mg of polyethylene glycol monooleyl ether, and 1 g of pure water was added, and heating and stirring were further carried out for 8 hours to obtain an aqueous dispersion of PSty / StA crosslinked fine particles. The aqueous dispersion thus obtained was coated on a glass substrate, and the contact angle of water measured after heating at 150 °C for 1 minute was 115 degrees. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 85%.

[0608] <Synthesis Example 89>

[0609] Except that the initially used emulsifier was 56 mg of glyceryl stearate and 144 mg of polyethylene glycol monooleyl ether, polymerization was carried out in the same manner as in Synthesis Example 88 to obtain an aqueous dispersion of PSty / StA crosslinked fine particles. The obtained aqueous dispersion was coated on a glass substrate, and the contact angle of water measured after heating at 150 °C for 1 minute was 118 degrees. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 90%.

[0610] <Synthesis Example 90>

[0611] Except that the initially used emulsifier was 56 mg of glyceryl stearate and 144 mg of polyethylene glycol monooleyl ether, polymerization was carried out in the same manner as in Synthesis Example 88 to obtain an aqueous dispersion of PSty / StA crosslinked fine particles. The obtained aqueous dispersion was coated on a glass substrate, and the contact angle of water measured after heating at 150 °C for 1 minute was 118 degrees. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 90%.

[0612] <Synthesis Example 91>

[0613] In a reaction vessel purged with nitrogen, 0.32 g of tBuSty, 0.38 g of GMA, 17 mg of DVB, 0.015 g of stearyl trimethyl ammonium chloride, and 19 g of pure water were added as initial monomers and emulsified. Then, 18 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65 °C. Thirty minutes after adding 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 0.32 g of tBuSty and 17 mg of DVB were added as additional monomers, and the mixture was heated and stirred for 8 hours to obtain an aqueous dispersion of crosslinked fine particles. To the particles of the obtained aqueous dispersion, binder B8 with a solid content of 25 wt% was mixed, and the treatment liquid was adjusted so that the concentration of the particles became 2.25%. The treatment liquid was coated on a PET cloth, and the water repellency was evaluated. As a result, the water repellency was 90 points. In addition, the contact angle of the cloth was 140 degrees. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 90%.

[0614] <Synthesis Examples 92 to 110>

[0615] Using the monomers and amounts shown in Table 4 as initial monomers and additional monomers, and the emulsifiers and amounts used, except for this, the same steps as in Synthesis Example 91 were repeated. In Synthesis Example 109, the additional monomers were emulsified with an emulsifier at 1.5% relative to the monomers and then added. In Synthesis Example 110, instead of 2,2'-azobis(2-methylpropionamidine) dihydrochloride, tBu hydroperoxide and L-ascorbic acid were added at 1 mol% each in the synthesis of the monomers, and the synthesis was carried out at a temperature of 75 °C.

[0616] <Examples 156 to 174>

[0617] Regarding Synthesis Examples 92 to 110, the water contact angle measured after heating at 150°C for 1 minute for the obtained particle aqueous dispersions coated on a glass substrate is shown in Table 4.

[0618] Regarding Synthesis Examples 92 to 96, with respect to the obtained particles, 25 wt% of binder B8 with a solid content was mixed, and the treatment liquid was adjusted so that the particle concentration became 2.25%. Regarding Synthesis Examples 97 to 110, 25 wt% of binder B3 with a solid content with respect to the obtained particles was mixed, and the treatment liquid was adjusted so that the particle concentration became 2.25%. The treatment liquid was coated on a PET cloth, and the results of the sliding speed measurement, water repellency, and strong water repellency tests are shown as the sliding speed, water repellency, and strong water repellency for each synthesis example in Table 4. An aqueous solution of crosslinking agent 1 at 1.1 g per 1 g of the binder resin was added to the treatment liquid. In Synthesis Examples 92 to 110, the retention rate of the particle diameter before and after heating at 170°C for 1 minute was 85% or more.

[0619] The scanning electron microscope (SEM) photograph of the PET cloth (Example 157) coated with the organic fine particles of Synthesis Example 93, binder B8, and crosslinking agent 1 is shown in Figure 2 .

[0620] [Table 3]

[0621]

[0622] -: Not measured

[0623] [Table 4]

[0624]

[0625] <Synthesis Example 111>

[0626] 1.00 g of tert-butylstyrene (tBuSty), 0.049 g of divinylbenzene (DVB), 52 mg of emulsifier 1, and 19 ml of pure water were added to a reaction vessel and dispersed. After nitrogen replacement, 16.9 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 4.54%. The particle size (average particle size) of the aqueous dispersion was 234 nm. The aqueous dispersions of the organic fine particles and Synthesis Example B8 were diluted with pure water so that their respective solid contents became 0.6% and 0.4% and the total became 1 wt% to obtain a treatment liquid. After immersing a PET cloth in this treatment liquid, the cloth was wrung out with a wringer, and the water repellency was evaluated using a heat-treated test cloth. As a result, the sliding speed was 209 mm / s, the water repellency was 100 points, and the strong water repellency was 3++ points. In addition, the retention rate of the particle diameter before and after heating at 170°C for 1 minute was 80%.

[0627] <Synthesis Example 112>

[0628] In a reaction vessel, 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 were added and dispersed. After nitrogen replacement, 15.1 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 particles. The solid content was 4.80%. The particle size (average particle size) of the aqueous dispersion was 302 nm. The aqueous dispersions of the organic particles and Synthesis Example B8 were diluted with pure water such that their respective solid contents were 0.8% and 0.2%, and the total was 1 wt% to obtain a treatment liquid. After impregnating a PET cloth in this treatment liquid, the cloth was tied with a tying machine, and the water repellency was evaluated using a heat-treated test cloth. As a result, the slipping speed was 179 mm / s, the water repellency score was 100, and the strong water repellency score was 3. In addition, the retention rate of the particle diameter before and after heating at 170°C for 1 minute was 85%.

[0629] <Synthesis Example 113>

[0630] In a reaction vessel, 0.90 g of iBMA, 0.052 g of DVB, 0.083 g of StA, 22 mg of Emulsifier 1, a 23% aqueous solution of 65 mg of Emulsifier 6, and 19 ml of pure water were added and dispersed. After nitrogen replacement, 12.1 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 particles. The solid content was 3.28%. The particle size (average particle size) of the aqueous dispersion was 137 nm. The aqueous dispersions of the organic particles and Synthesis Example B8 were diluted with pure water such that their respective solid contents were 0.8% and 0.2%, and the total was 1 wt% to obtain a treatment liquid. After impregnating a PET cloth in this treatment liquid, the cloth was tied with a tying machine, and the water repellency was evaluated using a heat-treated test cloth. As a result, the slipping speed was 183 mm / s, the water repellency score was 95, and the strong water repellency score was 3. In addition, the retention rate of the particle diameter before and after heating at 170°C for 1 minute was 85%.

[0631] <Examples 175 to 178>

[0632] The treatment liquid was adjusted in the proportions shown in Table 5 and coated on PET Q15 (unit area weight: 88 g / m 2 、70 denier, gray) and PET R964 (unit area weight 40 g / m 2 、black) cloths, and various measurements (water repellency test, measurement of the ΔL value of dark color) were performed. The results are shown in Table 5.

[0633] [Table 5]

[0634]

[0635] Existing colorants tend to reduce water repellency, but Table 5 shows that the particles of the present invention can exhibit a strong color effect without impairing water repellency.

[0636] Industrial applicability

[0637] The organic fine particles of the present invention can be used as an oil repellent, an antifouling agent, a soil release agent, a release agent or a mold release agent.

[0638] Other aspects of the present invention are as follows. [1]

[0640] An organic fine particle comprising a polymer having a repeating unit formed from (1) a hydrophobic monomer, (3) a reactive / hydrophilic monomer, and (4) a crosslinkable monomer,

[0641] (1) A hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 30 carbon atoms;

[0642] (3) A reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group; and

[0643] (4) A crosslinkable monomer having at least two ethylenically unsaturated double bonds. [2]

[0645] The organic fine particle according to [1], wherein the polymer further has a repeating unit formed from (5) a high glass transition temperature monomer having a glass transition temperature of 100°C or higher for the homopolymer. [3]

[0647] The organic fine particle according to [1] or [2], wherein the contact angle of the homopolymer of the hydrophobic monomer (1) is 70 to 120 degrees. [4]

[0649] The organic fine particle according to [2] or [3], wherein the hydrophobic monomer (1) is a monomer represented by the following formula:

[0650] CH 2 =C(-R 12 )-C(=O)-Y 11 (R 11 ) k

[0651] or

[0652] CH 2 =C(-R 22 )-Y 21(H) 5－l (R 21 ) l

[0653] [In the formula, R 11 and R 21 are each independently a hydrocarbon group having 3 to 40 carbon atoms,

[0654] R 12 and R 22 are a hydrogen atom, a monovalent organic group or a halogen atom,

[0655] Y 11 is a group having a valence of 2 to 4 selected from hydrocarbon groups having 1 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 composed of at least one of them (excluding the case of only a divalent hydrocarbon group),

[0656] Y 21 is a benzene ring,

[0657] H is a hydrogen atom,

[0658] H and R 21 are directly bonded to Y 21 respectively,

[0659] k and l are 1 to 3.];

[0660] The reactive / hydrophilic monomer (3) is a monomer represented by the following formula:

[0661] CH 2 =C(-R 32 )-C(=O)-Y 31 -(R 33 ) o (R 31 ) m

[0662] or

[0663] CH 2 =C(-R 42 )-Y 41 -(H) 5－n (R 41 ) n

[0664] [In the formula, R 31 and R 41 are each independently a reactive group or a hydrophilic group,

[0665] R 32and R 42 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0666] Y 31 is a valence bond, -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0667] R 33 is a hydrocarbon group having 2 to 4 valences and 1 to 10 carbon atoms,

[0668] Y 41 is a benzene ring,

[0669] H is a hydrogen atom,

[0670] H and R 41 and Y 41 are directly bonded respectively,

[0671] m and n are 1 to 3,

[0672] o is 0 or 1.];

[0673] The crosslinkable monomer (4) is a monomer represented by the following formula:

[0674]

[0675] [In the formula,

[0676] R 51 and R 61 are each independently a group having 2 to 4 valences composed of at least one selected from a valence bond, a hydrocarbon group having 1 to 20 carbon atoms, -(CH 2 CH 2 O)r- (r is an integer of 1 to 10), -C 6 H 4 -, -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0677] R 52 and R 62 are each independently a hydrogen atom, a monovalent organic group or a halogen atom,

[0678] Y 51 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms),

[0679] p is 2 to 4,

[0680] q is 1 to 5.];

[0681] The high glass transition temperature monomer (5) is a monomer represented by the following formula:

[0682]

[0683] [In the formula, R 71 and R 81 are groups composed of at least one selected from hydrocarbon groups having 1 to 30 carbon atoms, -C 6 H 4 -, -O-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms).

[0684] R 72 and R 82 are hydrogen atoms, monovalent organic groups, or halogen atoms.

[0685] Y 71 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms).]. [5]

[0687] 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, a blocked isocyanate group, and the hydrophilic group is selected from a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a phosphoric acid group; an alkali metal or alkaline earth metal base of a carboxylic acid, a sulfonic acid, or a phosphoric acid; an ammonium base in which a chloride ion, a bromide ion, or an iodide ion is a paired anion. [6]

[0689] The organic fine particles according to any one of [1] to [5], wherein the hydrophobic monomer (1) is selected from tert-butyl (meth)acrylate, N-tert-butyl (meth)acrylamide, tert-butylstyrene, stearyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-tert-butylstyrene, 2,4,6-trimethylstyrene, stearic acid amidoethyl (meth)acrylate, CH 2 =CHC(=O)OC 2 H 4 NHSO 2 C 18 H 37 and at least one monomer thereof;

[0690] The reactive / hydrophilic monomer (3) is at least one monomer selected from glycidyl (meth)acrylate, glycerol (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (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, glycidyl ether of 4-hydroxybutyl acrylate, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, quaternized dimethylaminoethyl methacrylate, tetrahydrofuranyl (meth)acrylate;

[0691] The crosslinkable monomer (4) is at least one monomer selected from 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, polytetramethylene glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentyl di(meth)acrylate, 5-hydroxy-1,3-adamantyl di(meth)acrylate;

[0692] The high glass transition temperature monomer (5) is at least one monomer selected from isobornyl (meth)acrylate, bornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, phenyl (meth)acrylate, naphthyl acrylate, benzyl acrylate. [7]

[0694] The organic fine particles according to any one of [2] to [6], wherein the molar ratio of the hydrophobic monomer (1) / reactive-hydrophilic monomer (3) / high glass transition temperature monomer (5) is 20 to 99.9 / 0.1 to 50 / 0 to 70, and the crosslinkable monomer (4) is 0.1 to 30 mol parts with respect to 100 mol parts in total of the hydrophobic monomer (1) and the reactive-hydrophilic monomer (3). [8]

[0696] The organic fine particles according to any one of [1] to [7], wherein when treating cloth, they have a slipping speed of 150 mm / second or more. [9]

[0698] The organic fine particles according to any one of [1] to [8], wherein the average particle diameter is 30 nm to 1000 nm.

[10]

[0700] A water-repellent composition, which is an aqueous dispersion of organic fine particles, and the dispersion is a dispersion containing (A) the organic fine particles according to any one of [1] to [9] and (B) an aqueous medium.

[11]

[0702] The water-repellent composition according to

[11] , which further contains one or both of (C) an adhesive resin and (D) a surfactant.

[12]

[0704] The water-repellent composition according to

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

[13]

[0706] The water-repellent composition according to

[12] or

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

[14]

[0708] The water-repellent composition according to any one of

[11] to

[13] , wherein the adhesive resin (C) is an acrylic polymer, a polyurethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, a polystyrene, a silicone polymer, and combinations thereof.

[15]

[0710] The water-repellent composition according to any one of

[10] to

[14] , which can prevent frosting.

[16]

[0712] The method for producing the water-repellent composition according to any one of

[10] to

[15] , which includes: in an aqueous medium, in the presence of a surfactant of 15 parts by weight or less relative to 100 parts by weight of the monomer, polymerizing monomers (1) to (4) and, if necessary, monomer (5) to obtain an aqueous dispersion of the organic fine particles (A).

[17]

[0714] The production method according to

[16] , which further includes the following steps:

[0715] A step of obtaining an aqueous dispersion in which organic fine particles (A) and an adhesive resin (C) are dispersed by adding an aqueous dispersion of an adhesive resin (C) to an aqueous dispersion of the organic fine particles (A), or by polymerizing a monomer for the adhesive resin in the aqueous dispersion of the organic fine particles (A), or by polymerizing a monomer for the organic fine particles in the aqueous dispersion of the adhesive resin.

[18]

[0717] A method for treating a fiber product, wherein a treatment liquid containing the water-repellent composition according to any one of

[10] to

[15] is applied to the fiber product.

[19]

[0719] A fiber product, wherein organic fine particles and / or an adhesive resin in the water-repellent composition according to any one of

[10] to

[15] are attached to the surface.

[20]

[0721] A fiber product, wherein organic fine particles and / or an adhesive resin in the water-repellent composition according to any one of

[10] to

[15] are attached to the surface and has a slipping speed of 200 mm / second or more.

Claims

1. A water-repellent composition, characterized in that: it contains organic fine particles and an aqueous medium, the organic fine particles can adhere to a substrate in a state having a particle shape, and the organic fine particles exhibit water repellency on the substrate when adhered to the substrate, the organic fine particles are formed of a non-fluorine polymer, the non-fluorine polymer includes a repeating unit composed of a monomer having a tert-butyl group and at least one monomer other than styrene selected from monomers having a glass transition temperature of 50 °C or higher for the homopolymer, in the polymer forming the organic fine particles, the amount of the repeating unit formed of the monomer having a tert-butyl group is 50 mol% or more, or the amount of the repeating unit formed of the monomer having a glass transition temperature of 50 °C or higher for the homopolymer is 50 mol% to 70 mol%.

2. The water-repellent composition according to claim 1, characterized in that: it satisfies at least any one of the following conditions: (i) When adhered to a glass substrate, the static contact angle of water on the glass substrate is 100 degrees or more; (ii) When adhered to cloth, the static contact angle of water on the cloth is 120 degrees or more; or (iii) When adhered to cloth, the sliding speed of water on the cloth is 100 mm / s or more.

3. The water-repellent composition according to claim 1 or 2, characterized in that: when heat-treated at 170 °C for 1 minute after being adhered to a substrate, the average diameter of the heat-treated organic fine particles is 50% or more of the average diameter of the organic fine particles before heat treatment, or the particle size of the fine particles observable on the cloth is 50 to 700 nm.

4. A water-repellent composition, characterized in that: it contains organic fine particles and an aqueous medium, the organic fine particles are organic fine particles containing a polymer, and the polymer contains a repeating unit formed of one selected from the following (1) hydrophobic monomers and (5) high glass transition temperature monomers, and the polymer further contains a repeating unit formed of (4) crosslinkable monomers, (1) A hydrophobic monomer having 1 ethylenically unsaturated double bond and at least 1 tert-butyl group; (5) A high glass transition temperature monomer of a monomer having a glass transition temperature of 50 °C or higher for the homopolymer, excluding styrene; (4) A crosslinkable monomer having at least 2 ethylenically unsaturated double bonds, in the polymer forming the organic fine particles, the amount of the repeating unit formed of (1) hydrophobic monomers is 50 mol% or more, or the amount of the repeating unit formed of (5) high glass transition temperature monomers is 50 mol% to 70 mol%.

5. The water-repellent composition according to claim 4, characterized in that: the crosslinkable monomer (4) is a crosslinkable monomer having 2 ethylenically unsaturated double bonds.

6. The water-repellent composition according to claim 4 or 5, characterized in that: the polymer is a random copolymer.

7. The water-repellent composition according to claim 4 or 5, characterized in that: the polymer further has a repeating unit formed of the following (3) reactive / hydrophilic monomers, (3) A reactive / hydrophilic monomer having 1 ethylenically unsaturated double bond and at least 1 reactive group and / or hydrophilic group; And as an optional component, the polymer further contains repeating units formed from (2) (meth)acrylic monomers having a polydimethylsiloxanyl group; The glass transition temperature of the homopolymer of the high glass transition temperature monomer (5) is 100 °C or higher.

8. The water repellent composition according to claim 4 or 5, characterized in that: The polymer further contains repeating units formed from (2) (meth)acrylic monomers having a polydimethylsiloxanyl group; Among the hydrophobic monomers (1), a combination of a (meth)acrylic monomer having a hydrocarbon group with 12 to 24 carbon atoms in the side chain and a (meth)acrylic monomer having a polydimethylsiloxanyl group (2) is used in an amount such that the total weight of the two monomers is less than 80% by weight of the total amount of the monomer components.

9. The water repellent composition according to claim 4 or 5, characterized in that: After polymerizing the monomers containing the crosslinkable monomer (4), a part of the particles obtained by polymerizing the monomers without the crosslinkable monomer (4) can be melted.

10. The water repellent composition according to claim 4 or 5, characterized in that: The static contact angle of water on the silicon substrate treated with the homopolymer of the hydrophobic monomer (1) is 70 to 120 degrees.

11. The water repellent composition according to claim 7, characterized in that: The hydrophobic monomer (1) is a monomer represented by the following formula: CH 2 =C(-R 12 )-C(=O)-Y 11 (R 11 ) k or CH 2 =C(-R 22 )-Y 21 (H) 5－l (R 21 ) l wherein, R 11 and R 21 are tert-butyl groups, 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 composed of at least one or more selected from hydrocarbon groups having 1 carbon atom with a valence of 2 to 4, -C 6 H 4 -, -O-, -C(=O)-, -S(=O) 2 -, or -NR'- provided that the case of only a divalent hydrocarbon group is excluded, where 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 are directly combined with Y 21 respectively k and l are 1 to 3; The (meth)acrylic monomer (2) having a polydimethylsiloxanyl group is a monomer represented by the following formula: CH 2 =C(-R 92 )-C(=O)-Y 91 -R 91 In the formula, R 91 is a group having a polydimethylsiloxanyl group, R 92 is a hydrogen atom, a monovalent organic group or a halogen atom, Y 91 is a divalent to tetravalent group composed of at least one or more selected from hydrocarbon groups having 1 carbon atom with a valence of 2 to 4, -C 6 H 4 -, -O-, -C(=O)-, -S(=O) 2 -, or -NR'-; wherein R' is H or a hydrocarbon group having 1 to 4 carbon atoms; The reactive / hydrophilic monomer (3) is a monomer represented by the following 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 valence bond, -O-, or -NR'- wherein R' is H or a hydrocarbon group having 1 to 4 carbon atoms, R 33 is a hydrocarbon group having 1 to 10 carbon atoms with a valence of 2 to 4 Y 41 is a benzene ring, H is a hydrogen atom, H and R 41 are directly combined with Y 41 respectively m and n are 1 to 3, o is 0 or 1; The crosslinkable monomer (4) is a monomer represented by the following formula: In the formula, R 51 and R 61 are each independently a divalent to tetravalent group composed of at least one selected from a valence bond, a hydrocarbon group having 1 to 20 carbon atoms, -(CH 2 CH 2 O)r-, -C 6 H 4 -, -O-, or -NR'- wherein r is an integer of 1 to 10, and 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'- where R' is H or a hydrocarbon group having 1 to 4 carbon atoms p is 2 to 4, q is 1 to 5; The high glass transition temperature monomer (5) is a monomer represented by the following formula: In the formula, R 71 and R 81 are groups composed of at least one or more selected from hydrocarbon groups having 1 to 30 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'- wherein R' is H or a hydrocarbon group having 1 to 4 carbon atoms.

12. The water repellent composition according to claim 7, characterized in that: Among the reactive monomers (3), the reactive group is an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a blocked isocyanate group, and the hydrophilic group is at least one group selected from 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 base of a carboxylic acid, a sulfonic acid, a phosphoric acid; an ammonium base having a chloride ion, a bromide ion or an iodide ion as a counter anion.

13. The water repellent composition according to claim 7, characterized in that: The hydrophobic monomer (1) is at least one monomer selected from tert-butyl (meth)acrylate, N-tert-butyl (meth)acrylamide, tert-butylstyrene, 2,4-di-tert-butylstyrene, (The (meth)acrylic monomer (2) is at least one monomer selected from the following formulas: In the formula, n is a number from 1 to 500; The reactive / hydrophilic monomer (3) is at least one monomer selected from glycidyl (meth)acrylate, glycerol (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (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, glycidyl ether of 4-hydroxybutyl acrylate, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, quaternized dimethylaminoethyl methacrylate, tetrahydrofuranyl (meth)acrylate; The crosslinkable monomer (4) is at least one monomer selected from 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, polytetramethylene glycol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentyl di(meth)acrylate, 5-hydroxy-1,3-adamantyl di(meth)acrylate; The high glass transition temperature monomer (5) is at least one monomer selected from isobornyl (meth)acrylate, bornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, phenyl (meth)acrylate, naphthyl acrylate, benzyl acrylate.

14. The water repellent composition according to claim 7, characterized in that: The molar ratio of the hydrophobic monomer (1) or the (meth)acrylic acid monomer (2) / (reactive / hydrophilic monomer (3)) / high glass transition temperature monomer (5) is 20 to 100 / 0 to 50 / 0 to 70, the crosslinkable monomer (4) is 0.1 to 30 parts by mole relative to 100 parts by mole in total of the hydrophobic monomer (1) and the reactive / hydrophilic monomer (3), and the (meth)acrylic acid monomer (2) is 0 to 30 parts by mole relative to 100 parts by mole in total of the hydrophobic monomer (1), the (meth)acrylic acid monomer (2) and the reactive / hydrophilic monomer (3).

15. The water repellent composition according to any one of claims 1, 2, 4 or 5, characterized in that: When treating cloth with organic particles, the slipping speed is 150 mm / second or more.

16. The water-repellent composition according to any one of claims 1, 2, 4 or 5, characterized in that: The average particle size of the organic particles is 30 nm to 1000 nm.

17. A method for manufacturing a water-repellent composition for manufacturing the water-repellent composition according to any one of claims 4 to 16, characterized in that: By polymerizing a monomer containing a crosslinkable monomer (4) and then polymerizing a monomer not containing a crosslinkable monomer (4), organic particles are obtained.

18. A water-repellent composition, characterized in that: It is an aqueous dispersion of organic particles containing (A) organic particles and (B) an aqueous medium, wherein, (A) The organic particles are formed of a non-fluorinated polymer having a repeating unit formed of a monomer having a tert-butyl group, and the organic particles can be attached to the substrate in a particulate state, and the substrate exhibits water repellency when the organic particles are attached to the substrate; or, (A) The organic particles are formed of a polymer containing a repeating unit formed of the following (1) hydrophobic monomer or (2) (meth)acrylic monomer, and the polymer further contains an organic particle having a repeating unit formed of (4) crosslinkable monomer, (1) A hydrophobic monomer having 1 ethylenically unsaturated double bond and at least 1 tert-butyl group; (2) A (meth)acrylic monomer having a polydimethylsiloxanyl group; (4) A crosslinkable monomer having at least 2 ethylenically unsaturated double bonds, In the polymer forming (A) the organic particles, the amount of the repeating unit formed of the monomer having a tert-butyl group or the repeating unit formed of the hydrophobic monomer (1) is 50 mol% or more.

19. The water-repellent composition according to claim 18, characterized in that: It further contains any one or more of (C) an adhesive resin, (D) a surfactant and (E) a crosslinking agent.

20. The water-repellent composition according to claim 19, characterized in that: The adhesive resin (C) is at least one polymer selected from 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. The water-repellent composition according to claim 19 or 20, characterized in that: The amount of the surfactant (D) is 15 parts by weight or less based on 100 parts by weight of the organic particles (A).

22. The water-repellent composition according to claim 19 or 20, characterized in that: The adhesive resin (C) is one or more of an acrylic polymer, a polyurethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, a polystyrene, and a silicone polymer.

23. The water-repellent composition according to any one of claims 18 to 20, characterized in that: It can prevent frosting.

24. The water-repellent composition according to any one of claims 18 to 20, characterized in that: The organic fine particles (A) are organic fine particles formed of a polymer containing repeating units formed from the following (1) hydrophobic monomers or (2) (meth)acrylic monomers, and the polymer further contains repeating units formed from (4) crosslinkable monomers. (1) A hydrophobic monomer having one ethylenically unsaturated double bond and at least one tert-butyl group; (2) A (meth)acrylic monomer having a polydimethylsiloxanyl group; (4) A crosslinkable monomer having at least two ethylenically unsaturated double bonds.

25. A method for producing a water-repellent composition for producing the water-repellent composition according to any one of claims 18 to 24, characterized in that: It includes: A step of polymerizing monomers in an aqueous medium in the presence of a surfactant of 15 parts by weight or less based on 100 parts by weight of the monomers to obtain an aqueous dispersion of organic fine particles (A).

26. The production method according to claim 25, characterized in that: It further includes the following step: 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 the aqueous dispersion of organic fine particles (A), or by polymerizing monomers for the binder resin in the aqueous dispersion of organic fine particles (A), or by polymerizing monomers for organic fine particles in the aqueous dispersion of the binder resin.

27. A method for treating a fiber product, characterized in that: Applying a treatment liquid containing the water-repellent composition according to any one of claims 1 to 16 and 18 to 24 to the fiber product.

28. A fiber product, characterized in that: Organic fine particles in the water-repellent composition according to any one of claims 1 to 16 and 18 to 24 are attached to the surface.

29. A fiber product, characterized in that: Organic fine particles in the water-repellent composition according to any one of claims 1 to 16 and 18 to 24 are attached to the surface, and satisfy at least any one of the conditions that the static contact angle of water on the fabric is 120 degrees or more or the sliding speed of water on the fabric is 200 mm / second or more.

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