Fine organic particles that are waterproof and have an anti-slip effect.

Abstract

Invention details;

Description

Water-repellent organic fine particles with anti-slip properties

[0001] The present disclosure relates to water-repellent organic fine particles having an anti-slip effect, particularly non-fluorine organic fine particles.

[0002] Conventionally, a water repellent agent is applied to a substrate, particularly a textile product such as a fabric, to impart water repellency to the substrate. The water repellent agent increases the slipperiness of the fibers, which can cause misalignment of the textile product. Misalignment is likely to occur when a force is applied to the textile product, for example, when sewing the textile product or when wearing the textile product. Water repellents that impart water repellency while also having an anti-slip effect (slip resistance) to prevent misalignment have been investigated.

[0003] Patent Document 1 discloses that seam slippage is suppressed by a water repellent composition containing an acrylic copolymer obtained by polymerizing 40% by weight or more and less than 80% by weight of a (meth)acrylate having an alkyl group having 12 to 24 carbon atoms and no cyclic structure, and 10% by weight or more and less than 50% by weight of a polymerizable monomer containing an aromatic ring having 6 to 12 carbon atoms or an aromatic ring having a substituent, or a cycloalkane having 5 to 12 carbon atoms or a cycloalkane having a substituent.

[0004] Anti-slip agents are used, but the most commonly available commercially available anti-slip agents are inorganic silica-based particles. However, silica-based particles reduce water repellency. There is a demand for anti-slip agents that provide anti-slip effects without reducing water repellency.

[0005] International Publication No. 2015 / 178471

[0006] The present disclosure provides water-repellent organic fine particles that can impart excellent slip resistance (anti-slip properties) to a substrate.

[0007] The present disclosure relates to organic microparticles that can be present on a substrate in a particulate state and that, when present on the substrate, impart good slip resistance to the substrate. The organic microparticles can also impart good water repellency. The organic microparticles can be attached to a substrate in a particulate state. In the present disclosure, the exhibited slip resistance is preferably 8.0 mm or less. In the present disclosure, the exhibited water repellency means at least one of the following: (i) when the organic microparticles are attached to a cloth, the cloth to which the organic microparticles are attached has a water contact angle of 120 degrees or more; (ii) when the organic microparticles are attached to a cloth, the cloth to which the organic microparticles are attached has a sliding speed of 100 mm / s or more; or (iii) when the organic microparticles are attached to a cloth, the cloth to which the organic microparticles are attached scores 80 points or more in a water repellency test.

[0008] The present disclosure relates to a water repellent composition comprising: (A) organic fine particles; and (B) an aqueous medium. Additionally, the present disclosure relates to organic fine particles comprising a polymer having repeating units formed from: (I) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms. The polymer constituting the organic fine particles may also have repeating units formed from: (II) a crosslinkable monomer having at least two ethylenically unsaturated double bonds, in addition to the monomer (I). The polymer constituting the organic fine particles may further have a repeating unit formed from at least one monomer selected from: (III) a reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group, or a short-chain hydrocarbon-containing monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 1 or 2 carbon atoms; and (IV) a (meth)acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms or a polydimethylsiloxane group.

[0009] Preferred aspects of the present disclosure are as follows. Aspect 1: Organic fine particles that can be present on a substrate in a particulate state and that exhibit a slip-resistant effect on the substrate. Aspect 2: Organic fine particles according to Aspect 1, which have a slip resistance on the substrate of 8.0 mm or less. Aspect 3: Organic fine particles according to Aspect 1 or 2, which satisfy at least one of the following: (i) when attached to cloth, the cloth to which the organic fine particles are attached has a water contact angle of 120 degrees or more; (ii) when attached to cloth, the cloth to which the organic fine particles are attached has a sliding speed of 100 mm / s or more; or (iii) when attached to cloth, the cloth to which the organic fine particles are attached scores 80 points or more in a water repellency test. Aspect 4: Organic fine particles according to any one of Aspects 1 to 3, in which the particle diameter of the fine particles observable on cloth is 50 to 700 nm. Aspect 5: Organic fine particles according to any one of Aspects 1 to 4, comprising a polymer having a repeating unit formed from (I) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms. Aspect 6: Organic fine particles comprising a polymer having repeating units formed from (I) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms, and (II) a crosslinkable monomer having at least two ethylenically unsaturated double bonds. Aspect 7: Organic fine particles comprising a polymer having repeating units formed from (I) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms, wherein the hydrophobic monomer (I) contains 20 mol % or more of a high glass transition point monomer, the glass transition point of which homopolymer has a glass transition point of 100°C or higher. Aspect 8: The organic fine particles according to any one of Aspects 5 to 7, wherein the polymer further comprises a repeating unit formed from at least one monomer selected from (III) a reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group, or a short-chain hydrocarbon-containing monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 1 or 2 carbon atoms, and / or (IV) a (meth)acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms or a polydimethylsiloxane group.Aspect 9: The organic fine particles according to any one of Aspects 5 to 8, wherein in the hydrophobic monomer (I), the branched hydrocarbon group has a carbon number of 3 to 11, and the cyclic hydrocarbon group has a carbon number of 4 to 15. Aspect 10: The hydrophobic monomer (I) is a compound represented by the formula: CH. ２ =C(-R １２ )-C(=O)-Y １１ (R １１ ) ｋ or CH ２ =C(-R １４ )-Y １２ (H) ５－ｌ (R １３ ) ｌ [In the formula, R １１ and R １３ are each independently a branched or cyclic hydrocarbon group having 3 to 40 carbon atoms; R １２ and R １４ is a hydrogen atom, a monovalent organic group or a halogen atom, １１ is —O—, —, or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), and Y １２ is a benzene ring, H is a hydrogen atom, H and R １３ Is Y １２ and k is 1 to 3, and l is 0 to 3.], and the crosslinking monomer (II) is a monomer represented by the formula: or [In the formula, R ３１ and R ３３ each independently represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms (which may contain a hydrocarbon moiety having an —OH group), —(CH ２ CH ２ O) r- (r is an integer of 1 to 10), -C ６ H ４ a divalent to tetravalent group consisting of at least one selected from -, -O-, and -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), ３２ , R ３４ , R ３５ and R ３６ are each independently a hydrogen atom, a monovalent organic group, or a halogen atom; ３１is —O— or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), p is 2 to 4, and q is 1 to 5.], and the reactive and hydrophilic monomer (III) is a monomer represented by the formula: ２ =C(-R ４２ )-C(=O)-Y ４１ - (R ４３ ) ｏ (R ４１ ) ｔ or CH ２ =C(-R ４５ )-Y ４２ - (H) ５－ｎ (R ４４ ) ｕ [In the formula, R ４１ and R ４４ are each independently a reactive group or a hydrophilic group, R ４２ and R ４５ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y ４１ is a direct bond, —O—, or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), and R ４３ is a direct bond, —O—, or a group having a divalent to tetravalent hydrocarbon group having 1 to 10 carbon atoms (which may contain a hydrocarbon moiety having an —OH group), and Y ４２ is a benzene ring, H is a hydrogen atom, H and R ４４ Is Y ４２ t and u are each directly bonded to one of the following monomers: t and u are each 1 to 3; and o is 0 or 1.] or a monomer represented by the formula: CH ２ =C(-R ４７ )-C(=O)-Y ４３ -R ４６ [In the formula, R ４６ is a hydrocarbon group having 1 or 2 carbon atoms, R ４７ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y ４３ is a direct bond, —O—, or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), and (IV) is a monomer represented by the formula: ２ =C(-R ５２)-C(=O)-Y ５１ (R ５１ ) ｓ [In the formula, R ５１ are each independently a linear hydrocarbon group having 3 to 40 carbon atoms; R ５２ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y ５１ represents a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH ２ -, -CH= and -C≡), -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 a divalent to tetravalent group (excluding the case where the group is only a divalent hydrocarbon group), and s is 1 to 3.] or a (meth)acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms, represented by the formula: CH ２ =C(-R ６２ )-C(=O)-Y ６１ -R ６１ [In the formula, R ６１ is a group having a polydimethylsiloxane group, R ６２ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y ６１ represents a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms). ]. Aspect 11: In the reactive monomer (III), the reactive group is an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group, or a blocked isocyanate group, and the hydrophilic group is a hydroxyl group, an amino group (including those in which H bonded to N is replaced with a methyl group, an ethyl group, a propyl group, or a butyl 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, sulfonic acid, or phosphoric acid, an ammonium base with a chlorine, bromine, or iodine ion as a counter anion, an ethylene glycol group, a polyethylene glycol group, a group having an acetone skeleton (-C(=O)-CH ３11. The organic fine particles according to any one of Aspects 8 to 10, wherein the reactive hydrophilic monomer (III) is at least one group selected from the group consisting of: Aspect 12: The hydrophobic monomer (I) is at least one monomer selected from the group consisting of t-butyl(meth)acrylate, isopropyl(meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, isobornyl(meth)acrylate, bornyl(meth)acrylate, adamantyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyl(meth)acrylate, phenyl(meth)acrylate, naphthyl acrylate, benzyl acrylate, t-butylstyrene, methylstyrene, styrene, cyclohexyl(meth)acrylate, cyclopentyl(meth)acrylate, cyclobutyl(meth)acrylate, cycloheptyl(meth)acrylate, 2,4-di-t-butylstyrene, and 2,4,6-trimethylstyrene; The crosslinkable monomer (II) is selected from the group consisting of divinylbenzene, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, methylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, 5-hydroxy-1,at least one monomer selected from the group consisting of 3-adamantanedi(meth)acrylates, The reactive and hydrophilic monomer (III) is selected from the group consisting of glycidyl (meth)acrylate, glycerol (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate. the short-chain hydrocarbon group-containing monomer (III) is at least one monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, α-chloromethyl acrylate, and α-chloroethyl acrylate; the (meth)acrylic monomer (IV) is at least one monomer selected from the group consisting of stearyl (meth)acrylate, stearamidoethyl (meth)acrylate, CH, ２ =CHC(=O)OC ２ H ４ NHC(=O)C １７ H ３５、 CH ２=CHC(=O)OC ２ H ４ NHSO ２ C １８ H ３７ 、CH ２ =CHC(=O)OC ２ H ４ NHC(=O)OC １８ H ３７ 、CH ２ =CHC(=O)OC ２ H ４ OC(=O)NHC １８ H ３７ 、CH ２ =CHC(=O)OC ２ H ４ NHC(=O)NHC １８ H ３７ 、 Formula: or wherein n is a number from 1 to 500. Aspect 13: The organic fine particles according to any one of aspects 5 to 12, wherein the at least one monomer selected from the group consisting of: (i) the molar ratio of hydrophobic monomer (I) to reactive hydrophilic monomer and / or short-chain hydrocarbon group-containing monomer (III) is 100 / 0 to 50 / 50, (ii) the crosslinkable monomer (II) is 0.1 to 30 parts by mole per 100 parts by mole of the total of the hydrophobic monomer (I), the reactive hydrophilic monomer and / or short-chain hydrocarbon group-containing monomer (III), and the (meth)acrylic monomer (IV), or (iii) the (meth)acrylic monomer (IV) is 0 to 30 parts by mole per 100 parts by mole of the total of the hydrophobic monomer (I) and the reactive hydrophilic monomer and / or short-chain hydrocarbon group-containing monomer (III). Aspect 14: An anti-slip agent comprising the organic fine particles according to any one of Aspects 1 to 13. Aspect 15: Use of the organic fine particles according to any one of Aspects 1 to 13 as an anti-slip agent. Aspect 16: An anti-slip agent composition comprising (A) the organic fine particles according to any one of Aspects 1 to 13, and (B) an aqueous medium. Aspect 17: The anti-slip agent composition according to Aspect 16, wherein the amount of the organic fine particles (A) is 50% by weight or less based on the anti-slip agent composition. Aspect 18: The anti-slip agent composition according to Aspect 16 or 17, further comprising any one or more of (C) a binder resin, (D) a surfactant, and (E) a crosslinking agent. Aspect 19: The anti-slip agent composition according to Aspect 18, wherein the binder resin (C) is at least one polymer selected from a non-fluorinated polymer having a hydrocarbon group having 3 to 40 carbon atoms in its side chain and a fluorinated polymer having a fluoroalkyl group having 1 to 20 carbon atoms in its side chain. Aspect 20: The anti-slip agent composition according to Aspect 18 or 19, wherein the binder resin (C) is an acrylic polymer, a urethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, a polystyrene, a silicone polymer, or a combination thereof.Aspect 21: The slip-proof composition according to any one of Aspects 18 to 20, wherein the weight ratio of binder resin (C) / organic fine particles (A) is 20 / 80 to 99 / 1, or the amount of binder resin (C) is 30 to 99% by weight, where the total weight of binder resin (C) and organic fine particles (A) is 100. Aspect 22: A method for producing the slip-proof composition according to any one of Aspects 16 to 21, comprising: a step of polymerizing monomers in an aqueous medium in the presence of a surfactant in an amount of 30 parts by weight or less per 100 parts by weight of the monomers to obtain an aqueous dispersion of organic fine particles (A). Aspect 23: The method according to aspect 22, further comprising the step of obtaining an aqueous dispersion in which organic fine particles (A) and binder resin (C) are dispersed by adding an aqueous dispersion of binder resin (C) to an aqueous dispersion of organic fine particles (A), or by polymerizing a monomer for the binder resin in the aqueous dispersion of organic fine particles (A) to obtain the binder resin (C), or by polymerizing a monomer for the organic fine particles in the aqueous dispersion of binder resin. Aspect 24: A method for treating a textile product, comprising applying to the textile product a treatment liquid containing the slip-resistant composition according to any one of aspects 16 to 21. Aspect 25: A textile product to which the slip-resistant composition according to any one of aspects 16 to 21 has been applied. Aspect 26: The textile product according to aspect 25, having a slip resistance of 8.0 mm or less. Aspect 27: The textile product according to aspect 25 or 26, which is a fabric for clothing, outdoor use, or sporting goods.

[0010] The anti-slip agent (organic fine particles or water repellent composition) of the present disclosure can impart excellent slip resistance to substrates such as textiles. The anti-slip agent of the present disclosure provides excellent water repellency (contact angle and sliding velocity). While conventional anti-slip agents reduce water repellency, the anti-slip agent of the present disclosure does not reduce water repellency.

[0011] The anti-slip agent comprises organic fine particles. The anti-slip agent may consist of only organic fine particles, or may contain other components in addition to the organic fine particles. The water repellent composition functions as an anti-slip agent. The water repellent composition (i.e., the anti-slip agent) comprises: (A) organic fine particles; and (B) an aqueous medium. 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.

[0012] In a preferred embodiment, the water repellent composition contains the following components: organic fine particles (A), organic fine particles (A) + aqueous medium (B), organic fine particles (A) + aqueous medium (B) + binder resin (C), organic fine particles (A) + aqueous medium (B) + surfactant (D), organic fine particles (A) + aqueous medium (B) + binder resin (C) + surfactant (D), organic fine particles (A) + aqueous medium (B) + binder resin (C) + crosslinking agent (E), or organic fine particles (A) + aqueous medium (B) + binder resin (C) + surfactant (D) + crosslinking agent (E).

[0013] (A) Organic Fine Particles The organic fine particles act as an active ingredient that exhibits water repellency and slip resistance. The organic fine particles are preferably formed from a non-fluorinated polymer. From the viewpoint of slip resistance and stability of the aqueous dispersion, the average particle size of the organic fine particles may be 30 to 1,000 nm, preferably 40 to 700 nm or 45 to 300 nm. The average particle size refers to the average particle size of the particles measured by dynamic light scattering (DLS).

[0014] Organic fine particles remain in particle shape on the substrate, and exhibit water repellency and slip resistance.The slip resistance exhibited can be achieved by adhering organic fine particles to fabric, and the value of slip resistance test can be improved by 0.5 mm or more compared with the case where only a water repellent agent without fluorine is used.For example, when the value of slip resistance test of fabric that only a water repellent agent without organic fine particles is adhered is 9.5 mm, it is preferable that it is 9.0 mm or less, 8.5 mm or less, further 8.0 mm or less, further 7.0 mm or less, 6.0 mm or less.In addition, slip resistance is not compared with the case where organic fine particles are not adhered, but it is preferable that the value of slip resistance test is 8.0 mm or less, 7.0 mm or less, 6.0 mm or less, further 4.0 mm or less.

[0015] The slip resistance test value indicating slip resistance may be 8.0 mm or less, 6.0 mm or less, 4.0 mm or less, 3.0 mm or less, 2.0 mm or less, 1.5 mm or less, or 1.0 mm or less (lower limit: 0 mm). Slip resistance is measured in accordance with JIS L 1096 (seam slippage method B). Specifically, slip resistance when organic fine particles are attached is measured in accordance with JIS L 1096 (seam slippage method B) by immersing a cloth, for example, a PET cloth (white), in a composition containing organic fine particles, passing it through a mangle, and passing it through a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. Five 10cm x 17cm test pieces of water-repellent treated polyester fabric (white) were taken in both the warp and weft directions, folded in half with the right side in, cut along the fold, and sewn together 1cm from the cut end with a lock stitch, 5 stitches / cm, and polyester filament 78dex x 3 thread, using a standard 11-inch sewing machine needle. Using a tensile tester, a specified load (49.0N (5kgf)) was applied using the grab method with a grip spacing of 7.62cm and a tensile strength of 30cm per minute. The test piece was then removed from the grips and left for one hour, after which the size of the maximum hole (mm) in slippage at a load large enough to remove slack near the seam was measured. It is most preferable that the slip resistance (i.e., the value in the slip resistance test) is the same as that of an untreated fabric, i.e., 2.0 mm or less. However, it is sufficient if the value in the slip resistance test is improved by 0.5 mm or more compared to when only a non-fluorine-containing water repellent agent is used, and more preferably, it is 8.0 mm or less, 7.0 mm or less, 6.0 mm or less, for example, 5.0 mm or less.

[0016] The water repellency exhibited means that (i) when the organic fine particles are attached to a cloth, the contact angle of water on the cloth to which the organic fine particles are attached is 120 degrees or more, or (ii) when the organic fine particles are attached to a cloth, the sliding speed of the cloth to which the organic fine particles are attached is 100 mm / s or more, or (iii) when the organic fine particles are attached to a cloth, the water repellency test score of the cloth to which the organic fine particles are attached is 80 points or more.

[0017] The contact angle of water on a cloth to which a composition containing organic fine particles is applied (the contact angle of water on a cloth to which organic fine particles are applied or the contact angle of water on a cloth to which organic fine particles and a binder (and other components) are applied) is preferably 120 degrees or more, more preferably 130 degrees or more, and even more preferably 140 degrees or more. Specifically, the contact angle of water on a cloth is measured by applying a composition containing organic fine particles to a PET cloth (basis weight: 88 g / m 2 After immersing a PET cloth (70 denier, gray), the cloth was passed through a mangle and then through a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. 2 μL of water was dropped onto the PET cloth, and the static contact angle was measured 1 second after the drop had been attached using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science).

[0018] In the case of a cloth (PET cloth), the water sliding speed is preferably 100 mm / s or more, for example, 130 mm / s or more, further preferably 150 mm / s or more or 200 mm / s or more. The sliding speed is the average sliding speed over a distance of about 40 mm when 20 μL of water is dropped from a microsyringe onto a substrate tilted at an angle of 30 degrees. Specifically, a composition containing organic fine particles is applied to a PET cloth (basis weight: 88 g / m 2 A PET cloth (70 denier, gray) was immersed in the solution, and then passed through a mangle and a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. 20 μL of water was dropped from a microsyringe onto the PET cloth tilted at 30 degrees using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.). The state of the dropped water sliding down was measured using a high-speed camera (VW-9000 manufactured by Keyence Corporation), and the average sliding speed over a distance of approximately 40 mm was recorded as the sliding speed.

[0019] The water repellency test score is preferably 80 points or more or 90 points or more. The water repellency test is carried out in accordance with the spray method of JIS-L-1092 (AATCC-22). Details of the water repellency test are explained in the examples of the present specification.

[0020] The unevenness of the microparticles on the substrate can be observed using a laser microscope or a scanning electron microscope. After applying the particles to the substrate, the average diameter (average particle size) of the particles after heating (for example, at 170°C for 1 minute) is preferably 50% or more, more preferably 60% or more, of the average diameter before heating. Alternatively, the average particle size of the microparticles observable on the fabric is preferably 30 to 1000 nm, more preferably 40 to 700 nm or 50 to 500 nm. This average particle size is generally preferably the average particle size after applying the particles to the substrate and heating (at 170°C for 1 minute).

[0021] In some embodiments, the organic fine particles comprise a polymer having a repeating unit formed from: (I) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms; and further, the polymer may or may not have a repeating unit formed from: (II) a crosslinkable monomer having at least two ethylenically unsaturated double bonds.

[0022] In some embodiments, the organic fine particles further comprise a polymer having repeating units formed from: (III) a reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group, or a short-chain hydrocarbon-containing monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 1 or 2 carbon atoms, and / or (IV) a (meth)acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms or a polydimethylsiloxane group. Each of the monomers (I) to (IV) (and other monomers (V)) may have two or more types of monomers. The polymer constituting the organic fine particles is preferably a non-fluorinated polymer.

[0023] (I) Hydrophobic Monomer The hydrophobic monomer (I) has at least one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms. The hydrophobic monomer (I) is preferably a branched hydrocarbon group (e.g., a branched alkyl group), particularly a t-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 compound has the following structure:

[0024] The hydrophobic monomer (I) is preferably an acrylate compound, an acrylamide compound, or a styrene compound containing a branched or cyclic hydrocarbon group having 3 to 40 carbon atoms. That is, the hydrophobic monomer (I) is preferably an acrylate compound containing a branched or cyclic hydrocarbon group having 3 to 40 carbon atoms, an acrylamide compound containing a branched or cyclic hydrocarbon group having 3 to 40 carbon atoms, or a styrene compound containing a branched or cyclic hydrocarbon group having 3 to 40 carbon atoms (excluding a benzene ring). The hydrophobic monomer (I) is preferably a non-fluorine-containing monomer.

[0025] The hydrophobic monomer (I) has the formula: CH ２ =C(-R １２ )-C(=O)-Y １１ (R １１ ) ｋ or CH ２ =C(-R １４ )-Y １２ (H) ５－ｌ (R １３ ) ｌ [In the formula, R １１ and R １３ are each independently a branched or cyclic hydrocarbon group having 3 to 40 carbon atoms; R １２ and R １４ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y １１ is —O— or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), or a divalent to tetravalent linking group having at least one group selected from —O— or —NR′—; Y １２ is a benzene ring, H is a hydrogen atom, H and R １３ Is Y １２ and k is 1 to 3, and l is 1 to 5.

[0026] R １１ and R １３is a branched or cyclic hydrocarbon group. The branched hydrocarbon group (for example, having 3 to 11 (particularly 3 to 8 or 4 to 6) or 12 to 30 carbon atoms) is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The cyclic hydrocarbon group may be an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group. -CH ３ The group is -CH ２ - has a lower surface free energy and is more likely to be water-repellent. ３ In the branched hydrocarbon group, a structure with many —CH ３ The number of groups may be 2-15, for example 3-10, 3-9, 4-8 or 4-6.

[0027] The branched hydrocarbon group (for example, a branched alkyl group) is an alkyl group having 3 or 4 carbon atoms, particularly a t-butyl group or an isopropyl group, or a hydrocarbon group (particularly an alkyl group) having a multi-branched structure having 5 to 30 carbon atoms, for example, a group represented by the following formula: It may be a group having a multi-branched structure as shown in the following.

[0028] The cyclic hydrocarbon group may be a saturated or unsaturated monocyclic group, polycyclic group, bridged ring group, or the like. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group preferably has 4 to 20 carbon atoms (for example, 6 to 15 or 6 to 10). Examples of the cyclic hydrocarbon group include cyclic aliphatic groups having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and araliphatic groups having 7 to 20 carbon atoms. The cyclic hydrocarbon group may have 15 or less carbon atoms, for example 10 or less carbon atoms. A carbon atom in the ring of the cyclic hydrocarbon group may be bonded directly to the ester group in the (meth)acrylate group, or may be bonded via a hydrocarbon spacer. R １１ In the above formula, the cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.

[0029] Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a cyclopentyl group, a cyclobutyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, an isobornyl group, a naphthalene group, a bornyl group, a tricyclodecanyl group, a phenyl group, a biphenyl group, and a triphenyl group.

[0030] R １２ and R １４ represents a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or —CF ３ R may be a group. １２ and R １４ Examples of R may be a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group. １２ and R １４ is preferably a hydrogen atom, a methyl group, or a chlorine atom. １２ More preferably, R is a methyl group. １２ When R is a methyl group, higher slip resistance is obtained. １４ is preferably a hydrogen atom, particularly from the viewpoint of reactivity.

[0031] Y １１ is preferably a divalent group. １１ is preferably —O— or —NH—.

[0032] Y １２ is a benzene ring. １２ The monomer having Y has a styryl group. １２ In the monomer having １３ A group and 2 to 4 hydrogen atoms are attached to the benzene ring.

[0033] k is preferably 1. l may be 1 to 3, but is preferably 1 or 2.

[0034] The hydrophobic monomer may be a combination of a monomer having a branched hydrocarbon group and a monomer having a cyclic hydrocarbon group, or a combination of a monomer having a monocyclic hydrocarbon group and a monomer having a polycyclic or bridged cyclic hydrocarbon group. In the hydrophobic monomer, the weight ratio of the monomer having a branched hydrocarbon group to the monomer having a cyclic hydrocarbon group, and the weight ratio of the monomer having a monocyclic hydrocarbon group to the monomer having a polycyclic or bridged cyclic hydrocarbon group may be 10 / 90 to 90 / 10, 30 / 70 to 70 / 30, or 40 / 60 to 60 / 40.

[0035] Specific examples of hydrophobic monomers are as follows: The compound of the following chemical formula is an acrylic compound having a hydrogen atom at the α-position, but specific examples may be a methacrylic compound having a methyl group at the α-position and an α-chloroacrylic compound having a chlorine atom at the α-position, with a methacrylic compound having a methyl group at the α-position being preferred. Also, among styrene derivatives, the compound of the following chemical formula is an acrylic compound having a hydrogen atom at the α-position, but specific examples may be an α-methylstyrene compound having a methyl group at the α-position and an α-chlorostyrene compound having a chlorine atom at the α-position, with a styrene compound having a hydrogen atom at the α-position being preferred.

[0036]

[0037]

[0038]

[0039]

[0040] [In the formula, tBu is t-butyl.]

[0041] Specific examples of the monomer having a cyclic hydrocarbon group include cyclobutyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate.

[0042] Specific preferred examples of the hydrophobic monomer (I) include t-butyl(meth)acrylate, t-butylstyrene, methylstyrene, styrene, isopropyl(meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, cyclobutyl(meth)acrylate, cyclopropyl(meth)acrylate, cyclopentyl(meth)acrylate, cyclohexyl(meth)acrylate, cycloheptyl(meth)acrylate, cyclooctyl(meth)acrylate, isobornyl(meth)acrylate, 4-t-butylphenyl(meth)acrylate, and 2,3,4-methylphenyl(meth)acrylate.

[0043] More preferred specific examples of the hydrophobic monomer (I) include t-butyl(meth)acrylate, isobornyl methacrylate, cyclohexyl methacrylate, t-butylstyrene, cyclopentyl(meth)acrylate, cycloheptyl(meth)acrylate, adamantyl(meth)acrylate, and 2-ethyl-2-adamantyl(meth)acrylate.

[0044] The hydrophobic monomer (I) may be a high glass transition point monomer (high Tg monomer). When the organic fine particles do not contain a crosslinkable monomer (II), the hydrophobic monomer (I) is preferably a high Tg monomer. A high Tg monomer refers to a monomer whose homopolymer has a Tg of 50°C or higher. Among the monomers (I), the high Tg monomer (I-a) has a glass transition point of 50°C or higher, preferably 100°C or higher. The glass transition point of the homopolymer may be, for example, 120°C or higher, particularly 150°C or higher, and may be 250°C or lower. The glass transition point (glass transition temperature) of the homopolymer was calculated by differential scanning calorimetry (DSC). A DSC curve was obtained by heating 10 mg of a sample at a rate of 10°C / min, and the temperature was determined as the midpoint between the intersection of the extensions of the baselines before and after the second-order transition of the DSC curve and the tangent to the inflection point of the DSC curve. The organic fine particles may contain only one type of hydrophobic monomer or two or more types of monomers, and may independently contain a high Tg hydrophobic monomer (I-a) and / or a non-high Tg hydrophobic monomer (I).

[0045] The high glass transition temperature monomer has the formula: or [In the formula, R ２１ and R ２３ represents a hydrocarbon group having 1 to 30 carbon atoms, -C ６ H ４ is a group consisting of at least one selected from -, -O-, and -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), ２２ and R ２４ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y ２１ is —O—, or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms).]

[0046] R ２１ and R ２３ Examples of the aryl group include a cyclohexyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, an isobornyl group, a naphthalene group, a bornyl group, a tricyclodecanyl group, and a phenyl group.

[0047] R２２ and R ２４ represents 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 —CF ３ R may be a group. ２２ and R ２４ Examples of the group include a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, and —CF ３ group, and a cyano group. ２２ and R ２４ is preferably a hydrogen atom, a methyl group, or a chlorine atom. ２２ More preferably, R is a methyl group. ２２ When R is a methyl group, higher water repellency and high slip resistance are obtained. ２４ is preferably a hydrogen atom, particularly from the viewpoint of reactivity, but is preferably a methyl group from the viewpoint of water repellency and slip resistance. R ２４ It is preferable to select Y. ２１ is preferably —O— or —NH—.

[0048] Specific examples of high glass transition point monomers include acrylate esters such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, bornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, 2-t-butylphenyl (meth)acrylate, and naphthyl (meth)acrylate; styrene, α-methylstyrene, and styrene derivatives.

[0049] (II) Crosslinkable Monomer The crosslinkable monomer (II) is a compound having at least two (particularly, two, three, or four) ethylenically unsaturated double bonds. The crosslinkable monomer (II) is preferably a non-fluorine-containing monomer.

[0050] The crosslinking monomer (II) is represented by the formula: or [In the formula, R ３１ and R ３３ each independently represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms (which may contain a hydrocarbon moiety having an —OH group), —(CH ２ CH ２ O) ｒ -(r is an integer from 1 to 10), -C ６ H ４ a divalent to tetravalent group consisting of at least one selected from -, -O-, and -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), ３２ , R ３４ , R ３５ and R ３６ are each independently a hydrogen atom, a monovalent organic group, or a halogen atom; ３１ is —O— or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), p is 2 to 4, and q is 1 to 5.

[0051] R ３１ and R ３３ Examples of R are a direct bond, a divalent to tetravalent (e.g., divalent to trivalent) hydrocarbon group having 1 to 20 (or 2 to 10) carbon atoms which may be interrupted by an oxygen atom and / or in which a hydrogen atom may be substituted with an OH group, an ethylene glycol group, a propylene glycol group, a glycerol group, a cyclohexyl group, a dicyclopentanyl group, an adamantyl group, an isobornyl group, a naphthalene group, a bornyl group, a tricyclodecanyl group, and a phenyl group, or a group containing any of these groups. ３１ and R ３３ may be a polymer group, and the structural unit constituting the polymer group may be any of the groups exemplified above (for example, an ethylene glycol group). ３１ and R ３３ is preferably a divalent group.

[0052] Y ３１ is preferably —O— or —NH—. ３２ , R ３４ , R ３５ and R ３６may each independently be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. ３ R may be a group. ３２ , R ３４ , R ３５ and R ３６ Examples of the group include a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, and —CF ３ group, and a cyano group. ３２ , R ３４ , R ３５ and R ３６ is preferably a hydrogen atom, a methyl group, or a chlorine atom. ３２ More preferably, R is a methyl group. ３２ When R is a methyl group, higher water repellency and high slip resistance are obtained. ３４ , R ３５ and R ３６ is preferably a hydrogen atom, particularly from the viewpoint of reactivity.

[0053] p may be 2 or 3, especially 2. q may be 1 to 3, especially 1.

[0054] Specific examples of the crosslinkable monomer (II) include divinylbenzene, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, methylene glycol di(meth)acrylate, ) acrylate, polytetramethylene glycol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and 5-hydroxy-1,3-adamantane di(meth)acrylate.

[0055] The crosslinkable monomer (II) is preferably a di(meth)acrylate compound or divinylbenzene.

[0056] (III) Reactive Hydrophilic Monomer or Short-Chain Hydrocarbon Group-Containing Monomer The reactive hydrophilic monomer (III) has one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group. The short-chain hydrocarbon group-containing monomer (III) has one ethylenically unsaturated double bond and at least one hydrocarbon group having 1 or 2 carbon atoms. Examples of the reactive group are an epoxy group (e.g., a glycidyl group), a chloromethyl group, a bromomethyl group, an iodomethyl group, and a blocked isocyanate group. Examples of the hydrophilic group include a hydroxyl group, an amino group (including those in which the H bonded to N is converted to a methyl group, an ethyl group, a propyl group, or a butyl 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, sulfonic acid, or phosphoric acid, an ammonium base with a counter anion of chlorine, bromine, or iodine ion, an ethylene glycol group, a polyethylene glycol group, and a group having an acetone skeleton (-C(=O)-CH ３ ). The reactive and hydrophilic monomer (III) includes compounds having not only the reactive group and hydrophilic group described above, but also groups that impart higher hydrophilicity than the hydrophobic monomer (I). The reactive and hydrophilic monomer (III) has an octanol / water partition coefficient that causes it to partition more in water than the hydrophobic monomer (I), and also includes those that do not contain the reactive and hydrophilic groups described above. For example, a (meth)acrylamide having a short-chain hydrocarbon group having 6 or less carbon atoms on the side chain can be mentioned. Specific examples include methyl(meth)acrylamide, ethyl(meth)acrylamide, n-butyl(meth)acrylamide, t-butyl(meth)acrylamide, propyl(meth)acrylamide, and isopropyl(meth)acrylamide. The reactive and hydrophilic monomer (III) is preferably a non-fluorine-containing monomer.

[0057] The reactive hydrophilic monomer (III) has the formula: ２ =C(-R ４２ )-C(=O)-Y ４１ - (R ４３ ) ｏ(R ４１ ) ｔ or CH ２ =C(-R ４５ )-Y ４２ - (H) ５－ｎ (R ４４ ) ｕ [In the formula, R ４１ and R ４４ are each independently a reactive group or a hydrophilic group, R ４２ and R ４５ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y ４１ is a direct bond, —O—, or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), and R ４３ is a direct bond, —O—, or a group having a divalent to tetravalent hydrocarbon group having 1 to 10 carbon atoms (which may contain a hydrocarbon moiety having an —OH group), and Y ４２ is a benzene ring, H is a hydrogen atom, H and R ４４ Is Y ４２ are directly bonded to each other, t and u are 1 to 3, and o is 0 or 1.

[0058] The short chain hydrocarbon group-containing monomer (III) is represented by the formula: CH ２ =C(-R ４７ )-C(=O)-Y ４３ -R ４６ [In the formula, R ４６ is a hydrocarbon group having 1 or 2 carbon atoms, R ４７ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y ４３ is a direct bond, —O—, or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms).]

[0059] R ４１ and R ４４ is a monovalent group. ４１ and R ４４ In R, examples of the reactive group or hydrophilic group are as described above (e.g., epoxy group, hydroxyl group, etc.). ４６is a hydrocarbon group having 1 or 2 carbon atoms, examples of which include a methyl group and an ethyl group. A methyl group is preferred.

[0060] R ４２ , R ４５ and R ４７ may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. ３ R may be a group. ４２ , R ４５ and R ４７ Examples of the group include a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, and —CF ３ group, and a cyano group. ４２ , R ４５ and R ４７ is preferably a hydrogen atom, a methyl group, or a chlorine atom. ４２ and R ４７ is more preferably a methyl group. ４２ and R ４７ When R is a methyl group, higher water repellency and high slip resistance are obtained. ４５ is preferably a hydrogen atom, particularly from the viewpoint of reactivity. ４１ and Y ４３ is preferably —O— or —NH—.

[0061] R ４３ is preferably a divalent to tetravalent hydrocarbon group having 1 to 10 carbon atoms (which may contain a hydrocarbon moiety having an -OH group). Examples of divalent to tetravalent hydrocarbon groups having 1 carbon atom include -CH ２ -, -CH= having a branched structure, and -C≡ having a branched structure. ４３ is a divalent alkylene group, for example, —(CH ２ ) ｒ - (r is a number from 1 to 5), or a divalent, trivalent or tetravalent alkyl group, for example, -(CH ２ ) ｒ -(CH-) ｓ -H (r is a number from 1 to 5, and s is 1, 2, or 3. CH ２The positions of the groups and CH- groups do not have to be in the order shown.) is preferred. A divalent alkylene group (e.g., having 1 to 4 carbon atoms) is more preferred.

[0062] Y ４２ is a benzene ring. ４２ The monomer having Y has a styryl group. ４２ In the monomer having ４４ A group and 2 to 4 hydrogen atoms are attached to the benzene ring.

[0063] o is preferably 1. t is preferably 1. u may be 1 to 3, but is preferably 1 or 2.

[0064] Specific examples of the reactive hydrophilic monomer (III) include glycidyl (meth)acrylate, glycerol (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate. Quaternized products, tetrahydrofurfuryl (meth)acrylate, polyethylene glycol (meth)acrylate, diacetone (meth)acrylamide, isopropyl (meth)acrylamide, t-butyl (meth)acrylamide, ethyl (meth)acrylamide, methyl (meth)acrylamide; and 4-hydroxymethylstyrene, 4-hydroxyethylstyrene, 4-aminomethylstyrene, 4-aminoethylstyrene, 2-(4-vinylphenyl)oxirane, 2-(4-vinylbenzoyl)oxirane.

[0065] Specific examples of the short-chain hydrocarbon group-containing monomer (III) are methyl (meth)acrylate, ethyl (meth)acrylate, α-chloromethyl acrylate, and α-chloroethyl acrylate.

[0066] (IV) (Meth)acrylic Monomer The (meth)acrylic monomer (IV) has a linear hydrocarbon group having 3 to 40 carbon atoms or a polydimethylsiloxane group. The (meth)acrylic monomer (IV) may be a (meth)acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms.

[0067] The (meth)acrylic monomer (IV) is a compound represented by the formula:２ =C(-R ５２ )-C(=O)-Y ５１ (R ５１ ) ｓ [In the formula, R ５１ are each independently a linear hydrocarbon group having 3 to 40 carbon atoms; R ５２ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y ５１ represents a divalent to tetravalent hydrocarbon group having one carbon atom (particularly, —CH ２ -, -CH= and -C≡), -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 s is 1 to 3.

[0068] R ５１ is a linear hydrocarbon group. ５１ The number of carbon atoms in R is preferably 12 to 24 or 16 to 22. ５１ Specific examples are n-lauryl, n-stearyl, and n-behenyl.

[0069] s is 1, 2 or 3. s is preferably 1 or 2.

[0070] s is 1, 2 or 3. ５１ has a tetravalent hydrocarbon group having one carbon atom (specifically, a branched -C≡), s=3. ５１ has a trivalent hydrocarbon group having one carbon atom (for example, a branched -CH= group), s=2. ５１ does not have a trivalent or tetravalent hydrocarbon group having one carbon atom (for example, Y ５１ is a divalent hydrocarbon group having one carbon atom (-CH ２ -) (for example, 1 to 6), then s=1.

[0071] R ５２represents a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or —CF ３ R may be a group. ５２ Examples of R may be a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group. ５２ is preferably a hydrogen atom, a methyl group, or a chlorine atom. ５２ More preferably, R is a methyl group. ５２ When the group is a methyl group, higher slip resistance is obtained.

[0072] Y ５１ is preferably a divalent group or a trivalent group, particularly preferably a divalent group. Examples of divalent to tetravalent hydrocarbon groups having one carbon atom include -CH ２ -, a branched -CH=, and a branched -C≡.

[0073] Y ５１ When is a divalent group, -CH ２ - may or may not have Y. ５１ When is a trivalent group, it preferably has a branched structure -CH=, ２ -(-H(C-)-)-CH ２ -, i.e. It is particularly preferred that

[0074] Y ５１ represents -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'- (wherein each Y' independently represents a direct bond, -O-, -NR'- (R' represents H or a hydrocarbon group having 1 to 4 carbon atoms), or -S(=O) ２ - and X' is -(CH ２ ) ｍ -(m is an integer of 1 to 5), a linear hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure having 1 to 5 or 3 to 5 carbon atoms, or -(CH２ ) ｌ -C ６ H ４ -(CH ２ ) ｌ -(each l is independently an integer of 0 to 5, -C ６ H ４ - is a phenylene group). The hydrocarbon group having a branched structure and having 3 to 5 carbon atoms may be divalent, trivalent, or tetravalent. Specific examples of the hydrocarbon group having a branched structure and having 3 to 5 carbon atoms include: -CH(CH ３ )-CH ２ - (divalent), (divalent), -CH ２ -(-H(C-)-)-CH ２ - (trivalent), i.e., is.

[0075] A divalent group Y ５１ Specific examples are -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=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-(CH ２ ) m -C(=O)-O-, -NH-(CH ２ ) m -OC(=O)-, -NH-(CH ２ ) m -C(=O)-O-, -O-(CH ２ ) m -OC(=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 -OC(=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 H ４ wherein m is an integer from 1 to 5, particularly 2 or 4.

[0076] A divalent group Y ５１ is -O-, -NH-, -O-(CH ２ ) m -O-C(=O)-, -O-(CH ２ ) m -NH-C(=O)-, -O-(CH ２ ) m-OC(=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 -OC(=O)-, -NH-(CH ２ ) m -NH-C(=O)-, -NH-(CH ２ ) m -OC(=O)-NH-, -NH-(CH ２ ) m -NH-C(=O)-O-, -NH-(CH ２ ) m -NH-C(=O)-NH- [wherein m is an integer of 1 to 5, particularly 2 or 4] is preferred.

[0077] A divalent group Y ５１ is -O-, -O-(CH ２ ) m -OC(=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)- [wherein m is an integer of 1 to 5, particularly 2 or 4] is more preferred. ５１ is particularly preferably —O—.

[0078] Trivalent group Y ５１ teeth, It is preferable that:

[0079] Specific examples of the (meth)acrylic monomer (IV) having a linear hydrocarbon group having 3 to 40 carbon atoms are as follows:

[0080]

[0081]

[0082]

[0083] [In the above formula, n is a number from 3 to 40, and m is a number from 1 to 5.]

[0084] Preferred specific examples of the (meth)acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms include n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, n-behenyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, n-lauryl (meth)acrylamide, n-stearyl (meth)acrylamide, n-behenyl (meth)acrylamide, CH ２ =CHC(=O)OC ２ H ４ NHSO ２ C １８ H ３７、 CH ２ =CHC(=O)OC ２ H ４ NHC(=O)C １７ H ３５、 CH ２ =CHC(=O)OC ２ H ４ NHC(=O)OC １８ H ３７ , C.H. ２ =CHC(=O)OC ２ H ４ OC(=O)NHC １８ H ３７ , C.H. ２ =CHC(=O)OC ２ H４ NHC(=O)NHC １８ H ３７ The above structural formula shows acryl and acrylamide with hydrogen at the α-position, but also includes methacryl and methacrylamide with methyl at the α-position.

[0085] The (meth)acrylic monomer (IV) may be a (meth)acrylic monomer having a polydimethylsiloxane group. The (meth)acrylic monomer (IV) may have a polydimethylsiloxane group on its side chain.

[0086] The (meth)acrylic monomer (IV) is a compound represented by the formula: ２ =C(-R ６２ )-C(=O)-Y ６１ -R ６１ [In the formula, R ６１ is a group having a polydimethylsiloxane group, R ６２ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y ６１ represents a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms) and is a divalent to tetravalent group.]

[0087] R ６１ is a group having a polydimethylsiloxane group and has the average formula: -(SiR ２ O) ａ SiR ３ [wherein a is 2 to 4000, for example 3 to 400, each R is independently a monovalent alkyl group having 1 to 12 carbon atoms, and at least two R are methyl groups.] ６２ is preferably a hydrogen atom, a methyl group or a chlorine atom. ６１ represents a hydrocarbon group having 1 to 8 carbon atoms (for example, an alkylene group having 1 to 8 or 2 to 4 carbon atoms, particularly -C ３ H ６ -), -O-(CH ２ ) ｐ-, -O-(CH ２ ) ｐ -NHC(=O)-(CH ２ ) ｑ -, or -NH-(CH ２ ) ｑ - (where p is a number from 1 to 5, and q is a number from 1 to 5).

[0088] Specific examples of the (meth)acrylic monomer (IV) having a polydimethylsiloxane group are: [wherein n is a number from 1 to 500.]

[0089] (V) Other Monomers Other monomers (V) besides the monomers (I) to (IV) may also be used. Examples of the other monomers (V) include ethylene, vinyl acetate, acrylonitrile, vinyl chloride, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and vinyl alkyl ether. The other monomers are not limited to these examples. The other monomers (V) are preferably non-fluorine-containing monomers.

[0090] In this specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylamide" means acrylamide or methacrylamide.

[0091] Each of the monomers (I) to (V) may be a single type or a mixture of two or more types.

[0092] In the present disclosure, preferred combinations of monomers in the polymer are as follows: Monomer (I) + Monomer (II) Monomer (I) + Monomer (III) Monomer (I) + Monomer (II) + Monomer (III) Monomer (I) + Monomer (II) + Monomer (IV) Monomer (I) + Monomer (III) + Monomer (IV) Monomer (I) + Monomer (II) + Monomer (III) + Monomer (IV)

[0093] Particularly preferred combinations are as follows: Monomer (I) + Monomer (II) Monomer (I) + Monomer (III) Monomer (I) + Monomer (II) + Monomer (III) Monomer (I) + Monomer (II) + Monomer (IV) Monomer (I) + Monomer (II) + Monomer (III) + Monomer (IV) Each of the above monomers may be used alone or in combination of two or more. For example, a combination of two types of monomers (I), one type of monomer (II), and one type of monomer (III) may be used.

[0094] In the polymer, the amount of hydrophobic monomer (I) may be 40 to 100 wt %, 50 to 99 wt %, 55 to 98 wt %, or 58 to 97 wt %, based on the weight of the polymer. In the polymer, the molar ratio of hydrophobic monomer (I) to reactive hydrophilic monomer and / or short-chain hydrocarbon group-containing monomer (III) may be 50 / 50 to 100 / 0, 80 / 20 to 99.5 / 0.5, 85 / 15 to 98 / 2, 90 / 10 to 99 / 1, or 40 / 60 to 90 / 10, 55 / 45 to 85 / 15, 58 / 42 to 80 / 20, or 60 / 40 to 78 / 22. Since the short-chain hydrocarbon group-containing monomer (III) is more hydrophobic than the reactive hydrophilic monomer (III), the molar ratio of hydrophobic monomer (I) / short-chain hydrocarbon group-containing monomer (III) may be 100 / 0 to 0.05 / 99.95, 99 / 1 to 1 / 99, or 98 / 2 to 2 / 98. The amount of crosslinkable monomer (II) may be 0 to 30 mol, 0.5 to 25 mol, 1 to 20 mol, or 0 to 15 mol, 0.2 to 10 mol, or 0.5 to 5 mol, relative to 100 mol in total of the hydrophobic monomer (I) and the reactive hydrophilic monomer and / or the short-chain hydrocarbon group-containing monomer (II). The amount of the (meth)acrylic monomer (IV) may be 0 to 60 mol, 0.5 to 40 mol, 1 to 30 mol, or 1 to 20 mol, relative to a total of 100 mol of the hydrophobic monomer (I) and the reactive hydrophilic monomer and / or short-chain hydrocarbon group-containing monomer (II). The amount of the other monomer (V) may be 0 to 30 mol, 0.5 to 25 mol, 1 to 20 mol, or 1 to 10 mol, relative to a total of 100 mol.

[0095] Alternatively, relative to 100 moles of the polymer, the hydrophobic monomer (I) may be 40 to 99.5 moles, 50 to 99 moles, or 60 to 99 moles; the crosslinkable monomer (II) may be 0 to 30 moles, 0.5 to 25 moles, or 1 to 20 moles, or 0 to 10 moles, 0.2 to 6 moles, or 0.5 to 4 moles; the reactive hydrophilic monomer and / or short-chain hydrocarbon group-containing monomer (III) may be 0 to 50 moles, 0.5 to 40 moles, or 1 to 20 moles, or 0 to 15 moles, 0.2 to 10 moles, or 0.5 to 5 moles; and the (meth)acrylic monomer (IV) may be 0 to 50 moles, 1 to 40 moles, or 1 to 30 moles, or 0 to 15 moles, 0.2 to 10 moles, or 0.5 to 5 moles. When the monomer (II) is not present, the amount of the high Tg monomer (Ia) in the monomer (I) may be 1 to 80 mol, 2 to 70 mol, or 5 to 60 mol.

[0096] The water-repellent polymer may be a random polymer or a block copolymer, but is preferably a random polymer.

[0097] The amount of the organic fine particles (A) may be up to 50% by weight, for example 0.01 to 40% by weight, particularly 0.05 to 30% by weight or 0.1 to 20% by weight, based on the anti-slip agent composition.

[0098] (B) Aqueous Medium The slip-resistant agent composition (or water-repellent agent composition) contains an aqueous medium. The aqueous medium is water or a mixture of water and an organic solvent. The water-repellent agent composition is generally an aqueous dispersion in which a polymer is dispersed in an aqueous medium (water or a mixture of water and an organic solvent). The aqueous medium may be water alone or a mixture of water and a (water-miscible) organic solvent. The amount of the organic solvent may be 30% by weight or less, for example 10% by weight or less, based on the liquid medium. The aqueous medium is preferably water alone. The amount of the aqueous medium may be 50 to 99.5 parts by weight, particularly 70 to 99.5 parts by weight, when the total of the water-repellent polymer and the aqueous medium is 100 parts by weight.

[0099] (C) Binder Resin The binder resin functions as a binder that binds organic fine particles to the substrate. A water-repellent resin is preferred as the binder resin. The water-repellent resin also functions as an active ingredient that exhibits water repellency. Examples of binder resins include acrylic polymers, urethane polymers, polyolefins, polyesters, polyethers, polyamides, polyimides, polystyrenes, and silicone polymers. The water-repellent resin is a non-fluorine-containing polymer having a hydrocarbon group having 3 to 40 carbon atoms in its side chain, or a fluorine-containing polymer having a fluoroalkyl group having 1 to 20 carbon atoms in its side chain. The water-repellent resin is preferably a non-fluorine-containing polymer. In the non-fluorine-containing polymer having a hydrocarbon group having 3 to 40 carbon atoms, the hydrocarbon group is preferably a branched hydrocarbon group or a long-chain (or long-chain linear) hydrocarbon group. Examples of water-repellent resins include urethane polymers, silicone polymers, acrylic polymers, and polystyrene. An example of a non-fluorine-containing polymer is an amidoamine dendrimer having a long-chain hydrocarbon group, as described in U.S. Patent No. 8,703,894, the disclosure of which is incorporated herein by reference.

[0100] A urethane polymer having a hydrocarbon group having 3 to 40 carbon atoms in its side chain can be produced, for example, by reacting an isocyanate group-containing compound (e.g., a monoisocyanate or polyisocyanate, specifically a diisocyanate or triisocyanate) with a hydroxyl group-containing compound having a hydrocarbon group having 3 to 40 carbon atoms. A polyurethane having a branched structure such as a t-butyl group, an isopropyl group, or a 2,6,8-trimethylnonan-4-yl group in its side chain can be produced, for example, by reacting an isocyanate group-containing compound (e.g., a monoisocyanate or polyisocyanate, specifically a diisocyanate or triisocyanate) with a hydroxyl group-containing compound having a branched structure such as a t-butyl group, an isopropyl group, or a 2,6,8-trimethylnonan-4-yl group. Examples of urethane polymers include urethane compounds having long-chain hydrocarbon groups, which comprise sorbitan tristearate, sorbitan monostearate, and polyfunctional isocyanurates, and are described in U.S. Patent Publication No. 2014 / 0295724, the disclosure of which is incorporated herein by reference. Examples of urethane polymers include polyurethanes having long-chain hydrocarbon groups, which are described in Japanese Patent Publication No. 2019-519653 (WO 2018 / 007549), the disclosure of which is incorporated herein by reference.

[0101] Silicone polymers having hydrocarbon groups of 3 to 40 carbon atoms in their side chains can be produced, for example, by reacting a dichlorosilane compound containing a dichlorosilane having a hydrocarbon group of 3 to 40 carbon atoms. Polysilicones having a branched structure such as t-butyl, isopropyl, or 2,6,8-trimethylnonan-4-yl groups in their side chains can be produced, for example, by reacting a dichlorosilane compound containing a dichlorosilane having a branched structure such as t-butyl, isopropyl, or 2,6,8-trimethylnonan-4-yl groups. An example of a silicone polymer is long-chain alkyl-modified polydimethylsiloxane.

[0102] The acrylic polymer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain can be produced by polymerizing a monomer including an acrylic monomer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain. Examples of the acrylic monomer are the same as those explained above for the hydrophobic monomer (I). Specific examples of the acrylic monomer include, for example, stearyl (meth)acrylate, behenyl (meth)acrylate, (In particular, stearic acid amide ethyl (meth)acrylate) [wherein n is a number from 7 to 40, and m is a number from 1 to 5.]

[0103] An acrylic polymer having a branched structure such as a t-butyl group, an isopropyl group, or a 2,6,8-trimethylnonan-4-yl group in the side chain can be produced by polymerizing a monomer containing an acrylic monomer having a branched structure such as a t-butyl group, an isopropyl group, or a 2,6,8-trimethylnonan-4-yl group in the side chain. Examples of the acrylic monomer are the same as those described above for the hydrophobic monomer (I). Specific examples of the acrylic monomer include t-butyl(meth)acrylate, isopropyl(meth)acrylate, and 2,6,8-trimethylnonan-4-yl acrylate.

[0104] Examples of acrylic polymers include polymers containing repeating units derived from an acrylic monomer having a long-chain hydrocarbon group, such as behenyl (meth)acrylate or stearyl (meth)acrylate, and repeating units derived from vinylidene chloride and / or vinyl chloride. Examples of acrylic polymers include polymers containing repeating units derived from an acrylic monomer having a long-chain hydrocarbon group, such as behenyl (meth)acrylate or stearyl (meth)acrylate, repeating units derived from vinylidene chloride and / or vinyl chloride, and repeating units derived from styrene or α-methylstyrene. These acrylic polymers may be used in combination with paraffin wax. Examples of such polymers are described in JP 2012-522062 (WO 2010 / 115496). The disclosure of this document is incorporated herein by reference. Examples of acrylic polymers include polymers containing repeating units derived from an acrylic monomer having a long-chain hydrocarbon group such as stearyl (meth)acrylate, repeating units derived from vinylidene chloride and / or vinyl chloride, and repeating units derived from a reactive emulsifier such as polyoxyalkylene alkenyl ether, and are described in JP 2017-25440 (WO 2017 / 014131), the disclosure of which is incorporated herein by reference.

[0105] In fluorine-containing polymers having a fluoroalkyl group having 1 to 20 carbon atoms in the side chain, the fluoroalkyl group is preferably a perfluoroalkyl group. Examples of fluorine-containing water-repellent resins include fluorine-containing acrylic polymers containing repeating units formed from a (meth)acrylate having a perfluoroalkyl group having 4 to 8 carbon atoms in the side chain and a long-chain alkyl (meth)acrylate such as behenyl (meth)acrylate or stearyl (meth)acrylate. Other monomers may be used for non-fluorine-containing polymers and fluorine-containing polymers such as urethane polymers, silicone polymers, acrylic polymers, and polystyrene. Examples of other monomers include ethylene, vinyl acetate, acrylonitrile, vinyl chloride, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, (meth)acrylates having polydimethylsiloxane in the side chain, and vinyl alkyl ethers. The other monomers are not limited to these examples.

[0106] The weight ratio of binder resin (C) to organic fine particles (A) may be 1 / 99 to 99 / 1, 20 / 80 to 99 / 1, or 30 / 70 to 95 / 5, for example, 55 / 45 to 90 / 10. The amount of binder resin (C) is preferably 30 to 99 wt %, more preferably 50 to 98 wt %, and more preferably 60 to 97 wt %, based on the total weight of binder resin (C) and organic fine particles (A).

[0107] (D) Surfactant The water repellent composition may or may not contain a surfactant (emulsifier). Generally, to stabilize the particles during polymerization and the aqueous dispersion after polymerization, a small amount of surfactant (for example, 0.01 to 30 parts by weight per 100 parts by weight of the monomer) may be added during polymerization, or the surfactant may be added after polymerization. Particularly when the object to be treated is a textile product, the surfactant in the water repellent composition preferably contains a nonionic surfactant. Furthermore, the surfactant preferably contains one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

[0108] The nonionic surfactant, cationic surfactant, and amphoteric surfactant may each be one type or a combination of two or more types. The amount of surfactant may be 30 parts by weight or less (e.g., 0 to 15 parts by weight or 0.01 to 15 parts by weight) per 100 parts by weight of the organic fine particles (A) (e.g., 0.1 to 10 parts by weight), preferably 15 parts by weight or less (e.g., 0.1 to 10 parts by weight). Generally, the addition of a surfactant improves the stability of the aqueous dispersion and its permeability into fabrics, but reduces water repellency. It is preferable to select the type and amount of surfactant so as to achieve both of these effects.

[0109] (E) Crosslinking Agent The crosslinking agent (E) is preferably one that crosslinks when the aqueous dispersion of organic fine particles is applied to a cloth and then heated. The crosslinking agent itself is preferably one that is dispersed in water.

[0110] A preferred example of the crosslinking agent (E) is a blocked isocyanate compound. The blocked isocyanate compound is represented by the formula [A(NCO) ｍ (wherein A is the group remaining after removal of the isocyanate group from the polyisocyanate, and m is an integer from 2 to 8) with a blocking agent (which may be RH (wherein R may be a hydrocarbon group which may be substituted with a heteroatom such as a nitrogen atom or an oxygen atom, and H is a hydrogen atom)).

[0111] A (NCO) ｍ are, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), etc. Examples of blocking agents that form R groups are oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, and active methylene compounds.

[0112] The crosslinking agent (E) is preferably a blocked isocyanate such as oxime-blocked toluene diisocyanate, blocked hexamethylene diisocyanate, blocked diphenylmethane diisocyanate, etc. The amount of the crosslinking agent (E) may be 0 to 30 parts by weight or 0.01 to 20 parts by weight, for example, 0.1 to 18 parts by weight, per 100 parts by weight of the total of the organic fine particles (A) and the binder resin (C).

[0113] (F) Additives The water repellent composition may contain an additive (F) in addition to the organic fine particles (A) and aqueous medium (B), and, if necessary, the binder resin (C), surfactant (D), and / or crosslinking agent (E). Examples of the additive include other water repellents, oil repellents, drying speed modifiers, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, antifoaming agents, texture modifiers, slip modifiers, antistatic agents, hydrophilizing agents, antibacterial agents, preservatives, insect repellents, fragrances, and flame retardants. The amount of the additive may be 0 to 20 parts by weight, or 0.05 to 20 parts by weight, for example, 0.1 to 10 parts by weight, per 100 parts by weight of the total of the organic fine particles (A) and the binder resin (C).

[0114] The polymers (polymers constituting the organic fine particles and polymers constituting the binder resin) can be produced by any of the usual polymerization methods, and the polymerization reaction conditions can be selected arbitrarily. Such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. Emulsion polymerization is preferred. From the viewpoints of ease of synthesis and stability of the fine particles, it is preferable to produce the organic fine particles by emulsion polymerization.

[0115] As long as a water repellent composition in the form of an aqueous dispersion can be obtained, the method for producing the polymer is not limited. For example, a polymer (organic fine particles) may be produced by polymerizing a monomer for organic fine particles in an aqueous medium in the presence or absence of a surfactant. Alternatively, an aqueous dispersion can be obtained by producing a polymer by solution polymerization, followed by adding a surfactant and water and removing the solvent.

[0116] When the water repellent composition contains organic fine particles and a binder resin, the production of an aqueous dispersion of organic fine particles and the production of an aqueous dispersion of the binder resin are carried out separately, and the aqueous dispersion of organic fine particles and the aqueous dispersion of the binder resin are mixed to produce a water repellent composition containing organic fine particles and a binder resin. Alternatively, the water repellent composition containing organic fine particles and a binder resin can be produced by polymerizing a monomer for the binder resin in an aqueous dispersion of organic fine particles. Furthermore, the water repellent composition containing organic fine particles and a binder resin can be produced by polymerizing a monomer for the organic fine particles in an aqueous dispersion of the binder resin.

[0117] In emulsion polymerization without using a surfactant, it is preferred to polymerize the monomer in an aqueous medium at a low concentration (for example, a monomer concentration of 1 to 30% by weight, particularly 1 to 15% by weight).

[0118] In emulsion polymerization using a surfactant or a reactive emulsifier, it is preferable to add a small amount (30 parts by mole or less, for example, 0.1 to 20 parts by mole per 100 parts by mole of the total monomers) of a monomer (I) or a monomer (IV) whose homopolymer has a static contact angle with water of 90 degrees or more. This allows polymerization at a high concentration and improves the water repellency of the polymer. Examples of the added monomer include t-butylstyrene, stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl (meth)acrylamide, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, stearic acid amide ethyl (meth)acrylate, CH ２ =CHC(=O)OC ２ H ４ NHSO ２C １８ H ３７、 4-t-butylphenyl (meth)acrylate, 2,3,4-methylphenyl (meth)acrylate, and CH (meth)acrylic monomer having a polydimethylsiloxane group. ２ =C(-R ６２ )-C(=O)-Y ６１ -R ６１ [In the formula, R ６１ is a group having a polydimethylsiloxane group, R ６２ is a hydrogen atom, a monovalent organic group, or a halogen atom; Y ６１ represents a divalent to tetravalent hydrocarbon group having one carbon atom, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms) and is a divalent to tetravalent group.

[0119] In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by mole, for example, 0.01 to 10 parts by mole, per 100 parts by mole of the monomer.

[0120] The organic solvent is inert to the monomers and dissolves or uniformly disperses them, and may be, for example, an ester (e.g., an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (e.g., a ketone having 2 to 30 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol, ethanol, or methanol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 50 to 99.5 parts by weight, for example, 70 to 99 parts by weight, assuming that the total of the monomer and the organic solvent is 100 parts by weight.

[0121] In emulsion polymerization, a method is employed in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the mixture is polymerized by stirring at a temperature ranging from 30 to 80°C for 1 to 10 hours. Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[2- Examples of suitable initiators include water-soluble initiators such as 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], sodium peroxide, potassium persulfate, and ammonium persulfate, and oil-soluble initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 10 moles per 100 moles of monomer. If necessary, a reducing agent such as Rongalit, ascorbic acid, tartaric acid, sodium disulfite, isoascorbic acid, or ferrous sulfate may be used in combination.

[0122] Various anionic, cationic, or nonionic emulsifiers can be used as the emulsifier, and are used in the range of 0.5 to 30 parts by weight per 100 parts by weight of the monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely compatible with each other, it is also preferable to add a compatibilizer, such as a water-soluble organic solvent, that will fully compatibilize these monomers. Addition of a compatibilizer can improve emulsifiability and copolymerizability.

[0123] Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, isopropanol, ethanol, and methanol, and these may be used in an amount of 0.1 to 50 parts by weight, for example, 1 to 40 parts by weight, per 100 parts by weight of water.

[0124] A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (e.g., having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0125] The water repellent composition is generally preferably an aqueous dispersion. The water repellent composition comprises a polymer (the active ingredient of the water repellent composition) and an aqueous medium. The amount of the aqueous medium may be, for example, 50 to 99.9% by weight, particularly 70 to 99.5% by weight, based on the weight of the water repellent composition. In the water repellent composition, the concentration of the polymer may be 0.1 to 50% by weight, for example 0.5 to 40% by weight.

[0126] The water repellent composition (and the aqueous dispersion of organic fine particles) can be used as an external treatment agent (surface treatment agent) or an internal treatment agent. The water repellent composition (and the aqueous dispersion of organic fine particles) can be used as an oil repellent, an antifouling agent, a soil release agent, a stripping agent, or a mold release agent.

[0127] When the water repellent composition is an external treatment agent, it can be applied to the substrate by a conventionally known method. Typically, the water repellent composition is dispersed and diluted in an organic solvent or water, and then applied to the surface of the substrate by a known method such as dip coating, spray coating, or foam coating, followed by drying. If necessary, the water repellent composition may be applied together with an appropriate crosslinking agent (e.g., blocked isocyanate) and cured. Furthermore, the water repellent composition may be used in combination with an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixative, or an anti-wrinkle agent. The polymer concentration in the treatment solution to be brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), e.g., 0.05 to 10% by weight.

[0128] The object to be treated with the water repellent composition (and the aqueous dispersion of organic fine particles) is preferably one that requires slip resistance. Examples of the object to be treated include textile products. Various examples of textile products can be mentioned. Examples include natural fibers of animal and plant origin, such as cotton, hemp, wool, and silk; synthetic fibers, such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers, such as rayon and acetate; inorganic fibers, such as glass fiber, carbon fiber, and asbestos fiber; and mixtures of these fibers.

[0129] The textile product may be in the form of fiber, cloth, etc. The water repellent composition can also be used as a stain repellent, a release agent, or a release agent (e.g., an internal or external release agent). For example, it can easily release the surface of a substrate from another surface (another surface of the substrate or a surface of another substrate).

[0130] The organic microparticles can be applied to a fibrous substrate (e.g., a textile) by any of the known methods for treating textiles with a liquid. When the textile is a fabric, the fabric can be immersed in the solution, or the solution can be applied or sprayed onto the fabric. The treated textile is dried and preferably heated, for example, at 100°C to 200°C, to develop water repellency.

[0131] Alternatively, the organic microparticles may be applied to the textile by a cleaning process, such as in a laundry application or a dry cleaning process.

[0132] The textiles to be treated are typically fabrics, including woven, knitted and nonwoven fabrics, textiles in the form of apparel and carpets, but may also be fibres or yarns or intermediate textile products (such as slivers or rovings). The textile material may be natural fibres (such as cotton or wool), chemical fibres (such as viscose rayon or leocell), or synthetic fibres (such as polyester, polyamide or acrylic fibres), or may be a mixture of fibres (such as a mixture of natural and synthetic fibres).

[0133] The organic fine particles can be used in applications where slip resistance is required, preferably in fabrics for clothing, outdoor and sporting goods.

[0134] "Treatment" means applying a treatment agent to an object to be treated by immersion, spraying, coating, or the like. Through treatment, organic fine particles, which are the active ingredient of the treatment agent, adhere to the object to be treated. Through treatment, the organic fine particles penetrate into the interior of the object to be treated and / or adhere to the surface of the object to be treated.

[0135] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0136] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples. In the following, parts, percentages, or ratios represent parts by weight, percentages by weight, or ratios by weight unless otherwise specified. The test procedures are as follows.

[0137] [Falling speed test] In the falling speed test, PET cloth (basis weight: 88 g / m 2A PET cloth (70 denier, gray) was immersed in an aqueous dispersion of organic fine particles or a composition containing organic fine particles and a binder resin, and then passed through a mangle and a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. 20 μL of water was dropped from a microsyringe onto the PET cloth tilted at 30° using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.), and the rolling of the dropped water was measured using a high-speed camera (VW-9000 manufactured by Keyence Corporation), and the average rolling speed over a distance of about 40 mm was taken as the rolling speed. [Contact Angle Measurement] The static contact angle of water on a cloth (PET cloth) treated with an aqueous dispersion of organic fine particles or a composition containing organic fine particles and a binder resin was measured using a PET cloth (basis weight: 88 g / m 2 PET cloth (70 denier, gray) was immersed in an aqueous dispersion of organic fine particles or a composition containing organic fine particles and a binder resin, then passed through a mangle and a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles attached. 2 μL of water was dropped onto the PET cloth, and the static contact angle 1 second after the drop was measured using a fully automatic contact angle meter (DropMaster 701, manufactured by Kyowa Interface Science). The contact angle of the organic fine particles on the cloth (PET cloth) is preferably 120° or greater, more preferably 130° or greater, and even more preferably 140° or greater. The contact angle of the aqueous dispersion of the binder resin was measured by drop-casting the aqueous dispersion of the binder resin onto a glass substrate (soda-lime glass slide) and heating it at 150°C for 3 minutes to form a coating film. 2 μL of water was dropped onto the coating film, and the static contact angle 1 second after the drop was measured using a fully automatic contact angle meter (DropMaster 701, manufactured by Kyowa Interface Science).

[0138] [Solid content measurement] 1 g of the obtained aqueous dispersion of organic fine particles was placed in an aluminum cup and dried at 150°C for 1 hour. The solid content was calculated from the weight before and after drying. Solid content % = (weight before drying - weight after drying) / weight before drying x 100

[0139] [Water repellency test] An aqueous dispersion of organic fine particles was prepared to a predetermined concentration, and a cloth was immersed in the test solution and then passed through a mangle. The water repellency of the heat-treated test cloth was evaluated. The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). It is expressed by a water repellency number as shown in the table below. The higher the score, the better the water repellency. A "+" next to a number means that the water repellency is better than that number, and a "-" means that the water repellency is worse than that number. Polyester cloth (PET) (basis weight: 88 g / m 2 The evaluation was carried out using a fabric made of a 70 denier, gray material. The water repellency test score is preferably 80 points or more or 90 points or more.

[0140]

[0141] [Strong Water Repellency Test] When testing using the spray method of JIS-L-1092 (AATCC-22), the ease with which water that came into contact with the fabric was repelled and the speed at which water flowed off the fabric were visually evaluated. A higher score indicates better water repellency.

[0142]

[0143] [Slip Resistance Test] The slip resistance test was conducted according to JIS-L-1096 Method B. Five 10 cm x 17 cm test pieces were taken from water-repellent-treated white polyester fabric in both the warp and weft directions. The test pieces were folded in half, right side up, and cut along the fold. The cut edge was then sewn together 1 cm from the edge with a lockstitch stitch, 5 stitches per cm, and 3 x 78dex polyester filament thread using a standard 11-inch sewing machine needle. Using a tensile tester, a specified load (49.0 N (5 kgf)) was applied using the grab method with a grip spacing of 7.62 cm and a tensile strength of 30 cm per minute. The test pieces were then removed from the grips and left for one hour. The maximum slip hole size (mm) was measured at a load large enough to remove slack near the seam. It is most preferable that the slippage resistance test value is the same as that of an untreated fabric, i.e., 2.0 mm or less, but it is sufficient if the slippage resistance test value is improved by 0.5 mm or more compared to when only a fluorine-free water repellent is used, and more preferably 8.0 mm or less, 7.0 mm or less, 6.0 mm or less, for example 5.0 mm or less. If the slippage resistance test value (mm) when only a fluorine-free water repellent is used is taken as 100%, it is sufficient if the slippage resistance test value is reduced by 95% or less, and more preferably 90% or less, 80% or less, or 70% or less.

[0144] [Measurement of particle size of dispersion] Dynamic light scattering (DLS) measurement was performed using nanoSAQLA manufactured by Otsuka Electronics Co., Ltd. to determine the average diameter of particles in the dispersion. The aqueous dispersion of organic fine particles was diluted with pure water to a solids concentration of 0.1%, and measurement was performed at 25°C. Analysis of particle size distribution was performed based on scattering intensity.

[0145] [Washing durability of water repellency and strong water repellency (water repellency (after washing) and strong water repellency (after washing)] Washing is repeated 20 times according to the method of JIS L-0217-103, and the water repellency and strong water repellency thereafter are evaluated. After washing, it is preferable that the water repellency is 80 points or more and the strong water repellency is 2 points or more.

[0146] In the examples and comparative examples, the abbreviations have the following meanings. tBuMA: t-butyl methacrylate iBMA: isobornyl methacrylate CHMA: cyclohexyl methacrylate DVB: divinylbenzene GMA: glycidyl methacrylate MMA: methyl methacrylate DAAM: diacetone acrylamide tBuAAm: t-butyl acrylamide DM: 2-dimethylaminoethyl methacrylate EGDMA: ethylene glycol dimethacrylate NPDMA: neopentyl glycol dimethacrylate GDMA: glycerin dimethacrylate DCMA: dicyclopentyl dimethacrylate Emulsifier 1: polyethylene glycol monooleyl ether (liquid) Emulsifier 2: stearyltrimonium chloride Emulsifier 3: cetrimonium chloride Emulsifier 4: polyoxyalkylene alkenyl ether (HLB 13) Crosslinker 1: oxime-blocked toluene diisocyanate Crosslinker 2: Blocked Diphenylmethane Diisocyanate

[0147] Synthesis Example B1: 30 g of tripropylene glycol, CH ２ =CHC(=O)OC ２ H ４ NHC(=O)C １７ H ３５ 45g of (C17AEA), 34g of StA, 1g of N-alkylol acrylamide, 2g of trialkylammonium chloride, 2g of sorbitan monoalkylate, 2.5g of polyoxyethylene trialkyl ether, 3.5g of polyoxyethylene alkyl ether, and 180g of pure water were added, and the mixture was stirred at 2000 rpm for 1 minute at 80°C with a homomixer, and then ultrasonically dispersed for 15 minutes. The emulsified dispersion was transferred to an autoclave, and after nitrogen substitution, 0.2g of alkyl mercaptan and 20g of vinyl chloride were added, and 1g of azo-based initiator was added, and the mixture was heated and stirred at 60°C for 20 hours to obtain an aqueous dispersion of the polymer (binder B1). The water contact angle of a film formed by applying the emulsified dispersion to a glass substrate was 109°.

[0148] Synthesis Example B2: 28.9 g of sorbitan tristearate, 0.31 g of sorbitan monostearate, 7.5 g of hexamethylene triisocyanate (biuret), 37.5 g of methyl isobutyl ketone, and 0.03 g of dibutyltin laurate were placed in a nitrogen-purged reaction vessel and heated and stirred at 80°C. 9 g of tripropylene glycol, 1.8 g of sorbitan tristearate, 0.75 g of polyethylene glycol monooleyl ether, 0.6 g of trimethyloctadecylammonium chloride, and 40 g of pure water were added to this solution and stirred. The methyl isobutyl ketone was removed using an evaporator, yielding an aqueous dispersion of the reaction product of sorbitan stearate and isocyanate (Binder B2). An aqueous dispersion of long-chain alkyl-modified polydimethylsiloxane wax was then added to obtain an aqueous dispersion of the mixture. The water contact angle of the film formed by applying the dispersion to a glass substrate was 105°.

[0149] <Synthesis Example B3> In a 200ml poly container, 10g of tripropylene glycol, 20g of StA, 0.05g of trialkylammonium chloride, 2.0g of sorbitan monoalkylate, 1.0g of polyoxyethylene alkyl ether, and 60g of pure water are placed, and the mixture is stirred at 2000rpm for 1 minute with a homomixer, and then dispersed by ultrasonic waves for 15 minutes.The emulsified dispersion is transferred to an autoclave, and after nitrogen substitution, 0.05g of alkyl mercaptan and 8.6g of vinyl chloride are added, and 0.5g of azo-based initiator is added, and the mixture is heated and stirred at 60°C for 4 hours to obtain an aqueous dispersion of a polymer (binder B3).The water contact angle of the film formed by applying the emulsified dispersion to a glass substrate is 108°.

[0150] Synthesis Example 1 In a nitrogen-purged reaction vessel, 0.66 g of t-butylstyrene (tBuSty), 0.39 g of glycidyl methacrylate (GMA), 0.018 g of divinylbenzene (DVB), and 33 ml of pure water were added and dispersed. After nitrogen substitution, 18.6 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content was 2.23%. PET (cloth) (basis weight: 88 g / m) treated with the aqueous dispersion of organic fine particles was dispersed. 2The static contact angle of water on the polyester (70 denier, gray) was 143.1° and the sliding speed was 265 mm / s.

[0151] Synthesis Example 2: 0.50 g of t-butyl methacrylate (tBuMA), 0.20 g of glycidyl methacrylate (GMA), 0.47 g of isobornyl methacrylate (iBMA), 0.091 g of divinylbenzene (DVB), and 39 ml of pure water were added to a reaction vessel purged with nitrogen and dispersed. After purging with nitrogen, 19.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content was 2.32%. PET (fabric) (basis weight: 88 g / m) treated with the aqueous dispersion of organic fine particles was dispersed. 2 The static contact angle of water on the polyester (70 denier, gray) was 156.2° and the sliding speed was 227 mm / s.

[0152] Synthesis Example 3: 0.39 g of t-butyl methacrylate (tBuMA), 0.16 g of glycidyl methacrylate (GMA), 0.37 g of isobornyl methacrylate (iBMA), 0.072 g of divinylbenzene (DVB), 43 mg of polyethylene glycol monooleyl ether (liquid), 1.5 wt % stearyltrimonium chloride based on the total monomers, and 19 ml of pure water were added and dispersed in a nitrogen-purged reaction vessel. After nitrogen substitution, 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 fine particles. The solid content was 4.71%. The particle size (average particle size) of the aqueous dispersion was 71.1 nm. An aqueous dispersion of organic fine particles and Synthesis Example B2 was prepared so that the solid content of the organic fine particles was 0.2% and the solid content of Synthesis Example B1 was 0.8%. Further, to this aqueous dispersion, a crosslinking agent 1 was added in an amount of 17% solids based on the solids content of Synthesis Example B2. PET (fabric) (basis weight: 88 g / m) treated with this aqueous dispersion was used. 2 The falling speed of the fabric (70 denier, gray) was 117 mm / s, the water repellency test was 95 points, and the strong water repellency test was 3 points.

[0153] Synthesis Example 4: 9.61 g of t-butylstyrene (tBuSty), 11.37 g of glycidyl methacrylate (GMA), 0.52 g of divinylbenzene (DVB), 0.24 g of emulsifier 2, and 570 ml of pure water were added to a reaction vessel and dispersed. After nitrogen substitution, 54.2 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65°C. After 30 minutes, 9.61 g of t-butylstyrene (tBuSty), 11.37 g of glycidyl methacrylate (GMA), and 0.52 g of divinylbenzene (DVB) were 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 5.4%. The particle size (average particle size) of the aqueous dispersion was 76 nm.

[0154] Synthesis Example 5: 1.00 g of t-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 substitution, 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.

[0155] Synthesis Examples 6 to 14 The same procedure as in Synthesis Example 3 was repeated except that the monomers shown in Table 1 were used instead. The results are shown in Table 1. The monomer molar ratios in Table 1 indicate molar equivalents relative to 1 mole of 2,2'-azobis(2-methylpropionamidine) dihydrochloride.

[0156]

[0157] Synthesis Examples 15 to 17 The same procedure as in Synthesis Example 3 was repeated except that the monomers shown in Table 2 were used instead. The results are shown in Table 2. The monomer molar ratios in Table 2 indicate molar equivalents relative to 1 mole of 2,2'-azobis(2-methylpropionamidine) dihydrochloride.

[0158]

[0159] Examples 1 to 35 Aqueous dispersions were prepared by adjusting the organic fine particles synthesized in Synthesis Examples 1 to 14 and the binders synthesized in Synthesis Examples B1 and B2 to the solid content ratios shown in Table 3. To these aqueous dispersions, crosslinking agent 1 was added in an amount of 17% solids relative to the solids of the binder. In Examples 27 to 35, the same amount of crosslinking agent 2 was used instead of crosslinking agent 1. The values ​​of the slippage resistance test for PET (cloth) (white) treated with the prepared aqueous dispersions and the basis weight of PET (cloth) treated with the same aqueous dispersions were compared. 2 The results of the water repellency test and strong water repellency test for the fabric (70 denier, gray) are shown in Table 3.

[0160] Comparative Examples 1 and 2 An aqueous dispersion was prepared using particles (Nicosolt) whose main component was inorganic silica and the binder synthesized in Synthesis Example B1 so as to have the predetermined solid content ratio shown in Table 3. To this aqueous dispersion was added a crosslinker 1 in an amount of 17% solids relative to the solids of the binder. The values ​​of the slippage resistance test for PET (cloth) (white) treated with the prepared aqueous dispersion and the basis weight of PET (cloth) treated with the same aqueous dispersion were compared. 2 The results of the water repellency test and strong water repellency test for the fabric (70 denier, gray) are shown in Table 3.

[0161] Comparative Examples 3 and 4: Aqueous dispersions were prepared using the binders synthesized in Synthesis Examples B1 and B2 so that the solid content was the predetermined amount shown in Table 3. Furthermore, crosslinking agent 1 was added to the aqueous dispersions in an amount of 17% solids relative to the solids of the binder. The values ​​of the slippage resistance test for PET (cloth) (white) treated with the prepared aqueous dispersions and the basis weight of PET (cloth) treated with the same aqueous dispersions were compared. 2 The water repellency test and strong water repellency test, and the washing durability of the water repellency test and strong water repellency test of the same fabric (70 denier, gray) are shown in Table 3.

[0162]

[0163] Examples 36 to 56 Aqueous dispersions were prepared by adjusting the organic fine particles synthesized in Synthesis Examples 15 to 17 and the binders synthesized in Synthesis Examples B1 to B3 to the solid content ratios shown in Table 4. Furthermore, crosslinking agent 2 was added to these aqueous dispersions in an amount of 17% solids relative to the solids of the binder. The values ​​of the slippage resistance test for PET (cloth) (white) treated with the prepared aqueous dispersions and the basis weight of PET (cloth) treated with the same aqueous dispersions were compared. 2 The results of the water repellency test and strong water repellency test for the fabric (70 denier, gray) are shown in Table 4. The slip resistance test was conducted in accordance with JIS-L-1096 B method, except that the specified load was set to 60N.

[0164] <Comparative Examples 5 and 6> Aqueous dispersions were prepared using the binders synthesized in Synthesis Examples B1 and B3 so that the solid content was the predetermined amount shown in Table 4. Furthermore, crosslinking agent 2 was added to this aqueous dispersion in an amount of 17% solids relative to the solids content of the binder. The values ​​of the slippage resistance test for PET (cloth) (white) treated with the prepared aqueous dispersions and the basis weight of PET (cloth) treated with the same aqueous dispersions were compared. 2 The water repellency test and strong water repellency test, and the washing durability of the water repellency test and strong water repellency test of the same fabric (70 denier, gray) are shown in Table 4. The slippage resistance test was carried out with a predetermined load of 60N.

[0165]

[0166] The organic fine particles of the present disclosure can be used as a water repellent, oil repellent, stain repellent, stain release agent, release agent, or mold release agent with anti-slip effect. The organic fine particles of the present disclosure can be used as an anti-slip agent. Particularly preferred uses of the organic fine particles are in fabrics for clothing, outdoor and sports equipment.