Organic fine particle

Abstract

To provide an organic fine particle that can impart excellent water repellency to a substrate.SOLUTION: This organic fine particle can adhere, in the state having a particle shape, to a substrate, and exhibits water repellency on the substrate upon adhesion to the substrate. The organic fine particle contains: (1) a hydrophobic monomer which has one ethylenically unsaturated double bond and at least one hydrocarbon group having 3-40 carbon atoms; or (2) a polymer which has a repeating unit formed from a (meth)acrylic monomer having a polydimethylsiloxane group.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to organic microparticles, and more particularly to non-fluorinated organic microparticles.

Background Art

[0002] Conventionally, water repellency has been imparted to the surface of substrates such as metals, glasses, papers, cloths, plastics, etc. by chemical treatments such as coating with fluororesins or silicone resins. For example, it is known that a water-repellent substrate surface with a water contact angle of about 120° can be obtained by coating with a fluororesin.

[0003] In addition, by a method of forming a fine concavo-convex structure on the substrate surface, or a method combining the formation of such a fine concavo-convex structure on the substrate surface with the above coating treatment, super water repellency with a water contact angle of 150° or more is imparted to the substrate surface. The methods for creating the concavo-convex structure mainly include a method using microparticles and a method of performing patterning such as etching. The patterning methods such as etching have limited ranges of use and substrates.

[0004] When hydrophobic inorganic microparticles are used as the microparticles, a large amount of a dispersant such as an emulsifier is required to obtain an aqueous dispersion of the hydrophobic inorganic microparticles. When using hydrophobic inorganic microparticles with a reduced hydrophobicity, that is, hydrophobic inorganic microparticles with hydrophilic groups remaining, although the dispersion in water becomes slightly easier, the hydrophobicity of the microparticles themselves decreases, so the performance as a water repellent decreases.

[0005] On the other hand, there are soap-free polymerization and organic microparticle synthesis methods with few emulsifiers. Since these are dispersed in water without an emulsifier or with a small amount of an emulsifier, hydrophilic monomers are generally used, and most of the microparticles also exhibit hydrophilicity. Since it is difficult to use highly hydrophobic monomers, it has been difficult to synthesize organic microparticles that exhibit water repellency using soap-free polymerization or organic microparticle synthesis methods with few emulsifiers.

[0006] Although prior literature (especially patent gazettes) has disclosed imparting water repellency with organic microparticles, the examples have been limited to inorganic microparticles.

[0007] Patent Document 1 discloses a first step of forming an abrasion-resistant base film using fine particles (A) with an average particle diameter of 15 to 500 μm, a resin composition (B), and a solvent (C), and a second step of forming a super water-repellent finish film using fine particles (a) with an average particle diameter of 5 to 500 nm and being hydrophobic, a resin composition (b), and a solvent (c). The manufacturing method of a water-repellent coating film is characterized by including these steps. In the examples of Patent Document 1, the fine particles (a) used for forming the super water-repellent finish film are silica, which are inorganic microparticles. Patent Document 2 discloses a non-fluorine polymer containing a structural unit derived from a (meth)acrylate monomer and a structural unit derived from a silicone oil having a (meth)acryloyl group.

[0008] Conventionally, there has been a problem of color intensity. Generally, among textile products, synthetic fibers, especially polyester fibers, are widely used in various applications. However, compared with natural fibers such as wool and silk, they are inferior in characteristics such as color depth, darkness, and vividness in dyed products, so their commercial value in the market has tended to be evaluated low.

[0009] As countermeasures for such problems, various proposals have been made to improve the characteristics such as color depth, darkness, and vividness of dyed products obtained from synthetic fibers such as polyester fibers. For example, a color intensifying agent composed of an aqueous dispersion of a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a cationic surfactant, the polymer having a refractive index of 1.50 or less and a glass transition point exceeding 110°C, and a polymer having a refractive index of 1.50 or less and a glass transition point of less than 20°C has been proposed (see, for example, Patent Document 3). Such a color intensifying agent is said to give a good color intensifying effect to textile products. However, in fibers that require water repellency, the color intensifying agent tends to reduce water repellency.

Prior Art Documents

Patent Document

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0011] The present disclosure provides organic microparticles capable of imparting excellent water repellency to a substrate.

Means for Solving the Problems

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

[0013] The polymer constituting the organic microparticles is (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms, and / or (2) a (meth)acrylic monomer having a polydimethylsiloxane group preferably has a repeating unit formed from the above.

[0014] The present disclosure relates to (A) organic microparticles, and (B) an aqueous medium and relates to a water repellent composition comprising the same. In addition, the present disclosure (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms, and / or (2) a (meth)acrylic monomer having a polydimethylsiloxane group relates to organic microparticles comprising a polymer having a repeating unit formed from Furthermore, the present disclosure (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms, (3) a reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group, and (4) a crosslinkable monomer having at least two ethylenically unsaturated double bonds relates to organic microparticles comprising a polymer having a repeating unit formed from

[0015] Preferred embodiments of the present disclosure are as follows. Embodiment 1: Organic microparticles that can adhere to a substrate in a state having a particle shape and exhibit water repellency on the substrate when adhered to the substrate. Embodiment 2: (i) The static contact angle of water on the glass substrate is 100 degrees or more when adhered to the glass substrate, (ii) the static contact angle of water on the cloth is 120 degrees or more when adhered to the cloth, or (iii) the falling speed of water on the cloth is 100 mm / s or more when adhered to the cloth. The organic microparticles according to Embodiment 1 that satisfy at least any one of the above. Embodiment 3: When heat treatment is performed at 170 °C for 1 minute after adhesion to the substrate, the average diameter of the organic microparticles after heat treatment is 50% or more of the average diameter of the organic microparticles before heat treatment, or the average particle diameter of the microparticles observable on the cloth is 50 to 700 nm. The organic microparticles according to Embodiment 1 or 2. Embodiment 4: (1) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms, or (2) (Meth)acrylic monomer having a polydimethylsiloxane group 1. Organic fine particles comprising a polymer having a repeating unit formed from: Aspect 5: The polymer is (4) a crosslinking monomer having at least two ethylenically unsaturated double bonds; The organic fine particles according to embodiment 4, further comprising a repeating unit formed from Aspect 6: The polymer further comprises: (3) a reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group; and (5) A high glass transition point monomer whose homopolymer has a glass transition point of 100°C or higher. 6. The organic fine particles according to embodiment 4 or 5, having a repeating unit formed from at least one monomer selected from the group consisting of: Aspect 7: The organic fine particles according to any one of aspects 4 to 6, wherein a combination of a (meth)acrylic monomer having a hydrocarbon group having 12 to 24 carbon atoms in a side chain among the hydrophobic monomers (1) and the (meth)acrylic monomer (2) is used in an amount in which the total weight of both monomers is less than 80% by weight of the total amount of the monomer components. Aspect 8: The organic fine particles according to any one of aspects 4 to 7, which are obtained by polymerizing a monomer containing the monomer (4) and then polymerizing a monomer not containing the monomer (4), and which are partly meltable. Aspect 9: 9. The organic fine particles according to any one of aspects 4 to 8, wherein the static contact angle of water on a silicon substrate treated with a homopolymer of the hydrophobic monomer (1) is 70 to 120 degrees. Aspect 10: The hydrophobic monomer (1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 (R 11 ) k or CH2=C(-R 22 )-Y 21 (H)5-l (R 21 ) l [wherein, R 11 and R 21 are each independently a hydrocarbon group having 3 to 40 carbon atoms, R 12 and R 22 are a hydrogen atom, a monovalent organic group or a halogen atom, Y 11 is a divalent to tetravalent group composed of at least one selected from a hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2- or -NR'-(R' is H or a hydrocarbon group having from 1 to 4 carbon atoms) (except for the case of only a divalent hydrocarbon group), Y 21 is a benzene ring, H is a hydrogen atom, H and R 21 are each directly bonded to Y 21 , k and l are 1 to 3.] is a monomer represented by The (meth)acrylic monomer (2) has the formula: CH2=C(-R 92 )-C(=O)-Y 91 -R 91 [wherein, R 91 is a group having a polydimethylsiloxane group, R 92 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 91 is a divalent to tetravalent group composed of at least one selected from a hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2- or -NR'-(R' is H or a hydrocarbon group having from 1 to 4 carbon atoms).] is a monomer represented by The reactive / hydrophilic monomer (3) has the formula: CH2=C(-R 32 )-C(=O)-Y 31 -(R 33 ) o (R31 ) m or CH2=C(-R 42 )-Y 41 -(H) 5-n (R 41 ) n [In the formula, R 31 and R 41 are each independently a reactive group or a hydrophilic group, R 32 and R 42 are a hydrogen atom, a monovalent organic group, or a halogen atom, Y 31 is a direct bond, -O-, or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R 33 is a hydrocarbon group having 2 to 4 valences and 1 to 10 carbon atoms, Y 41 is a benzene ring, H is a hydrogen atom, H and R 41 are each directly bonded to Y 41 respectively, m and n are 1 to 3, o is 0 or 1.] is a monomer represented by, The crosslinkable monomer (4) has the formula: JPEG2025111494000002.jpg8131 or JPEG2025111494000003.jpg3942[In the formula, R 51 and R 61 are each independently a divalent to tetravalent group composed of at least one selected from a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -(CH2CH2O)r- (r is an integer of 1 to 10), -C6H4-, -O-, or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R 52 and R 62 are each independently a hydrogen atom, a monovalent organic group, or a halogen atom, Y 51is -O- or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms), p is 2 to 4, q is 1 to 5.] is a monomer represented by, The high glass transition point monomer (5) has the formula: JPEG2025111494000004.jpg3422 or JPEG2025111494000005.jpg3433 [wherein R 71 and R 81 are each a group composed of at least one selected from hydrocarbon groups having 1 to 30 carbon atoms, -C6H4-, -O-, or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R 72 and R 82 are each a hydrogen atom, a monovalent organic group, or a halogen atom, Y 71 is -O- or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms).] The organic fine particles according to any one of Aspects 4 to 9, which are monomers represented by. Aspect 11: In the reactive monomer (3), the reactive group is an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group, or a blocked isocyanate group, and the hydrophilic group is a hydroxyl group, an amino group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, an alkali metal or alkaline earth metal salt group of a carboxylic acid, a sulfonic acid, or a phosphoric acid, or an ammonium salt group in which chlorine or bromine or iodine ion is a counter anion, and is at least one group selected from the group consisting of: The organic fine particles according to any one of Aspects 4 to 10. Aspect 12: The hydrophobic monomer (1) is at least one monomer selected from the group consisting of t-butyl (meth)acrylate, N-t-butyl (meth)acrylamide, t-butylstyrene, stearyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, stearic acid amidoethyl (meth)acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 and is at least one monomer selected from the group consisting of (The (meth)acrylic monomer (2) is of the formula: JPEG2025111494000006.jpg25035 or JPEG2025111494000007.jpg5233 [wherein n is a number from 1 to 500.] and is at least one monomer selected from the group consisting of The reactive / hydrophilic monomer (3) is at least one monomer 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, dimethylaminoethyl methacrylate quaternary compound, tetrahydrofurfuryl (meth)acrylate The crosslinkable monomer (4) is at least one monomer 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, dimethylol tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, 5-hydroxy-1,3-adamantane di(meth)acrylate, The organic fine particles according to any one of Aspects 4 to 11, wherein the high glass transition point monomer (5) is at least one monomer selected from the group consisting of isobornyl (meth)acrylate, bornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, phenyl (meth)acrylate, naphthyl acrylate, benzyl acrylate. Aspect 13: The organic fine particles according to any one of Aspects 3 to 12, wherein the molar ratio of the hydrophobic monomer (1) or (meth)acrylic monomer (2) / reactive hydrophilic monomer (3) / high glass transition point monomer (5) is 20 to 100 / 0 to 50 / 0 to 70, the crosslinkable monomer (4) is 0.1 to 30 mol parts with respect to 100 mol parts in total of the hydrophobic monomer (1) and the reactive hydrophilic monomer (3), and the (meth)acrylic monomer (2) is 0 to 30 mol parts with respect to 100 mol parts in total of the hydrophobic monomer (1), the (meth)acrylic monomer (2) and the reactive hydrophilic monomer (3). Aspect 14: The organic fine particles according to any one of Aspects 1 to 13, which have a falling speed of 150 mm / second or more when treated on a cloth. Aspect 15: The organic fine particles according to any one of Aspects 1 to 14, having an average particle diameter of 30 nm to 1000 nm. Aspect 16: A method for producing the organic fine particles according to any one of Aspects 3 to 14, wherein the organic fine particles are obtained by polymerizing a monomer containing monomer (4) and then polymerizing a monomer not containing monomer (4). Aspect 17: (A) The organic fine particles according to any one of Aspects 1 to 15, and (B) An aqueous medium A water repellent composition which is an aqueous dispersion of organic fine particles comprising the same. Aspect 18: Furthermore, the water repellent composition according to Aspect 17, comprising any one or more of (C) a binder resin, (D) a surfactant, and (E) a crosslinking agent. Aspect 19: The water repellent 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 with 3 to 40 carbon atoms in the side chain and a fluorinated polymer having a fluoroalkyl group with 1 to 20 carbon atoms in the side chain. Aspect 20: The water repellent composition according to Aspect 18 or 19, wherein the amount of the surfactant (D) is 15 parts by weight or less with respect to 100 parts by weight of the organic fine particles (A). Aspect 21: The water repellent composition according to any one of Aspects 18 to 20, wherein the binder resin (C) is an acrylic polymer, a urethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, a polystyrene, a silicone polymer, or a combination thereof. Aspect 22: The water repellent composition according to any one of Aspects 17 to 21, which can prevent frosting. Aspect 23: In an aqueous medium, a step of polymerizing a monomer in the presence of a surfactant having an amount of 15 parts by weight or less with respect to 100 parts by weight of the monomer to obtain an aqueous dispersion of organic fine particles (A), A method for producing the water repellent composition according to any one of Aspects 17 to 22, comprising the same. Aspect 24: Furthermore, By adding an aqueous dispersion of a binder resin (C) to an aqueous dispersion of organic fine particles (A), or by polymerizing a monomer for a binder resin in an aqueous dispersion of organic fine particles (A) to obtain a binder resin (C), or by polymerizing a monomer for organic fine particles in an aqueous dispersion of a binder resin, a step of obtaining an aqueous dispersion in which the organic fine particles (A) and the binder resin (C) are dispersed The production method according to embodiment 23 having Embodiment 25: A method for treating a textile product, which comprises applying a treatment liquid containing a water-repellent composition according to any one of embodiments 17 to 22 to the textile product Embodiment 26: A textile product in which organic fine particles and / or a binder resin in the water-repellent composition according to any one of embodiments 17 to 22 are adhered to the surface Embodiment 27: In the water-repellent composition according to any one of embodiments 17 to 22, organic fine particles and / or a binder resin are adhered to the surface A textile product that satisfies at least one of the following: a static contact angle of water on the fabric is 120 degrees or more, or a water drop-off rate on the fabric is 200 mm / second or more

Advantages of the Invention

[0016] The organic fine particles and the water-repellent composition of the present disclosure can impart excellent water repellency (particularly, high strong water repellency) to a substrate such as a textile product. In the textile product treated with the water-repellent composition of the present disclosure, the drop-off property of water droplets is excellent. Further, since the drop-off rate is particularly high, it is suitable for applications that require high water repellency In the case of organic fine particles, compared with inorganic fine particles, by making the main chain flexible, it becomes possible to give the particles themselves motility by heating. Therefore, in water, it can be stably dispersed by localizing hydrophilic groups on the outermost surface, and after coating on a substrate and drying, it becomes possible to localize a hydrophobic part with a small surface free energy on the outermost surface. Even for particles imparted with hydrophilicity, after coating, the hydrophobic part segregates on the surface, resulting in particles exhibiting high water repellency While color-enhancing agents tend to reduce water repellency, the organic fine particles of the present disclosure can exert a color-enhancing effect without impairing water repellency. [Brief explanation of the drawings]

[0017]

Figure 1

Figure 2

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

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

[0020] (A) Organic fine particles The organic microparticles act as an active ingredient that exhibits water repellency. The organic microparticles are preferably formed of a non-fluorine polymer. From the viewpoints of water repellency and the stability of the aqueous dispersion, the average particle diameter of the organic microparticles may be 30 to 1000 nm, preferably 50 to 700 nm or 200 to 600 nm. The average particle diameter means the average particle diameter of the particles measured by the dynamic light scattering method (DLS).

[0021] The organic microparticles retain their particle shape on the substrate and exhibit water repellency. The water repellency exhibited is (i) When adhered to a glass substrate, the contact angle of water is 100 degrees or more, (ii) When adhered to a cloth, the contact angle of water is 120 degrees or more, or (iii) When adhered to a cloth, the falling speed is 100 mm / s or more which means.

[0022] On the glass substrate to which the composition containing the organic microparticles is adhered (that is, the contact angle of water on the glass substrate to which the organic microparticles are adhered or the contact angle of water on the glass substrate to which the organic microparticles and the binder (and other components) are adhered), the contact angle of water may be 100 degrees or more, for example, 110 degrees or more, particularly 118 degrees or more and 180 degrees or less. Specifically, the contact angle of water on the glass substrate to which the composition containing the organic microparticles is adhered is obtained by drop-casting the composition containing the organic microparticles onto a glass substrate (slide glass, made of soda-lime glass), heating it at 150 °C for 3 minutes to prepare a substrate to which the organic microparticles are adhered, dropping 2 μL of water onto the glass substrate to which the organic microparticles are adhered, and measuring the static contact angle 1 second after the droplet adheres using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.).

[0023] The contact angle of water on the cloth to which the composition containing organic fine particles is attached (the contact angle of water on the cloth to which the organic fine particles are attached or the contact angle of water on the cloth to which the organic fine particles and the binder (and other components) are attached) is preferably 120 degrees or more, more preferably 130 degrees or more, and still more preferably 140 degrees or more. Specifically, the contact angle of water on the cloth is determined by dipping a PET cloth (basis weight: 88 g / m 2 , 70 denier, gray) into the composition containing organic fine particles, passing it through a mangle, passing it through a pin tenter at 170 °C for 1 minute to prepare a PET cloth with the organic fine particles attached, dropping 2 μL of water onto this PET cloth, and measuring the static contact angle 1 second after the drop has landed using an automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.).

[0024] In the cloth (PET cloth), it is preferable that the falling speed of water is 100 mm / s or more, for example 130 mm / s or more, further 150 mm / s or more, or 200 mm / s or more. The falling speed is the average falling speed of the distance of about 40 mm as the water dripped from a microsyringe falls on a substrate with a 30-degree inclination. Specifically, a PET cloth (basis weight: 88 g / m 2 , 70 denier, gray) is dipped into the composition containing organic fine particles, passed through a mangle, passed through a pin tenter at 170 °C for 1 minute to prepare a PET cloth with the organic fine particles attached. Using an automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.), 20 μL of water is dropped from a microsyringe onto the PET cloth with a 30-degree inclination, and the state of the dropped water falling is measured using a high-speed camera (VW-9000 manufactured by Keyence Corporation). The average falling speed of the distance of about 40 mm is taken as the falling speed.

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

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

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

[0028] (1) Hydrophobic monomer The hydrophobic monomer (1) has at least one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms. The static contact angle of water with the homopolymer of the hydrophobic monomer (1) is preferably 70 to 120 degrees, for example, 75 to 115 degrees. For example, when the glass transition temperature of the homopolymer of the hydrophobic monomer (1) is 80 °C or higher, the static contact angle of water with the homopolymer is preferably 90 degrees or higher, more preferably 97 degrees or higher. Further, when the hydrophobic monomer (1) has a branched hydrocarbon group (for example, a branched alkyl group), particularly a t-butyl group or an isopropyl group, or a group having a multi-branched structure as shown in the following formula, the static contact angle of water with the homopolymer is preferably 75 to 115 degrees. JPEG2025111494000008.jpg3662

[0029] The static contact angle of the homopolymer is the value of the static contact angle measured with a 2 μl water droplet after a solution obtained by dissolving the homopolymer in a good solvent (particularly, chloroform) is applied to a silicon substrate and heated at 80 °C. Specifically, a chloroform solution of the homopolymer (solid content concentration: 1.0%) is spin-coated on a silicon wafer substrate (high-purity silicon wafer for research, AS ONE 2-960-55), heated at 80 °C for 15 minutes to form a coating film, 2 μL of water is dropped onto this coating film, and the static contact angle 1 second after the drop is measured using a fully automatic contact angle meter (DropMaster701 manufactured by Kyowa Interface Science Co., Ltd.).

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

[0031] The hydrophobic monomer (1) has the formula: CH2=C(-R 12 )-C(=O)-Y 11 (R 11 ) k or CH2=C(-R 22 )-Y 21 (H) 5-l (R 21 ) l [wherein, R 11 and R 21 are each independently a hydrocarbon group having 3 to 40 carbon atoms, R 12 and R 22 are a hydrogen atom, a monovalent organic group, or a halogen atom, Y 11 is a divalent to tetravalent hydrocarbon group having 1 carbon atom (particularly, -CH2-, -CH= and -C≡), -C6H4-, -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 composed of at least one or more selected therefrom (excluding the case of only a divalent hydrocarbon group), Y 21 is a benzene ring, H is a hydrogen atom, H and R 21 are each directly bonded to Y 21 respectively, and k and l are 1 to 3.] It is preferably a monomer represented by .

[0032] R 11 and R 21is preferably a branched or long-chain (or straight-chain long-chain) hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The -CH3 group has a lower surface free energy and is more likely to exhibit water repellency than the -CH2- group. Therefore, a structure with many branches and many -CH3 groups is preferred. In the branched hydrocarbon group, the number of -CH3 groups is preferably 2 to 15, for example 3 to 10 or 4 to 9. On the other hand, a long-chain alkyl group of a certain length (preferably having 16 to 40 carbon atoms) exhibits high water repellency due to its crystallinity. Therefore, a branched hydrocarbon group (for example, a branched alkyl group), particularly a t-butyl group or an isopropyl group, or a hydrocarbon group with a multi-branched structure having 5 to 30 carbon atoms, for example, a group with a multi-branched structure as shown in the following formula, or a long-chain hydrocarbon group (or a straight-chain long-chain hydrocarbon group), for example, an alkyl group having 16 to 40 or 16 to 26 carbon atoms, particularly 18 to 22 carbon atoms, is preferred. The long-chain hydrocarbon group is preferably a stearyl group, an icosyl group or a behenyl group. JPEG2025111494000009.jpg3662

[0033] k is 1, 2 or 3. However, when Y 11 has a tetravalent hydrocarbon group having 1 carbon atom (specifically, -C≡ having a branched structure), etc., k = 3. When Y 11 has a trivalent hydrocarbon group having 1 carbon atom (for example, -CH= having a branched structure), etc., k = 2. When Y 11 does not have a trivalent and tetravalent hydrocarbon group having 1 carbon atom (for example, when Y 11 has a divalent hydrocarbon group having 1 carbon atom (-CH2-) (for example, 1 to 6), k = 1.

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

[0035] Y 11 is a divalent group or a trivalent group, and is particularly preferably a divalent group. Examples of the C1 hydrocarbon group having 2 to 4 valences are -CH2-, -CH= having a branched structure, and -C≡ having a branched structure. Y 11 When Y is a divalent group, it may or may not have -CH2-. Y 11 When Y is a trivalent group, it preferably has -CH= having a branched structure, -CH2-(-H(C-)-)-CH2-, that is, it particularly preferably has JPEG2025111494000010.jpg2141.

[0036] Y 11 is -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’ is independently a direct bond, -O-, -NR’- (R’ is H or a C1-C4 hydrocarbon group) or -S(=O)2-, X’ is -(CH2) m -(m is an integer from 1 to 5), a linear hydrocarbon group having an unsaturated bond with 1 to 5 carbon atoms, a hydrocarbon group having a branched structure with 1 to 5 or 3 to 5 carbon atoms, or -(CH2)l -C6H4-(CH2) l -(l is an integer of 0 to 5 independently, and -C6H4- is a phenylene group).] It may be. The hydrocarbon group having a branched structure with 3 to 5 carbon atoms may be divalent, trivalent or tetravalent. Specific examples of the hydrocarbon group having a branched structure with 3 to 5 carbon atoms are -CH(CH3)-CH2- (divalent), JPEG2025111494000011.jpg1540(divalent), -CH2-(-H(C-)-)-CH2- (trivalent), That is, JPEG2025111494000012.jpg2141 It is.

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

[0038] Y which is a divalent group 11 is -O-, -NH-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -NH-C(=O)-NH- [wherein, m is an integer of 1 to 5, particularly 2 or 4]. is preferably.

[0039] Y which is a divalent group 11 is -O-, -O-(CH2) m-O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, or -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH-, particularly -O-(CH2) m -NH-C(=O)- [In the formula, m is an integer from 1 to 5, particularly 2 or 4.] It is more preferable that it is.

[0040] Y which is a trivalent group 11 is JPEG2025111494000013.jpg1553 It is preferable that it is.

[0041] Y 21 is a benzene ring. Y 21 The monomer having has a styryl group. Y 21 In the monomer having, 1 to 3 R 21 groups and 2 to 4 hydrogen atoms are bonded to the benzene ring.

[0042] Specific examples of the hydrophobic monomer are as follows. The compounds of the following chemical formulas are acrylic compounds in which the α-position is a hydrogen atom, but specific examples may be methacrylic compounds in which the α-position is a methyl group and α-chloroacrylic compounds in which the α-position is a chlorine atom, and methacrylic compounds in which the α-position is a methyl group are preferred. Also in styrene derivatives, the compounds of the following chemical formulas are acrylic compounds in which the α-position is a hydrogen atom, but specific examples may be α-methylstyrene compounds in which the α-position is a methyl group and α-chlorostyrene compounds in which the α-position is a chlorine atom, and styrene compounds in which the α-position is a hydrogen atom are preferred. JPEG2025111494000014.jpg2452

[0043] JPEG2025111494000015.jpg8554

[0044] JPEG2025111494000016.jpg8761

[0045] JPEG2025111494000017.jpg9366

[0046] JPEG2025111494000018.jpg8969 [In the above formula, n is a number from 3 to 40, and m is a number from 1 to 5.]

[0047] JPEG2025111494000019.jpg5824

[0048] JPEG2025111494000020.jpg131116

[0049] JPEG2025111494000021.jpg5728

[0050] JPEG2025111494000022.jpg20539[wherein, tBu is t-butyl.]

[0051] Preferred specific examples of the hydrophobic monomer (1) are t-butyl (meth)acrylate, N-t-butyl (meth)acrylamide, t-butylstyrene, stearyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, stearic acid amidoethyl (meth)acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37、 4-t-butylphenyl (meth)acrylate, 2,3,4-methylphenyl (meth)acrylate.

[0052] (2) (Meth)acrylic monomer having a polydimethylsiloxane group (Meth)acrylic monomer (2) has a polydimethylsiloxane group in its side chain. (Meth)acrylic monomer (2) has the formula: CH2=C(-R 92 )-C(=O)-Y 91 -R 91 [wherein, R 91 is a group having a polydimethylsiloxane group, R 92 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 91 is a divalent to tetravalent group composed of at least one or more selected from a C1 hydrocarbon group having 2 to 4 carbon atoms, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms).] It is preferably a monomer represented by.

[0053] R 91 is a group having a polydimethylsiloxane group, and the average formula: -(SiR2O) a SiR3 [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 Rs are methyl groups.] It is preferably a group represented by. R 92 is preferably a hydrogen atom, a methyl group or a chlorine atom. Y 91 is a hydrocarbon group having 1 to 8 carbon atoms (for example, an alkylene group having 1 to 8 or 2 to 4 carbon atoms, particularly -C3H6-), -O-(CH2) p -, -O-(CH2) p No. -NHC(=O)-(CH2) q -, or -NH-(CH2) q - (p is a number from 1 to 5, and q is a number from 1 to 5). It is preferably.

[0054] Specific examples of (meth)acrylic monomer (2) are JPEG2025111494000023.jpg25035 TIFF2025111494000024.tif5133 [wherein, n is a number from 1 to 500.] is.

[0055] (Meth)acrylic monomer (2) is used together with a (meth)acrylic monomer having a hydrocarbon group with 3 to 40 or 3 to 30 (especially 12 to 24) carbon atoms among the hydrophobic monomers (1) (or any of the hydrophobic monomers (1)), it is preferable that the total weight of the (meth)acrylic monomer (2) and the hydrophobic monomer (1) is used in an amount of less than 80% by weight, particularly less than 50% by weight or less than 40% by weight of the total amount of the monomer components. That is, it is preferable to use a combination of repeating units formed from a (meth)acrylic monomer having a hydrocarbon group with 3 to 40 or 12 to 24 carbon atoms among the hydrophobic monomers (1) and repeating units formed from the (meth)acrylic monomer (2) in an amount of less than 80% by weight, particularly less than 50% by weight or less than 40% by weight of the total amount of the monomer components. In some embodiments, the constituent monomer does not consist only of a combination of a hydrophobic monomer (1) which is a (meth)acrylic monomer having a hydrocarbon group with 3 to 40 or 3 to 30 (especially 12 to 24) carbon atoms and a (meth)acrylic monomer (2). In some embodiments, a combination of a hydrophobic monomer (1) which is a (meth)acrylic monomer having a hydrocarbon group with 3 to 4 or 3 to 30 (especially 12 to 24) carbon atoms and a (meth)acrylic monomer (2) may not be used.

[0056] (3) Reactive / hydrophilic monomer The reactive / hydrophilic monomer (3) has one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group. Examples of the reactive group are an epoxy group (e.g., glycidyl group), chloromethyl group, bromomethyl group, iodomethyl group, blocked isocyanate group. Examples of hydrophilic groups include hydroxyl groups, amino groups, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, alkali metal or alkaline earth metal salts of carboxylic acids, sulfonic acids, and phosphoric acids, chlorine or bromine, and ammonium bases in which iodine ions are counter anions. The reactive / hydrophilic monomer (3) is preferably a non-fluorine monomer.

[0057] The reactive / hydrophilic monomer (3) has the formula: CH2=C(-R 32 )-C(=O)-Y 31 -(R 33 ) o (R 31 ) m or CH2=C(-R 42 )-Y 41 -(H) 5-n (R 41 ) n [wherein R 31 and R 41 are each independently a reactive group or a hydrophilic group, R 32 and R 42 are a hydrogen atom, a monovalent organic group, or a halogen atom, Y 31 is a direct bond, -O-, or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R 33 is a direct bond or a group having a divalent to tetravalent hydrocarbon group having 1 to 10 carbon atoms, Y 41 is a benzene ring, H is a hydrogen atom, H and R 41 are each directly bonded to Y 41 , m and n are 1 to 3, o is 0 or 1.] It is preferably a monomer represented by

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

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

[0060] R 33 is preferably a hydrocarbon group having 2 to 4 valences and 1 to 10 carbon atoms. Examples of the hydrocarbon group having 2 to 4 valences and 1 carbon atom are -CH2-, -CH= having a branched structure, and -C≡ having a branched structure. R 33 is a divalent alkylene group, for example, -(CH2) r -(r is a number from 1 to 5.) or a divalent or trivalent or tetravalent alkyl group, for example, -(CH2) r -(CH-) s -H (r is a number from 1 to 5, s is 1, 2 or 3. The positions of the CH2 group and the CH- group do not have to be in the described order.) is preferred.

[0061] Y 41 is a benzene ring. Y 41 The monomer having has a styryl group. Y 41 In the monomer having, 1 to 3 R 41A group and 2 to 4 hydrogen atoms are bonded to the benzene ring.

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

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

[0064] The crosslinkable monomer (4) has the formula: TIFF2025111494000025.tif7329 or TIFF2025111494000026.tif3639 [wherein R 51 and R 61 are each independently a direct bond, or a hydrocarbon group having 1 to 20 carbon atoms, -(CH2CH2O)r -(where r is an integer from 1 to 10), -C6H4-, -O-, or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbon atoms), and is a divalent to tetravalent group composed of at least one or more selected therefrom, R 52 and R 62 are a hydrogen atom, a monovalent organic group, or a halogen atom, Y 51 is -O- or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbon atoms), p is from 2 to 4, q is from 1 to 5.] It is preferable that it is a monomer represented by.

[0065] R 51 and R 61 Examples of are a direct bond, a divalent to tetravalent (e.g., divalent to trivalent) hydrocarbon group with 1 to 20 (or 2 to 10) carbon atoms that may be interrupted by an oxygen atom and / or 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. R 51 and R 61 may be a polymer group, and the structural unit constituting the polymer group may be the above-exemplified group (e.g., an ethylene glycol group).

[0066] R 52 and R 62 may each independently be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group. Alternatively, it may be a -CF3 group. R 52 and R 62 Examples of are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a -CF3 group, and a cyano group. R 52 and R 62 are preferably a hydrogen atom, a methyl group, or a chlorine atom. R 52is more preferably a methyl group. R 52 When R is a methyl group, higher water repellency can be obtained. 62 From the viewpoint of reactivity in particular, R is preferably a hydrogen atom, but from the viewpoint of water repellency, a methyl group is preferable, and it is preferable to select R so as to balance its reactivity and water repellency. 62 The crosslinkable monomer (4) is preferably di(meth)acrylate or divinylbenzene.

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

[0068] (5) High glass transition point monomer [[ID=P18]]The polymer may have a repeating unit formed from a high glass transition point monomer. The glass transition point of the homopolymer of the high glass transition point monomer (5) is 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 the sample at a rate of 10 °C / min, and it can be determined as the temperature indicated by the midpoint of the intersection between the extension lines of the respective baseline before and after the secondary transition of the DSC curve and the tangent line at the inflection point of the DSC curve. The high glass transition point monomer (5) is preferably a non-fluorine monomer.

[0069] The high glass transition point monomer (5) has the formula: TIFF2025111494000027.tif3121 or TIFF2025111494000028.tif3130 [wherein R 71 and R 81 are groups composed of at least one or more selected from hydrocarbon groups having 1 to 30 carbon atoms, -C6H4-, -O-, or -NR' - (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R 72 and R 82 are a hydrogen atom, a monovalent organic group, or a halogen atom, Y 71 is -O- or -NR' - (R' is H or a hydrocarbon group having 1 to 4 carbon atoms).] and is a monomer represented by

[0070] R 71 and R 81 Examples of are cyclohexyl group, dicyclopentanyl group, dicyclopentenyl group, adamantyl group, isobornyl group, naphthalene group, bornyl group, tricyclodecanyl group, phenyl group.

[0071] R 72 and R 82 may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group. Alternatively, it may be a -CF3 group. R 72 and R 82 Examples of are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, a -CF3 group, a cyano group. R72 and R 82 is preferably a hydrogen atom, a methyl group, or a chlorine atom. R 72 is more preferably a methyl group. R 72 being a methyl group provides higher water repellency. On the other hand, R 82 is preferably a hydrogen atom from the perspective of reactivity, but a methyl group is preferred from the perspective of water repellency. It is preferable to select R 82 so as to balance its reactivity and water repellency. Y 71 is preferably -O- or -NH-.

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

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

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

[0075] In this specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.

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

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

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

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

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

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

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

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

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

[0085] The urethane polymer having a hydrocarbon group with 3 to 40 carbon atoms in the side chain can be produced, for example, by reacting an isocyanate group-containing compound (for example, a monoisocyanate or a polyisocyanate, specifically, a diisocyanate or a triisocyanate) with a hydroxyl group-containing compound having a hydrocarbon group with 3 to 40 carbon atoms. The polyurethane having a branched structure such as a t-butyl group, an isopropyl group, a 2,6,8-trimethylnonan-4-yl group, etc. in the side chain can be produced, for example, by reacting an isocyanate group-containing compound (for example, a monoisocyanate or a polyisocyanate, specifically, a diisocyanate or a triisocyanate) with a hydroxyl group-containing compound having a branched structure such as a t-butyl group, an isopropyl group, a 2,6,8-trimethylnonan-4-yl group, etc. Examples of urethane polymers include urethane compounds having a long-chain hydrocarbon group comprising sorbitan tristearate, sorbitan monostearate, and polyfunctional isocyanurate, which are described in US Patent Publication 2014 / 0295724. The disclosure of this document is incorporated herein by reference. Examples of urethane polymers include polyurethanes having a long-chain hydrocarbon group, which are described in Japanese Patent Application Laid-Open No. 2019-519653 (International Publication No. 2018 / 007549). The disclosure of this document is incorporated herein by reference.

[0086] A silicone polymer having a hydrocarbon group with 3 to 40 carbon atoms in the side chain can be produced, for example, by reacting a dichlorosilane compound containing a dichlorosilane having a hydrocarbon group with 3 to 40 carbon atoms. A polysilicon 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, for example, by reacting a dichlorosilane compound containing a dichlorosilane having a branched structure such as a t-butyl group, an isopropyl group, or a 2,6,8-trimethylnonan-4-yl group. Examples of silicone polymers include long-chain alkyl-modified polydimethylsiloxane.

[0087] An acrylic polymer having a hydrocarbon group with 3 to 40 carbon atoms in the side chain can be produced by polymerizing a monomer containing an acrylic monomer having a hydrocarbon group with 3 to 40 carbon atoms in the side chain. Examples of acrylic monomers are the same as those described for the above hydrophobic monomer (1). Specific examples of acrylic monomers are, for example, stearyl (meth) acrylate, behenyl (meth) acrylate, TIFF2025111494000029.tif2452 (in particular, stearic acid amidoethyl (meth) acrylate) [In the above formula, n is a number from 7 to 40, and m is a number from 1 to 5.] is.

[0088] An acrylic polymer having a branched structure such as a t-butyl group, isopropyl group, 2,6,8-trimethylnonan-4-yl group, etc. 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, isopropyl group, 2,6,8-trimethylnonan-4-yl group, etc. in the side chain. Examples of the acrylic monomer are the same as those described for the above hydrophobic monomer (1). Specific examples of the acrylic monomer are, for example, t-butyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate.

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

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

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

[0092] Each of the nonionic surfactant, cationic surfactant, and amphoteric surfactant may be one kind or a combination of two or more kinds. The amount of the surfactant may be 15 parts by weight or less (for example, 0 to 15 parts by weight or 0.01 to 15 parts by weight), preferably 8 parts by weight or less, based on 100 parts by weight of the organic fine particles (A). Generally, when a surfactant is added, the stability of the aqueous dispersion and the permeability to the fabric are improved, but the water repellency performance is deteriorated. It is preferable to select the type and amount of the surfactant so as to achieve both of these effects.

[0093] (E) Crosslinking agent The crosslinking agent (E) is preferably one that crosslinks when heated after treating the aqueous dispersion of the organic fine particles on the fabric. Further, it is preferable that the crosslinking agent itself is also dispersed in water.

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

[0095] A(NCO) m is, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), or the like. Examples of the blocking agent forming the R group are oxime, phenol, alcohol, mercaptan, amide, imide, imidazole, urea, amine, imine, pyrazole, and active methylene compounds.

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

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

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

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

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

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

[0102] In emulsion polymerization using a surfactant or a reactive emulsifier, it is preferable to add a small amount (30 mole parts or less, for example, 0.1 to 20 mole parts with respect to 100 mole parts of the total monomer) of a monomer (1) having a static contact angle of water of the homopolymer of 95 degrees or more or a monomer (2). Thereby, polymerization can be carried out at a high concentration, and the water repellency of the polymer becomes high. Examples of the monomer to be added are t-butylstyrene, stearyl (meth) acrylate, behenyl (meth) acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, stearic acid amidoethyl (meth) acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37、 4-t-butylphenyl (meth) acrylate, 2,3,4-methylphenyl (meth) acrylate, and a (meth) acrylic monomer having a polydimethylsiloxane group, CH2=C(-R 92 )-C(=O)-Y 91 -R 91 [wherein, R 91is a group having a polydimethylsiloxane group, R 92 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 91 is a divalent to tetravalent group composed of at least one selected from hydrocarbon groups having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms). is a monomer represented by. When the proportion of monomer (5) and monomer (3) is 35 mol parts or more with respect to all the monomers constituting the organic fine particles, the monomer of homopolymer having a static contact angle of water of 95 degrees or more in monomer (1) is preferably 1 to 70 mol parts, for example, 1 to 60 mol parts.

[0103] In solution polymerization, in the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen substitution, heating and stirring are carried out at 30 to 120 ° C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator is used in the range of 0.01 to 20 mol parts, for example, 0.01 to 10 mol parts, per 100 mol parts of the monomer.

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

[0105] In emulsion polymerization, a method is adopted in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, they are stirred and polymerized at a temperature in the range of 30 to 80 °C for 1 to 10 hours. As the polymerization initiator, water-soluble ones such as 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-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], sodium peroxide, potassium persulfate, ammonium persulfate, etc., and oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 mol parts with respect to 100 mol parts of the monomers. If necessary, a reducing agent such as Rongalit, ascorbic acid, tartaric acid, sodium bisulfite, isoascorbic acid, ferrous sulfate, etc. may be used in combination.

[0106] As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomers. It is preferable to use an anionic and / or nonionic and / or cationic emulsifier. When the monomers are not completely compatible, it is also preferable to add a compatibilizer such as a water-soluble organic solvent that can be sufficiently compatible with these monomers. By adding the compatibilizer, it is possible to improve the emulsifying property and copolymerizability.

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

[0108] In the polymerization, a chain transfer agent may be used. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially, (for example, alkyl mercaptans having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of the chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, relative to 100 parts by weight of the total amount of the monomers.

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

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

[0111] When the water-repellent composition is an external treatment agent, it can be applied to the object to be treated by a conventionally known method. Usually, the water-repellent composition is dispersed and diluted in an organic solvent or water, and then adhered to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. If necessary, it may be applied together with a suitable cross-linking agent (for example, blocked isocyanate) and cured. Furthermore, it is also possible to add and use together with the water-repellent composition an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, etc. The concentration of the polymer in the treatment liquid in contact with the substrate may be 0.01 to 10% by weight (especially in the case of dip coating), for example, 0.05 to 10% by weight.

[0112] Examples of the object to be treated with the water-repellent composition (and the aqueous dispersion of organic fine particles) include textile products, stone, filters (for example, electrostatic filters), dust masks, parts of fuel cells (for example, gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster, etc. Various examples can be given as textile products. For example, animal and plant natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or mixed fibers thereof can be mentioned.

[0113] The textile product may be in any form such as fiber, cloth, etc. The water-repellent composition can also be used as an antifouling agent, a release agent, a mold release agent (for example, an internal mold release agent or an external mold release agent). For example, the surface of the substrate can be easily peeled from another surface (another surface on the substrate or a surface on another substrate).

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

[0115] Alternatively, the organic microparticles may be applied to the textile product by a cleaning method, for example, applied to the textile product in a washing application or a dry cleaning method, etc.

[0116] When heat treatment is performed at 170°C for 1 minute after being adhered to the substrate, it is preferable that the average diameter of the organic microparticles after the heat treatment is 50% or more of the average diameter of the organic microparticles before the heat treatment. It is preferable that the average diameter (average particle size) of the organic microparticles after the heat treatment is 60% or more, for example, 70% or more of the average diameter (average particle size) of the organic microparticles before the heat treatment. Alternatively, after applying the particles onto the substrate (including cloth), it is preferable that the average particle size of the microparticles observable on the substrate is 50 to 700 nm. The average diameter of the organic microparticles before the heat treatment refers to the particle size of the microparticles measured by the dynamic light scattering method (DLS) from an aqueous dispersion of the organic microparticles (when two or more peaks are observed in the DLS measurement, the average particle size calculated not from the average particle sizes of all the peaks but only from the peak with the smaller particle size is used), or the average diameter of the organic microparticles before the heat treatment adhered to the substrate. When the values of both are different, the smaller one is used.

[0117] The average diameter of the organic fine particles on the substrate means the average of the particle diameters of 10 randomly extracted independent minimum units observed by a scanning electron microscope (SEM) after the organic fine particles are attached to the substrate. Generally, the average diameter of the organic fine particles after heat treatment means the average of the particle diameters of 10 randomly extracted independent minimum units observed by a scanning electron microscope (SEM) on the substrate after applying a dispersion liquid of the organic fine particles to the substrate (for example, cloth) and performing heat treatment at 170 °C for 1 minute. For example, when the substrate is cloth, after immersing the cloth in an aqueous dispersion containing organic fine particles, passing it through a mangle, and passing it through a pin tenter at 170 °C for 1 minute, a cloth with the organic fine particles attached can be produced. The average diameter of the organic fine particles before heat treatment means the average of the particle diameters of 10 randomly extracted independent minimum units observed by a scanning electron microscope (SEM) on the substrate after applying a dispersion liquid of the organic fine particles to the substrate (for example, cloth) and air-drying for 1 hour or more.

[0118] The fiber product to be treated is typically cloth, which includes woven fabrics, knitted fabrics and non-woven fabrics, cloth in the form of clothing items and carpets, but may also be fibers or yarns or intermediate fiber products (for example, slivers or rovings, etc.). The fiber product material may be natural fibers (for example, cotton or wool, etc.), chemical fibers (for example, viscose rayon or lyocell, etc.), or synthetic fibers (for example, polyester, polyamide or acrylic fibers, etc.), or may be a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.).

[0119] Alternatively, the fibrous substrate may be leather. The organic fine particles may be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, for example, during the wet processing of the leather or during the finishing of the leather, in order to make the leather hydrophobic and oleophobic. Alternatively, the fibrous substrate may be paper. The organic fine particles may be applied to the pre-formed paper, or may be applied at various stages of papermaking, for example, during the drying period of the paper.

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

[0121] In the treated substrate (especially a fiber product), it is preferable that the water dripping rate is 100 mm / s or more, for example, 130 mm / s or more, further 150 mm / s or more, or 200 mm / s or more. The treated substrate exhibits the effect of preventing frosting.

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

Examples

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

[0124] 〔Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)〕 The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC). For GPC, tetrahydrofuran was used as the eluent, and KF-606M, KF-601, and KF-800D manufactured by Shodex were used as columns, and the molecular weight and the like were calculated in terms of polystyrene.

[0125] 〔Measurement of thermal physical properties by differential scanning calorimetry (DSC)〕 The melting point of the polymer was calculated by differential scanning calorimetry (DSC). For the DSC measurement, after cooling to -20°C under a nitrogen atmosphere, the temperature was raised to 200°C at a rate of 10°C / min, then cooled again to -20°C, and the melting point observed during the subsequent heating process from -20°C to 200°C at a rate of 10°C / min was measured. For polymers showing multiple melting peaks, the peak with the largest heat of fusion derived from the melting of the long-chain alkyl was taken as the melting point. The glass transition point (glass transition temperature) was determined as the temperature indicated by the midpoint of the intersection between the extension lines of the respective baseline before and after the secondary transition of the DSC curve and the tangent line at the inflection point of the DSC curve.

[0126] [Measurement of the particle size of the dispersion] For the dynamic light scattering (DLS) measurement, the average diameter of the particles in the dispersion was determined using ZEN1600 manufactured by MALVERN. An aqueous dispersion of organic microparticles was diluted with pure water to a solid content concentration of 0.1% and measured at 25°C. The analysis of the particle size distribution was performed based on the scattering intensity criterion.

[0127] [Measurement of the static contact angle] (Synthesis Examples L1 to L5) A chloroform solution of the polymer (solid content concentration: 1.0%) was spin-coated onto a silicon wafer substrate (high-purity silicon wafer for research, AS ONE 2-960-55), and heated at 80°C for 15 minutes to form a coating film. 2 μL of water was dropped onto this coating film, and the static contact angle 1 second after the droplet was placed was measured using an automatic contact angle meter (DropMaster701 manufactured by Kyowa Interface Science Co., Ltd.).

[0128] (Organic microparticles) For the contact angle of the organic microparticles, an aqueous dispersion of the organic microparticles was drop-cast onto a glass substrate (slide glass made of soda-lime glass), and heated at 150°C for 3 minutes to prepare a substrate with the organic microparticles adhered thereto. 2 μL of water was dropped onto the glass substrate with the organic microparticles adhered thereto, and the static contact angle 1 second after the droplet was placed was measured using an automatic contact angle meter (DropMaster701 manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of the organic microparticles on the glass substrate is preferably 100° or more, more preferably 110° or more, and even more preferably 118° or more.

[0129] In addition, 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 is measured as follows: A PET cloth (basis weight: 88 g / m 2 ; 70 denier; gray) is immersed in an aqueous dispersion of organic fine particles or a composition containing organic fine particles and a binder resin, passed through a mangle, passed through a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles adhered thereto. Then, 2 μL of water is dropped onto this PET cloth, and the static contact angle 1 second after the drop is placed is measured using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of the organic fine particles on the cloth (PET cloth) is preferably 120° or more, more preferably 130° or more, and even more preferably 140° or more. The contact angle of the aqueous dispersion of the binder resin is measured as follows: The aqueous dispersion of the binder resin is drop-cast onto a glass substrate (soda lime glass slide glass), heated at 150°C for 3 minutes to form a coating film, 2 μL of water is dropped onto this coating film, and the static contact angle 1 second after the drop is placed is measured using a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.).

[0130] 〔Falling speed test〕 In the falling speed test, a PET cloth (basis weight: 88 g / m 2 ; 70 denier; gray) is immersed in an aqueous dispersion of organic fine particles or a composition containing organic fine particles and a binder resin, passed through a mangle, passed through a pin tenter at 170°C for 1 minute to prepare a PET cloth with organic fine particles adhered thereto. Then, 20 μL of water is dropped from a microsyringe onto the PET cloth inclined at 30° by a fully automatic contact angle meter (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.), and the state of the dropped water falling is measured using a high-speed camera (VW-9000 manufactured by Keyence Corporation). The average falling speed at a distance of about 40 mm is defined as the falling speed.

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

[0132] 〔Water repellency test〕 An aqueous dispersion of organic fine particles was prepared at a predetermined concentration. A cloth was immersed in this test solution and then passed through a mangle, and the water repellency was evaluated using the heat-treated test cloth. The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). As shown in the table described below, it is represented by the water repellency No. The larger the score, the better the water repellency. The “+” attached to the number means that it is better than that number, and the “-” means that it is worse than that number. Evaluation was carried out using a polyester cloth (PET) (basis weight: 88 g / m 2 , 70 denier, gray).

[0133] TIFF2025111494000030.tif45151

[0134] 〔Super water repellency test〕 When testing by the spray method of JIS-L-1092 (AATCC-22), the ease of water repellency from the cloth and the flow-down rate from the cloth were visually evaluated. The larger the score, the better the super water repellency.

[0135] TIFF2025111494000031.tif71156

[0136] 〔Washing durability of water repellency and super water repellency (water repellency (after washing) and super water repellency (after washing))〕 Washing according to the JIS L-0217-103 method was repeated 20 times, and then the water repellency and super water repellency were evaluated. After washing, it is preferable that the water repellency is 80 or more and the super water repellency is 2 or more.

[0137] 〔Scanning electron microscope (SEM) observation (particle size)〕 SEM observations were carried out using an ERA9000 manufactured by ELONIX at an acceleration voltage of 3.5 kV with Pt evaporation and a working distance (W.D.) of 5.0 mm, and an SU8020 manufactured by Hitachi High-Tech Corporation at an acceleration voltage of 3.0 kV with Pt evaporation. The particle sizes obtained by both devices were the same. After immersing a cloth in a composition containing organic fine particles, passing it through a mangle, and then passing it through a pin tenter at 170 °C for 1 minute, a cloth with adhered organic fine particles was prepared, and the average of the particle diameters of 10 randomly extracted independent minimum units observed on the cloth was determined using a scanning electron microscope (SEM). The retention rate (%) of the particle diameter before and after heating was determined from the following formula using the average particle diameter of the organic fine particles on the substrate after heating determined by SEM observation (the average diameter of the particles on the cloth heated at 170 °C for 1 minute) and the average particle diameter of the organic fine particles before heating (the average particle diameter of the fine particle dispersion determined by DLS measurement or the smaller of the average particle diameters on the substrate before heating determined by SEM observation). Retention rate (%) of the average particle diameter before and after heating = (average particle diameter after heating) / (average particle diameter before heating) × 100

[0138] 〔Measurement of color density〕 L was measured at three locations on each treated cloth using a color difference meter (Minolta Co., Ltd., Color Difference Meter CR-200, the detection part is a circular shape with a diameter of 8 mm). The color difference (ΔL) was calculated from the L of the cloth before treatment with the treatment liquid and the L after treatment using the following formula. ΔL = (L value after cloth treatment) - (L value before cloth treatment)

[0139] In the examples and comparative examples, the meanings of the abbreviations are as follows. tBuSty: 4-t-butylstyrene tBuMA: t-butyl methacrylate StMA: stearyl methacrylate Sty: styrene MeSty: 4-methylstyrene C17AEA: CH2=CHCO2-CH2CH2-NH-C(=O)-C 17 H 35 iBMA: isobornyl methacrylate GMA: Glycidyl methacrylate DHMA: 2,3 - Dihydroxypropyl methacrylate HEMA: Hydroxyethyl methacrylate HBA: 4 - Hydroxybutyl acrylate DQ: Dimethylaminoethyl methacrylate quaternary compound BCPMA: Dicyclopentanyl methacrylate CHMA: Cyclohexyl methacrylate DVB: Divinylbenzene NP - A: Neopentyl glycol diacrylate NP - MA: Neopentyl glycol dimethacrylate DMS - MA: Polydimethylsiloxyethyl methacrylate DMS - MA1: Polydimethylsiloxyethyl methacrylate (molecular weight 1000) DMS - MA2: Polydimethylsiloxyethyl methacrylate (molecular weight 500) DMS - MA3: Polydimethylsiloxyethyl methacrylate (molecular weight 12000) DCP: Dicyclopentanyl diacrylate DCP - M: Dicyclopentanyl dimethacrylate ADDA: Adamantyl diacrylate HADDM: 5 - Hydroxy - 1,3 - adamantane dimethacrylate EGDMA: Ethylene glycol dimethacrylate tBuA: t - Butyl acrylate MMA: Methyl methacrylate VAc: Vinyl acetate tBuAAm: t - Butyl acrylamide StA: Stearyl acrylate

[0140] Emulsifier 1: Polyethylene glycol monooleyl ether (liquid) Emulsifier 2: Polyethylene glycol monooleyl ether (solid) Emulsifier 3: Glyceryl stearate Emulsifier 4: Lauryl trimonium chloride Emulsifier 5: Cetrimonium chloride Emulsifier 6: Stearyl trimonium chloride Emulsifier 7: Polyoxyalkylene alkenyl ether (HLB 16) Emulsifier 8: Polyoxyalkylene alkenyl ether (HLB 14) Emulsifier 9: Polyoxyalkylene alkenyl ether (HLB 13) Emulsifier 10: Tetraglyceryl monostearate Emulsifier 11: Diethanolamine laurate Emulsifier 12: Sorbitan tristearate Crosslinking agent 1: Oxime-blocked toluene diisocyanate Crosslinking agent 2: Oxime-blocked hexamethylene diisocyanate PDMS-A: Long-chain alkyl-modified dimethylsiloxane StOH: Stearyl alcohol

[0141] <Synthesis Example 1> 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 to a nitrogen-substituted reaction vessel and dispersed. After nitrogen substitution, 18.6 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65 °C for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content was 2.85%. The particle size (average particle size) of the aqueous dispersion was 250 nm. The contact angle of water on the glass substrate of the organic fine particles was 120°. The aqueous dispersion of organic fine particles was treated with PET (fabric) (basis weight: 88 g / m 2The static contact angle of water with (70 denier, gray) was 143.1°, and the falling speed was 265 mm / s. Also, an aqueous dispersion of organic microparticles was cast on a glass substrate, air-dried, and then left in an environment at -30°C for 2 days. After that, when the substrate was taken out to an environment at 25°C, frost adhered to the glass, but no frosting was confirmed on the organic microparticles. The retention rate of the particle diameter before and after heating at 170°C for 1 minute was 80%.

[0142] <Synthesis Examples 2 to 44> The same procedure as in Synthesis Example 1 was repeated except that the monomers shown in Table 1 were used. The results are shown in Table 1. In Synthesis Examples 25 to 28, in addition to the monomers shown in the table, a cationic emulsifier (lauryl trimonium chloride) was added in the predetermined amounts shown in the table based on the total monomer amount and polymerized. In Synthesis Example 29, in addition to the monomers shown in the table, a cationic emulsifier (lauryl trimonium chloride) and polyethylene glycol monooleyl ether were added at 0.5% based on the total monomer amount and polymerized. An aqueous dispersion of the organic microparticles synthesized in Synthesis Example 13 was cast on a glass substrate, air-dried, and then left in an environment at -30°C for 2 days. After that, when the substrate was taken out to an environment at 25°C, frost adhered to the glass, but no frosting was confirmed on the coating film of the organic microparticles. In Synthesis Examples 2 to 44, the retention rate of the particle diameter before and after heating at 170°C for 1 minute was 80%.

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

[0144]

Table 1

[0145] <Synthesis Example L1> 1.50 g of tBuSty, 0.015 g of azobisisobutyronitrile, and 10 ml of toluene were added into a nitrogen-substituted reaction vessel. After heating and stirring at 65 °C for 8 hours, PtBuSty was obtained by reprecipitation into methanol. The molecular weight (Mw) was 21,000, and the molecular weight distribution (Mw / Mn) was 2.0. The water contact angle of the obtained polymer was 100°. The glass transition temperature (Tg) was 125 °C.

[0146] <Synthesis Example L2> 1.50 g of MeSty, 0.021 g of azobisisobutyronitrile, and 10 ml of toluene were added into a nitrogen-substituted reaction vessel. After heating and stirring at 65 °C for 8 hours, PMeSty was obtained by reprecipitation into methanol. The molecular weight (Mw) was 15,000, and the molecular weight distribution (Mw / Mn) was 2.0. The water contact angle of the obtained polymer was 95°. The glass transition temperature (Tg) was 107 °C.

[0147] <Synthesis Example L3> 1.00 g of Sty, 0.015 g of azobisisobutyronitrile, and 3.4 ml of toluene were added into a nitrogen-substituted reaction vessel. After heating and stirring at 65 °C for 8 hours, PSty was obtained by reprecipitation into methanol. The molecular weight (Mw) was 15,000, and the molecular weight distribution (Mw / Mn) was 2.1. The water contact angle of the obtained polymer was 89°. The glass transition temperature (Tg) was 100 °C.

[0148] <Synthesis Example L4> 2.00 g of tBuMA, 0.023 g of azobisisobutyronitrile, and 20 ml of toluene were added into a nitrogen-substituted reaction vessel. After heating and stirring at 65 °C for 8 hours, PtBuMA was obtained by reprecipitation into a mixed solution of methanol and water. The molecular weight (Mw) was 18,000, and the molecular weight distribution (Mw / Mn) was 2.0. The water contact angle of the obtained polymer was 89°. The glass transition temperature (Tg) was 107 °C.

[0149] <Synthesis Example L5> 2.00 g of StMA, 0.0097 g of azobisisobutyronitrile, and 20 ml of toluene were added into a nitrogen-substituted reaction vessel. After heating and stirring at 65 °C for 8 hours, PStMA was obtained by reprecipitation in methanol. The molecular weight (Mw) was 35,000, and the molecular weight distribution (Mw / Mn) was 2.1. The water contact angle of the obtained polymer was 109°. The melting point (Tm) was 50 °C.

[0150] <Synthesis Example B1> 3.00 g of StA, 0.149 g of polyethylene glycol monooleyl ether, 0.020 g of sorbitan tristearate, and 60 ml of pure water were added into a nitrogen-substituted reaction vessel and emulsified. 25 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and a water dispersion of PStA was obtained by heating and stirring at 65 °C for 8 hours. The solid content was 4.6%. The water contact angle of the film formed by coating the emulsion dispersion on a glass substrate was 110°.

[0151] <Synthesis Example B2> 3.00 g of StA, 0.262 g of polyethylene glycol monooleyl ether, 0.037 g of sorbitan tristearate, and 60 ml of pure water were added into a nitrogen-substituted reaction vessel and emulsified. 25 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and a water dispersion of PStA was obtained by heating and stirring at 65 °C for 8 hours. The solid content was 4.7%. The water contact angle of the film formed by coating the emulsion dispersion on a glass substrate was 110°.

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

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

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

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

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

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

[0158] <Synthesis Example B9> 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-substituted reaction vessel and heated and stirred at 80 °C. To this solution, 9 g of tripropylene glycol, 1.8 g of sorbitan tristearate, 0.75 g of polyethylene glycol monooleyl ether, 0.6 g of trimethyloctadecylammonium chloride, and 40 g of pure water were added and stirred. Methyl isobutyl ketone was removed by an evaporator to obtain an aqueous dispersion of the reaction product of sorbitan stearate and isocyanate. The water contact angle of the film obtained by applying the dispersion to a glass substrate was 105°.

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

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

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

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

[0163] <Examples 1 to 117> The aqueous dispersions of the organic fine particles synthesized in Synthesis Examples 1 to 44, the binder resins synthesized in Synthesis Examples B1 to B9, and the emulsifier were mixed at the ratios shown in Table 2 to prepare a treatment solution. The treatment solution was applied to a PET cloth (basis weight: 88 g / m 2 , 70 denier, gray), and various measurements (falling speed test, contact angle measurement, water repellency test, strong water repellency test, washing durability) were performed. The results are shown in Table 2. However, among the ratios (g) shown in Table 2, those other than Synthesis Examples 1 to 44 indicate only the weight of the solid content, not the weight of the entire emulsion dispersion. In addition, emulsifiers, crosslinking agents, etc. with small addition amounts were separately prepared as a 3 wt% diluted aqueous solution and added. A scanning electron microscope (SEM) photograph of the PET cloth (Example 1) to which the organic fine particles of Synthesis Example 1 adhered is shown in Fig. 1.

[0164]

Table 2-1

[0165]

Table 2-2

[0166]

Table 2-3

[0167]

Table 2-4

[0168]

Table 2-5

[0169]

Table 2-6

[0170]

Table 2-7

[0171]

Table 2-8

[0172] <Synthesis Examples 45 to 82> The same procedure as in Synthesis Example 1 was repeated except that the monomers shown in Table 3 were used and the emulsifiers shown in Table 3 were added in the predetermined amounts shown in the table based on the total monomer amount and polymerized. <Examples 118 to 155> To the particles obtained in Synthesis Examples 45 to 82, Binder B3 with a solid content of 25 wt% was mixed, and the treatment liquid was adjusted so that the particle concentration became 2.25%. The treatment liquid was applied to a PET cloth, and the results of measuring the falling speed were shown in Table 3 as the falling speed of each synthesis example. To the treatment liquid, an aqueous solution of 1.1 g of Crosslinking Agent 1 was added per 1 g of the binder resin. In Synthesis Examples 45 to 82, the retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 85% or more. In Synthesis Example 46, the particle size of the particles on the cloth was 198 nm.

[0173] <Synthesis Example 83> To a reaction vessel purged with nitrogen, 10 ml of an aqueous dispersion of crosslinked fine particles of polymethyl methacrylate (PMMA) with a solid content concentration of 20 wt% and a particle size of 300 nm, 400 mg of polyethylene glycol monooleyl ether, 100 mg of sorbitan stearate, and 1 g of StA were added, and stirred at 45 °C. After 3 hours, 16 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and heated and stirred at 65 °C for 8 hours to obtain an aqueous dispersion of PMMA / StA fine particles. The obtained aqueous dispersion was applied to a glass substrate, and the contact angle of water measured after heating at 150 °C for 1 minute was 105 degrees. The retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 90%.

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

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

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

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

[0178] <Synthesis Example 88> 1.5 g of Sty, 38 mg of DVB, 86 mg of glyceryl stearate, 219 mg of polyethylene glycol monooleyl ether, and 10 g of pure water were added to a nitrogen-substituted reaction vessel and emulsified. Then, 40 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and heating and stirring were carried out at 65°C. After 28 hours, an emulsion prepared by emulsifying 0.2 g of StA with 28 mg of glyceryl stearate, 95 mg of polyethylene glycol monooleyl ether, and 1 g of pure water was added, and heating and stirring were continued for another 8 hours to obtain an aqueous dispersion of PSty / StA cross-linked microparticles. The obtained aqueous dispersion was applied to a glass substrate, and the contact angle of water measured after heating at 150°C for 1 minute was 115°. The retention rate of the particle diameter before and after heating at 170°C for 1 minute was 85%.

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

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

[0181] <Synthesis Example 91> Into a nitrogen-substituted reaction vessel, 0.32 g of tBuSty, 0.38 g of GMA, 17 mg of DVB, 0.015 g of stearyltrimonium chloride, and 19 g of pure were added as initial monomers, emulsified, and then 18 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added and heated with stirring at 65°C. 30 minutes after adding 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 0.32 g of tBuSty and 17 mg of DVB were added as additional monomers, and heated with stirring for 8 hours to obtain an aqueous dispersion of crosslinked fine particles. Binder B8 with a solid content of 25 wt% was mixed with the particles of the obtained aqueous dispersion, and the treatment liquid was adjusted so that the particle concentration became 2.25%. When the treatment liquid was applied to a PET cloth and the water repellency was evaluated, the water repellency was 90 points. Also, the contact angle of the cloth was 140 degrees. The retention rate of the particle diameter before and after heating at 170°C for 1 minute was 90%.

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

[0183] <Examples 156 to 174> Regarding Synthesis Examples 92 to 110, the contact angle of water measured after applying the obtained aqueous dispersion of particles to a glass substrate and heating at 150°C for 1 minute is shown in Table 4. Regarding Synthesis Examples 92 to 96, 25 wt% of binder B8 with a solid content was mixed with the obtained particles, and the treatment liquid was adjusted so that the particle concentration became 2.25%. Regarding Synthesis Examples 97 to 110, 25 wt% of binder B3 with a solid content was mixed with the obtained particles, and the treatment liquid was adjusted so that the particle concentration became 2.25%. The treatment liquid was applied to a PET cloth, and the results of measuring the falling speed, water repellency, and strong water repellency tests were shown in Table 4 as the falling speed, water repellency, and strong water repellency of each synthesis example. An aqueous solution of 1.1 g of crosslinking agent 1 was added to 1 g of the binder resin in the treatment liquid. In Synthesis Examples 92 to 110, the retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 85% or more. A scanning electron microscope (SEM) photograph of a PET cloth (Example 157) to which the organic fine particles, binder B8, and crosslinking agent 1 of Synthesis Example 93 adhered is shown in Fig. 2.

[0184]

Table 3

[0185]

Table 4

[0186] <Synthesis Example 111> 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 microparticles. The solid content was 4.54%. The particle size (average particle size) of the aqueous dispersion was 234 nm. The aqueous dispersions of these organic microparticles and Synthesis Example B8 were diluted with pure water so that their solid contents were 0.6% and 0.4% respectively, and the total was 1 wt% to obtain a treatment liquid. When a PET cloth was immersed in this treatment liquid and then passed through a mangle and the water repellency of the heat-treated test cloth was evaluated, the falling speed was 209 mm / s, the water repellency was 100 points, and the strong water repellency was 3++ points. Also, the retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 80%.

[0187] <Synthesis Example 112> 0.39 g of tBuMA, 0.37 g of iBMA, 0.16 g of GMA, 0.072 g of DVB, 55 mg of emulsifier 1, and 19 ml of pure water were added to a reaction vessel and dispersed. 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 microparticles. The solid content was 4.80%. The particle size (average particle size) of the aqueous dispersion was 302 nm. The aqueous dispersions of these organic microparticles and Synthesis Example B8 were diluted with pure water so that their solid contents were 0.8% and 0.2% respectively, and the total was 1 wt% to obtain a treatment liquid. When a PET cloth was immersed in this treatment liquid and then passed through a mangle and the water repellency of the heat-treated test cloth was evaluated, the falling speed was 179 mm / s, the water repellency was 100 points, and the strong water repellency was 3 points. Also, the retention rate of the particle diameter before and after heating at 170 °C for 1 minute was 85%.

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

[0189] <Examples 175 to 178> The treatment liquid was adjusted at the ratios shown in Table 5 and applied to PET Q15 (basis weight: 88 g / m 2 , 70 denier, gray) and PET R964 (basis weight 40 g / m 2 , black) cloths, and various measurements (water repellency test, measurement of dark color ΔL value) were performed. The results are shown in Table 5.

[0190] [Table 5]

[0191] Conventional dark colorants tended to reduce water repellency, but Table 5 shows that the particles of the present disclosure can exhibit a dark color effect without impairing water repellency. [Industrial Applicability]

[0192] The organic fine particles of the present disclosure can be used as an oil repellent, a stain repellent, a soil release agent, a peeling agent, or a mold release agent.

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

[0194] [4] The hydrophobic monomer (1) is of the formula: CH2=C(-R 12 )-C(=O)-Y 11 (R 11 ) k or CH2=C(-R 22 )-Y 21 (H) 5-l (R 21 ) l [wherein, R 11 and R 21 are each independently a hydrocarbon group having 3 to 40 carbon atoms, R 12 and R 22 are a hydrogen atom, a monovalent organic group or a halogen atom, Y 11 is a divalent to tetravalent group composed of at least one selected from a hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2- or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms) (excluding the case of only a divalent hydrocarbon group), Y 21 is a benzene ring, H is a hydrogen atom, H and R 21 is Y 21 are directly bonded to k and l are 1 to 3. is a monomer represented by The reactive / hydrophilic monomer (3) has the formula: CH2=C(-R 32 )-C(=O)-Y 31 -(R 33 ) o (R 31 ) m or CH2=C(-R 42 )-Y 41 -(H) 5-n (R 41 ) n [In the formula, R 31 and R 41 are each independently a reactive group or a hydrophilic group, R 32 and R 42 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 31 is a direct bond, -O-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R 33 is a divalent to tetravalent hydrocarbon group having 1 to 10 carbon atoms, Y 41 is a benzene ring, H is a hydrogen atom, H and R 41 is Y 41 are directly bonded to m and n are 1 to 3; o is 0 or 1.] is a monomer represented by The crosslinking monomer (4) has the formula: JPEG2025111494000044.jpg8131 or JPEG2025111494000045.jpg3842[where, R 51 and R 61 are each independently a divalent to tetravalent group consisting of at least one selected from a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -(CHCHO)r- (r is an integer of 1 to 10), -CH-, -O-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R 52 and R 62 are each independently a hydrogen atom, a monovalent organic group, or a halogen atom, Y 51 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), p is 2 to 4; q is 1 to 5. is a monomer represented by The high glass transition temperature monomer (5) has the formula: JPEG2025111494000046.jpg3422 or JPEG2025111494000047.jpg3433 [In the formula, R 71 and R 81 is a group consisting of at least one selected from a hydrocarbon group having 1 to 30 carbon atoms, —C6H4—, —O—, or —NR′— (R′ is H or a hydrocarbon group having 1 to 4 carbon atoms), R 72 and R 82 is a hydrogen atom, a monovalent organic group, or a halogen atom, Y 71 is -O- or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms). The organic fine particles according to [2] or [3], wherein the monomer is a monomer represented by the formula:

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

[0196] [6] The hydrophobic monomer (1) is at least one monomer selected from the group consisting of t-butyl (meth) acrylate, N-t-butyl (meth) acrylamide, t-butyl styrene, stearyl (meth) acrylate, isopropyl (meth) acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, stearic acid amidoethyl (meth) acrylate, CH2=CHC(=O)OC2H4NHSO2C 18 H 37 and is The reactive / hydrophilic monomer (3) is at least one monomer 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, dimethylaminoethyl methacrylate quaternary compound, tetrahydrofurfuryl (meth)acrylate, The crosslinkable monomer (4) is at least one monomer 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, glycerol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, 5-hydroxy-1,3-adamantane di(meth)acrylate, The organic fine particles according to any one of [1] to [5], wherein the high glass transition point monomer (5) is at least one monomer selected from the group consisting of isobornyl (meth) acrylate, bornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, phenyl (meth) acrylate, naphthyl acrylate, and benzyl acrylate.

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

[0198]

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

[11] The water repellent composition according to

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

[0199]

[12] The water repellent composition according to

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

[13] The water-repellent composition according to

[12] or

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

[0200]

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

[11] to

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

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

[10] to

[14] , which can prevent frosting.

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

[10] to

[15] , comprising the step.

[0201]

[17] Furthermore, By adding an aqueous dispersion of the binder resin (C) to the aqueous dispersion of the organic fine particles (A), or by polymerizing a monomer for the binder resin in the aqueous dispersion of the 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 the binder resin, a step of obtaining an aqueous dispersion in which the organic fine particles (A) and the binder resin (C) are dispersed. The production method according to

[16] , comprising the step.

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

[10] to

[15] to the fiber product.

[19] A fiber product in which the organic fine particles and / or the binder resin in the water-repellent composition according to any one of

[10] to

[15] are adhered to the surface.

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

[10] to

[15] adhere to the surface and which has a falling speed of 200 mm / second or more.

Claims

1. Organic microparticles that can adhere to a substrate in a state having a particle shape and exhibit water repellency on the substrate when adhered to the substrate.

2. The organic microparticles according to claim 1, satisfying at least one of the following: (i) when adhered to a glass substrate, the static contact angle of water on the glass substrate is 100 degrees or more; (ii) when adhered to a cloth, the static contact angle of water on the cloth is 120 degrees or more; or (iii) when adhered to a cloth, the falling speed of water on the cloth is 100 mm / s or more.

3. The organic microparticles according to claim 1 or 2, wherein when heat treatment is performed at 170 °C for 1 minute after adhering to the substrate, the average diameter of the organic microparticles after heat treatment is 50% or more of the average diameter of the organic microparticles before heat treatment, or the particle size of the microparticles observable on the cloth is 50 to 700 nm.

4. (1) A hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms, or (2) A (meth)acrylic monomer having a polydimethylsiloxane group Organic microparticles comprising a polymer having a repeating unit formed therefrom.

5. The polymer is (4) A crosslinkable monomer having at least two ethylenically unsaturated double bonds The organic microparticles according to claim 4, also having a repeating unit formed therefrom.

6. The polymer further comprises (3) A reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or hydrophilic group, and (5) A high glass transition point monomer having a glass transition point of 100 °C or more for the homopolymer The organic microparticles according to claim 4 or 5, having a repeating unit formed from at least one monomer selected from the group consisting of.

7. The organic microparticles according to any one of claims 4 to 6, wherein a combination of a (meth)acrylic monomer having a hydrocarbon group having 12 to 24 carbon atoms in the side chain among the hydrophobic monomers (1) and the (meth)acrylic monomer (2) is used in an amount such that the total weight of both monomers is less than 80% by weight of the total amount of the monomer components.

8. The organic microparticles according to any one of claims 4 to 7, obtained by polymerizing a monomer containing the monomer (4) and then polymerizing a monomer not containing the monomer (4), and a part of the particles being meltable.

9. The organic microparticles according to any one of claims 4 to 8, wherein the static contact angle of water on a silicon substrate treated with a homopolymer of the hydrophobic monomer (1) is 70 to 120 degrees.

10. The hydrophobic monomer (1) has the formula: CH ２ =C(-R １２ )-C(=O)-Y １１ (R １１ ) ｋ or CH ２ =C(-R ２２ )-Y ２１ (H) ５－ｌ (R ２１ ) ｌ [wherein, R １１ and R ２１ are each independently a hydrocarbon group having 3 to 40 carbon atoms, R １２ and R ２２ is a hydrogen atom, a monovalent organic group or a halogen atom, Y １１ is a divalent to tetravalent group having 1 to 4 carbon atoms, -C ６ H ４ -, -O-, -C(=O)-, -S(=O) ２ - or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms), and is composed of at least one or more selected therefrom (excluding the case of only a divalent hydrocarbon group). Y ２１ is a benzene ring, H is a hydrogen atom, H and R ２１ are directly bonded to Y ２１ respectively, k and l are 1 to 3. ] and is a monomer represented by The (meth)acrylic monomer (2) has the formula: CH ２ =C(-R 9２ )-C(=O)-Y ９１ -R 9１ [wherein, R 9１ is a group having a polydimethylsiloxane group, R ９２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y ９１ is a divalent to tetravalent group composed of at least one group selected from a hydrocarbon group having 1 to 4 carbon atoms, -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 monomer represented by The reactive / hydrophilic monomer (3) has the formula: CH ２ =C(-R ３２ )-C(=O)-Y ３１ -(R ３３ ) ｏ (R ３１ ) ｍ or CH ２ =C(-R ４２ )-Y ４１ -(H) ５－ｎ (R ４１ ) ｎ [wherein, R ３１ and R ４１ are each independently a reactive group or a hydrophilic group, R ３２ and R ４２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y ３１ is a direct bond, -O-, or -NR'-(wherein R' is H or a hydrocarbon group having 1 to 4 carbon atoms), R ３３ is a hydrocarbon group having 2 to 4 carbon atoms and 1 to 10 carbon atoms, Y ４１ is a benzene ring, H is a hydrogen atom, H and R ４１ are directly bonded to Y ４１ respectively, m and n are 1 to 3, o is 0 or 1. ] and is a monomer represented by The crosslinkable monomer (4) has the formula: or [wherein, R ５１ and R ６１ are each independently a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -(CH ２ CH ２ O)r- (r is an integer of 1 to 10), -C ６ H ４ -, -O-, or -NR' - (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), and is a divalent to tetravalent group composed of at least one or more selected therefrom, R ５２ and R ６２ are each independently a hydrogen atom, a monovalent organic group, or a halogen atom, Y ５１ is -O- or -NR'-(where R' is H or a hydrocarbon group having 1 to 4 carbon atoms), p is 2 to 4, q is 1 to 5. ] and is a monomer represented by The high glass transition point monomer (5) has the formula: or [wherein, R 7１ and R 8１ are each a hydrocarbon group having 1 to 30 carbon atoms, -C ６ H ４ -, -O-, or -NR'- (R' is H or a hydrocarbon group having 1 to 4 carbon atoms), and is a group composed of at least one or more selected therefrom, R ７２ and R ８２ is a hydrogen atom, a monovalent organic group, or a halogen atom, Y ７１ is -O- or -NR'-(R' is H or a hydrocarbon group having 1 to 4 carbon atoms). The organic microparticles according to any one of claims 4 to 9, which are monomers represented by

11. In the reactive monomer (3), the reactive group is an epoxy group, chloromethyl group, bromomethyl group, iodomethyl group, blocked isocyanate group, and the hydrophilic group is a hydroxyl group, amino group, carboxylic acid group, sulfonic acid group, phosphoric acid group, carboxylic acid, sulfonic acid, an alkali metal or alkaline earth metal salt base of phosphoric acid, chlorine or bromine, and an ammonium base in which an iodine ion is a counter anion, and is at least one group selected from the group consisting of. The organic microparticles according to any one of claims 4 to 10.

12. The hydrophobic monomer (1) is at least one monomer selected from the group consisting of t-butyl (meth)acrylate, N-t-butyl (meth)acrylamide, t-butylstyrene, stearyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl acrylate, 2,4-di-t-butylstyrene, 2,4,6-trimethylstyrene, stearic acid amidoethyl (meth)acrylate, CH ２ =CHC(=O)OC ２ H ４ NHSO ２ C １８ H ３７ and is a monomer selected from the group consisting of The (meth)acrylic monomer (2) has the formula: or [wherein, n is a number from 1 to 500. ] and is at least one monomer selected from the group consisting of The reactive / hydrophilic monomer (3) is at least one monomer 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, dimethylaminoethyl methacrylate quaternary compound, tetrahydrofurfuryl (meth)acrylate, The crosslinkable monomer (4) is at least one monomer 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, dimethylol tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glycerol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, 5-hydroxy-1,3-adamantane di(meth)acrylate, The organic fine particles according to any one of claims 4 to 11, wherein the high glass transition point monomer (5) is at least one monomer selected from the group consisting of isobornyl (meth) acrylate, bornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, phenyl (meth) acrylate, naphthyl acrylate, and benzyl acrylate.

13. The molar ratio of the hydrophobic monomer (1) or (meth) acrylic monomer (2) / reactive hydrophilic monomer (3) / high glass transition point monomer (5) is 20 to 100 / 0 to 50 / 0 to 70, and the crosslinkable monomer (4) is 0.1 to 30 parts by mole with respect to 100 parts by mole in total of the hydrophobic monomer (1) and the reactive hydrophilic monomer (3), and the (meth) acrylic monomer (2) is 0 to 30 parts by mole with respect to 100 parts by mole in total of the hydrophobic monomer (1), the (meth) acrylic monomer (2), and the reactive hydrophilic monomer (3). The organic fine particles according to any one of claims 3 to 12.

14. The organic fine particles according to any one of claims 1 to 13, which have a falling speed of 150 mm / second or more when treated on a cloth.

15. The organic fine particles according to any one of claims 1 to 14, having an average particle diameter of 30 nm to 1000 nm.

16. A method for producing organic fine particles, comprising polymerizing a monomer containing the monomer (4) and then polymerizing a monomer not containing the monomer (4), the organic fine particles according to any one of claims 3 to 14.

17. (A) The organic fine particles according to any one of claims 1 to 15, and (B) an aqueous medium A water repellent composition which is an aqueous dispersion of organic fine particles containing the same.

18. The water repellent composition according to claim 17, further containing any one or more of (C) a binder resin, (D) a surfactant, and (E) a crosslinking agent.

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

20. The water repellent composition according to claim 18 or 19, wherein the amount of the surfactant (D) is 15 parts by weight or less with respect to 100 parts by weight of the organic fine particles (A).

21. The water-repellent composition according to any one of claims 18 to 20, wherein the binder resin (C) is an acrylic polymer, a urethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, a polystyrene, a silicone polymer, or a combination thereof.

22. The water-repellent composition according to any one of claims 17 to 21, which can prevent frosting.

23. A step of polymerizing a monomer in the presence of a surfactant that is 15 parts by weight or less with respect to 100 parts by weight of the monomer in an aqueous medium to obtain an aqueous dispersion of organic fine particles (A). The method for producing a water-repellent composition according to any one of claims 17 to 22, which has the above step.

24. Furthermore, By adding an aqueous dispersion of the binder resin (C) to the aqueous dispersion of the organic fine particles (A), or by polymerizing a monomer for the binder resin in the aqueous dispersion of the 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 the binder resin, a step of obtaining an aqueous dispersion in which the organic fine particles (A) and the binder resin (C) are dispersed. The production method according to claim 23, which has the above step.

25. A method for treating a fiber product, which comprises applying a treatment liquid containing the water-repellent composition according to any one of claims 17 to 22 to the fiber product.

26. A fiber product in which the organic fine particles and / or the binder resin in the water-repellent composition according to any one of claims 17 to 22 are adhered to the surface.

27. In the water-repellent composition according to any one of claims 17 to 22, the organic fine particles and / or the binder resin are adhered to the surface. A fiber product that satisfies at least one of the following conditions: the static contact angle of water on the fabric is 120 degrees or more, or the falling speed of water on the fabric is 200 mm / second or more.

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