TW202235525A - Water-repellent organic fine particles having water pressure resistance improving effects - Google Patents

Abstract

The present invention provides an organic fine particle and a water pressure resistance-improving agent composition capable of imparting excellent water pressure resistance and waterproofness to substrates. The organic fine particle of the present invention includes a polymer having a repeating unit formed from (I) below and optionally (II): (I) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms; (II) a crosslinkable monomer having at least two ethylenically unsaturated double bonds. The water pressure resistance-improving agent composition includes (A) organic fine particles and (B) an aqueous medium.

Description

Water-repellent organic microparticles with water pressure-resistant lifting effect

The disclosure relates to water-repellent organic microparticles, especially fluorine-free organic microparticles, which have the effect of resisting water pressure rise.

In the past, super water repellency was imparted to the surface of the substrate by forming a fine uneven structure on the surface of the substrate, or by combining the formation of the fine uneven structure on the surface of the substrate with the above-mentioned coating treatment. The production of the concavo-convex structure mainly includes a method using fine particles and a method of patterning such as etching. Patterning methods such as etching are limited in the scope and substrates that can be used.

When hydrophobic inorganic fine particles are used as the fine particles, a large amount of dispersing agent such as an emulsifier is required in order to obtain an aqueous dispersion of the hydrophobic inorganic fine particles. If the degree of hydrophobicity of the hydrophobic inorganic fine particles is reduced, that is, the hydrophobic inorganic fine particles with remaining hydrophilic groups are used, the dispersion of water becomes slightly easier, but the performance of the water repellent agent is reduced because the hydrophobicity of the fine particles themselves decreases. reduce.

On the other hand, there is a method for synthesizing organic fine particles without soap polymerization or with less emulsifier. These are dispersed in water without emulsifier or with a small amount of emulsifier. Therefore, hydrophilic monomers are generally used, and the fine particles are almost hydrophilic. Because it is difficult to use highly hydrophobic monomers, it is difficult to synthesize organic microparticles exhibiting water repellency using soap-free polymerization or organic microparticle synthesis methods with less emulsifiers.

In order to improve water pressure resistance or water resistance, it is mainly improved by increasing the density of materials, laminating and laminating the structure.

Patent Document 1 discloses that a water-repellent fabric with fine particles of 0.01 to 10.0 μm immobilized on the surface of the fabric has improved water pressure resistance. The fine particles used in Example 1 of Patent Document 1 are silica fine particles and inorganic fine particles.

The improvement of water pressure resistance is mainly improved by the high density of materials, lamination and laminated structure. Therefore, there is almost no technology that only uses water repellent to improve water pressure resistance.

[Prior Art Literature]

[Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2004-256939

The present disclosure provides an organic microparticle capable of imparting excellent water pressure resistance and water repellency to a substrate.

The present disclosure relates to an organic microparticle that can exist on a substrate in a state of particle shape, and exhibits a water pressure resistance effect on the substrate. The organic fine particles can adhere to the base material in the state of particle shape.

The water pressure resistance effect shown in this disclosure,

When attaching organic microparticles to the cloth, it is preferable to satisfy at least one of the following: (i) the water pressure resistance ratio (=water pressure resistance of the treated cloth with organic microparticles attached / water pressure resistance of the untreated control cloth) is 1.03 or more , (ii) The air permeability ratio (=the air permeability of the treated cloth with organic microparticles/the air permeability of the untreated cloth of the contrast) is below 0.9.

The water repellency shown in this disclosure refers to at least one of the following:

(i) In the case of cloth with organic microparticles attached, the contact angle between the cloth with organic microparticles and water is 120 degrees or more; or

(ii) When the cloth with organic fine particles is attached, the falling speed of the cloth with organic fine particles is 100mm/s or more; or

(iii) In the case of a cloth with organic fine particles attached, the water repellency test of the cloth with organic fine particles is 80 points or more.

This disclosure is about including

(A) organic microparticles; and

(B) A water-repellent composition for an aqueous medium.

Furthermore, the present disclosure relates to organic microparticles comprising polymers having repeating units formed by (I):

(I) A hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbons.

In addition to the hydrophobic monomer (I), the polymer constituting the organic microparticles may also have repeating units formed by the following (II):

(II) A crosslinkable monomer having at least two ethylenically unsaturated double bonds.

The polymer constituting the organic microparticles may further have a repeating unit formed from at least one monomer selected from the following (III) and (IV):

(III) Reactive and hydrophilic monomers having 1 ethylenically unsaturated double bond and at least 1 reactive group and/or hydrophilic group, or having 1 ethylenically unsaturated double bond and at least 1 carbon Monomers containing short-chain hydrocarbon groups with hydrocarbon groups of 1 or 2,

(IV) A (meth)acrylic monomer having a straight-chain hydrocarbon group or a polydimethylsiloxane group having 3 to 40 carbon atoms.

Preferred aspects of the present disclosure are as follows.

Pattern 1:

An organic fine particle that can exist on a substrate in a state of particle shape, and exhibits a water pressure resistance effect on the substrate.

Pattern 2:

The organic fine particles according to Aspect 1, when attached to cloth, satisfy at least one of the following (i) and (ii):

(i) The water pressure resistance ratio (= water pressure resistance of the treated cloth with organic microparticles / water pressure resistance of the control untreated cloth) is above 1.03;

(ii) The air permeability ratio (= air permeability of treated cloth with organic microparticles/air permeability of untreated cloth as compared) is 0.9 or less.

Pattern 3:

Organic microparticles as described in aspect 1 or 2, wherein the particles of the microparticles can be observed on the cloth The diameter is 50 to 700nm.

Pattern 4:

The organic fine particle as described in any one of aspects 1 to 3, it is to comprise the polymer that has the repeating unit that is formed by following (I):

(I) A hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbons.

Pattern 5:

An organic microparticle comprising a polymer having repeating units formed by the following (I) and (II):

(1) Hydrophobic monomers having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group with 3 to 40 carbons;

(II) A crosslinkable monomer having at least two ethylenically unsaturated double bonds.

Pattern 6:

A kind of organic fine particle, it is to comprise the polymer that has the repeating unit formed by following (I):

(1) Hydrophobic monomers having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group with 3 to 40 carbons;

The content of the high glass transition point monomer whose glass transition point of the homopolymer in the hydrophobic monomer (I) is 100° C. or higher is 20 mol % or more.

Pattern 7:

The organic fine particle according to any one of aspects 4 to 6, wherein the polymer also has repeating units formed from at least one monomer selected from the following (III) and/or (IV):

(III) Reactive and hydrophilic monomers having 1 ethylenically unsaturated double bond and at least 1 reactive group and/or hydrophilic group, or having 1 ethylenically unsaturated double bond and at least 1 carbon number 1 or 2 hydrocarbyl monomers containing short-chain hydrocarbyl groups;

(IV) A (meth)acrylic monomer having a straight-chain hydrocarbon group or a polydimethylsiloxane group having 3 to 40 carbon atoms.

Pattern 8:

The organic fine particle according to any one of aspects 4 to 7, wherein in the hydrophobic monomer (I), the carbon number of the branched hydrocarbon group is 3 to 11, and the carbon number of the cyclic hydrocarbon group is 4 to 15.

Pattern 9:

The organic fine particle according to any one of aspects 4 to 8, wherein

Hydrophobic monomer (I) is a monomer represented by the following formula:

CH ₂ =C(-R ¹² )-C(=O)-Y ¹¹ (R ¹¹ ) _k

or

CH ₂ =C(-R ¹⁴ )-Y ¹² (H) _5-l (R ¹³ ) _l

[wherein, R ¹¹ and R ¹³ are independently branched or cyclic hydrocarbon groups with 3 to 40 carbons,

R ¹² and R ¹⁴ are hydrogen atoms, monovalent organic groups or halogen atoms,

Y ¹¹ is -O- or -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons),

Y ¹² is a benzene ring,

H is a hydrogen atom,

H and R ¹³ are respectively directly bonded to Y ¹² ,

k is 1 to 3, l is 0 to 3];

The cross-linking monomer (II) is a monomer represented by the following formula:

Mode:

or

[In the formula, R ³¹ and R ³³ are each independently a direct bond, or a hydrocarbon group selected from a carbon number of 1 to 20 (can also include a hydrocarbon site with an -OH group), -(CH ₂ CH ₂ O )r-(r is an integer from 1 to 10), -C ₆ H ₄ -, -O- or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbons) constituted by 2 to the base of 4 valences,

R ³² , R ³⁴ , R ³⁵ and R ³⁶ are each independently a hydrogen atom, a monovalent organic group or a halogen atom,

Y ³¹ is -O- or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbons),

p is 2 to 4,

q is 1 to 5];

Reactive, hydrophilic monomer (III) is a monomer represented by the following formula:

CH ₂ =C(-R ⁴² )-C(=O)-Y ⁴¹ -(R ⁴³ ) _o (R ⁴¹ ) _t

or

CH ₂ =C(-R ⁴⁵ )-Y ⁴² -(H) _5-n (R ⁴⁴ ) _u

[wherein, R ⁴¹ and R ⁴⁴ are each independently a reactive group or a hydrophilic group,

R ⁴² and R ⁴⁵ are hydrogen atoms, monovalent organic groups or halogen atoms,

Y ⁴¹ is a direct bond, -O- or -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons),

R ⁴³ is a direct bond, -O-, or a hydrocarbon group having 2 to 4 valences of carbon number 1 to 10 (which may also include a hydrocarbon site having an -OH group),

Y ⁴² is a benzene ring,

H is a hydrogen atom,

H and R ⁴⁴ are respectively directly bonded to Y ⁴² ,

t and u are 1 to 3,

o is 0 or 1]; or

The monomer (III) containing a short-chain hydrocarbon group is a monomer represented by the following formula:

CH ₂ =C(-R ⁴⁷ )-C(=O)-Y ⁴³ -R ⁴⁶

[wherein, R ⁴⁶ is a hydrocarbon group with 1 or 2 carbons,

R ⁴⁷ is a hydrogen atom, a monovalent organic group or a halogen atom,

Y ⁴³ is a direct bond, -O- or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbons)];

The (meth)acrylic monomer (IV) is a (meth)acrylic monomer having a straight-chain hydrocarbon group with 3 to 40 carbons represented by the following formula:

CH ₂ =C(-R ⁵² )-C(=O)-Y ⁵¹ (R ⁵¹ ) _s

[wherein, R ⁵¹ are each independently a linear hydrocarbon group with 3 to 40 carbons,

R ⁵² is a hydrogen atom, a monovalent organic group or a halogen atom,

Y ⁵¹ is a hydrocarbon group with 1 carbon number selected from 2 to 4 valences (especially -CH ₂ -, -CH= and -C≡), -C ₆ H ₄ -, -O-, -C(=O) -, -S(=O) ₂ - or -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons) composed of 2 to 4 valent groups (but excluding only divalent hydrocarbon groups) situation),

s is 1 to 3]; or

A (meth)acrylic monomer having a polydimethylsiloxane group represented by the following formula:

CH ₂ =C(-R ⁶² )-C(=O)-Y ⁶¹ -R ⁶¹

[wherein, ^R61 is a group with a polydimethylsiloxane group,

^R62 is a hydrogen atom, a monovalent organic group or a halogen atom,

Y ⁶¹ is a hydrocarbon group selected from 2 to 4 valent carbon number 1, -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ - or -NR'-(R 'is a 2 to 4 valent group formed by at least one of H or a hydrocarbon group having 1 to 4 carbons].

Pattern 10:

The organic fine particle according to any one of aspects 7 to 9, wherein,

In the reactive monomer (III), the reactive group is an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group, and a blocked isocyanate group, and the hydrophilic group is selected from a hydroxyl group, an amino group (including a group bonded to N H is converted to methyl, ethyl, propyl or butyl), carboxylic acid, sulfonic acid, phosphoric acid, alkali metal or alkaline earth metal salts of carboxylic acid, sulfonic acid, phosphoric acid, chlorine, bromine or The iodide ion is at least one of the group consisting of ammonium salt base, ethylene glycol base, polyethylene glycol base, and base with acetone skeleton (-C(=O)-CH ₃ ), or the reaction The neutral and hydrophilic monomer (III) is (meth)acrylamide having a short-chain hydrocarbon group having 6 or less carbon atoms in the side chain.

Pattern 11:

The organic fine particle according to any one of aspects 4 to 10, wherein

Hydrophobic monomer (I) is selected from

Tertiary butyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl=acrylate,

Isocamyl (meth)acrylate, Camphenyl (meth)acrylate, Adamantyl (meth)acrylate, Dicyclopentyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, (Meth) ) phenyl acrylate, naphthyl acrylate, benzyl acrylate,

Tertiary butylstyrene, methylstyrene, styrene, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclobutyl (meth)acrylate, cycloheptyl (meth)acrylate , at least one monomer from the group consisting of 2,4-di-tert-butylstyrene and 2,4,6-trimethylstyrene,

The cross-linking monomer (II) is selected from divinylbenzene, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol Glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, Ethylene glycol di(meth)acrylate (Meth)acrylate, Methylene glycol di(meth)acrylate, Polytetramethylene glycol di(meth)acrylate, Dihydroxymethyltricyclodecane di(meth)acrylate , trihydroxymethylpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glyceryl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, di(meth)acrylate base) at least one monomer from the group consisting of dicyclopentyl acrylate and 5-hydroxy-1,3-adamantane di(meth)acrylate,

Reactivity, hydrophilic monomer (III) is selected from glycidyl (meth)acrylate, glyceryl (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-Acetylacetyloxyethyl (meth)acrylate, 4-Hydroxybutyl glycidyl acrylate, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, (methyl ) 2-(dimethylamino)ethyl acrylate, 2-(tertiary butylamino)ethyl (meth)acrylate, quaternary dimethylaminoethyl (meth)acrylate, (form Base) Tetrahydrofuryl Methyl Acrylate, Polyethylene Glycol (Meth) Acrylate, Diacetone (Meth) Acrylamide, Isopropyl (Meth) Acrylamide, Tertiary Butyl (Meth) Acrylamide , ethyl(meth)acrylamide, methyl(meth)acrylamide; and

4-hydroxymethylstyrene, 4-hydroxyethylstyrene, 4-aminomethylstyrene, 4-aminoethylstyrene, 2-(4-vinylphenyl)oxirane, 2 -(4-vinylbenzoyl)oxirane at least 1 monomer in a group,

The short-chain hydrocarbon group-containing monomer (III) is at least one monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, α-chloromethyl acrylate, and α-chloroethyl acrylate,

(Meth)acrylic acid monomer (IV) is selected from

Stearyl (meth)acrylate, stearylamide ethyl (meth)acrylate, CH ₂ =CHC(=O)OC ₂ H ₄ NHC(=O)C ₁₇ H ₃₅ , CH ₂ =CHC(= O)OC ₂ H ₄ NHSO ₂ C ₁₈ H ₃₇ , CH ₂ =CHC(=O)OC ₂ H ₄ NHC(=O)OC ₁₈ H ₃₇ , CH ₂ =CHC(=O)OC ₂ H ₄ OC(= O)NHC ₁₈ H ₃₇ , CH ₂ =CHC(=O)OC ₂ H ₄ NHC(=O)NHC ₁₈ H ₃₇ ,

Mode:

or

[wherein, n is a number from 1 to 500] at least one monomer in the group consisting of.

Pattern 12:

The organic fine particle according to any one of aspects 4 to 11, which satisfies at least one of the following (i), (ii) and (iii):

(i) The molar ratio of hydrophobic monomer (I)/reactive, hydrophilic monomer and/or short-chain hydrocarbon-containing monomer (III) is 100/0 to 50/50,

(ii) 100 mole parts relative to the total of hydrophobic monomer (I), reactive, hydrophilic monomer and/or short-chain hydrocarbon group-containing monomer (III) and (meth)acrylic monomer (IV) , the crosslinking monomer (II) is 0.1 to 30 mole parts; or

(iii) The (meth)acrylic monomer (IV) is 0 to 30 mole parts.

Pattern 13:

A water pressure raising agent comprising the organic microparticles described in any one of aspects 1-12.

Pattern 14:

A use of the organic microparticles described in any one of aspects 1 to 12 as a water pressure rise resistance agent.

Pattern 15:

A water pressure-resistant booster composition, comprising:

(A) organic microparticles as described in any one of aspects 1 to 12; and

(B) Aqueous medium.

Pattern 16:

The water pressure raising agent composition according to aspect 15, wherein the amount of the organic microparticles (A) is 50% by weight or less with respect to the water pressure raising agent composition.

Pattern 17:

The water pressure raising agent composition according to Aspect 15 or 16, which further includes any one or more of (C) binder resin, (D) surfactant, and (E) crosslinking agent.

Pattern 18:

The water pressure riser composition as described in Aspect 17, wherein the binder resin (C) is selected from non-fluoropolymers having hydrocarbon groups with 3 to 40 carbons in the side chain and non-fluoropolymers with 1 to 20 carbons in the side chain fluorine At least one of the alkyl fluoropolymers.

Pattern 19:

The water pressure raising agent composition according to Aspect 17 or 18, wherein the binder resin (C) is an acrylic polymer, a urethane polymer, a polyolefin, a polyester, a polyether, a polyamide, Polyimides, polystyrenes, silicone polymers, and combinations thereof.

Form 20:

The water pressure riser composition as described in any one of aspects 17 to 19, wherein the weight ratio of binder resin (C)/organic microparticles (A) is 1/99 to 90/10 or 20/80 to 99 /1, or the amount of the binder resin (C) is 30 to 99% by weight relative to the total weight of the binder resin (C) and the organic fine particles (A).

Pattern 21:

A method for producing a water pressure raising agent composition, which is a method for manufacturing the water pressure raising agent composition described in any one of aspects 15 to 20, which has the following steps: in the presence of 100 wt. Under the condition that the surfactant is less than 30 parts by weight, the monomer is polymerized in an aqueous medium to obtain an aqueous dispersion of organic microparticles (A).

Pattern 22:

The manufacturing method as described in aspect 21, which further includes the following steps:

By adding the aqueous dispersion of the binder resin (C) to the aqueous dispersion of the organic fine particles (A), or by polymerizing the monomer for the binder resin in the aqueous dispersion of the organic fine particles (A) To obtain the binder resin (C), or by polymerizing the monomer for the organic microparticles in the aqueous dispersion of the binder resin, the water in which the organic microparticles (A) and the binder resin (C) are dispersed is obtained. Dispersions.

Pattern 23:

A method for treating fiber products, which comprises applying the treatment liquid containing the water pressure raising agent composition described in any one of aspects 15 to 20 to the fiber products.

Pattern 24:

A fiber product, which is applied with the water pressure raising agent composition described in any one of aspects 15 to 20.

Pattern 25:

The fiber product according to Aspect 24, which satisfies at least one of the following:

(i) Water pressure resistance ratio (=water pressure resistance of fiber products with organic microparticles/water pressure resistance of control fiber products) is above 1.03; (ii) air permeability ratio (=air permeability of fiber products with organic microparticles/ The air permeability of the contrast fiber product) is below 0.9.

Pattern 26:

The fiber product according to aspect 24 or 25, wherein the fiber product is a cloth for outdoor products, a cloth for sports products, a cloth for rain gear, a cloth for medical use or a non-woven fabric.

Pattern 27:

The fiber product as described in Aspect 26, wherein the fiber product is medical surgical clothing, protective clothing, awning, shade, or tent.

The composition of the organic microparticles and the water-repellent agent disclosed herein can impart excellent water pressure resistance and water repellency to the substrate, such as fiber products.

The water pressure raising agent contains organic fine particles. The water pressure raising agent may consist of only organic fine particles, or may contain other components besides the organic fine particles.

The composition of the water repellent agent functions as a water pressure resistance raising agent.

The water repellent composition (ie, water pressure booster) includes:

(A) organic microparticles; and

(B) Aqueous medium.

The water repellent composition may further include:

(C) binder resin; and/or

(D) Surfactant.

Higher water pressure resistance can be obtained by including the binder resin (C).

The water repellent composition contains the following components in a preferable aspect.

Organic microparticles (A);

Organic microparticles (A) + aqueous medium (B);

Organic microparticles (A) + aqueous medium (B) + binder resin (C);

Organic microparticles (A) + aqueous medium (B) + surfactant (D);

Organic microparticles (A) + aqueous medium (B) + binder resin (C) + surfactant (D);

Organic microparticles (A) + aqueous medium (B) + binder resin (C) + crosslinking agent (E); or

Organic microparticles (A) + aqueous medium (B) + binder resin (C) + surfactant (D) + crosslinking agent (E)

(A) Organic fine particles

The function of organic microparticles is as an active ingredient to exert water repellency and water pressure resistance. The organic fine particles are preferably formed of non-fluoropolymers.

The average particle size of the organic fine particles may be 30 to 1000 nm, preferably 40 to 700 nm or 45 to 300 nm from the viewpoint of water pressure resistance and stability of aqueous dispersion. The average particle diameter refers to the average particle diameter of the particles measured by the dynamic light scattering method (DLS).

The organic microparticles maintain the particle shape on the substrate and exhibit water pressure resistance.

The exhibited water pressure resistance preferably refers to:

(i) When attached to the cloth, the water pressure resistance ratio is above 1.03; and/or

(ii) When attached to cloth, the air permeability ratio is 0.9 or less.

The water pressure resistance ratio (the water pressure resistance of the treated cloth with organic microparticles)/(the water pressure resistance of the untreated control cloth), the air permeability ratio (the air permeability of the treated cloth with organic microparticles)/(the control Air permeability of untreated cloth) ratio.

The water pressure resistance ratio may be 1.03 or more, 1.05 or more, 1.1 or more, 1.2 or more, or 1.3 to 3.0. Water pressure resistance is measured in accordance with JIS L 1092:2009 (Test method for water resistance of textile products). Specifically, the water pressure resistance of the treated cloth with organic fine particles is obtained by immersing a cloth such as PET cloth (basis weight: 88 g/m ² , 70 denier, gray) in a composition containing organic fine particles. After drying, it was passed through a rolling machine, and then passed through a pin tenter at 170° C. for 1 minute to prepare a PET cloth with organic fine particles adhered thereto. The water pressure resistance of the control untreated fabric is calculated for the untreated fabric, such as PET fabric (basis weight: 88g/m ² , 70 denier, gray). Untreated means that no organic fine particles have been applied, and the untreated cloth may be a cloth to which a binder resin has been applied. When an untreated cloth to which no binder resin was applied was used as a control, the water pressure resistance ratio may be 10 or more, further 12 or more and 100 or less.

The water pressure resistance is preferably higher than that of uncoated organic microparticles, and the water pressure resistance value is preferably increased by 3%, such as 5%, and further 10% compared with the water pressure resistance of the uncoated cloth.

The air permeability ratio may be 0.9 or less, 0.8 or less, or 0.7 to 0.3. Air permeability was measured in accordance with JIS P 8117:2009. Specifically, the air permeability when the organic fine particles are attached is obtained by impregnating, for example, PET cloth (basis weight: 88g/m ² , 70 denier, gray) in the composition containing the organic fine particles, passing it through a roller The press was passed through a pin tenter at 170° C. for 1 minute to prepare a PET cloth to which organic fine particles were attached. The air permeability of the control untreated fabric is determined for untreated PET fabric (basis weight: 88 g/m ² , 70 denier, gray). Untreated means that no organic fine particles have been applied, and the untreated cloth may be a cloth to which a binder resin has been applied. Also, depending on the purpose of use of the cloth, it may not be required to have the same air permeability as the untreated cloth, and in this case, the air permeability ratio may be out of the above range. For example, air permeability may not be required in furniture applications such as shade cloths and sofas.

The water repellency exhibited refers to:

(i) When attached to the cloth, the contact angle of water is greater than 120 degrees; or

(ii) When attached to the cloth, the falling speed is 100mm/s or more; or

(iii) When attached to cloth, the water repellency test of the cloth is 80 points or more.

The contact angle of water (the contact angle of water on the cloth attached with organic fine particles or the contact angle of water on the cloth attached with organic fine particles and binder (and other components) Angle) is preferably at least 120 degrees, more preferably at least 130 degrees, and more preferably at least 140 degrees. Specifically, the contact angle of water on the cloth was determined by the following method: After immersing PET cloth (basis weight: 88g/m ² , 70 denier, gray) in a composition containing organic fine particles, by Put it into the rolling machine, pass it into the pin tenter at 170°C for 1 minute, prepare the PET cloth with organic particles attached, and drop 2 μL of water on the PET cloth, use a fully automatic contact goniometer (Concord Interface Science DropMaster 701) was used to measure the static contact angle after 1 second of dropping.

In the cloth (PET cloth), the falling speed of water is 100 mm/s or more, for example, 130 mm/s or more, more preferably 150 mm/s or more or 200 mm/s or more. The falling speed is the average falling speed at which 20 μL of water is dripped from a microsyringe to a substrate inclined at 30 degrees and rolled down a distance of about 40 mm. Specifically, PET cloth (basis weight: 88g/m ² , 70 denier, gray) is impregnated with a composition containing organic microparticles, passed through a rolling machine, and passed through a pin tenter at 170°C for 1 minute , Prepare a PET cloth with organic fine particles, and use a fully automatic contact goniometer (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.), drop 20 μL of water from a microsyringe to the PET cloth inclined at 30 degrees, and use a high-speed camera (VW manufactured by KEYENCE Co., Ltd.) -9000) Measure the rolling state of the dropped water, and use the average falling speed at a distance of about 40 mm as the falling speed.

The water repellency test is preferably 80 points or more or 90 points or more.

The water repellency test was carried out in accordance with the spraying method of JIS-L-1092 (AATCC-22). The details of the water repellency test are described in the Examples of the present specification.

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

In some aspects, the organic microparticles comprise a polymer having a repeating unit formed from (I) below and further having or not having a repeating unit formed from (II):

(1) Hydrophobic monomers having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group with 3 to 40 carbons;

(II) A crosslinkable monomer having at least two ethylenically unsaturated double bonds.

In some aspects, the organic microparticles further comprise a polymer having repeating units formed by the following (III) and/or (IV):

(III) Reactive and hydrophilic monomers having 1 ethylenically unsaturated double bond and at least 1 reactive group and/or hydrophilic group, or having 1 ethylenically unsaturated double bond and at least 1 carbon Monomers containing short-chain hydrocarbon groups with a hydrocarbon group of 1 or 2;

(IV) A (meth)acrylic monomer having a straight-chain hydrocarbon group or a polydimethylsiloxane group having 3 to 40 carbon atoms.

Monomers (I) to (IV) (and other monomers (V)) may each have two or more kinds of monomers.

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

(I) Hydrophobic monomer

The hydrophobic monomer (I) has at least one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbons.

The hydrophobic monomer (I) preferably has a branched hydrocarbon group (for example, a branched alkyl group), especially a tertiary butyl group, an isopropyl group or a multi-branched structure represented by the following formula:

The hydrophobic monomer (I) is preferably an acrylate compound, an acrylamide compound or a styrene compound containing a branched or cyclic hydrocarbon group having 3 to 40 carbon atoms. That is, the hydrophobic monomer (I) is preferably an acrylate compound containing a branched or cyclic hydrocarbon group with a carbon number of 3 to 40, an acrylamide compound containing a branched or cyclic hydrocarbon group with a carbon number of 3 to 40, Styrenic compounds containing branched or cyclic hydrocarbon groups (except benzene ring) with 3 to 40 carbon atoms. The hydrophobic monomer (I) is preferably a non-fluorine monomer.

The hydrophobic monomer (I) is preferably a monomer represented by the following formula:

CH ₂ =C(-R ¹² )-C(=O)-Y ¹¹ (R ¹¹ ) _k

or

CH ₂ =C(-R ¹⁴ )-Y ¹² (H) _5-l (R ¹³ ) _l

[wherein, R ¹¹ and R ¹³ are independently branched or cyclic hydrocarbon groups with 3 to 40 carbons,

R ¹² and R ¹⁴ are hydrogen atoms, monovalent organic groups or halogen atoms,

Y ¹¹ is -O- or -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons), or a divalent to tetravalent one having at least one group selected from -O- or -NR'- link base,

Y ¹² is a benzene ring,

H is a hydrogen atom,

H and R ¹³ are respectively directly bonded to Y ¹² ,

k is 1 to 3, l is 1 to 5].

R ¹¹ and R ¹³ are branched or cyclic hydrocarbon groups. The branched hydrocarbon group (for example, having 3 to 11 carbons (especially 3 to 8 or 4 to 6) or 12 to 30 carbons) is preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group. The cyclic hydrocarbon group may be an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group. The surface free energy of the -CH ₃ group is lower than that of -CH ₂ - and easily exhibits water repellency. Therefore, it is preferably a structure with many branches and many _-CH3 groups. In the branched hydrocarbon group, the number of —CH ₃ groups is 2 to 15, for example, 3 to 10, 3 to 9, 4 to 8 or 4 to 6.

A branched hydrocarbon group (for example, a branched alkyl group) is an alkyl group with 3 or 4 carbons, especially a tertiary butyl group, an isopropyl group or a multi-branched hydrocarbon group (especially an alkyl group) with a carbon number of 5 to 30, For example, it can be the base of the multi-branch structure shown in the following formula:

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

Specific examples of the cyclic hydrocarbon group are cyclohexyl, cyclopentyl, cyclobutyl, dicyclopentyl, dicyclopentenyl, adamantyl, isobornyl, naphthyl, bornyl, tricyclodecanyl , phenyl, biphenyl, biterphenyl.

R ¹² and R ¹⁴ may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a -CF ₃ group. Examples of R ¹² and R ¹⁴ may be a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group. R ¹² and R ¹⁴ are preferably a hydrogen atom, a methyl group or a chlorine atom. R ¹² is more preferably methyl. Higher water pressure resistance can be obtained by making R ¹² a methyl group. Especially from the viewpoint of reactivity, R ¹⁴ is preferably a hydrogen atom.

Y ¹¹ is preferably a divalent group. Y ¹¹ is preferably -O- or -NH-.

Y ¹² is a benzene ring. The monomeric system with Y ¹² has a styryl group. In the monomer having ^Y12 , 1 to 3 ^R13 groups and 2 to 4 hydrogen atoms are bonded to the benzene ring.

k is preferably 1.

l can be 1 to 3, preferably 1 or 2.

The hydrophobic monomer can be a combination of a monomer with a branched hydrocarbon group and a monomer with a cyclic hydrocarbon group, or a monomer with a monocyclic cyclic hydrocarbon group and a monomer with a polycyclic or bridged cyclic hydrocarbon group The combination. Among the hydrophobic monomers, the weight ratio of monomers with branched hydrocarbon groups to monomers with cyclic hydrocarbon groups, and monomers with monocyclic cyclic hydrocarbon groups and monomers with polycyclic or bridged cyclic hydrocarbon groups The weight ratio can be 10/90 to 90/10, 30/70 to 70/30 or 40/60 to 60/40.

Specific examples of the hydrophobic monomer (I) are as follows. The compound of the following chemical formula is an acrylic compound with a hydrogen atom at the α position, and specific examples can be a methacrylic acid compound with a methyl group at the α position and an chloroacrylic acid compound with a chlorine atom at the α position, preferably a methyl group at the α position of methacrylic acid compounds. Among the styrene derivatives, the compound of the following chemical formula is an acrylic compound with a hydrogen atom at the α position, and specific examples can be α methyl styrene compounds with a methyl group at the α position and α chlorostyrene with a chlorine atom at the α position compound, preferably a styrene compound with a hydrogen atom at the alpha position.

[wherein, tBu is the third butyl group]

Specific examples of monomers having a cyclic hydrocarbon group include: cyclobutyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Cycloheptyl methacrylate, cyclooctyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate base) dicyclopentyl acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclopentyl (meth)acrylate, adamantane (meth)acrylate ester, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, etc.

Preferred specific examples of the hydrophobic monomer (I) are tertiary butyl (meth)acrylate, tertiary butylstyrene, methylstyrene, styrene, isopropyl (meth)acrylate, 2,6 ,8-trimethylnonan-4-yl=acrylate, 2,4-di-tert-butylstyrene, 2,4,6-trimethylstyrene, (meth)cyclobutyl acrylate, ( Cyclopropyl methacrylate, Cyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate, Cycloheptyl (meth)acrylate, Cyclooctyl (meth)acrylate, Iso(meth)acrylate Camphenyl, 4-tert-butylphenyl (meth)acrylate, 2,3,4-methylphenyl (meth)acrylate.

More preferable specific examples of the hydrophobic monomer (I) are tertiary butyl (meth)acrylate, isobornyl methacrylate, cyclohexyl methacrylate, tertiary butylstyrene, (meth)acrylic acid ring Pentyl ester, cycloheptyl (meth)acrylate, adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate.

The hydrophobic monomer (I) may be a high glass transition point monomer (high Tg monomer). When the organic microparticles do not contain the crosslinkable monomer (II), the hydrophobic monomer (I) is preferably a high Tg monomer. A high Tg monomer system refers to a monomer whose homopolymer Tg is above 50°C. Among the monomers (I), the glass transition point of the high Tg monomer (I-a) 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). It can be obtained as the following temperature: raise the temperature of 10 mg of the sample at 10°C/min to obtain the DSC curve, the intersection point of the extension line of each baseline before and after the second transition of the DSC curve and the tangent line of the inflection point of the DSC curve The temperature displayed at the middle point. In the organic microparticles, as the hydrophobic monomer, there may be only one kind of monomer, or two or more kinds, and each independently has a high Tg hydrophobic monomer (I-a) and/or a non-high Tg hydrophobic monomer. Monomer (I).

The high glass transition point monomer can be a monomer represented by the following formula:

or

[wherein, R ²¹ and R ²³ are selected from a hydrocarbon group with 1 to 30 carbons, -C ₆ H ₄ -, -O- or -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons) The base formed by at least one of them,

R ²² and R ²⁴ are hydrogen atoms, monovalent organic groups or halogen atoms,

Y ²¹ is -O- or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbons)].

Examples of R ²¹ and R ²³ are cyclohexyl, dicyclopentyl, dicyclopentenyl, adamantyl, isobornyl, naphthyl, camphenyl, tricyclodecanyl, phenyl.

R ²² and R ²⁴ 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, or a -CF ₃ group. Examples of ^R22 and ^R24 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 ²² and R ²⁴ are preferably a hydrogen atom, a methyl group, or a chlorine atom. R ²² is more preferably methyl. By making ^R22 a methyl group, higher water repellency and high water pressure resistance can be obtained. On the other hand, especially from the viewpoint of reactivity, R ²⁴ is preferably a hydrogen atom, and from the viewpoint of water repellency and water pressure resistance, R ²⁴ is preferably a methyl group, and it is preferable to have both its reactivity The way to choose R ²⁴ is water repellency.

Y ²¹ is preferably -O- or -NH-.

Specific examples of high glass transition point monomers are cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, camphenyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid Dicyclopentyl, Dicyclopentenyl (meth)acrylate, Tricyclodecanyl (meth)acrylate, Phenyl (meth)acrylate, Naphthyl (meth)acrylate, Benzyl (meth)acrylate , 2-tert-butylphenyl (meth)acrylate, acrylates such as naphthyl (meth)acrylate, styrene, α-methylstyrene, styrene derivatives, etc.

(II) Cross-linking monomer

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

The cross-linking monomer (II) is preferably a monomer represented by the following formula:

or

[In the formula, R ³¹ and R ³³ are each independently a direct bond, or a hydrocarbon group selected from a carbon number of 1 to 20 (can also include a hydrocarbon site with an -OH group), -(CH ₂ CH ₂ O ) _r - (r is an integer from 1 to 10), -C ₆ H ₄ -, -O-, or -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons) composed of 2 to the base of 4 valences,

R ³² , R ³⁴ , R ³⁵ and R ³⁶ are each independently a hydrogen atom, a monovalent organic group or a halogen atom,

Y ³¹ is -O- or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbons),

p is 2 to 4,

q is 1 to 5].

Examples of R ³¹ and R ³³ are direct bonds, 2 to 4 valent (for example, 2 to 3 valent) carbon numbers 1 to 20 (or 2 to 10) that can be interrupted by oxygen atoms and/or hydrogen atoms can be replaced by OH groups. of) hydrocarbon group, ethylene glycol group, propylene glycol group, glyceryl group, cyclohexyl group, dicyclopentyl group, adamantyl group, isocamphoryl group, naphthyl group, camphoryl group, tricyclodecanyl group and phenyl group, or include these The base of any of the bases. R ³¹ and R ³³ may be a polymer group, and the constituent units constituting the polymer group may be the groups exemplified above (for example, ethylene glycol group). R ³¹ and R ³³ are preferably divalent groups.

Y ³¹ is preferably -O- or -NH-.

R ³² , R ³⁴ , R ³⁵ and R ³⁶ may each independently be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Or it may be a -CF ₃ group. Examples of R ³² , R ³⁴ , R ³⁵ and R ³⁶ are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, fluorine atom, -CF ₃ group, and cyano group. R ³² , R ³⁴ , R ³⁵ and R ³⁶ are preferably a hydrogen atom, a methyl group or a chlorine atom. R ³² is more preferably methyl. By making ^R32 a methyl group, higher water repellency and high water pressure resistance can be obtained. Especially from the viewpoint of reactivity, R ³⁴ , R ³⁵ and R ³⁶ are preferably hydrogen atoms.

p is 2 or 3, especially can be 2.

q is 1 to 3, especially 1 is possible.

Specific examples of the crosslinkable monomer (II) are divinylbenzene, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9- Nonanediol Di(meth)acrylate, Neopentyl Glycol Di(meth)acrylate, Polyethylene Glycol Di(meth)acrylate, Triethylene Glycol Di(meth)acrylate, Ethylene Glycol Di(meth)acrylate, Methylene glycol di(meth)acrylate, Polytetramethylene glycol di(meth)acrylate, Dihydroxymethyltricyclodecane di(meth)acrylate, Trihydroxymethylpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glyceryl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, di(meth)acrylate ) Dicyclopentyl acrylate, 5-hydroxy-1,3-adamantane di(meth)acrylate.

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

(III) Reactive, hydrophilic monomers or monomers containing short-chain hydrocarbon groups

The reactive and hydrophilic monomer (III) has one ethylenically unsaturated double bond and at least one reactive group and/or hydrophilic group. The short-chain hydrocarbon group-containing monomer (III) has one ethylenically unsaturated double bond and at least one hydrocarbon group having 1 or 2 carbon atoms.

Examples of reactive groups are epoxy (eg, glycidyl), chloromethyl, bromomethyl, iodomethyl, blocked isocyanate groups.

Examples of hydrophilic groups are hydroxyl group, amino group (including H bonded to N converted to methyl, ethyl, propyl or butyl), carboxylic acid group, sulfonic acid group, phosphoric acid group, carboxylic acid, sulfonic acid , alkali metal or alkaline earth metal base of phosphoric acid, ammonium base with chlorine, bromine or iodide ion as the relative anion, ethylene glycol base, polyethylene glycol base, base with acetone skeleton (-C(=O)-CH ₃ ).

The reactive and hydrophilic monomer (III) also includes compounds having not only the above-mentioned reactive group and hydrophilic group but also a group capable of imparting higher hydrophilicity than the hydrophobic monomer (I). The reactive, hydrophilic monomer (III) has more octanol/water partitioning into water than the hydrophobic monomer (I) Coefficients also include those that do not contain the above-mentioned reactive groups and hydrophilic groups. Examples thereof include (meth)acrylamide having a short-chain hydrocarbon group having 6 or less carbon atoms in the side chain. Specifically, methyl(meth)acrylamide, ethyl(meth)acrylamide, n-butyl(meth)acrylamide, tert-butyl(meth)acrylamide, propyl(methyl)acrylamide ) acrylamide, isopropyl (meth)acrylamide.

The reactive, hydrophilic monomer (III) is preferably a non-fluorine monomer.

Reactive, hydrophilic monomer (III) is preferably a monomer represented by the following formula:

CH ₂ =C(-R ⁴² )-C(=O)-Y ⁴¹ -(R ⁴³ ) _o (R ⁴¹ ) _t

or

CH ₂ =C(-R ⁴⁵ )-Y ⁴² -(H) _5-u (R ⁴⁴ ) _u

[wherein, R ⁴¹ and R ⁴⁴ are each independently a reactive group or a hydrophilic group,

R ⁴² and R ⁴⁵ are hydrogen atoms, monovalent organic groups or halogen atoms,

Y ⁴¹ is a direct bond, -O- or -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons),

R ⁴³ is a direct bond, -O-, or a hydrocarbon group having 2 to 4 valent carbon numbers of 1 to 10 (which may contain a hydrocarbon site with an -OH group),

Y ⁴² is a benzene ring,

H is a hydrogen atom,

H and R ⁴⁴ are respectively directly bonded to Y ⁴² ,

t and u are 1 to 3,

o is 0 or 1].

The monomer (III) containing a short-chain hydrocarbon group is preferably a monomer represented by the following formula:

CH ₂ =C(-R ⁴⁷ )-C(=O)-Y ⁴³ -R ⁴⁶

[wherein, R ⁴⁶ is a hydrocarbon group with 1 or 2 carbons,

R ⁴⁷ is a hydrogen atom, a monovalent organic group or a halogen atom,

Y ⁴³ is a direct bond, -O- or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbons)].

R ⁴¹ and R ⁴⁴ are monovalent groups. In R ⁴¹ and R ⁴⁴ , examples of reactive groups or hydrophilic groups are as described above (epoxy groups, etc., or hydroxyl groups, etc.).

R ⁴⁶ is a hydrocarbon group having 1 or 2 carbon atoms, such as methyl and ethyl. Methyl is preferred.

R ⁴² , R ⁴⁵ and R ⁴⁷ may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Or it may be a -CF ₃ group. Examples of R ⁴² , R ⁴⁵ and R ⁴⁷ are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, fluorine atom, -CF ₃ group, and cyano group. R ⁴² , R ⁴⁵ and R ⁴⁷ are preferably a hydrogen atom, a methyl group, or a chlorine atom. R ⁴² and R ⁴⁷ are more preferably methyl. By making R ⁴² and R ⁴⁷ methyl, higher water repellency and high water pressure resistance can be obtained. Especially from the viewpoint of reactivity, R ⁴⁵ is preferably a hydrogen atom.

Y ⁴¹ and Y ⁴³ are preferably -O- or -NH-.

R ⁴³ is preferably a 2 to 4 valent hydrocarbon group with 1 to 10 carbon atoms (may include a hydrocarbon site having an -OH group). Examples of the 2- to 4-valent C1 hydrocarbon group are -CH ₂ -, -CH= having a branched structure, and -C≡ having a branched structure. R ⁴³ is a divalent alkylene group, such as -(CH ₂ ) _r - (r is a number from 1 to 5) or a divalent or trivalent or quadrivalent alkyl group, such as preferably -(CH ₂ ) _r -(CH-) _s -H (r is a number from 1 to 5, s is 1, 2 or 3; the positions of the CH ₂ group and the CH- group may not follow the order of the record). More preferred is a divalent alkylene group (for example, having 1 to 4 carbon atoms).

^Y42 is a benzene ring. Monosystems with Y ⁴² have styryl groups. In the monomer having Y ⁴² , 1 to 3 R ⁴⁴ groups and 2 to 4 hydrogen atoms are bonded to the benzene ring.

o is preferably 1.

t is preferably 1.

u can be 1 to 3, preferably 1 or 2.

Specific examples of reactive and hydrophilic monomers (III) are glycidyl (meth)acrylate, glyceryl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-Hydroxypropyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, 2,3-Dihydroxy(meth)acrylate Propyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate Butyl ester, 2-acetylacetyloxyethyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, (meth)acrylate Base) 2-(trimethylsilyloxy)ethyl acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(tertiary butylamino)ethyl (meth)acrylate , Dimethylaminoethyl (meth)acrylate quaternary compound, methyl tetrahydrofurfuryl (meth)acrylate, polyethylene glycol (meth)acrylate, diacetone (meth)acrylamide, isopropyl (meth)acrylamide, tert-butyl(meth)acrylamide, ethyl(meth)acrylamide, methyl(meth)acrylamide; and

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

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

(IV) (meth)acrylic acid monomer

The (meth)acrylic monomer (IV) has a straight-chain hydrocarbon group or a polydimethylsiloxane group having 3 to 40 carbon atoms.

The (meth)acrylic monomer (IV) may be a (meth)acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms.

The (meth)acrylic monomer (IV) is preferably a monomer represented by the following formula:

CH ₂ =C(-R ⁵² )-C(=O)-Y ⁵¹ (R ⁵¹ ) _s

[wherein, R ⁵¹ are each independently a linear hydrocarbon group with 3 to 40 carbons,

R ⁵² is a hydrogen atom, a monovalent organic group or a halogen atom,

Y ⁵¹ is a hydrocarbon group selected from 2 to 4 valent carbon number 1 (especially -CH ₂ -, -CH= and -C≡), -C ₆ H ₄ -, -O-, -C(=O) -, -S(=O) ₂ - or -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons) composed of 2 to 4 valent groups (but excluding only divalent hydrocarbon groups) situation),

s is 1 to 3].

R ⁵¹ is a linear hydrocarbon group. The carbon number of R ⁵¹ is preferably 12-24 or 16-22. Specific examples of ^R51 are n-lauryl, n-stearyl, and n-behenyl.

s is 1, 2 or 3. s is preferably 1 or 2.

s is 1, 2 or 3. Among them, when Y ⁵¹ has a tetravalent hydrocarbon group having 1 carbon number (specifically, -C≡ having a branched structure), s=3. When Y ⁵¹ has a trivalent hydrocarbon group having 1 carbon number (such as -CH= having a branched structure), s=2. When Y ⁵¹ does not have a trivalent or tetravalent C1 hydrocarbon group (for example, when ^Y51 has (for example, 1 to 6) divalent C1 hydrocarbon groups ( _-CH2- )), s=1.

R ⁵² may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a -CF ₃ group. Examples of R ⁵² may be a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group. R ⁵² is preferably a hydrogen atom, a methyl group or a chlorine atom. R ⁵² is more preferably methyl. By making R ⁵² a methyl group, higher water pressure resistance can be obtained.

Y ⁵¹ is a divalent group or a trivalent group, particularly preferably a divalent group.

Examples of the 2- to 4-valent C1 hydrocarbon group are -CH ₂ -, -CH= having a branched structure, and -C≡ having a branched structure.

When Y ⁵¹ is a divalent group, it may or may not have -CH ₂ -. When Y ⁵¹ is a trivalent group, it preferably has -CH= which is a branched structure, and the most preferred system has -CH ₂ -(-H(C-)-)-CH ₂ -, that is,

Y ⁵¹ can be -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y '-, -Y'-X'-, -Y'-X'-Y'-, -Y'-X'-Y'-C(=O)-, -Y'-X'-C(=O )-Y'-, -Y'-X'-Y'-C(=O)-Y'- or -Y'-X'-Y'-X'-

[wherein, Y' are independently direct bond, -O-, -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons) or -S(=O) ₂ -,

X' can be -(CH ₂ ) _m -(m is an integer from 1 to 5), a straight-chain hydrocarbon group with 1 to 5 carbons, or a branched hydrocarbon group with 1 to 5 or 3 to 5 carbons. The hydrocarbon group of the structure or -(CH ₂ ) _l -C ₆ H ₄ -(CH ₂ ) _l -(l is independently an integer from 0 to 5, and -C ₆ H ₄ - is a phenylene group)].

The hydrocarbon group having a branched structure having 3 to 5 carbon atoms may be divalent, trivalent or tetravalent. Specific examples of hydrocarbon groups having a branched structure with carbon numbers of 3 to 5 are:

-CH(CH ₃ )-CH ₂ -(2 valent),

(2價)、

(2 prices),

-CH ₂ -(-H(C-)-)-CH ₂ -(trivalent),

that is,

Specific examples of Y ⁵¹ belonging to a divalent group are -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=O)-NH-, -NH- C(=O)-O-, -NH-C(=O)-NH-, -OC ₆ H ₄ -, -NH-C ₆ H ₄ -, -O-(CH ₂ ) _m -O-, - NH-(CH ₂ ) _m -NH-, -O-(CH ₂ ) _m -NH-, -NH-(CH ₂ ) _m -O-, -O-(CH ₂ ) _m -OC(=O)- , -O-(CH ₂ ) _m -C(=O)-O-, -NH-(CH ₂ ) _m -OC(=O)-, -NH-(CH ₂ ) _m -C(=O)- O-, -O-(CH ₂ ) _m -OC(=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-O-, -O-(CH ₂ ) _m - C(=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-, -O-(CH ₂ ) _m -NH-C(=O)-NH-, -O- (CH ₂ ) _m -OC ₆ H ₄ -, -O-(CH ₂ ) _m -NH-S(=O) ₂ -, -O-(CH ₂ ) _m -S(=O) ₂ -NH-, -NH-(CH ₂ ) _m -NH-S(=O) ₂ -, -NH-(CH ₂ ) _m -S(=O) ₂ -NH-, -NH-(CH ₂ ) _m -OC(= O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-O-, -NH-(CH ₂ ) _m -C(=O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-, -NH-(CH ₂ ) _m -NH-C(=O)- NH-, -NH-(CH ₂ ) _m -OC ₆ H ₄ -or -NH- (CH ₂ ) _m -NH-C ₆ H ₄ -[wherein m is an integer of 1 to 5, especially 2 or 4].

Y ⁵¹ which is a divalent group is preferably -O-, -NH-, -O-(CH ₂ ) _m -OC(=O)-, -O-(CH ₂ ) _m -NH-C(=O) -, -O-(CH ₂ ) _m -OC(=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-O-, -O-(CH ₂ ) _m -NH -C(=O)-NH-, -O-(CH ₂ ) _m -NH-S(=O) ₂ -or -O-(CH ₂ ) _m -S(=O) ₂ -NH-, -NH -(CH ₂ ) _m -OC(=O)-, -NH-(CH ₂ ) _m -NH-C(=O)-, -NH-(CH ₂ ) _m -OC(=O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-O-, -NH-(CH ₂ ) _m -NH-C(=O)-NH-

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

Y ⁵¹ which is a divalent group is more preferably -O-, -O-(CH ₂ ) _m -OC(=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-O -or-O-(CH ₂ ) _m -NH-C(=O)-, -O-(CH ₂ ) _m -NH-S(=O) ₂ -or-O-(CH ₂ ) _m -S( =O) ₂ -NH-, especially -O-(CH ₂ ) _m -NH-C(=O)-

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

Y ⁵¹ is especially preferably -O-.

Y ⁵¹ belonging to a trivalent group is preferably:

Specific examples of the (meth)acrylic monomer (IV) having a straight-chain hydrocarbon group having 3 to 40 carbon atoms are as follows.

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

Preferable specific examples of (meth)acrylic monomers having a straight-chain hydrocarbon group having 3 to 40 carbons are n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, and n-lauryl (meth)acrylate. Behenyl ester, stearylamide ethyl (meth)acrylate, n-lauryl (meth)acrylamide, n-stearyl (meth)acrylamide, n-behenyl (meth)acrylamide base) acrylamide, CH ₂ =CHC(=O)OC ₂ H ₄ NHSO ₂ C ₁₈ H ₃₇ , CH ₂ =CHC(=O)OC ₂ H ₄ NHC(=O)C ₁₇ H ₃₅ , CH ₂ = CHC(=O)OC ₂ H ₄ NHC(=O)OC ₁₈ H ₃₇ , CH ₂ =CHC(=O)OC ₂ H ₄ OC(=O)NHC ₁₈ H ₃₇ , CH ₂ =CHC(=O)OC ₂ H ₄ NHC(=O)NHC ₁₈ H ₃₇ . The above structural formula shows acrylic acid and acrylamide with a hydrogen at the α position, but also includes methacrylic acid and methacrylamide with a methyl group at the α position.

The (meth)acrylic monomer (IV) may be a (meth)acrylic monomer having a polydimethylsiloxane group.

The (meth)acrylic monomer (IV) may have a polydimethylsiloxane group in the side chain.

(Meth)acrylic acid monomer (IV), preferably a monomer represented by the following formula:

CH ₂ =C(-R ⁶² )-C(=O)-Y ⁶¹ -R ⁶¹

[wherein, ^R61 is a group with a polydimethylsiloxane group,

^R62 is a hydrogen atom, a monovalent organic group or a halogen atom,

Y ⁶¹ is a hydrocarbon group selected from 2 to 4 valent carbon number 1, -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ - or -NR'-( R' is a 2 to 4 valent group formed by at least one of H or a hydrocarbon group having 1 to 4 carbons].

^R61 is a group having a polydimethylsiloxane group, preferably a group represented by the following average formula:

-(SiR ₂ O) _a SiR ₃

[wherein, a is 2 to 4000, such as 3 to 400,

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

R ⁶² is preferably a hydrogen atom, a methyl group or a chlorine atom.

Y ⁶¹ is preferably a hydrocarbon group with 1 to 8 carbons (for example, an alkylene group with 1 to 8 or 2 to 4 carbons, especially -C ₃ H ₆ -), -O-(CH ₂ ) _p -, - O-(CH ₂ ) _p -NHC(=O)-(CH ₂ ) _q - or -NH-(CH ₂ ) _q - (p is a number from 1 to 5, and q is a number from 1 to 5).

Specific examples of the (meth)acrylic monomer (IV) having a polydimethylsiloxane group are:

[wherein, n is a number from 1 to 500].

(V) Other monomers

Other monomers (V) other than monomers (I) to (IV) can also be used.

Examples of other monomers (V) include, for example, ethylene, vinyl acetate, acrylonitrile, vinyl chloride, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (Meth)acrylates and vinyl alkyl ethers. Other monomers are not limited to these examples. Other monomers (V) are preferably non-fluorine monomers.

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

Monomers (I) to (V) may each be independent of 1 type, or may be a mixture of 2 or more types.

In the present disclosure, preferred combinations of monomers in the polymer are as follows.

Monomer (I) + Monomer (II)

Monomer (I) + Monomer (III)

Monomer (I) + Monomer (II) + Monomer (III)

Monomer (I) + Monomer (II) + Monomer (IV)

Monomer (I) + Monomer (III) + Monomer (IV)

Monomer (I) + Monomer (II) + Monomer (III) + Monomer (IV)

Particularly preferred combinations are as follows.

Monomer (I) + Monomer (III)

Monomer (I) + Monomer (II) + Monomer (III)

Monomer (I) + Monomer (II) + Monomer (IV)

Monomer (I) + Monomer (II) + Monomer (III) + Monomer (IV)

Each of the above-mentioned monomers may be only one type, or two or more types. For example, a combination of two monomers (I) and one monomer (II) and one monomer (III) may be used.

In the polymer, the amount of the hydrophobic monomer (I) may be 40 to 100% by weight, 50 to 99% by weight, 55 to 98% by weight, or 58 to 97% by weight relative to the polymer.

In the polymer, the molar ratio of hydrophobic monomer (I)/reactive, hydrophilic monomer and/or monomer (III) containing short-chain hydrocarbon group can be 50/50 to 100/0, 80/20 to 99.5/0.5, 85/15 to 98/2 or 90/10 to 99/1, or 40/60 to 90/10, 55/45 to 85/15, 58/42 to 80/20 or 60/40 to 78 /twenty two.

The amount of the cross-linking monomer (II) can be 0 to 30 Molar, 0.5 to 25 Molar or 1 to 20 Molar or 0 to 15 Molar, 0.2 to 10 Molar or 0.5 to 5 Molar.

The amount of (meth)acrylic monomer (IV) can be 0 to 60 Molar, 0.5 to 40 Molar, 1 to 30 Molar, or 1 to 20 Molar.

The amount of other monomers (V) may be 0 to 30 moles, 0.5 to 25 moles, 1 to 20 moles, or 1 to 10 moles relative to a total of 100 moles.

or 100 moles relative to the polymer,

The hydrophobic monomer (I) may be 40 to 99.5 moles, 50 to 99 moles, or 60 to 99 moles,

The crosslinking monomer (II) may be 0 to 30 moles, 0.5 to 25 moles, or 1 to 20 moles, or 0 to 10 moles, 0.2 to 6 moles, or 0.5 to 4 moles,

Reactive, hydrophilic monomers and/or monomers (III) containing short chain hydrocarbon groups can be 0 to 50 moles, 0.5 to 40 moles or 1 to 20 moles or 0 to 15 moles, 0.2 to 10 moles ear or 0.5 to 5 moles,

The (meth)acrylic monomer (IV) may be 0 to 50 mol, 1 to 40 mol, or 1 to 30 mol, or 0 to 15 mol, 0.2 to 10 mol, or 0.5 to 5 mol.

When there is no monomer (II), among the monomers (I), the high Tg monomer (I-a) may be 1 to 80 moles, 2 to 70 moles, or 5 to 60 moles.

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

With respect to the water pressure raising agent composition, the amount of organic microparticles (A) may be 50% by weight or less, such as 0.01 to 40% by weight, especially 0.05 to 30% by weight or 0.1 to 20% by weight.

(B) Aqueous medium

The water pressure increasing agent composition (or 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 a polymer is dispersed in an aqueous medium (water, or a mixture of water and an organic solvent).

The aqueous medium can be water alone, or it can be a mixture of water and a (water-miscible) organic vehicle. The amount of the organic solvent may be 30% by weight or less, such as 10% by weight or less, relative to the liquid medium. The aqueous medium is preferably water alone.

When the total of the water-repellent polymer and the aqueous medium is 100 parts by weight, the amount of the aqueous medium may be 50 to 99.5 parts by weight, particularly 70 to 99.5 parts by weight.

(C) Binder resin

The binder resin functions as a binder that binds the organic fine particles to the substrate. The binder resin is preferably a water-repellent resin. The water-repellent resin also functions as an active ingredient for exhibiting water-repellency. Examples of binder resins are acrylic polymers, urethane polymers, polyolefins, polyesters, polyethers, polyamides, polyimides, polystyrene, silicone polymers.

The water-repellent resin is a non-fluoropolymer having a hydrocarbon group having 3 to 40 carbons in the side chain, or a fluoropolymer having a fluoroalkyl group having 1 to 20 carbons in the side chain. The water-repellent resin is preferably a non-fluoropolymer.

In the non-fluoropolymer having a hydrocarbon group having 3 to 40 carbons, the hydrocarbon group is preferably a branched hydrocarbon group or a long-chain (or long-chain linear) hydrocarbon group.

Examples of water-repellent resins are urethane polymers, silicone polymers, acrylic polymers, polystyrene.

Examples of non-fluoropolymers are amidoamine dendrimers with long chain hydrocarbon groups, which are described in US Pat. No. 8,703,894. The disclosure of this document is referred to in this specification.

The urethane polymer having a hydrocarbon group with a carbon number of 3 to 40 in the side chain, for example, can be obtained by combining an isocyanate group-containing compound (for example, a monoisocyanate or a polyisocyanate, specifically a diisocyanate or a triisocyanate) with a carbon number It is produced by reacting hydroxyl-containing compounds with hydrocarbon groups of 3 to 40.

Polyurethane with branched structures such as tertiary butyl, isopropyl, and 2,6,8-trimethylnonan-4-yl in the side chain can be obtained by, for example, making a compound containing an isocyanate group (such as Monoisocyanate or polyisocyanate, specifically diisocyanate or triisocyanate) reacts with hydroxyl-containing compounds having branched structures such as tertiary butyl, isopropyl, 2,6,8-trimethylnonan-4-yl, etc. manufacture.

Examples of urethane polymers include: urethane compounds with long-chain hydrocarbon groups including sorbitan tristearate, sorbitan monostearate and polyfunctional isocyanates, which are described in U.S. Patent Publication 2014/0295724. The indication of this document is referred and is incorporated in this specification. An example of a urethane polymer is: polyurethane having a long-chain hydrocarbon group, which is described in Japanese National Publication No. 2019-519653 (International Publication No. 2018/007549). The indication of this document is referred and is incorporated in this specification.

The polysiloxane polymer having a hydrocarbon group having 3 to 40 carbon atoms in its side chain can be produced, for example, by reacting a dichlorosilane compound containing dichlorosilane having a hydrocarbon group having 3 to 40 carbon atoms.

Polysiloxanes with branched structures such as tertiary butyl, isopropyl, and 2,6,8-trimethylnonan-4-yl in the side chain can be obtained by, for example, including tertiary butyl, isopropyl It is produced by reacting dichlorosilane compounds with branched dichlorosilanes such as 2,6,8-trimethylnonan-4-yl.

Examples of silicone polymers are long chain alkyl modified polydimethylsiloxanes.

The acrylic polymer having a hydrocarbon group having 3 to 40 carbons in the side chain can be produced by polymerizing a monomer including an acrylic monomer having a hydrocarbon group having 3 to 40 carbons in the side chain. Examples of acrylic monomers are the same as those described for the above-mentioned hydrophobic monomer (IV). Specific examples of acrylic monomers are, for example:

Stearyl (meth)acrylate, Behenyl (meth)acrylate,

(especially stearylaminoethyl (meth)acrylate)

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

Acrylic polymers with branched structures such as tertiary butyl, isopropyl, and 2,6,8-trimethylnonan-4-yl in the side chain can be , isopropyl, 2,6,8-trimethylnonan-4-yl and other branched acrylic monomers are polymerized and produced. Examples of acrylic monomers are the same as those described above for the hydrophobic monomer (I). Specific examples of acrylic monomers include, for example, tert-butyl (meth)acrylate, isopropyl (meth)acrylate, and 2,6,8-trimethylnonan-4-yl=acrylate.

Examples of acrylic polymers include polymers comprising repeating units derived from acrylic monomers having long-chain hydrocarbon groups such as behenyl (meth)acrylate or stearyl (meth)acrylate and Repeating units derived from vinylidene chloride and/or vinyl chloride.

Examples of acrylic polymers include polymers containing the following repeating units: repeating units derived from acrylic monomers having long-chain hydrocarbon groups such as behenyl (meth)acrylate or stearyl (meth)acrylate, The repeating unit derived from vinylidene chloride and/or vinyl chloride and the repeating unit derived from styrene or α-methylstyrene can also be used in combination with the acrylic polymer and paraffin. This example is described in Japanese Patent Application Publication No. 2012-522062 (International Publication No. 2010/115496). The disclosure of this document is referred to and incorporated into this specification.

Examples of acrylic polymers include polymers containing the following repeating units: repeating units derived from acrylic monomers having long-chain hydrocarbon groups such as stearyl (meth)acrylate, vinylidene chloride and/or vinyl chloride The repeating unit and the repeating unit derived from reactive emulsifiers such as polyoxyalkylene ethers are described in Japanese Patent Laid-Open No. 2017-25440 (International Publication No. 2017/014131). The disclosure of this document is referred to and incorporated into this specification.

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

Examples of fluorine-containing water-repellent resins include fluorine-containing acrylic polymers containing (meth)acrylate and (meth)acrylic acid having a perfluoroalkyl group having 4 to 8 carbon atoms in the side chain. Repeating unit formed by long-chain alkyl (meth)acrylate such as behenyl or stearyl (meth)acrylate.

Other monomers can also be used in urethane polymers, silicone polymers, acrylic polymers, and polystyrenes that are not fluoropolymers and fluoropolymers.

Examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, vinyl chloride, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (methyl ) acrylate, methoxypolypropylene glycol (meth)acrylate, (meth)acrylate with polydimethylsiloxane in the side chain, and vinyl alkyl ether. Other monomers are not limited to these examples.

The weight ratio of binder resin (C)/organic microparticles (A) can be 1/99 to 99/1, 20/80 to 99/1 or 30/70 to 95/5, for example, it can be 55/45 to 90/ 10. Relative to the total weight of the binder resin (C) and the organic microparticles (A), the amount of the binder resin (C) is preferably 30 to 99% by weight, preferably 50 to 98% by weight, more preferably 60 to 97% by weight. weight%.

(D) Surfactant

The water-repellent composition may or may not contain a surfactant (emulsifier). In general, in order to stabilize the particles during polymerization and the water dispersion after polymerization, a small amount of surfactant (for example, 0.01 to 30 parts by weight relative to 100 parts by weight of the monomer) can be added during polymerization. , or a surfactant can also be added after polymerization.

When the object to be treated is a fiber product, the water-repellent composition preferably contains a nonionic surfactant as the surfactant. Furthermore, the surfactant preferably contains one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. Preferably, a combination of a nonionic surfactant and a cationic surfactant is used.

A nonionic surfactant, a cationic surfactant, and an amphoteric surfactant may each be 1 type or a combination of 2 or more types.

With respect to 100 parts by weight of the organic microparticles (A), the amount of the surfactant can be less than 30 parts by weight (for example, 0 to 15 parts by weight or 0.01 to 15 parts by weight), preferably less than 15 parts by weight (for example, 0.1 to 10 parts by weight). In general, when a surfactant is added, the stability of the aqueous dispersion and the permeability to cloth are improved, but the water-repellent performance is reduced. It is preferable to select the type and amount of the surfactant so that these effects can be achieved.

(E) Cross-linking agent

The cross-linking agent (E) is preferably one that cross-links when heated after treating the aqueous dispersion of organic fine particles on the cloth. Also, it is preferred that the crosslinking agent itself is also dispersed in water

A preferable example of the crosslinking agent (E) is a blocked isocyanate compound. The blocked isocyanate compound can be obtained by making [can be A(NCO) _m (wherein, A is the residue after removing the isocyanate group from polyisocyanate, m is an integer from 2 to 8)] isocyanate and [can be RH( In the formula, R can be produced by reacting a hydrocarbon group substituted by a heteroatom such as a nitrogen atom or an oxygen atom, and H is a hydrogen atom)] end-capping agent.

A(NCO) _m is, for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), or the like.

Examples of capping agents that form R groups are oximes, phenols, alcohols, thiols, amides, imides, imidazoles, ureas, amines, imines, pyrazoles and active methylene compounds.

The crosslinking agent (E) is preferably blocked isocyanate such as oxime blocked toluene diisocyanate, blocked hexamethylene diisocyanate, blocked diphenylmethane diisocyanate, or the like.

The amount of the crosslinking agent (E) can be 0 to 30 parts by weight or 0.01 to 20 parts by weight, for example, 0.1 to 18 parts by weight, relative to the total of 100 parts by weight of the organic microparticles (A) and the binder resin (C). .

(F) Additives

In addition to the organic microparticles (A) and the aqueous medium (B), as well as the binder resin (C), surfactant (D) and/or crosslinking agent (E) as required, the water repellant composition may also contain Additive (F).

Examples of additives are other water-repellent agents, oil-repellent agents, drying speed regulators, film-forming aids, compatibilizers, antifreeze agents, viscosity regulators, ultraviolet absorbers, antioxidants, pH regulators, defoamers, Texture modifiers, smoothness modifiers, antistatic agents, hydrophilic 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, eg 0.1 to 10 parts by weight, relative to 100 parts by weight of the total of the organic fine particles (A) and the binder resin (C).

Polymers (polymers constituting organic microparticles and polymers constituting binder resin) can be generally produced by any polymerization method, and the conditions of the polymerization reaction can also be selected arbitrarily. As such a polymerization method, solution polymerization, suspension polymerization, and emulsion polymerization are mentioned. Emulsion polymerization is preferred.

Organic fine particles are preferably produced by emulsion polymerization from the viewpoints of easiness of synthesis and stability of fine particles.

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

When the water-repellent composition contains organic microparticles and binder resin, the production of the aqueous dispersion of organic microparticles and the production of the aqueous dispersion of the binder resin are performed separately, and the aqueous dispersion of the organic microparticles and the aqueous dispersion of the binder resin are mixed. body, whereby a water-repellent composition comprising organic microparticles and a binder resin can be produced. Or polymerize the monomer for the binder resin in the aqueous dispersion of organic microparticles, thereby producing a water repellent set containing organic microparticles and the binder resin into things. In addition, a water repellent composition including organic fine particles and a binder resin can be produced by polymerizing a monomer for organic fine particles in an aqueous dispersion of a binder resin.

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

In the emulsion polymerization that uses surfactant and reactive emulsifier, it is preferable to add a small amount (less than 30 mole parts relative to 100 mole parts of the whole monomer, such as 0.1 to 20 mole parts) of monomer (I ) monomer or monomer (IV) in which the static contact angle of water of the homopolymer is 90 degrees or more. Thereby, high concentration polymerization becomes possible, and the water repellency of a polymer becomes high.

Examples of additional monomers are tertiary butylstyrene, stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl (meth)acrylamide, 2,6,8 -Trimethylnonan-4-yl=acrylate, 2,4-di-tert-butylstyrene, 2,4,6-trimethylstyrene, stearamidoethyl (meth)acrylate , CH ₂ =CHC(=O)OC ₂ H ₄ NHSO ₂ C ₁₈ H ₃₇ , 4-tert-butylphenyl (meth)acrylate, 2,3,4-methylphenyl (meth)acrylate, Cyclohexyl (meth)acrylate, Isocamyl (meth)acrylate and

(meth)acrylic monomers with polydimethylsiloxane groups,

Monomer represented by CH ₂ =C(-R ⁶² )-C(=O)-Y ⁶¹ -R ⁶¹

[wherein, ^R61 is a group with a polydimethylsiloxane group,

^R62 is a hydrogen atom, a monovalent organic group or a halogen atom,

Y ⁶¹ is a hydrocarbon group selected from 2 to 4 valent carbon number 1, -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ - or -NR'-( R' is a 2 to 4 valent group composed of at least one of H or a hydrocarbon group having 1 to 4 carbons].

In solution polymerization, the following method is adopted: in the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen substitution, heating and stirring in the range of 30 to 120° C. for 1 to 10 hours is adopted. Examples of polymerization initiators include: azobisisobutyronitrile, benzoyl peroxide substances, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxytrimethylacetate, diisopropyl peroxydicarbonate, etc. The polymerization initiator may be used in a range of 0.01 to 20 mole parts, eg, 0.01 to 10 mole parts, relative to 100 mole parts of the monomer.

烷、甲乙酮、甲基異丁基酮、二異丁基酮、乙酸乙酯、乙酸丁酯、1,1,2,2-四氯乙烷、1,1,1-三氯乙烷、三氯乙烯、過氯乙烯、四氯二氟乙烷、三氯三氟乙烷等。若將單體與有機溶媒合計設為100重量份，則有機溶媒係在其中50至99.5重量份、例如60至99重量份的範圍中使用。 The organic solvent is inactive to the monomers and makes them dissolve or uniformly disperse, for example, it can be an ester (for example, an ester with 2 to 30 carbon atoms, specifically ethyl acetate, butyl acetate), a ketone (for example, a carbon number Ketones with 2 to 30 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (such as alcohols with 1 to 30 carbon atoms, specifically isopropanol, ethanol, methanol). Specific examples of organic solvents include: acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4- two

alkane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, three Chloroethylene, perchlorethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. When the total of the monomer and the organic solvent is 100 parts by weight, the organic solvent is used in the range of 50 to 99.5 parts by weight, for example, 60 to 99 parts by weight.

In the emulsion polymerization, the following method can be used: In the presence of a polymerization initiator and an emulsifier, the monomer is emulsified in water, and after nitrogen substitution, it is stirred for 1 to 10 hours in the range of 30 to 80°C to polymerize . The polymerization initiator is benzoyl peroxide, lauryl peroxide, tertiary 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)acrylamide], 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. Azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxytrimethylacetate, diiso Oil-soluble products such as propyl peroxydicarbonate. The polymerization initiator is used in the range of 0.01 to 10 mole parts with respect to 100 mole parts of the monomer. Reducing agents such as Rongalite, ascorbic acid, tartaric acid, sodium disulfite, erythorbic acid, and ferrous sulfate can also be used in combination according to demand.

As the emulsifier, various anionic, cationic, or nonionic emulsifiers can be used, and they can be used in the range of 0.5 to 30 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 completely incompatible, it is also preferable to add a compatibilizing agent for sufficiently compatibilizing the monomers, for example, adding a water-soluble organic solvent. The emulsification and copolymerization properties can be improved by adding a compatibilizer.

Water-soluble organic solvents can be exemplified: acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, isopropanol, ethanol, methanol, etc., relative to 100 parts by weight of water, can be in the range of 0.1 to 50 parts by weight, for example, 1 to 40 parts by weight.

Chain transfer agents may also be used in the polymerization. The molecular weight of the polymer can be changed according to the amount of chain transfer agent used. Examples of chain transfer agents are thiol-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (such as those with 1 to 30 carbon atoms), sodium hypophosphite, sodium bisulfite, etc. Inorganic salt etc. The chain transfer agent can be used in an amount 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 monomers.

The water-repellent composition is generally preferably an aqueous dispersion. The water-repellent composition includes 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, relative to the water repellant composition.

In the water-repellent composition, the concentration of the polymer may be 0.1 to 50% by weight, such as 0.5 to 40% by weight.

The water-repellent composition (and the aqueous dispersion of organic microparticles) 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 microparticles) can be used as an oil repellant, antifouling agent, stain remover, stripping agent or release agent.

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. Generally, the water-repellent composition can be dispersed in an organic solvent or water for dilution, and then adhered to the surface of the object to be treated by known methods such as dip coating, spray coating, foam coating, etc., and dried. method. Also, if necessary, it can also be used together with a suitable crosslinking agent (such as blocked isocyanate) for curing. Furthermore, an insect repellant, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, etc. can be added and used in the water repellent composition. The polymer concentration in the treatment liquid in contact with the substrate is 0.01 to 10% by weight (especially in dip coating), for example 0.05 to 10% by weight.

The object to be treated with water-repellent composition (and aqueous dispersion of organic microparticles) is preferably one requiring water pressure resistance. Examples of the object to be processed include fiber products, paper, wood, leather, fur, and the like. Various examples of fiber products can be given. Examples include natural animal and vegetable fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; Inorganic fibers such as synthetic fibers, glass fibers, carbon fibers, and asbestos fibers, or their mixed fibers.

Fiber products can be in any form of fiber, cloth, etc.

The water-repellent composition can also be used as an antifouling agent, a release agent, and a release agent (for example, an internal release agent or an external release agent). For example, a substrate surface can be easily peeled off from other surfaces (other surfaces in the substrate, or surfaces in other substrates).

Organic microparticles can be applied to fibrous substrates (eg, fibrous products, etc.) by any known method for treating fibrous products with liquids. When the fiber product is cloth, the cloth may be dipped in the solution, or the solution may be attached or sprayed on the cloth. The treated fiber product is preferably dried, for example, by heating at 100°C to 200°C in order to exhibit water repellency.

Alternatively, the organic microparticles can be applied to fiber products by a cleaning method, for example, they can be applied to fiber products in washing or in dry cleaning or the like.

The fiber products to be treated are typically cloth, including fabrics, knitted fabrics and non-woven fabrics, cloth and blankets in the form of clothing items, and can also be fibers, silk or intermediate fiber products (such as slivers or rovings, etc.). The fiber product material can be natural fibers (such as cotton or wool, etc.), chemical fibers (such as viscose rayon (viscose rayon) or lyocell fibers (lyocell), etc.), or synthetic fibers (such as polyester, polyamide or acrylic fibers, etc.), or may be a mixture of fibers (such as a mixture of natural fibers and synthetic fibers, etc.).

Alternatively the fibrous substrate may be leather. In order to render the leather hydrophobic and oleophobic, organic microparticles can be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, for example, during wet processing of the leather, or during the finishing of the leather.

Alternatively, the fibrous substrate may be paper. The organic microparticles can be applied to preformed paper, or can be applied at various stages of paper making, such as during drying of the paper.

Organic fine particles can be used in applications requiring water pressure resistance. Especially good applications are cloth for outdoor products, cloth for sporting goods, cloth for rain gear such as raincoats, medical cloth, especially non-woven fabrics, such as medical surgical clothing, protective clothing, sunshade, especially sunshade cloth , tents, etc.

"Treatment" refers to applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. Through the treatment, the organic fine particles which are the active ingredients of the treatment agent adhere to the object to be treated. Through the treatment, the organic fine particles penetrate into the inside of the object to be treated and/or adhere to the surface of the object to be treated.

Although the implementation forms are described in detail above, it should be understood that various forms and changes in details can be made without departing from the gist and scope of the scope of the patent application.

[Example]

The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

Hereinafter, parts, % or ratios represent parts by weight, % by weight or ratio by weight unless otherwise specified.

The sequence of tests is as follows.

[Falling speed test]

In the falling speed test, after impregnating the PET cloth (basis weight: 88g/m ² , 70 denier, gray) in the aqueous dispersion of organic microparticles or the composition containing organic microparticles and binder resin, it is passed through the The rolling machine was passed through the pin tenter at 170°C for 1 minute, and the PET cloth with organic fine particles was prepared, and a 20 μL water droplet was injected from a microsyringe with a fully automatic contact goniometer (DropMaster701 manufactured by Kyowa Interface Science Co., Ltd.). On the PET cloth inclined at 30°, the rolling state of the dripped water was measured using a high-speed camera (VW-9000 manufactured by KEYENCE Co., Ltd.), and the average falling speed at a distance of about 40 mm was taken as the falling speed.

[Contact angle measurement]

The static contact angle of the cloth (PET cloth) treated with the aqueous dispersion of organic microparticles or the composition containing organic microparticles and binder resin is measured in the following way: PET cloth (basis weight: 88g/ ^m2 , 70 deniers, gray) impregnated in the aqueous dispersion of organic microparticles or the composition containing organic microparticles and binder resin, then passed through the rolling machine, and passed through the pin tenter at 170 ° C for 1 minute, ready to be attached with organic particles. 2 μL of water was dropped on the PET cloth of fine particles, and the static contact angle 1 second after the drop was measured using a fully automatic contact goniometer (DropMaster 701 manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of the organic microparticles on the cloth (PET cloth) is preferably at least 120°, more preferably at least 130°, and still more preferably at least 140°.

The contact angle of the aqueous dispersion of the binder resin is drop-casting the aqueous dispersion of the binder resin on a glass substrate (made of glass slide soda-lime glass), and heating at 150°C for 3 minutes to make a coating film. 2 μL of water was dropped on the coating film, and the static contact angle 1 second after the drop was measured using a fully automatic contact goniometer (DropMaster 701 manufactured by Kyowa Interface Science).

[Determination of solid content]

1 g of the obtained aqueous dispersion of organic fine particles was placed in an aluminum cup, and dried at 150° C. for 1 hour. The solid content was calculated from the weight before drying and after drying.

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

[Water repellency test]

The aqueous dispersion of organic microparticles is adjusted to a predetermined concentration, and the cloth is dipped in the test solution and passed through a rolling machine, and the water repellency is evaluated with 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 expressed by water repellency No. A higher score indicates better water repellency. A "+" attached to a number means better than that number, and a "-" means worse than that number. Evaluation was performed using polyester cloth (PET) (basis weight: 88 g/m ² , 70 denier, gray).

The water repellency test is preferably 80 points or more or 90 points or more.

[Strong water repellency test]

When the test is carried out by the spraying method of JIS-L-1092 (AATCC-22), the repellency (pull-off) of water in contact with the cloth and the speed of the water flowing from the cloth are evaluated visually. A higher score indicates better water repellency.

[Water pressure resistance test]

Test according to AATCC 127 to determine water pressure resistance.

The water pressure test device uses a water resistance tester PHL-5000 (DAIEI KAGAKU SEIKI), and the part that contacts the water of the test piece uses a size ^100cm2 . Use ion-exchanged water or equivalent water, and the temperature during the test is 21°C ± 2°C. Install the test piece on the water resistance test device in such a way that the front side of the test piece is in contact with water, put the water level device into the water level device at a speed of 600mm/mm±30mm/mm to raise the water level, and measure the distance from the back of the test piece in mm. The water level when water seeps out at 3 places.

Compared with the case of uncoated organic microparticles, the water pressure resistance is preferably higher, and the water pressure resistance value is preferably increased by 3%, for example, 5%, and further 10% of the water pressure resistance of the uncoated cloth.

[Particle size measurement of dispersion]

The dynamic light scattering (DLS) measurement used nanoSAQLA manufactured by Otsuka Electronics Co., Ltd. to obtain the average diameter of the particles in the dispersion. Dilute the aqueous dispersion of organic microparticles with pure water to a solid content concentration of 0.1%, and measure at 25°C. The analysis of the particle size distribution was performed based on the scattering intensity.

[Washing durability of water repellency and strong water repellency (water repellency (after washing) and strong water repellency (after washing))]

After repeating 20 times of washing according to the JIS L-0217-103 method, the water repellency and strong water repellency were evaluated. The water repellency after washing is preferably above 80 points, and the strong water repellency is preferably above 2 points.

In Examples and Comparative Examples, the meanings of the abbreviations are as follows.

tBuMA: tertiary butyl methacrylate

iBMA: Isocamphoryl methacrylate

CHMA: Cyclohexyl methacrylate

StA: stearyl acrylate

DVB: divinylbenzene

GMA: glycidyl methacrylate

MMA: methyl methacrylate

MAA: methacrylic acid

DAAM: diacetone acrylamide

NIPAM: Isopropylacrylamide

tBuAAm: tertiary butylacrylamide

DM4: Dimethylaminoethyl methacrylate quaternary compound (methyl chloride)

DM: 2-Dimethylaminoethyl methacrylate

HBA: 4-Hydroxybutyl Acrylate

tBuAEMA: tert-butylaminoethyl methacrylate

EGDMA: Ethylene glycol dimethacrylate

NPDMA: Neopentyl glycol dimethacrylate

GDMA: Glyceryl Dimethacrylate

TMPTMA: Trihydroxymethylpropane trimethacrylate

NGDA: nonanediol diacrylate

Emulsifier 1: Polyethylene glycol monooleyl ether (liquid)

Emulsifier 2: Stearyltrimethylammonium chloride

Emulsifier 3: Cetyltrimethylammonium Chloride

Emulsifier 4: polyoxyalkylene alkenyl ether (HLB13)

Crosslinker 1: Oxime blocked toluene diisocyanate

Crosslinker 2: Blocked diphenylmethane diisocyanate

<Synthesis Example B1>

Put 30g of tripropylene glycol, 45g of CH ₂ =CHC(=O)OC ₂ H ₄ NHC(=O)C ₁₇ H ₃₅ (C17AEA), 34g of StA, 1g of N-alkanol in a 500ml plastic container acrylamide, 2 g of trialkylammonium chloride, 2 g of sorbitan monoalkylate, 2.5 g of polyoxyethylene trialkyl ether, 3.5 g of polyoxyethylene alkyl ether, 180 g of pure water was stirred at 80° C. by a homomixer at 2000 rpm for 1 minute, and dispersed by ultrasonic waves for 15 minutes. Transfer the emulsified dispersion to an autoclave, add 0.2g of alkyl mercaptan, 20g of vinyl chloride after nitrogen substitution, and then add 1g of azo-based initiator, heat and stir at 60°C for 20 hours, thereby obtaining polymerization aqueous dispersions of substances. The water contact angle of the film obtained by applying the emulsified dispersion to a glass substrate was 109°.

<Synthesis Example B2>

Put 28.9g of sorbitan tristearate (sorbitan tristearate), 0.31g of sorbitan monostearate, 7.5g of hexamethylene triisocyanate (sorbitan tristearate) in the reaction vessel replaced by nitrogen Diurea), 37.5g of methyl isobutyl ketone, and 0.03g of dibutyltin laurate were heated and stirred at 80°C. In this solution, put 9g of tripropylene glycol, 1.8g of sorbitan tristearate, 0.75g of polyethylene glycol monooleyl ether, 0.6g of trimethyl octadecyl ammonium chloride, 40g of pure water and stir. Methyl isobutyl ketone was removed by an evaporator to obtain an aqueous dispersion of a reactant of sorbitan stearate and isocyanate. Then add the water dispersion of long-chain alkyl modified polydimethylsiloxane wax to obtain the water dispersion of the mixture. The water contact angle of the film obtained by applying the dispersion to a glass substrate was 105°.

<Synthesis Example B3>

In a 1000mL autoclave, put 39.53g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0), 79.29g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOCH=CH ₂ (n=2.0), 46.01 g of stearyl acrylate, 415 g of pure water, 60 g of water-soluble glycol solvent, 15.8 g of polyoxyethylene Oleyl ether and 4.75 g of polyoxyethylene alkyl ether were stirred at 60° C. for 15 minutes, emulsified and dispersed with ultrasonic waves. After replacing the container with nitrogen, press-fill 50g of vinyl chloride (VCM), add 0.4g of azo group-containing water-soluble initiator, and react at 60°C for 20 hours to obtain an aqueous polymer dispersion . The composition of the polymer is almost identical to that of the incorporated monomer.

<Synthesis Example 1>

0.39 g of tertiary butyl methacrylate (tBuMA), 0.16 g of glycidyl methacrylate (GMA), and 0.37 g of isobornyl methacrylate (iBMA) were placed in a nitrogen-substituted reaction vessel. , 0.072 g of divinylbenzene (DVB), 43 mg of polyethylene glycol monooleyl ether (liquid), 1.5% by weight of stearyl trimethylammonium chloride relative to all monomers, 19 ml of pure water, and make it scattered. After nitrogen substitution, 15.1 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, and heated and stirred at 65°C for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content is 4.71%. The particle diameter (average particle diameter) of the aqueous dispersion was 71.1 nm.

<Example 1>

The aqueous dispersion of the organic fine particles of Synthesis Example 1 was mixed with the aqueous dispersion of Synthesis Example B1 so that the organic fine particles of Synthesis Example 1 had a solid content of 0.2%, and Synthesis Example B1 as a binder had a solid content of 0.8%. , making the aqueous dispersion of organic microparticles and Synthesis Example B1. Moreover, the crosslinking agent 1 with a solid content of 17% with respect to the solid content of Synthesis Example B1 was added to this aqueous dispersion. The PET (cloth) (basis weight: 88g/m ² , 70 denier, gray) treated with the aqueous dispersion has a falling speed of 117mm/s, a water pressure resistance of 395mm, a water repellency test of 95 points, and a strong water repellency test. 3 points.

<Synthesis Examples 2 to 62>

The same procedures as in Synthesis Example 1 were repeated except that those shown in Table 1 were used as monomers. The results are shown in Table 1. The monomer molar ratio in Table 1 represents the molar equivalent relative to 1 mole of 2,2'-azobis(2-methylpropionamidine) dihydrochloride.

<Examples 2 to 62>

The same procedure as in Example 1 was repeated except that the aqueous dispersion of fine particles of Synthesis Examples 2 to 62 was used instead of the aqueous dispersion of fine particles of Synthesis Example 1. The results are shown in Table 1.

<Comparative example 1>

The aqueous dispersion of Synthesis Example B1 was produced so that the solid content of Synthesis Example B1 would be 1.0%. The water pressure resistance of PET (cloth) (basis weight: 88 g/m ² , 70 denier, gray) treated with this aqueous dispersion was 357 mm.

<Comparative example 2>

The aqueous dispersion of Synthesis Example B2 was produced so that the solid content of Synthesis Example B2 would be 1.0%. The water pressure resistance of PET (cloth) (basis weight: 88 g/m ² , 70 denier, gray) treated with the aqueous dispersion was 329 mm.

<Synthesis Example 63>

Add 0.66g of tertiary butylstyrene (tBuSty), 0.39g of glycidyl methacrylate (GMA), 0.018g of divinylbenzene (DVB), and 33ml of pure water into a nitrogen-substituted reaction vessel , and make it dispersed. After nitrogen substitution, 18.6 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, followed by heating and stirring at 65° C. for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content is 2.23%. The static contact angle of PET (cloth) (basis weight: 88g/m ² , 70 denier, gray) treated only with water dispersion of organic microparticles and water is 143.1°, and the falling speed is 265mm/s.

<Synthesis Example 64>

Add 0.50 g of tertiary butyl methacrylate (tBuMA), 0.20 g of glycidyl methacrylate (GMA), 0.47 g of isobornyl methacrylate (iBMA) in a nitrogen-substituted reaction vessel, 0.091 g of divinylbenzene (DVB) and 39 ml of pure water were dispersed. After nitrogen substitution, 19.0 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, followed by heating and stirring at 65° C. for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content is 2.32%. The static contact angle of PET (cloth) (basis weight: 88g/m ² , 70 denier, gray) treated only with water dispersion of organic microparticles and water is 156.2°, and the falling speed is 227mm/s.

<Synthesis Example 65>

Add 9.61g of tertiary butylstyrene (tBuSty), 11.37g of glycidyl methacrylate (GMA), 0.52g of divinylbenzene (DVB), 0.24g of emulsifier 2, 570ml into the reaction vessel of pure water and disperse it. After nitrogen substitution, 54.2 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, followed by heating and stirring at 65°C. After 30 minutes, add 9.61g of tertiary butylstyrene (tBuSty), 11.37g of glycidyl methacrylate (GMA), 0.52g of divinylbenzene (DVB), and heat and stir at 65°C for 8 hours. This gives an aqueous dispersion of organic microparticles. The solid content is 5.4%. The particle diameter (average particle diameter) of the aqueous dispersion was 76 nm.

<Synthesis Example 66>

1.00 g of tertiary butylstyrene (tBuSty), 0.049 g of divinylbenzene (DVB), 52 mg of emulsifier 1, and 19 ml of pure water were added and dispersed in the reaction container. After nitrogen substitution, 16.9 mg of 2,2'-azobis(2-methylpropionamidine) dihydrochloride was added, followed by heating and stirring at 65°C for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content is 4.54%. The particle size (average particle size) of the aqueous dispersion was 234 nm.

<Examples 63 to 115>

In addition to using the aqueous dispersion of microparticles, the dispersion of the binder, the concentration of the microparticles and the binder, and the predetermined cloth shown in Tables 2 to 4, and using the crosslinking agent 2 instead of the crosslinking agent 1, the same procedure was repeated. Same procedure as Example 1. The results are shown in Tables 2 to 4.

<Comparative Examples 3 to 11>

The same procedure as in Example 1 was repeated except that the aqueous dispersion of fine particles was omitted, and the type and concentration of the binder dispersion shown in the table were used, and the predetermined cloth shown in the table was used. The results are shown in Tables 2 and 4.

Also, the water pressure resistance of untreated PET cloth (gray, basis weight: 88 g/m ² , 70 denier) was 25 mm.

The cloth systems shown in Tables 2 to 4 used the following ones.

Cloth 1: PET gray Basis weight: 88g/m ² , 70 denier

Cloth 2: High-density PET black

Cloth 3: non-woven fabric (PP) 44g/m ²

Cloth 4: Acrylic blue

Cloth 5: T/C twill (65/35) beige

[Table 1]

[Table 2]

[table 3]

[Table 4]

[industrial availability]

The organic microparticles disclosed in the present invention can be used as an oil repellant, antifouling agent, stain remover, stripping agent or release agent with the effect of improving water pressure resistance. The organic microparticles of the present disclosure can be used as a water pressure rise resistance agent.

Organic microparticles can be used in applications requiring water pressure resistance. Especially good applications are cloth for outdoor products, cloth for sporting goods, cloth for rain gear such as raincoats, medical cloth, especially non-woven fabrics, such as medical surgical clothing, protective clothing, sunshade, especially sunshade cloth , tents, etc.

Claims (27)

An organic fine particle that can exist on a substrate in a state of particle shape, and exhibits a water pressure resistance effect on the substrate. The organic microparticles as described in Claim 1, when attached to cloth, satisfy at least one of the following (i) and (ii), (i) The water pressure resistance ratio (= water pressure resistance of the treated cloth with organic microparticles / water pressure resistance of the control untreated cloth) is above 1.03; (ii) The air permeability ratio (= air permeability of treated cloth with organic microparticles/air permeability of untreated cloth as compared) is 0.9 or less. The organic microparticles as described in claim 1 or 2, wherein the particle diameter of the microparticles observable on the cloth is 50 to 700nm. The organic fine particle according to any one of claims 1 to 3, which comprises a polymer having a repeating unit formed from the following (I), (I) A hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbons. An organic microparticle comprising a polymer having repeating units formed from the following (I) and (II), (1) Hydrophobic monomers having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group with 3 to 40 carbons; (II) A crosslinkable monomer having at least two ethylenically unsaturated double bonds. An organic microparticle comprising a polymer having a repeating unit formed from the following (I), (1) Hydrophobic monomers having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group with 3 to 40 carbons; The content of the high glass transition point monomer whose glass transition point of the homopolymer in the hydrophobic monomer (I) is 100° C. or higher is 20 mol % or more. The organic microparticle according to any one of claims 4 to 6, wherein the polymer also has a repeating unit formed from at least one monomer selected from the following (III) and/or (IV), (III) Reactive and hydrophilic monomers having 1 ethylenically unsaturated double bond and at least 1 reactive group and/or hydrophilic group, or having 1 ethylenically unsaturated double bond and at least 1 carbon Monomers containing short-chain hydrocarbon groups with a hydrocarbon group of 1 or 2; (IV) A (meth)acrylic monomer having a straight-chain hydrocarbon group or a polydimethylsiloxane group having 3 to 40 carbon atoms. The organic fine particle according to any one of claims 4 to 7, wherein in the hydrophobic monomer (I), the carbon number of the branched hydrocarbon group is 3 to 11, and the carbon number of the cyclic hydrocarbon group is 4 to 15. The organic microparticles as described in any one of claims 4 to 8, wherein The hydrophobic monomer (I) is a monomer represented by the following formula, CH ₂ =C(-R ¹² )-C(=O)-Y ¹¹ (R ¹¹ ) _k or CH ₂ =C(-R ¹⁴ )-Y ¹² (H) _5-l (R ¹³ ) _l [wherein, R ¹¹ and R ¹³ are independently branched or cyclic hydrocarbon groups with 3 to 40 carbons, R ¹² and R ¹⁴ are hydrogen atoms, monovalent organic groups or halogen atoms, Y ¹¹ is -O- or -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons), Y ¹² is a benzene ring, H is a hydrogen atom, H and R ¹³ are respectively directly bonded to Y ¹² , k is 1 to 3, l is 0 to 3]; The cross-linking monomer (II) is a monomer represented by the following formula,

or

[In the formula, R ³¹ and R ³³ are each independently a direct bond, or a hydrocarbon group selected from a carbon number of 1 to 20 (can also include a hydrocarbon site with an -OH group), -(CH ₂ CH ₂ O )r-(r is an integer from 1 to 10), -C ₆ H ₄ -, -O- or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbons) constituted by 2 to the base of 4 valences, R ³² , R ³⁴ , R ³⁵ and R ³⁶ are each independently a hydrogen atom, a monovalent organic group or a halogen atom, Y ³¹ is -O- or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbons), p is 2 to 4, q is 1 to 5]; Reactive, hydrophilic monomer (III) is a monomer represented by the following formula, CH ₂ =C(-R ⁴² )-C(=O)-Y ⁴¹ -(R ⁴³ ) _o (R ⁴¹ ) _t or CH ₂ =C(-R ⁴⁵ )-Y ⁴² -(H) _5-n (R ⁴⁴ ) _u [wherein, R ⁴¹ and R ⁴⁴ are each independently a reactive group or a hydrophilic group, R ⁴² and R ⁴⁵ are hydrogen atoms, monovalent organic groups or halogen atoms, Y ⁴¹ is a direct bond, -O- or -NR'- (R' is H or a hydrocarbon group with 1 to 4 carbons), R ⁴³ is a group of a direct bond, -O-, or a hydrocarbon group having 2 to 4 valences of carbon number 1 to 10 (which may also contain a hydrocarbon site having an -OH group), Y ⁴² is a benzene ring, H is a hydrogen atom, H and R ⁴⁴ are respectively directly bonded to Y ⁴² , t and u are 1 to 3, o is 0 or 1]; or The monomer (III) containing a short-chain hydrocarbon group is a monomer represented by the following formula, CH ₂ =C(-R ⁴⁷ )-C(=O)-Y ⁴³ -R ⁴⁶ [wherein, R ⁴⁶ is a hydrocarbon group with 1 or 2 carbons, R ⁴⁷ is a hydrogen atom, a monovalent organic group or a halogen atom, Y ⁴³ is a direct bond, -O- or -NR'-(R' is H or a hydrocarbon group with 1 to 4 carbons)]; The (meth)acrylic monomer (IV) is a (meth)acrylic monomer having a straight-chain hydrocarbon group having 3 to 40 carbons represented by the following formula, CH ₂ =C(-R ⁵² )-C(=O)-Y ⁵¹ (R ⁵¹ ) _s [wherein, R ⁵¹ are each independently a linear hydrocarbon group with 3 to 40 carbons, R ⁵² is a hydrogen atom, a monovalent organic group or a halogen atom, Y ⁵¹ is a hydrocarbon group with 1 carbon number selected from 2 to 4 valence, -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ - or -NR'-( R' is a 2- to 4-valent group consisting of at least one of H or a hydrocarbon group with 1 to 4 carbons (but excluding the case of only a 2-valent hydrocarbon group), s is 1 to 3]; or A (meth)acrylic monomer having a polydimethylsiloxane group represented by the following formula, CH ₂ =C(-R ⁶² )-C(=O)-Y ⁶¹ -R ⁶¹ [wherein, ^R61 is a group with a polydimethylsiloxane group, ^R62 is a hydrogen atom, a monovalent organic group or a halogen atom, Y ⁶¹ is a hydrocarbon group selected from 2 to 4 valent carbon number 1, -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ - or -NR'-(R 'is a 2 to 4 valent group formed by at least one of H or a hydrocarbon group having 1 to 4 carbons]. The organic microparticles as described in any one of claims 7 to 9, wherein In the reactive monomer (III), the reactive group is an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group, and a blocked isocyanate group, and the hydrophilic group is selected from a hydroxyl group, an amine group (including a group bonded to N H is converted to methyl, ethyl, propyl or butyl), carboxylic acid, sulfonic acid, phosphoric acid, carboxylic acid, sulfonic acid, alkali metal or alkaline earth metal salt of phosphoric acid, chlorine, bromine or The iodide ion is at least one of the group consisting of ammonium salt base, ethylene glycol base, polyethylene glycol base, and base with acetone skeleton (-C(=O)-CH ₃ ), or the reaction The neutral and hydrophilic monomer (III) is (meth)acrylamide having a short-chain hydrocarbon group having 6 or less carbon atoms in the side chain. The organic microparticles as described in any one of claims 4 to 10, wherein Hydrophobic monomer (I) is selected from Tertiary butyl (meth)acrylate, isopropyl (meth)acrylate, 2,6,8-trimethylnonan-4-yl=acrylate, Isocamyl (meth)acrylate, Camphenyl (meth)acrylate, Adamantyl (meth)acrylate, Dicyclopentyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, (Meth) ) phenyl acrylate, naphthyl acrylate, benzyl acrylate, Tertiary butylstyrene, methylstyrene, styrene, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclobutyl (meth)acrylate, cycloheptyl (meth)acrylate , at least one monomer from the group consisting of 2,4-di-tert-butylstyrene and 2,4,6-trimethylstyrene, The cross-linking monomer (II) is selected from divinylbenzene, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol Glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, Ethylene glycol di(meth)acrylate (Meth)acrylate, Methylene glycol di(meth)acrylate, Polytetramethylene glycol di(meth)acrylate, Dihydroxymethyltricyclodecane di(meth)acrylate , trihydroxymethylpropane tri(meth)acrylate, adamantyl di(meth)acrylate, glyceryl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, di(meth)acrylate base) at least one monomer from the group consisting of dicyclopentyl acrylate and 5-hydroxy-1,3-adamantane di(meth)acrylate; Reactivity, hydrophilic monomer (III) is selected from glycidyl (meth)acrylate, glyceryl (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-Acetylacetyloxyethyl (meth)acrylate, 4-Hydroxybutyl glycidyl acrylate, acrylic acid, methacrylic acid, trimethylsilyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate, (methyl ) 2-(dimethylamino)ethyl acrylate, 2-(tertiary butylamino)ethyl (meth)acrylate, quaternary dimethylaminoethyl (meth)acrylate, (form base) tetrahydrofuryl methyl acrylate, polyethylene glycol (meth) acrylate, di Acetone(meth)acrylamide, isopropyl(meth)acrylamide, tert-butyl(meth)acrylamide, ethyl(meth)acrylamide, methyl(meth)acrylamide amines; and 4-hydroxymethylstyrene, 4-hydroxyethylstyrene, 4-aminomethylstyrene, 4-aminoethylstyrene, 2-(4-vinylphenyl)oxirane, 2 - at least one monomer from the group consisting of (4-vinylbenzoyl)oxirane; The short-chain hydrocarbon group-containing monomer (III) is at least one monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, α-chloromethyl acrylate, and α-chloroethyl acrylate; (Meth)acrylic acid monomer (IV) is selected from Stearyl (meth)acrylate, ethyl stearylamide (meth)acrylate, CH ₂ =CHC(=O)OC ₂ H ₄ NHC(=O)C ₁₇ H ₃₅ , CH ₂ =CHC(=O )OC ₂ H ₄ NHSO ₂ C ₁₈ H ₃₇ , CH ₂ =CHC(=O)OC ₂ H ₄ NHC(=O)OC ₁₈ H ₃₇ , CH ₂ =CHC(=O)OC ₂ H ₄ OC(=O )NHC ₁₈ H ₃₇ , CH ₂ =CHC(=O)OC ₂ H ₄ NHC(=O)NHC ₁₈ H ₃₇ , Mode:

or

[where n is a number from 1 to 500] At least one monomer in the group formed. The organic fine particle according to any one of claims 4 to 11, which satisfies at least one of the following (i), (ii) and (iii): (i) the molar ratio of (hydrophobic monomer (I))/(reactive, hydrophilic monomer and/or short-chain hydrocarbon-containing monomer (III)) is 100/0 to 50/50; (ii) 100 mole parts relative to the total of hydrophobic monomer (I), reactive, hydrophilic monomer and/or short-chain hydrocarbon group-containing monomer (III) and (meth)acrylic monomer (IV) , the cross-linking monomer (II) is 0.1 to 30 mole parts; (iii) The (meth)acrylic monomer (IV) is 0 to 30 mole parts. A water pressure raising agent comprising the organic microparticles as described in any one of Claims 1 to 12. A use of the organic microparticles described in any one of Claims 1 to 12 is used as a water pressure raising agent. A water pressure booster composition comprising: (A) organic microparticles as described in any one of Claims 1 to 12; and (B) Aqueous medium. The water pressure raising agent composition according to claim 15, wherein the amount of the organic microparticles (A) is 50% by weight or less relative to the water pressure raising agent composition. The water pressure raising agent composition according to claim 15 or 16, further comprising any one or more of (C) binder resin, (D) surfactant, and (E) crosslinking agent. The water pressure riser composition as described in Claim 17, wherein the binder resin (C) is selected from non-fluoropolymers having hydrocarbon groups with 3 to 40 carbons in the side chain and non-fluoropolymers with 1 to 20 carbons in the side chain At least one polymer among fluoroalkyl fluorine-containing polymers. The water pressure raising agent composition as described in Claim 17 or 18, wherein the binder resin (C) is acrylic polymer, urethane polymer, polyolefin, polyester, polyether, polyamide, poly imides, polystyrenes, silicone polymers, and combinations thereof. The water pressure raising agent composition as described in any one of claims 17 to 19, wherein the weight ratio of the binder resin (C)/organic microparticles (A) is 20/80 to 99/1, or the binder resin ( The amount of C) is 30 to 99% by weight relative to the total weight of the binder resin (C) and the organic fine particles (A). A method of manufacturing a water pressure raising agent composition, which is a method of manufacturing the water pressure raising agent composition described in any one of Claims 15 to 20, which has the following steps: in the presence of 100 wt. A step of polymerizing monomers in an aqueous medium to obtain an aqueous dispersion of organic microparticles (A) under the condition that the surfactant is less than 30 parts by weight. The manufacturing method as described in Claim 21, which further comprises the following steps: By adding the aqueous dispersion of the binder resin (C) to the aqueous dispersion of the organic fine particles (A), or by polymerizing the monomer for the binder resin in the aqueous dispersion of the organic fine particles (A) To obtain the binder resin (C), or by making the organic microparticles in the aqueous dispersion of the binder resin The step of polymerizing the monomers used to obtain an aqueous dispersion in which the organic microparticles (A) and the binder resin (C) are dispersed. A method for treating fiber products, which is to apply the treatment solution containing the anti-water pressure raising agent composition described in any one of claims 15 to 20 to the fiber products. A fiber product, which is applied with the water pressure rise resistance agent composition described in any one of claims 15 to 20. The fiber product as described in claim 24, which at least satisfies any of the following: (i) Water pressure resistance ratio (=water pressure resistance of fiber products with organic microparticles/water pressure resistance of control fiber products) is above 1.03; (ii) air permeability ratio (=air permeability of fiber products with organic microparticles/ The air permeability of the contrast fiber product) is below 0.9. The fiber product as described in claim 24 or 25, wherein the fiber product is cloth for outdoor products, cloth for sports products, cloth for rain gear, cloth for medical use or non-woven fabric. The fiber product as described in claim 26, wherein the fiber product is medical surgical clothing, protective clothing, sunshade, sunshade cloth, tent.