JP7146426B2 - Textile water repellent composition and use thereof - Google Patents

Description

The present invention relates to a textile water repellent composition and its use.

BACKGROUND ART Conventionally, textile products to which a fluorine-based water repellent agent having a fluorine-containing group is adhered have been widely used because they exhibit high water repellency. On the other hand, there are concerns about the accumulation of fluorine-based compounds in the human body, and many water-repellent materials using non-fluorine-based compounds have been developed.

Conventionally, acrylic resins having long-chain alkyl groups, polyurethane resins having long-chain alkyl groups, silicone resins, and the like have been well known as water-repellent compositions for textiles that do not contain fluorine. Compared to , the threads that make up the fabric are more slippery, so the threads at the seams slide with a small force, and there is a problem that it is not possible to maintain a practical level of seam strength for textile products such as clothes. It's here.

Japanese Patent Application Laid-Open No. 2004-059609 JP 2015-165056 A JP 2017-145521 A JP 2017-155095 A JP 2017-206775 A Japanese Patent No. 4996875 Japanese Patent No. 6224487 WO2015/083627

An object of the present invention is to provide a water repellent composition for fibers and a water-repellent textile product that exhibit low slipping properties when applied to textile products and the like.

As a result of intensive studies by the present inventors in order to solve the above problems, it was found that if the water repellent composition contains a specific component (A), a specific component (B), and water, the above problems can be solved.

That is, the water repellent composition for fibers of the present invention comprises a component (A) which is at least one selected from a urethane compound (A1) and a reactive silicone (A3), a silicone resin (B), water, wherein the urethane compound (A1) has at least one hydrocarbon group having 12 or more carbon atoms in the molecule, and the reactive silicone (A3) is epoxy-modified silicone, carboxy at least one selected from modified silicone and methyl hydrogen silicone, the weight ratio (A:B) of component (A) and component (B) is 15:1 to 1:15, and the silicone resin The units constituting (B) consist only of M units (MQ) represented by R ₃ SiO _1/2 and Q units (MQ) represented by SiO _4/2 or T units (T) represented by RSiO _3/2 , R represents a linear or branched monovalent alkyl group having 1 to 18 carbon atoms .

It is preferable that the reactive silicone (A3) is a polysiloxane having reactive groups on side chains and/or both ends .
It is preferable to further contain an organic solvent.

The water-repellent textile product of the present invention is obtained by treating a textile material with the water repellent composition for textiles.
The method for producing a water-repellent textile product of the present invention includes a step (I) of applying a treatment liquid containing the above-described textile water repellent composition to a textile material, and a step (II) of heat-treating the textile material to which the treatment liquid has been applied. ) and

The water repellent composition for textiles of the present invention exhibits low sliding property when applied to textile products and the like.

The present invention provides a repellent composition comprising a component (A) which is at least one selected from urethane compounds (A1), acrylic resins (A2) and reactive silicones (A3), a specific silicone resin (B), and water. It is a liquid medicine composition. A detailed description will be given below.

[Urethane compound (A1)]
The urethane compound (A1) is obtained by reacting an organic polyisocyanate compound (X) with an active hydrogen group-containing compound (Y), and comprises a structural unit (x) derived from the organic polyisocyanate compound (X) and an active hydrogen group. It has a structural unit (y) derived from the containing compound (Y). Only one kind of urethane compound (A1) may be used, or two or more kinds thereof may be used.

(Organic polyisocyanate compound (X))
The organic polyisocyanate compound (X) is an essential component of the urethane compound (A1) and contains two or more isocyanate groups in its molecule. The number of isocyanate groups in the molecule is preferably 2-4, more preferably 2-3. Only one kind of the organic polyisocyanate compound (X) may be used, or two or more kinds thereof may be used. Here, the structural unit derived from the organic polyisocyanate compound (X) refers to a unit constructed using the organic polyisocyanate compound (X) as a raw material, and the "-NHC(=O)-" of the urethane bonds. Including structure.

Examples of the organic polyisocyanate compound (X) include aromatic polyisocyanate (X1) having 8 to 26 carbon atoms, aliphatic polyisocyanate (X2) having 4 to 22 carbon atoms, alicyclic polyisocyanate having 8 to 18 carbon atoms ( X3), araliphatic polyisocyanates having 10 to 18 carbon atoms (X4), modified products of these polyisocyanates (X5), and the like.

Examples of the aromatic polyisocyanate (X1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter, tolylene diisocyanate is referred to as TDI). abbreviation), crude TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-methyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylenediisocyanate, 4,4',4''-triphenyl Methane triisocyanate and m- or p-isocyanatophenylsulfonyl isocyanate.

Examples of aliphatic polyisocyanates having 4 to 22 carbon atoms (X2) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-diisocyanatohexanoate can be mentioned.

Examples of the alicyclic polyisocyanate (X3) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, methyl Cyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

Examples of the araliphatic polyisocyanate (X4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate.

Modified products (X5) of polyisocyanate compounds (X1) to (X4) include urethane group, carbodiimide group, allohanate group, urea group, biuret group, uretdione group, uretimine group, isocyanurate group or oxazolidone group in the molecule. Examples include modified products of polyisocyanates (X1) to (X4) contained. Modified products (X5) include, for example, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI and isocyanurate-modified IPDI. .

Among these organic polyisocyanate compounds (X), from the viewpoint of water repellency, aromatic polyisocyanate (X1) having 8 to 26 carbon atoms and aliphatic polyisocyanate (X2) having 4 to 22 carbon atoms are preferable, and 4 carbon atoms. Aliphatic polyisocyanates (X2) of -22 are more preferred, and HDI is particularly preferred.

(The active hydrogen group-containing compound (Y))
The active hydrogen group-containing compound (Y) is an essential component of the urethane compound and refers to a compound having at least one active hydrogen group in the molecule. An active hydrogen group refers to a hydrogen-containing active group capable of reacting with an isocyanate group. Examples of active hydrogen groups include hydroxyl groups, amino groups, carboxyl groups, and thiol groups. Here, the structural unit (y) derived from the active hydrogen group-containing compound (Y) refers to a unit constructed using the active hydrogen group-containing compound (Y) as a raw material, and the active hydrogen group-containing compound (Y) It refers to the remainder after removing hydrogen (active hydrogen that contributes to the reaction with the organic polyisocyanate compound (X)).

The structural unit (y) derived from the active hydrogen group-containing compound (Y) comprises a structural unit (y1) derived from a polyol (Y1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule and a carboxyl group. It contains a structural unit (y2) derived from the active hydrogen group-containing compound (Y2) having That is, the urethane compound contains an organic polyisocyanate compound (X), a polyol (Y1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule, and an active hydrogen group-containing compound (Y2) having a carboxyl group. It becomes a reaction product with the active hydrogen group-containing compound (Y). The active hydrogen group-containing compound (Y) may contain other active hydrogen group-containing compounds other than the polyol (Y1) and the active hydrogen group-containing compound (Y2) within a range that does not impede the present invention.

(Polyol (Y1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule)
Polyol (Y1) is a compound having at least one hydrocarbon group having 12 or more carbon atoms in the molecule and at least one active hydrogen group. Only one kind of polyol (Y1) may be used, or two or more kinds thereof may be used.
The number of such hydrocarbon groups in the molecule is preferably 1-5, more preferably 1-4, still more preferably 1-3. The number of active water groups in the molecule is preferably 2-5, more preferably 2-4, still more preferably 2-3.

Examples of the hydrocarbon group of the polyol (Y1) include an alkyl group and an alkenyl group. The hydrocarbon group may have a straight chain structure or a branched structure, and may be saturated or unsaturated. The number of carbon atoms in the hydrocarbon group is 12 or more, preferably 12-26, more preferably 14-22, still more preferably 18-22. If the number of carbon atoms is less than 12, water repellency may be poor.

Polyol (Y1) is not particularly limited as long as it satisfies the above conditions, but the following compound (Y1-1) is preferable from the viewpoint of exhibiting the effects of the present invention more. That is, the structural unit (y1) is preferably a structural unit (y1-1) derived from compound (Y1-1).

A compound (Y1-1) which is an ester having a structure in which a fatty acid having 12 or more carbon atoms and a polyhydric alcohol having a valence of 3 or more are ester-bonded, and which has two or more hydroxyl groups in the molecule.
Fatty acids may have a linear structure or a branched structure, and may be saturated or unsaturated. The number of carbon atoms in the fatty acid is preferably 12-26, more preferably 14-22, even more preferably 18-22.

Fatty acids include lauric acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isocetyl acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, isoeicosanic acid, gadoleic acid, eicosenoic acid, docosanoic acid, isodocosanoic acid, erucic acid, tetracosanoic acid, isotetracosanoic acid, nervonic acid, cerotic acid, montanic acid, melissic acid and the like. Among these, myristic acid, palmitic acid, stearic acid, isostearic acid and behenic acid are preferred, and stearic acid and behenic acid are more preferred.

Trihydric or higher polyhydric alcohols include glycerin, sorbitan, sorbitol, pentaerythritol, alditols other than the above, trimethylolpropane, diglycerin, ditrimethylolpropane, dipentaerythritol, triglycerin, tetraglycerin, sucrose, and castor oil. , hydrogenated castor oil and alkylene oxide adducts thereof. Among these, glycerin, sorbitol and pentaerythritol are preferred, and sorbitol and pentaerythritol are more preferred.

The number of ester bonds in compound (Y1-1) is preferably 1-5, more preferably 2-4, still more preferably 2-3. The number of active water groups in the molecule of compound (Y1-1) is preferably 1-5, more preferably 2-4, still more preferably 2-3.

Examples of the compound (Y1-1) include sorbitan tristearate, sorbitan distearate, sorbitan monostearate, glycerin distearate, glycerin dibehenate, distearylerythritol and the like. Among these, preferred are sorbitan tristearate, sorbitan distearate, sorbitan monostearate and distearylerythritol, more preferred are sorbitan tristearate, sorbitan distearate and distearylerythritol, and sorbitan distearate and distearylerythritol. is more preferred.
The method for producing compound (Y1-1) is not particularly limited, and known methods can be employed.

Preferred compounds (Y1) include sorbitol-type polyols represented by the following general formula (1) and erythritol-type polyols represented by the following general formula (2).

In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 12 or more carbon atoms, and R ¹ , R ² , R ³ and R ⁴ At least two of them are hydrogen atoms, and at least one is an organic group having 12 or more carbon atoms. Preferably, two of R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms and two are organic groups having 12 or more carbon atoms.

In formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom or an organic group having 12 or more carbon atoms, and R ⁵ , R ⁶ , R ⁷ , At least two of R ⁸ are hydrogen atoms, and at least one is an organic group having 12 or more carbon atoms. Preferably, two of R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms and two are organic groups having 12 or more carbon atoms.

Examples of organic groups having 12 or more carbon atoms include hydrocarbon groups having 12 or more carbon atoms and acyl groups having 12 or more carbon atoms, and acyl groups having 12 or more carbon atoms are preferred. The hydrocarbon group may have a straight chain structure or a branched structure, and may be saturated or unsaturated. The acyl group is a residue obtained by removing the OH group from the aforementioned fatty acid having 12 or more carbon atoms. The preferred range of the fatty acid is the same as described above. The number of carbon atoms in the hydrocarbon group and acyl group is preferably 12-26, more preferably 14-22, still more preferably 18-22.

The structural unit (y1) derived from the compound (Y1) refers to the remainder of the compound (Y1) excluding active hydrogen (active hydrogen that contributes to the reaction with the organic polyisocyanate compound (X)), and has the general formula Taking the erythritol-type polyol represented by (2) as an example, it becomes a structural unit represented by any one of the following general formulas (3), (4), and (5).

In general formula (3), R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or an organic group having 12 or more carbon atoms, and at least one of R ⁵ , R ⁶ and R ⁷ is carbon It is an organic group of number 12 or more.

In general formula (4), R ⁵ and R ⁷ are each independently a hydrogen atom or an organic group having 12 or more carbon atoms, and at least one of R ⁵ and R ⁷ is an organic group having 12 or more carbon atoms. is.

In general formula (5), ^R7 is an organic group having 12 or more carbon atoms.

(Active Hydrogen Group-Containing Compound (Y2) Having a Carboxyl Group)
Examples of the active hydrogen group-containing compound (Y2) having a carboxyl group include polyols having a carboxyl group and monools having a carboxyl group. Only one kind of active hydrogen group-containing compound (Y2) may be used, or two or more kinds thereof may be used.
Examples of polyols having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2-dimethylolheptanoic acid, and dioxymaleic acid. , 2,6-dioxybenzoic acid and the like.
Examples of monools having a carboxyl group include glycolic acid, lactic acid, hydroxybutyric acid, salicylic acid, parahydroxybenzoic acid, and coumaric acid.
Among these, a polyol having a carboxyl group is preferable because many carboxyl groups can be introduced into the urethane compound and the resulting emulsion has good stability. - is preferably at least one selected from dimethylolbutanoic acid.

The active hydrogen group-containing compound (Y2) having a carboxyl group is preferably a compound represented by the following general formula (6).

In general formula ( ⁶ ), R9 is a hydrogen atom, an alkyl group or an alkenyl group. The number of carbon atoms in the alkyl group or alkenyl group is preferably 1-20, more preferably 1-15. More preferably 1-10.
M is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NRaRbRcRd. Among these, M is preferably a hydrogen atom, an alkali metal or NRaRbRcRd, more preferably a hydrogen atom or an alkali metal.

Alkali metals include, for example, lithium, sodium, potassium and the like. Examples of alkaline earth metals include magnesium, calcium, barium, and the like.

Ra, Rb, Rc and Rd are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-10. Examples of such alkyl groups include methyl, ethyl, n-propyl and isopropyl groups. The number of carbon atoms in the alkanol group is preferably 1-30, more preferably 1-10. Examples of such alkanol groups include methanol, ethanol, n-propanol and isopropanol groups. The polyoxyalkylene group preferably has 2 to 4 carbon atoms. Examples of such polyoxyalkylene groups include polyoxyethylene groups and polyoxypropylene groups.

The structural unit (b2) derived from the compound (Y2) refers to the remainder of the compound (Y2) excluding active hydrogen (active hydrogen that contributes to the reaction with the organic polyisocyanate compound (X)), and has the general formula Taking the compound represented by (6) as an example, it becomes a structural unit represented by the following general formula (7).

(Other active hydrogen group-containing compounds (Y3))
The active hydrogen group-containing compound (Y) may contain an active hydrogen group-containing compound (Y3) other than the polyol (Y1) and the active hydrogen group-containing compound (Y2) as long as the effects of the present invention are not impaired. good. In other words, the structural unit (y) may contain a structural unit (y3) derived from an active hydrogen group-containing compound (Y3) other than the polyol (Y1) and the active hydrogen group-containing compound (Y2).

Active hydrogen group-containing compounds (Y3) include monool components such as methanol, ethanol, propanol, butanol, hexanol, heptanol, octanol, nonanol, phenol, and benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene. Glycol, Dipropylene Glycol, Tripropylene Glycol, Polypropylene Glycol, Butylene Glycol, Dibutylene Glycol, Tributylene Glycol, Polybutylene Glycol, 1,3-Propanediol, 1,4-Butanediol, 1,6-Hexanediol, Neo Diol components such as pentyl glycol, tetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, N-methyldiethanolamine, diethanolamine, resorcinol, hydroquinone, bisphenol A or alkylene oxide adduct thereof; trimethylolethane, Tri- or more functional polyols such as trimethylolpropane, glycerin, sorbitol, pentaerythritol, ditrimethylolpropane; monoamines such as laurylamine, myristylamine, palmitylamine, stearylamine; melamine, diethylenetriamine, triethylenetetramine, tri(aminomethyl) ) tri- or higher functional polyamines such as propane.

The ratio of the structural units (y1) derived from the polyol (Y1) to the total structural units (y) derived from the active hydrogen group-containing compound (Y) is preferably 60 to 99.9 mol%, more preferably 64 to 99.9 mol%. 97 mol %, more preferably 67 to 93 mol %, particularly preferably 70 to 90 mol %. If the proportion is less than 60 mol %, sufficient water repellency may not be exhibited. On the other hand, when the ratio exceeds 90 mol %, the stability of the emulsion may be lowered, and the water repellency may be lowered due to aging.

The ratio of the structural units (y2) derived from the active hydrogen group-containing compound (Y2) to the total structural units (y) is preferably 0.1 to 40 mol%, more preferably 0.5 to 36 mol%, and further It is preferably 1 to 33 mol %, particularly preferably 2 to 30 mol %. If the proportion is less than 0.1 mol %, the stability of the emulsion may be lowered, and the water repellency may be lowered due to deterioration over time. On the other hand, when the ratio exceeds 40 mol %, sufficient water repellency may not be exhibited.

The total ratio of the structural unit (y1) and the structural unit (y2) to the total structural unit (y) is preferably 80 to 100 mol%, more preferably 82 to 99.5 mol%, and still more preferably 85 to 99 mol %, particularly preferably 88 to 98 mol %. If the proportion is less than 80 mol %, sufficient water repellency may not be exhibited.

When other active hydrogen group-containing compound (Y3) is included, the ratio of the structural unit (y3) derived from the active hydrogen group-containing compound (Y3) to the total structural units (y) is preferably 0 to 20 mol%, It is more preferably 0.5 to 18 mol %, still more preferably 1 to 15 mol %, particularly preferably 2 to 12 mol %. If the proportion is more than 20 mol %, sufficient water repellency may not be exhibited.

In the urethane compound (A1), the molar ratio (a:b) between the structural unit (x) derived from the organic polyisocyanate compound (X) and the structural unit (y) of the active hydrogen group-containing compound (Y) is preferably 1:8 to 2:1, more preferably 3:5 to 3:2, still more preferably 4:5 to 1:1. If the molar ratio is not within the range of 1:8 to 2:1, the molecular weight of the urethane compound is low, and the water repellency may be insufficient.
The molar ratio between the structural unit (x) and the structural unit (y) is the molar ratio between the active hydrogen group-containing compound (X) and the organic polyisocyanate compound (Y) when producing the urethane compound.

When the combined ratio of the organic polyisocyanate compound (X) and the active hydrogen group-containing compound (Y) is taken as 100 mol%, the ratio of the active hydrogen group-containing compound (Y) is preferably 10 to 90 mol%. . If the molar ratio of the active hydrogen group-containing compound (Y) is less than 10, water repellency may be insufficient. The proportion is preferably 20 to 80 mol %, more preferably 25 to 75 mol %, still more preferably 30 to 70 mol %.

The weight average molecular weight of the urethane compound (A1) is preferably 4,000 to 2,000,000, more preferably 6,000 to 1,000,000, still more preferably 8,000 to 500,000. If the molecular weight is less than 4,000, sufficient water repellency may not be exhibited. On the other hand, when the molecular weight exceeds 2,000,000, the stability of the emulsion may be lowered, and the water repellency may be lowered due to aging.

The degree of polymerization of the urethane compound (A1) is preferably 4-2,000, more preferably 6-1,000, still more preferably 8-500. If the degree of polymerization is less than 4, sufficient water repellency may not be exhibited. On the other hand, if the degree of polymerization exceeds 2,000, the stability of the emulsion may be lowered, and the water repellency may be lowered due to aging.

The urethane compound (A1) preferably has a hydroxyl value of 0 to 100 mgKOH/g, more preferably 5 to 90 mgKOH/g, still more preferably 10 to 80 mgKOH/g. Incidentally, the hydroxyl value was measured according to JIS K 1557-1970.

The method for producing the urethane compound (A1) is not particularly limited, and known methods can be employed. For example, a one-shot method in which all components are reacted simultaneously, or a multistage method in which active hydrogen group-containing compound (Y) is added stepwise to organic polyisocyanate compound (X) and reacted, or active hydrogen group-containing compound (Y ) is reacted with the organic polyisocyanate compound (X) to synthesize a prepolymer having an isocyanate at the terminal, and then reacted with a chain extender.

Chain extenders include, for example, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3' -dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, -hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylamino Propylamine, ethylenetriamine, dipropylenetriamine, triethylenetetramine, hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic dihydrazide, adipic dihydrazide, glutaric dihydrazide, sebacic dihydrazide, isophthalate Chain extenders having an amino group such as acid dihydrazide, β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazidemethyl-3,5,5-trimethylcyclohexane; ethylene Glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin, sorbitol, bisphenol A, 4, A chain extender having a hydroxyl group such as 4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, and trimethylolpropane can be used. These chain extenders may be used alone or in combination of two or more.

A urethanization catalyst can be used if necessary when preparing the urethane compound (A1). Examples of urethanization catalysts that can be used in the present invention include nitrogen-containing compounds such as triethylamine, triethylenediamine, or N-methylmorpholine, metal salts such as potassium acetate, zinc stearate, or tin octylate, and dibutyl laurate. Organometallic compounds and the like.

When the urethane compound (A1) is emulsified and dispersed in water, the median particle size of the urethane compound (A1) is preferably 0.01 to 8 μm, more preferably 0.05 to 7 μm, and even more preferably 0.05 to 7 μm. is 0.10 to 6 μm. In the present invention, the median value (median value) means the median value (median value) of particle diameters based on volume.

Suitable surfactants are mainly nonionic surfactants, but may also include cationic surfactants and anionic surfactants. Surfactants may be used singly or in combination of two or more.

Examples of nonionic surfactants include polyoxyalkylene linear alkyl ethers such as polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, and polyoxyethylene cetyl ether; Polyoxyalkylene branched primary alkyl ethers such as oxyethylene 2-ethylhexyl ether, polyoxyethylene isocetyl ether, polyoxyethylene isostearyl ether; polyoxyethylene 1-hexylhexyl ether, polyoxyethylene 1-octylhexyl ether, Polyoxyalkylene branched secondary alkyl ethers such as polyoxyethylene 1-hexyloctyl ether, polyoxyethylene 1-pentylheptyl ether, polyoxyethylene 1-heptylpentyl ether; polyoxyalkylenes such as polyoxyethylene oleyl ether alkenyl ether; polyoxyalkylene alkylphenyl ether such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene dodecylphenyl ether; polyoxyethylene tristyrylphenyl ether, polyoxyethylene distyrylphenyl ether, polyoxy Polyoxyalkylene alkylaryl phenyl ethers such as ethylene styryl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, polyoxyethylene benzyl phenyl ether; polyoxyethylene monolaurate, polyoxyethylene monooleate, Polyoxyalkylene fatty acid esters such as polyoxyethylene monostearate, polyoxyethylene monomyristylate, polyoxyethylene dilaurate, polyoxyethylenediolate, polyoxyethylene dimyristylate, polyoxyethylene distearate; sorbitan esters such as palmitate and sorbitan monooleate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; glycerin monostearate, glycerin monolaurate, glycerin monopalmitate and the like glycerin fatty acid ester; polyoxyalkylene sorbitol fatty acid ester; sucrose fat acid ester; polyoxyalkylene castor oil ether such as polyoxyethylene castor oil ether; polyoxyalkylene hydrogenated castor oil ether such as polyoxyethylene hydrogenated castor oil ether; polyoxyalkylene alkyl such as polyoxyethylene lauryl amino ether and polyoxyethylene stearyl amino ether Amino ether; oxyethylene-oxypropylene block or random copolymer; terminal alkyl ether of oxyethylene-oxypropylene block or random copolymer; terminal sucrose ether of oxyethylene-oxypropylene block or random copolymer; etc. can be mentioned.

Examples of anionic surfactants include fatty acids (salts) such as oleic acid, palmitic acid, sodium oleate, potassium palmitate, and triethanolamine oleate; hydroxyacetic acid, potassium hydroxyacetic acid, lactic acid, lactic acid hydroxyl group-containing carboxylic acids (salts) such as potassium salts; polyoxyalkylene alkyl ether acetic acids (salts) such as polyoxyethylene tridecyl ether acetic acid (sodium salts); salts of substituted aromatic compounds; alkylbenzene sulfonic acids (salts) such as dodecylbenzene sulfonic acid (sodium salt); polyoxyalkylene alkyl ether sulfonic acids (salts) such as polyoxyethylene 2-ethylhexyl ether sulfonic acid (potassium salt); Higher fatty acid amidosulfonic acids (salts) such as stearoylmethyltaurate (sodium), lauroylmethyltaurate (sodium), myristoylmethyltaurate (sodium), palmitoylmethyltaurate (sodium); N-acylsarcosine such as lauroylsarcosinate (sodium) Acid (salt); Alkylphosphonic acid (salt) such as octylphosphonate (potassium salt); Aromatic phosphonic acid (salt) such as phenylphosphonate (potassium salt); 2-ethylhexylphosphonate mono 2-ethylhexyl ester (potassium salt), etc. Alkyl phosphonic acid alkyl phosphate (salt); Nitrogen-containing alkyl phosphonic acid (salt) such as aminoethylphosphonic acid (diethanolamine salt); Alkyl sulfate ester (salt) such as 2-ethylhexyl sulfate (sodium salt); Polyoxy Polyoxyalkylene sulfate esters (salts) such as ethylene 2-ethylhexyl ether sulfate (sodium salt); long-chain sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium N-lauroyl glutamate, N- long-chain N-acylglutamates such as disodium stearoyl-L-glutamate;

Examples of cationic surfactants include lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palmityltrimethylammonium chloride, stearyltrimethylammonium chloride, oleyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, coconut oil alkyltrimethyl Ammonium chloride, beef tallow alkyltrimethylammonium chloride, stearyltrimethylammonium bromide, coconut oil alkyltrimethylammonium bromide, cetyltrimethylammonium methosulfate, oleyldimethylethylammonium ethosulfate, dioctyldimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride Alkyl quaternary ammonium salts such as , octadecyldiethylmethylammonium sulfate, etc.; (Polyoxyalkylene) such as ethylene)laurylethylammonium ethosulfate, di(polyoxyethylene) hydrogenated tallow alkylethylamine ethosulfate, di(polyoxyethylene)laurylmethylammonium dimethylphosphate, di(polyoxyethylene)stearylamine lactate, etc. Alkyl amino ether salts; acyl such as N-(2-hydroxyethyl)-N,N-dimethyl-N-stearoylamidopropylammonium nitrate, lanolin fatty acid amidopropylethyldimethylammonium ethosulfate, lauroylamidoethylmethyldiethylammonium methosulfate amidoalkyl quaternary ammonium salts; alkylethenoxy quaternary ammonium salts such as dipalmitylpolyethenoxyethylammonium chloride and distearylpolyethenoxymethylammonium chloride; alkylisoquinolinium salts such as laurylisoquinolinium chloride Salts; benzalkonium salts such as lauryldimethylbenzylammonium chloride and stearyldimethylbenzylammonium chloride; benzethonium salts such as nooxy)ethoxy]ethyl}ammonium chloride; pyridinium salts such as cetylpyridinium chloride; imidazolinium salts such as oleylhydroxyethylimidazolinium ethosulfate and laurylhydroxyethylimidazolinium ethosulfate; Acyl basic amino acid alkyl ester salts such as ester pyrrolidone carboxylate and N-lauroyl lysine ethyl ethyl ester chloride; primary amine salts such as laurylamine chloride, stearylamine bromide, hydrogenated beef tallow alkylamine chloride and rosinamine acetate; cetyl Secondary amine salts such as methylamine sulfate, laurylmethylamine chloride, dilaurylamine acetate, stearylethylamine bromide, laurylpropylamine acetate, dioctylamine chloride, octadecylethylamine hydroxide; dilaurylmethylamine sulfate, lauryldiethylamine chloride , laurylethylmethylamine bromide, diethanolstearylamidoethylamine trihydroxyethyl phosphate salt, stearylamidoethylethanolamine urea polycondensate acetate, and other tertiary amine salts; fatty acid amide guanidinium salts; lauryltriethyleneglycol ammonium hydroxide and alkyltrialkylene glycol ammonium salts such as

[Acrylic polymer (A2)]
The acrylic polymer (A2) is a polymer containing, as a monomer unit, a (meth)acrylic acid ester having 12 or more carbon atoms in the ester portion.

Here, "(meth)acrylic acid ester" means "acrylic acid ester" or the corresponding "methacrylic acid ester", and is synonymous with "(meth)acrylic acid", "(meth)acrylamide", etc. be.

The (meth)acrylic acid ester monomer has an ester moiety having 12 or more carbon atoms as described above, and this ester moiety is preferably a hydrocarbon group. The hydrocarbon group may be linear or branched, saturated or unsaturated, and may have an alicyclic or aromatic ring. You may have Among these, a linear group is preferable, and a linear alkyl group is more preferable. In this case, the water-repellent composition becomes more excellent.

The number of carbon atoms in the above ester moiety is preferably 12-24. If the number of carbon atoms is less than 12, sufficient water repellency cannot be exhibited when the water repellent composition is adhered to a textile product or the like. On the other hand, when the number of carbon atoms exceeds 24, when the water repellent composition is adhered to a textile product, etc., the texture of the textile product tends to be rough and hard compared to the case where the number of carbon atoms is in the above range. be.

More preferably, the number of carbon atoms in the ester moiety is 12-21. When the number of carbon atoms is within this range, the water repellency and feel are particularly excellent. A linear alkyl group having 12 to 18 carbon atoms is particularly preferred as the ester moiety.

The acrylic polymer (A2) contains, as monomer units, a (meth)acrylic acid ester having 12 or more carbon atoms in the ester portion, and a monofunctional or polyfunctional monomer copolymerizable therewith. You can

Examples of copolymerizable monofunctional or polyfunctional monomers include fumaric acid ester, maleic acid ester, (meth)acrylic acid ester having a hydrocarbon group having 1 to 11 carbon atoms, (meth)acrylic acid, Examples thereof include fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, vinyl chloride, vinylidene chloride, ethylene, fluorine-free vinyl monomers such as styrene.

In the (meth)acrylic acid ester having a hydrocarbon group having 1 to 11 carbon atoms, the hydrocarbon group is a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, a blocked isocyanate group, or a quaternary It may have a substituent such as an ammonium group, and may have an ether bond, an ester bond, an amide bond, or a urethane bond.

Examples of (meth)acrylic acid esters having a hydrocarbon group having 1 to 11 carbon atoms include methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ( dimethylaminoethyl meth)acrylate, glycidyl (meth)acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, ethylene glycol di(meth)acrylate and the like. These monomers may be used alone or in combination of two or more.

The acrylic polymer (A2) has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group and an isocyanate group, thereby improving the washing durability of the water repellency of textile products. It is preferable because it allows The isocyanate group may form a blocked isocyanate group protected with a blocking agent. These functional groups are introduced into the acrylic polymer (A2), for example, by copolymerizing reactive monomers having these functional groups. As the reactive monomer, among the monomers listed above, 2-hydroxyethyl (meth)acrylate, N-methylolacrylamide, and (meth)acrylic acid that can react with the crosslinking agent and textile products described later. dimethylaminoethyl acid, (meth)acrylic acid, glycidyl (meth)acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate. Moreover, the (meth)acrylic acid ester whose ester portion has 12 or more carbon atoms may have the above functional group.

[Method for producing acrylic polymer (A2)]
The acrylic polymer (A2) can be produced by a radical polymerization method. Among these radical polymerization methods, emulsion polymerization or dispersion polymerization is preferred from the viewpoint of the performance of the resulting water repellent agent and the environment.

When homopolymerizing or copolymerizing a monomer such as a (meth)acrylic acid ester having 12 or more carbon atoms in the ester portion by emulsion polymerization or dispersion polymerization, the monomer and an emulsifier or dispersion are added to the medium. agents are added, and the mixture is emulsified or dispersed. Then, by adding a polymerization initiator to the emulsified or dispersed liquid mixture, a polymerization reaction is initiated and the monomers can be polymerized. Examples of means for emulsifying or dispersing the mixed liquid described above include a homomixer, a high-pressure emulsifier, and ultrasonic waves.

As the emulsifier and the like, one or more selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants can be used. The content of the emulsifier and the like is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total monomers. When the amount of the emulsifier, etc. is less than 0.5 parts by mass, the dispersion stability of the mixed liquid tends to be lower than when the amount of the emulsifier, etc. is within the above range. When the amount exceeds parts by mass, the resulting water repellent agent comprising a non-fluorinated polymer tends to have lower water repellency than when the amount of the emulsifier and the like is within the above range.

The medium for emulsion polymerization or dispersion polymerization is preferably water. As the medium, if necessary, water and an organic solvent may be mixed. The organic solvent used here is not particularly limited as long as it is miscible with water. Examples include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, diethyl Examples include ethers such as ethers, and glycols such as propylene glycol, dipropylene glycol and tripropylene glycol. In addition, the ratio of water and the organic solvent is not particularly limited.

As the polymerization initiator, known polymerization initiators such as azo-based, peroxide-based, or redox-based polymerization initiators can be appropriately used. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total monomers. When the content of the polymerization initiator is within the above range, the acrylic polymer (A2) having a weight average molecular weight of 100,000 or more can be efficiently produced.

Also, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent is preferably 0.1 parts by mass or less with respect to 100 parts by mass of all the monomers. If the content of the chain transfer agent exceeds 0.1 parts by mass, the molecular weight tends to decrease, making it difficult to efficiently produce the acrylic polymer (A2) having a weight average molecular weight of 100,000 or more. .

A polymerization inhibitor may be used for molecular weight adjustment. An acrylic polymer (A2) having a desired weight average molecular weight can be easily obtained by adding a polymerization inhibitor.

The temperature of the polymerization reaction is preferably 20°C to 150°C. When the temperature is less than 20°C, the polymerization tends to be insufficient compared to when the temperature is within the above range, and when the temperature exceeds 150°C, it may become difficult to control the heat of reaction. .

In the polymerization reaction, the weight average molecular weight of the obtained acrylic polymer (A2) can be adjusted by increasing or decreasing the content of the polymerization initiator, chain transfer agent, and polymerization inhibitor described above, and the melt viscosity at 160°C is It can be adjusted by increasing or decreasing the content of the polyfunctional monomer and the content of the polymerization initiator. If it is desired to lower the melt viscosity at 160° C., the content of the monomer having two or more polymerizable functional groups may be reduced, or the content of the polymerization initiator may be increased.

[Reactive silicone component (A3)]
The reactive silicone component (A3) includes side chains, one end, both ends, side chains and both ends, and polysiloxanes having reactive groups. Polysiloxanes having reactive groups on side chains and/or both terminals are preferred from the standpoint of superiority.
The reactive silicone component (A3) is not particularly limited as long as it has a reactive group in the molecule, and examples thereof include amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and methylhydrogensilicone.

Examples of amino-modified silicone include those having a structure in which an amino group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. As the alkylene group, those having 2 or more carbon atoms are preferred. As the divalent aromatic group, those having 6 or more carbon atoms are preferred. The amino group may be a primary amino group, a secondary amino group, or a tertiary amino group. Examples of organic groups to which amino groups are bonded include the following. 2-aminoethyl group, N-methyl-2-aminoethyl group, N,N-dimethyl-2-aminoethyl group, N-ethyl-2-aminoethyl group, N,N-diethyl-2-aminoethyl group, N,N-methylethyl-2-aminoethyl group, 3-aminopropyl group, N-methyl- 3 -aminopropyl group, N,N-dimethyl-3-aminopropyl group, N-ethyl-3-anopropyl group, N,N-diethyl-3-aminopropyl group, N,N-methylethyl-3-aminopropyl group. These functional groups can be on the side chains of the polysiloxane or on the terminals.

Epoxy-modified silicones include those having a structure in which an epoxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. As such a form, it is usually bonded in the form of a glycidyl ether to the organic group. Examples of such functional groups include a 3-glycidoxypropyl group and a 2-glycidoxyethyl group. These functional groups can be on the side chains of the polysiloxane or on the terminals.

Examples of carboxy-modified silicones include those having a structure in which a carboxy group is bonded to an organic group directly bonded to a silicon atom. The organic group may be either an alkylene group or a divalent aromatic group. As the alkylene group, those having 2 or more carbon atoms are preferred. As the divalent aromatic group, those having 6 or more carbon atoms are preferred. Examples of such functional groups include a 3-carboxypropyl group and a 2-carboxyethyl group. These functional groups can be on the side chains of the polysiloxane or on the terminals.

Methylhydrogensilicone is a polydiorganosiloxane whose side chains are partly substituted with hydrogen and the hydrogen atoms are directly linked to silicon atoms. When using methylhydrogensilicone, a catalyst may be used to improve reactivity. For example, zinc, tin, manganese, cobalt, iron and amine based catalysts can be used. Organic acid metal salts are preferred as these catalysts, and fatty acids are preferred as organic acids. From the viewpoint of safety, zinc stearate or the like can be used. It is preferable to use the catalyst in an amount of 10 to 40% relative to the methylhydrogensilicone, because the effect can be easily exhibited. Two or more kinds of amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone and methyl hydrogen silicone may be mixed. All of them are silicones having reactive groups, preferably silicones having film-forming properties. The term "film-forming" refers to the ability to form a solid film, not an oily or gel-like film, after adhering each of the silicones in an emulsion state to the fiber surface.

[Silicone resin (B)]
The silicone resin (B) is a silicone resin comprising at least one selected from R ₃ SiO _1/2 units (M units), RSiO _3/2 units (T units) and SiO _4/2 units (Q units). , R is a linear or branched monovalent alkyl group having 1 to 18 carbon atoms, and silicone resins consisting of only M units and only Q units are excluded). The silicone resin (B) preferably does not contain R ₂ SiO _2/2 units (D units) from the viewpoint of exhibiting the effects of the present application.
The silicone resin (B) is preferably in a sol state from the viewpoint of exhibiting the effects of the present application.
Examples of R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, cetyl group and stearyl group. In terms of stability when (B) is in a sol state, availability of raw materials, and cost, R is preferably a methyl group, and in particular, 90% or more of all Rs are methyl groups. is preferred. In addition, R may use different types of groups in combination.

If the silicone resin (B) contains R ₂ SiO _2/2 units (D units), the low slip properties of the water repellent composition are impaired. Moreover, the silicone resin (B) consisting only of Q units impairs the water repellent performance as a water repellent composition.
The structure of the silicone resin (B) is composed of (i) M units and Q units, (ii) M units, T units and Q units, (iii) M units and T units, (iv) T units and Q units, (v ) Silicone resins consisting only of T units are exemplified, and preferred are (i) silicone resins consisting of M and Q units and (v) silicone resins consisting only of T units. (i) The molar ratio (M/Q) of M units and Q units in a silicone resin comprising M units and Q units is preferably M/Q = 0.6 to 1.3, and M/Q = 0. 0.8 to 1.1 is more preferred. Two or more of these silicone resins may be used in combination.
In addition, the silicone resin (B) can contain structural units containing hydroxyl groups bonded to silicon atoms. Specifically, (HO)RSiO _2/2 units, (HO) ₂ RSiO _1/2 units, (HO)SiO _3/2 units, (HO) ₂ SiO _2/2 units, (HO) ₃ SiO _{1 /2} unit, and an alkoxy group in which a part of the hydroxyl group is represented by an RO group may be used.

[Method for producing sol containing silicone resin (B)]
A sol containing a silicone resin (B) is produced by uniformly dispersing and polymerizing an organodisiloxane, a tetraalkoxysilane, and a partial hydrolysis condensate thereof in water containing a surfactant, as described in Japanese Patent No. 3852921. , can be obtained by a production method of hydrolyzing a silane compound shown below in water.

A manufacturing method for hydrolyzing a silane compound in water will be described in detail. As a raw material for production, any silane compound having a chloro or alkoxy hydrolyzable group, 1, 3 or 4 hydrolyzable groups and an alkyl group satisfying the above conditions can be used. can also be used. Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Propyltrichlorosilane, Propyltrimethoxysilane, Propyltriethoxysilane, Isopropyltrichlorosilane, Isopropyltrimethoxysilane, Isopropyltriethoxysilane, Butyltrichlorosilane, Butyltrimethoxysilane, Butyltriethoxy silane, isobutyltrichlorosilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, 2-ethylhexyltrichlorosilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, cetyltrichlorosilane, cetyltrimethoxysilane, cetyltriethoxysilane, stearyltrichlorosilane, stearyltrimethoxysilane, stearyltriethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, Trimethylethoxysilane, trimethylisopropoxysilane, dimethylethylchlorosilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylpropylchlorosilane, dimethylpropylmethoxysilane, dimethylpropylethoxysilane, dimethylisopropylchlorosilane, dimethylisopropylmethoxysilane, dimethyl isopropylethoxysilane, dimethylhexylchlorosilane, dimethylhexylmethoxysilane, dimethylhexylethoxysilane, dimethyldecylchlorosilane, dimethyldecylmethoxysilane, dimethyldecylethoxysilane, dimethylcetylchlorosilane, dimethylcetylmethoxysilane, dimethylcetylethoxysilane, dimethyl Silane compounds that can be used include stearylchlorosilane, dimethylstearylmethoxysilane, dimethylstearylethoxysilane, and partial hydrolysates thereof, but the silane compounds that can be used are not limited to these. It is more preferable to use methoxysilane or ethoxysilane in terms of operability, ease of distilling off by-products, and availability of starting materials. One or a mixture of two or more of these silane compounds may be used.

As a method for hydrolyzing the silane compound in water, a generally known method can be used. That is, there is a method in which the hydrolysis reaction is performed while dropping the silane compound into water, and there is a method in which the water and the silane compound are mixed together and then the hydrolysis reaction is performed.
A hydrolysis catalyst may be used in carrying out the hydrolysis reaction. A conventionally known catalyst can be used as the hydrolysis catalyst, and an acidic or alkaline catalyst is preferably used. In the case of acidic catalysts, hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and solid acids such as ion exchange resins are preferred. In the case of alkaline catalysts, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate, alkali metal silanolates such as sodium silanolate and potassium silanolate, amines such as triethylamine, diethylamine and aniline. , ammonia water and the like can be used. The amount of catalyst added is preferably adjusted so that the pH of the aqueous solution is 2-7 and 7-12. A neutralizing agent for neutralizing the acidic or alkaline catalyst may be added after the reaction is finished, if necessary.

A surfactant may be added to the aqueous solution to disperse the silane compound and hydrolysis reaction product in water. Surfactants are not particularly limited, but examples include anionic surfactants such as alkyl sulfates, alkylbenzenesulfonates, and alkyl phosphates, polyoxyethylene alkyl ethers, polyoxyethyleneoxypropylene alkyl ethers, and polyoxyethylene. Nonionic surfactants such as alkylphenyl ethers and polyoxyethylene fatty acid esters, cationic surfactants such as quaternary ammonium salts and alkylamine acetates, and amphoteric surfactants such as alkylbetaines and alkylimidazolines can be used. , these can be used alone or in combination of two or more. Surfactants exhibiting acidity or alkalinity can also be used as hydrolysis catalysts. The amount of the surfactant added is not particularly limited, but it is preferably 1 to 50 parts by weight per 100 parts by weight of the silane compound. If the amount is less than 1 part by weight, the effect of adding the surfactant cannot be sufficiently obtained, and if the amount is more than 50 parts by weight, the water repellency of the water repellent composition may be impaired.

If necessary, a hydrolysis catalyst and a surfactant are added to the mixture of water and the silane compound, and the hydrolysis reaction is carried out at 0 to 90° C. for 10 minutes to 24 hours. A silicone resin (B) can be obtained by carrying out a neutralization reaction as necessary thereafter. Also, alcohols, neutralized salts, etc., which are by-produced by the hydrolysis reaction can be removed by distillation under reduced pressure, filtration, or the like.
Various additives can be added to this silicone resin. For example, antiseptics, thickeners and the like can be blended depending on the purpose.

[Crosslinking agent]
It is preferable that the water repellent composition for textiles of the present invention further contains a cross-linking agent because high water repellency and durability to washing can be obtained.
Examples of cross-linking agents include melamine, blocked isocyanate, carbodiimide-based cross-linking agents, and oxazoline-based cross-linking agents.

Melamine includes commonly used N-methylolmelamine such as trimethylolmelamine and hexamethylolmelamine, and melamine catalysts include commonly used amine salt catalysts. Examples of melamine include Beccamine M-3 (manufactured by DIC Corporation), and examples of catalysts for melamine include Catalyst ACX.

A blocked isocyanate can be obtained by reacting a bifunctional or higher functional isocyanate with an appropriate blocking agent by a known method. Isocyanates include 4,4'-bisisocyanatophenylmethane, toluene diisocyanate, hexamethylene diisocyanate, trimers of diisocyanates, and trimethylolpropane adducts.

Examples of isocyanate blocking agents include secondary or tertiary alcohols, active methylene compounds, phenols, oximes, substituted pyrazoles, caprolactam and the like. These blocked isocyanates are usually emulsified and dispersed using a surfactant by a known method. In addition, after blocking 70 to 95% of all isocyanate groups in advance, polyalkylene glycol having an appropriate molecular weight, especially polyethylene glycol, is reacted with the remaining isocyanate groups. It is effective not only in improving the washing durability of the water repellent composition but also in improving the stability of the product.
Carbodiimide-based cross-linking agents are polymers having carbodiimide groups in the molecule, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β- Naphthylcarbodiimides may be mentioned. A carbodiimide-based cross-linking agent is a cross-linking agent that exhibits excellent reactivity with carboxy groups, amino groups, and active hydrogen groups in the water repellent composition. Carbodiimide catalysts include Carbodilite E-02 (Nisshinbo Chemical Co., Ltd.) and Carbodilite V-02 (Nisshinbo Chemical Co., Ltd.).
The oxazoline-based cross-linking agent is a polymer having oxazoline groups in the molecule, and is a cross-linking agent that exhibits excellent reactivity with the carboxy groups in the water repellent composition. Examples of oxazoline-based cross-linking agents include Epocross WS-300 (Nippon Shokubai Co., Ltd.) and Epocross WS-500 (Nippon Shokubai Co., Ltd.).

〔water〕
The water may be pure water, distilled water, purified water, soft water, ion-exchanged water, tap water, or the like.

〔Organic solvent〕
It is preferable that the water repellent composition for textiles of the present invention further contains an organic solvent because the uniform adhesion of the water repellent composition to the textile material is excellent.
Examples of organic solvents include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetic acid ester solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; Solvents, aromatic-containing solvents such as toluene and xylene, alcohols such as methanol, ethanol, propanol, butanol, octanol, benzyl alcohol and isopropyl alcohol, methyl glycol, isopropyl glycol, butyl glycol, butyl diglycol, butyl propylene glycol, tri Glycol-based solvents such as propylene glycol and dipropylene glycol can be used. Among them, methanol, ethanol, methyl ethyl ketone, benzyl alcohol, isopropyl alcohol, butyl glycol, butyl propylene glycol, and tripropylene glycol are preferable from the viewpoint of improving the stability of the textile water repellent composition and exhibiting the effects of the present application. , isopropyl alcohol, butyl glycol, and butyl propylene glycol are more preferred.
The weight ratio of the organic solvent to the water repellent composition for fibers is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight, from the viewpoint of exhibiting the effects of the present invention. is more preferred.

[Textile water repellent composition]
The weight ratio of component (A) to the non-volatile content of the textile water repellent composition is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, still more preferably 20 to 70% by weight. If it is less than 10% by weight, the water repellency may be insufficient, and if it exceeds 90% by weight, the sliding property may be insufficient.
Here, the non-volatile content (also referred to as solid content) means that a certain amount of the sample is spread evenly on an aluminum sheet and dried at 110 ° C. under infrared lamp irradiation, and the fluctuation range of the volatile content for 150 seconds is 0.15% by weight. It is the remainder when the end point of the measurement is the time when it becomes.

The weight ratio of the component (B) in the non-volatile matter of the water repellent composition for fibers is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, still more preferably 20 to 70% by weight. If it is less than 10% by weight, the sliding property may be insufficient, and if it exceeds 90% by weight, the water repellency may be insufficient.

When the urethane compound (A1) is dissolved, emulsified or dispersed in water and/or an organic solvent, it is preferable to use a surfactant. The proportion of the surfactant is preferably 5-50% by weight, more preferably 10-30% by weight, still more preferably 10-20% by weight, relative to the urethane compound (A1).
When the acrylic resin (A2) is dissolved, emulsified or dispersed in water and/or an organic solvent, it is preferable to use a surfactant. The proportion of the surfactant is preferably 5-50% by weight, more preferably 10-30% by weight, still more preferably 10-20% by weight, relative to the acrylic resin (A2).
When the reactive silicone (A3) is dissolved, emulsified or dispersed in water and/or an organic solvent, it is preferred to use a surfactant. The proportion of the surfactant is preferably 5-50% by weight, more preferably 10-30% by weight, still more preferably 10-20% by weight, relative to the reactive silicone (A3).

The weight ratio (A:B) of the component (A) and the component (B) is preferably 15:1 to 1:15, more preferably 10:1 to 1:10, and 5:1 to 1:5. More preferably, 3:1 to 1:3 is particularly preferred. If it exceeds 15:1, the amount of hydrocarbon and silicone in the water repellent composition may become excessive, resulting in poor sliding properties. Water may be poor.

The weight ratio of non-volatile matter in the water repellent composition for fibers is preferably 1 to 80% by weight, more preferably 5 to 50% by weight, even more preferably 10 to 30% by weight, relative to the composition. If it is less than 1% by weight, water repellency may be insufficient, and if it exceeds 80% by weight, the stability of the water repellent composition may be insufficient.

The pH of the water repellent composition for textiles at a concentration of 1% by weight of non-volatile matter is preferably 3 to 9, more preferably 4 to 8, more preferably 4 to 7, from the viewpoint of easily adsorbing to the fibers and exhibiting the effect of the present application. More preferred.

Additives and the like may be added to the water repellent composition for fibers of the present invention, if necessary. Additives such as other water repellents, cross-linking agents, discoloration inhibitors, antibacterial agents, antifungal agents, insect repellents, anti-mite agents, deodorants, antistatic agents, water and oil repellent agents, ultraviolet absorbers, Fiber post-processing agents such as flame retardants, antifouling agents, darkening agents, smoothing agents, softeners and water absorbing agents, oils, inorganic substances, preservatives, pH adjusters, antifoaming agents, solvents, fatty acids (salts), etc. is mentioned.
The water repellent composition for fibers of the present invention preferably does not substantially contain a fluorine-based water repellent for fibers (non-fluorine-based water repellent composition for fibers), but is not limited thereto.

The method for producing the water repellent composition for fibers of the present invention is not particularly limited, and known methods can be employed. For example, at least one selected from the urethane compound (A1), the acrylic resin (A2) and the reactive silicone component (A3) obtained by the above method, a surfactant, water and/or an organic solvent, and emulsified using a general stirring device and an emulsifier such as a homomixer, a homogenizer, a high-pressure emulsifier, a colloid mill, or a line mixer.

[Water-repellent textile products]
The water-repellent textile product of the present invention is obtained by treating a textile material with the water repellent composition for textiles.

The fiber material may be either natural fiber or chemical fiber. Examples of natural fibers include plant fibers such as cotton, hemp, flax, palm, and rush; animal fibers such as wool, goat hair, mohair, cashmere, camel, and silk; and mineral fibers such as asbestos. Chemical fibers include, for example, mineral fibers such as rock fiber, metal fiber, graphite, silica, and titanate; regenerated cellulose fibers such as rayon, cupra, viscose, polynosic, and purified cellulose fibers; melt-spun cellulose fibers; Protein-based fibers such as milk protein and soy protein; regenerated/semi-synthetic fibers such as regenerated silk and alginic acid fiber; polyamide fiber, polyester fiber, cationic dyeable polyester fiber, polyvinyl fiber, polyacrylic alcohol fiber, polyurethane fiber, acrylic fiber, Synthetic fibers such as polyethylene fibers, polyvinylidene fibers and polystyrene fibers can be mentioned. Also, two or more of these fibers may be combined (mixed spinning, mixed fiber, mixed weave, mixed knit, etc.).
When the water repellent agent composition contains the urethane compound (A1) and/or the acrylic resin (A2), polyester fiber, cationic dyeable polyester fiber, polyurethane fiber, and acrylic fiber are used as fiber materials from the viewpoint of easily exhibiting water repellency. Alternatively, it is preferable to treat polyethylene fibers.
When the water repellent composition contains a reactive silicone (A3), polyester fibers, cationic dyeable polyester fibers, polyurethane fibers, acrylic fibers, cotton, silk or rayon can be treated from the viewpoint of easily exhibiting water repellency. preferable.

Examples of the form of the fiber material include woven fabric, knitted fabric, fabric, filament, non-woven fabric, and the like. Applications of textile materials include objects to which antibacterial properties, water absorbency, and resistance to washing are to be imparted, such as underwear, sportswear, bedding, covers, and the like.

[Method for producing water-repellent textile]
The method for producing a water-repellent textile product of the present invention includes a step (I) of applying a treatment liquid containing the above-described textile water repellent composition to a textile material, and a step (II) of heat-treating the textile material to which the treatment liquid has been applied. ) and
(Step (I))
Step (I) is a step of applying a treatment liquid containing the textile water repellent composition to the textile material, and the textile material is treated by an immersion method, an impregnation method, a pad dry method, a spray method, or a coating method. is. Among these methods, the pad dry method is most suitable in terms of productivity and economy.

In the case of the immersion method, the impregnation method and the pad dry method, the weight ratio of the fiber material to the immersion bath is preferably 1:2 to 1:100, more preferably 1:20 to 1:100.
The weight ratio of the water repellent composition for textiles of the present invention to the immersion bath is preferably 1:200 to 2:3, more preferably 1:20 to 1:5.

(Step (II))
Step (II) is a step of heat-treating the fiber material to which the treatment liquid has been applied.
As a method of heat-treating, it is preferable to use a normal heat-treating machine such as a pin tenter.
From the viewpoint of exhibiting the effects of the present application, the heat treatment temperature is preferably 80°C or higher, more preferably 100 to 200°C. From the viewpoint of exhibiting the effects of the present application, the heat treatment time is preferably 30 seconds to 120 minutes, more preferably 1 minute to 30 minutes.

EXAMPLES Hereinafter, the present invention will be described in more detail by showing examples of the present invention, but the present invention is not limited to these examples. "Parts" and "%" in the examples represent "parts by weight" and "% by weight", respectively.

<Evaluation of water repellency>
The evaluation was made according to the spray method of JIS L1092 (2017) with the shower water temperature set at 25°C. As a criterion for judgment, if the grade was 4 or higher, it was evaluated as having sufficient water repellency.

<Evaluation of sliding property>
Evaluation was performed according to the seam sliding method (method A) of JIS L1096 (2017). A load of 147.1 N was applied to confirm slippage of the seams.

<Evaluation of SR property>
A drop of the sebum substitute was applied to the fabric, and the fabric was left to stand overnight and then washed. After washing, it was visually confirmed whether or not the substitute sebum had been removed. If it is removed, it is judged to be acceptable and marked with ◯ in the table.
Substitute sebum composition: 30 parts by weight of oleic acid, 15 parts by weight of triolein, 10 parts by weight of liquid paraffin, 15 parts by weight of cholesterol, 10 parts by weight of palmitic acid, 10 parts by weight of gelatin, 0.5 parts by weight of oil red

These results are shown in Tables 1-6.
(A1-1) Polyurethane water repellent (anionic)
In a four-necked flask equipped with a stirrer, a thermometer and a reflux tube, sorbitan distearate as a polyol (Y1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule is added to 500 parts by weight of methyl ethyl ketone. 400 parts by weight, 72 parts by weight of hexamethylene diisocyanate (HDI) as a polyisocyanate compound (X), 2 parts by weight of dimethylolpropanoic acid as an active hydrogen group-containing compound (Y2) having a carboxyl group, and added at 90 to 100 ° C. for 60 minutes, and then methyl ethyl ketone (MEK) was removed to obtain a urethane compound (A1-1).
Then, in a pressure-resistant autoclave, 100 parts by weight of the obtained urethane compound (A1-1), 10 parts by weight of polyoxyethylene (10 mol addition) lauryl ether, 5 parts of 13.6% by weight ammonia water, water was added, and sufficiently stirred and dispersed at 100 to 110° C. for 60 minutes to obtain an aqueous dispersion (A1-A).

(A1-2) Polyurethane water repellent (cationic)
In a four-necked flask equipped with a stirrer, a thermometer and a reflux tube, sorbitan distearate as a polyol (Y1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule is added to 500 parts by weight of methyl ethyl ketone. 400 parts by weight of, 72 parts by weight of hexamethylene diisocyanate (HDI) as a polyisocyanate compound (X), and 2 parts by weight of diethanolamine as an active hydrogen group-containing compound (Y3) are added, reacted at 90 to 100 ° C. for 60 minutes, After that, methyl ethyl ketone (MEK) was removed to obtain a urethane compound (A1-2).
Then, 100 parts by weight of the urethane compound (A1-2) obtained in the pressure-resistant autoclave, 10 parts by weight of polyoxyethylene (10 mol addition) lauryl ether, 5 parts of 90.0% by weight acetic acid water, and water. 385 parts by weight were added and sufficiently stirred and dispersed at 100 to 110° C. for 60 minutes to obtain a water dispersion (A1-B).

(A2-1) Acrylic polymer water repellent 55 parts by weight of stearyl methacrylate, 20 parts by weight of lauryl methacrylate, 1 part by weight of stearyldimethylamine hydrochloride, 4 parts by weight of polyoxyethylene (10 mol) lauryl ether, 25 parts by weight of tripropylene glycol Parts by weight and 144.8 parts by weight of water were added and mixed and stirred at 45° C. to obtain a mixed solution. This mixed liquid was emulsified and dispersed by a homomixer. Next, 0.25 parts by weight of azobis(isobutylamidine) dihydrochloride is added to the mixed solution, and radical polymerization is performed at 60° C. for 6 hours under a nitrogen atmosphere to obtain an acrylic resin (A2-1) having a polymer concentration of 30% by mass. A water dispersion (A2-A) in which was dispersed was obtained.

(A3-1) H silicone emulsion 200 parts by weight of methylhydrogenpolysiloxane, 100 parts by weight of dimethyl silicone, 50 parts by weight of stearylamine, 10 parts by weight of palmitic acid, 5 parts by weight of polyoxyethylene (10 mol) lauryl ether, poly 5 parts by weight of oxyethylene (5 mol) lauryl ether, 5 parts by weight of acetic acid and 625 parts by weight of water were mixed and emulsified and dispersed using a homomixer to obtain H silicone emulsion (A3-A).

(A3-2) Amino-modified silicone emulsion 200 parts by weight of amino-modified silicone, 15 parts by weight of polyoxyethylene (9 mol) lauryl ether, 15 parts by weight of polyoxyethylene (5 mol) lauryl ether, 1 part by weight of acetic acid, 769 parts by weight of water Parts by weight were mixed and emulsified and dispersed using a homomixer to obtain an amino-modified silicone emulsion (A3-B).

(A3-3) Carbinol-modified silicone emulsion Carbinol-modified silicone 200 parts by weight, polyoxyethylene (15 mol) lauryl ether 15 parts by weight, polyoxyethylene (9 mol) lauryl ether 15 parts by weight, isopropyl alcohol 5 parts by weight , and 765 parts by weight of water, and emulsified and dispersed using a homomixer to obtain a carbinol-modified silicone emulsion (A3-C).

(B-1) Anionic silicone resin sol Mix 4 parts by weight of dodecylbenzenesulfonic acid and 738 parts by weight of water, heat to 45 to 50° C., and then partially add 100 parts by weight of hexamethyldisiloxane and tetramethoxysilane. A mixture of 145 parts by weight of a decomposition condensate (methyl silicate 51: SiO ₂ minutes 51% by weight, manufactured by Colcoat Co.) was added dropwise over 2 hours, followed by further polymerization at 50° C. for 6 hours. These were combined to obtain a bluish-white translucent silicone resin (B-1) sol. The M/Q of the obtained silicone resin was 1.0.
(B-2) Cationic silicone resin sol 0.6 parts by weight of alkylbenzyldimethylammonium chloride, 83.3 parts by weight of water, and 0.04 parts by weight of sodium hydroxide are mixed and heated to 75 to 80°C. 14.9 parts by weight of methyltriethoxysilane was added dropwise over 1 hour, polymerized at 75 to 80° C. for 1 hour, and then neutralized with 0.06 parts by weight of acetic acid to give a bluish-white translucent silicone resin (B- 2) was obtained.

(Production of water repellent composition for textiles)
Parts by weight in Examples 1 to 48 and Comparative Examples 1 to 21 below are parts by weight as non-volatile matter. However, Examples 25-33 and 37-42 are referred to as Reference Examples 25-33 and 37-42, respectively.
(Example 1)
Anionic urethane compound (A1-1) 1 part by weight, Beccamine M-3 (manufactured by DIC Corporation) 0.4 parts by weight, Catalyst ACX (manufactured by DIC Corporation) 0.04 parts by weight, anionic silicone resin 0.5 parts by weight of sol (B-1), 1.2 parts by weight of isopropyl alcohol, and 97 parts by weight of water were stirred and mixed at room temperature to obtain a water repellent composition.
(Examples 2 to 48, Comparative Examples 1 to 16)
Each component was mixed at room temperature in the same manner as in Example 1 to obtain a water repellent composition.

(Method for producing water-repellent textile products)
The resulting water repellent composition was processed into a textile material under the following conditions to obtain a water repellent textile product.
<Processing conditions>
Sample cloth: polyester tropical, T/C broadcloth, cotton broadcloth Padding: dipped twice and squeezed twice, squeeze rate 100% by weight
Treatment liquid: Water repellent compositions shown in Examples 1 to 48 and Comparative Examples 1 to 16 Heat treatment (drying) conditions: 110°C x 3 minutes, 160°C x 1 minute

As can be seen from Tables 1 to 6, the water repellent composition of the present invention contains at least one component (A) selected from urethane compounds (A1), acrylic resins (A2) and reactive silicones (A3) and , a silicone resin (B) and water, wherein the urethane compound (A1) and the acrylic resin (A2) have at least one hydrocarbon having 12 or more carbon atoms in the molecule. and the unit constituting the silicone resin (B) is at least one selected from M units represented by R ₃ SiO _1/2 , Q units represented by SiO _4/2 and T units represented by RSiO _3/2 . species (excluding only M units and only Q units), and R represents a linear or branched monovalent alkyl group having 1 to 18 carbon atoms. It is excellent in slip resistance and exhibits low slippage (slip suppression). Moreover, when the component (A) contains the reactive silicone (A3), it is found that not only the low slip property (slip prevention), which is the subject of the present application, is excellent, but also the antifouling property is excellent.
On the other hand, it can be seen that in the comparative examples, sliding cannot be suppressed or the water repellency is low.

The textile water repellent composition of the present invention is particularly effective when applied to textile products and the like. In addition, since the water repellent composition for textiles of the present invention does not contain a fluorine compound, it is inexpensive and useful as a water repellent with low adverse effects on the human body and the environment. Furthermore, since it has low sliding properties, it is effective in improving the quality of final products such as textile products.

Claims (5)

A water repellent composition comprising a component (A) that is at least one selected from a urethane compound (A1) and a reactive silicone (A3), a silicone resin (B), and water,
The urethane compound (A1) has at least one hydrocarbon group having 12 or more carbon atoms in the molecule, and the reactive silicone (A3) is at least selected from epoxy-modified silicone, carboxy-modified silicone and methylhydrogensilicone. is one type,
The weight ratio (A:B) of the component (A) and the component (B) is 15:1 to 1:15,
The units constituting the silicone resin (B) are only M units (MQ) represented by R ₃ SiO _1/2 and Q units (MQ) represented by SiO _4/2 or T units (T) represented by RSiO _3/2 . A water repellent composition for textiles , wherein R represents a linear or branched monovalent alkyl group having 1 to 18 carbon atoms. 2. The water repellent composition for fibers according to claim 1, wherein said reactive silicone (A3) is a polysiloxane having reactive groups on side chains and/or both ends. The textile water repellent composition according to claim 1 or 2 , further comprising an organic solvent. A water-repellent textile product obtained by treating a textile material with the water repellent composition for textiles according to any one of claims 1 to 3 . A step (I) of applying a treatment liquid containing the textile water repellent composition according to any one of claims 1 to 3 to a textile material, and a step (II) of heat-treating the textile material to which the treatment liquid has been applied. A method for producing a water-repellent textile product, comprising: