JP2018104866A - Water-repellent composition, water-repellent fiber product and method for producing water-repellent fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent composition that can give better water repellency to a fiber product and the like as compared to the conventional fluorine-free water repellents, provide a water-repellent fiber product having excellent water repellency and a method for producing the fiber product.SOLUTION: A water-repellent composition contains (I) silica modified with a hydrophilizing agent and a hydrophobizing agent, and (II) resin.SELECTED DRAWING: None

Description

  The present invention relates to a water repellent composition, a water repellent fiber product, and a method for producing a water repellent fiber product.

  Conventionally, a fluorine-based water repellent having a fluorine group is known, and a fiber product in which water repellency is imparted to its surface by treating such a fluorine-based water repellent to a fiber product or the like is known. Such a fluorine-based water repellent is generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group. Although the fiber product treated with the fluorine-based water repellent exhibits excellent water repellency, the monomer having a fluoroalkyl group is hardly decomposable and has a problem in terms of environment.

  In recent years, therefore, research has been conducted on non-fluorinated water repellents that do not contain fluorine. For example, Patent Document 1 below proposes a water-repellent agent composed of a specific non-fluorinated polymer containing a (meth) acrylic acid ester having an ester moiety having 12 or more carbon atoms as a monomer unit.

JP 2006-328624 A

  However, the non-fluorinated water repellent described in Patent Document 1 is still insufficient in water repellency in practical use, and further improvement in water repellency is required.

  The present invention has been made in view of the above circumstances, and has a water repellent composition capable of imparting good water repellency to textiles and the like as compared with conventional non-fluorinated water repellents, and has good water repellency. An object is to provide a water-repellent fiber product and a method for producing the fiber product.

  As a result of intensive studies to solve the above problems, the present inventors have found that a combination of specific silica and a resin exhibits better water repellency than conventional non-fluorinated water repellents. The present invention has been completed based on this finding.

  That is, the present invention provides a water repellent composition containing (I) silica modified with a hydrophilizing agent and a hydrophobizing agent, and (II) a resin.

  According to the water repellent composition of the present invention, a better water repellency can be imparted to textiles and the like than conventional non-fluorinated water repellents.

  From the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium, the above (I) silica has a hydrophilic group-containing silyl group represented by the following general formula (4) and the following general formula (5). It preferably has a hydrophobic group-containing silyl group represented by

［式（４）中、Ａは、１級アミノ基、２級アミノ基、３級アミノ基、アミノ基の酸中和基、４級アンモニウム塩基、スルホ基、スルホ基の塩基中和基、カルボキシル基、カルボキシル基の塩基中和基、メルカプト基及びグリシジル基からなる群から選ばれる少なくとも１種の官能基を含有する１価の炭化水素基を表し、ｎは１〜３の整数を表し、結合手のｓ及びｔは０又は１を表し、ｎ、ｓ及びｔの合計は３である。］

[In Formula (4), A is a primary amino group, secondary amino group, tertiary amino group, amino acid neutralizing group, quaternary ammonium base, sulfo group, sulfo group base neutralizing group, carboxyl Represents a monovalent hydrocarbon group containing at least one functional group selected from the group consisting of a group, a base neutralizing group of a carboxyl group, a mercapto group and a glycidyl group, n represents an integer of 1 to 3, S and t of the hand represent 0 or 1, and the sum of n, s and t is 3. ]

［式（５）中、Ｂは、ハロゲンで置換されていてもよい炭素数１〜２０のアルキル基、ハロゲンで置換されていてもよい炭素数１〜２０のアルコキシ基、ハロゲンで置換されていてもよい炭素数２〜２０のアルケニル基、又はハロゲンで置換されていてもよい炭素数１〜３のアルキル基若しくはハロゲンで置換されていてもよい炭素数６〜１２のアリール基を表し、ｍは１〜３の整数を表し、結合手のｕ及びｖは０又は１を表し、ｍ、ｕ及びｖの合計は３である。］

[In the formula (5), B is an alkyl group having 1 to 20 carbon atoms which may be substituted with halogen, an alkoxy group having 1 to 20 carbon atoms which may be substituted with halogen, or halogen. Represents an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 3 carbon atoms which may be substituted with halogen, or an aryl group having 6 to 12 carbon atoms which may be substituted with halogen; Represents an integer of 1 to 3, the bonds u and v represent 0 or 1, and the sum of m, u and v is 3. ]

  Further, from the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium, the (I) silica is a hydrophilic group-containing silyl group represented by the general formula (4). An amino group-containing silyl group that is a monovalent hydrocarbon group containing at least one amino group selected from the group consisting of an amino group, a secondary amino group, and a tertiary amino group, and represented by the above general formula (5) It is preferable to have a trimethylsilyl group as the hydrophobic group-containing silyl group.

  In addition, the water repellent composition of the present invention preferably contains at least one resin selected from the group consisting of a silicone resin, an acrylic resin, a urethane resin, and an epoxy resin from the viewpoint of water repellency. .

  Furthermore, the water repellent composition of the present invention preferably contains a silicone resin as the resin from the viewpoint of water repellency.

  The present invention also provides a water-repellent fiber product treated with a treatment liquid containing the water repellent composition according to the present invention.

  The water-repellent fiber product of the present invention can have good water repellency.

  The present invention also provides a method for producing a water-repellent fiber product comprising a step of treating a fiber with a treatment liquid containing the water repellent composition according to the present invention.

  According to the present invention, a water repellent composition capable of imparting a good water repellency to a fiber product or the like as compared with a conventional non-fluorinated water repellent, a water repellent fiber product having a good water repellency, and the fiber product A manufacturing method can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The water repellent composition of the present embodiment comprises (I) silica modified with a hydrophilizing agent and a hydrophobizing agent (hereinafter also referred to as (I) component) and (II) resin (hereinafter referred to as ( II) component)).

<(I) Silica modified with hydrophilizing agent and hydrophobizing agent>
The component (I) is obtained by modifying silica with a hydrophilizing agent and a hydrophobizing agent. Examples of the raw material silica to be modified include hydrophilic silica having a hydroxyl group (silanol group) on the surface of silica particles.

The raw material silica is not particularly limited. Even if the silica is produced by burning a silicon compound (especially, a silicon halide such as silicon tetrachloride) in an oxygen / hydrogen flame, the precipitation method, the gel Silica produced by a wet method such as a method or a sol-gel method may be used. Such silica was measured by the BET one-point method based on the amount of adsorbed nitrogen using Shibata Scientific Instruments Industrial Specific Surface Area Measuring Device SA-1000 from the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium. preferably has a BET specific surface area of 10 to 500 m ² / g, and more preferably 50 to 400 m ² / g.

  Moreover, it is preferable that the raw material silica has an average primary particle diameter measured by an electron microscope of 1 to 500 nm, and more preferably 5 to 300 nm. Examples of such silica include Leolosil QS series, CP series (above, manufactured by Tokuyama Co., Ltd.); AEROSIL 50, 200 (above, manufactured by Nippon Aerosil Co., Ltd.), nip seal series, nip gel series (Tosoh Silica) And Toxeal series (manufactured by Maruo Calcium Co., Ltd.).

  The raw material silica may be used alone or in combination of two or more.

  The component (I) can be obtained by treating the raw material silica with a hydrophilizing agent and a hydrophobizing agent according to a conventional method. In the treatment with the hydrophilizing agent and the hydrophobizing agent of silica, the hydrophilizing agent and the hydrophobizing agent may be treated simultaneously or separately. When processing separately, the order may be any order.

  The treatment of the raw material silica with the hydrophilizing agent and the hydrophobizing agent for obtaining the component (I) may be a wet treatment or a dry treatment. Here, the wet treatment is a method in which silica is dispersed in a solvent such as water or an organic compound and contacted with a hydrophilizing agent and a hydrophobizing agent. The treatment by the dry method includes all modes in which silica is brought into contact with a hydrophilizing agent and a hydrophobizing agent while maintaining fluidity as a powder. Examples of the dry process include a method of bringing the vapor of the hydrophilizing agent and the hydrophobizing agent conveyed with a carrier gas such as nitrogen into contact with the agitated state or the fluidized bed silica, and the hydrophilizing agent and the hydrophobizing agent. And a method of making the stock solution or solution of mist into a mist form by spraying or the like and contacting with silica under stirring.

  The hydrophilizing agent is selected from the group consisting of primary amino group, secondary amino group, tertiary amino group, acid neutralizing group of amino group, quaternary ammonium base, sulfo group, carboxyl group, mercapto group and glycidyl group. A silane coupling agent containing at least one functional group (hereinafter sometimes referred to as a hydrophilized silane coupling agent); an amino group, a carboxy group, or a hydroxyl group in at least one of the side chain and terminal of the organopolysiloxane. And a modified silicone oil containing at least one functional group selected from the group consisting of a mercapto group, a glycidyl group and a polyether group (hereinafter sometimes referred to as a hydrophilized silicone oil).

Examples of the hydrophilic silane coupling agent include compounds represented by the following general formula (1).
Si [-A] _(n) [-X] _(4-n) (1)
[In the formula (1), A represents a primary amino group, a secondary amino group, a tertiary amino group, an amino acid neutralizing group, a quaternary ammonium base, a sulfo group, a carboxyl group, a mercapto group, and a glycidyl group. Represents a monovalent hydrocarbon group containing at least one functional group selected from the group consisting of: X represents a monovalent hydrolyzable group; and n represents an integer of 1 to 3. When n is 2 or more, a plurality of A may be the same or different. ]

  Examples of the monovalent hydrolyzable group include an alkoxy group having 1 to 3 carbon atoms and a halogen group.

  Specific examples of the hydrophilic silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine N-phenyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N N-dimethyl-3-aminopropyltrimethoxysilane, N, N-diethyl -3-aminopropyltrimethoxysilane, N, N-dibutyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -3-aminopropyltrimethoxysilane hydrochloride, octadecyldimethyl (3-trimethoxysilylpropyl) Ammonium chloride, tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, N-trimethoxysilylpropyl-N, N, N-tri-n-butylammonium bromide, N-trimethoxysilylpropyl-N, N, N -Tri-n-butylammonium chloride, N-trimethoxysilylpropyl-N, N, N-trimethylammonium chloride, 3-sulfopropyltrimethoxysilane, 3-carboxypropyltrimethoxysilane, 3-glycidoxy B pills trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, and 3-mercaptopropyl trimethoxysilane can be exemplified.

  As the hydrophilizing agent, it is preferable to use a compound represented by the general formula (1) from the viewpoint of water repellency and dispersibility in an aqueous medium of the water repellent composition. Among the general formula (1), It is more preferable to use a compound in which A is a hydrocarbon group containing an ionic hydrophilic group. As a hydrocarbon group containing a hydrophilic group, a C1-C5 alkylene group is preferable and a propylene group is more preferable.

  The ionic hydrophilic group may be either a cationic hydrophilic group or an anionic hydrophilic group. Examples of the cationic hydrophilic group include at least one functional group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, an acid neutralizing group of an amino group, and a quaternary ammonium base. . Examples of the anionic hydrophilic group include at least one functional group selected from the group consisting of a sulfo group and a carboxyl group.

  From the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium, among the ionic hydrophilic groups, a cationic hydrophilic group is preferable, and a primary amino group, a secondary amino group, and a tertiary group are preferable. More preferably, it is at least one amino group selected from the group consisting of amino groups.

  You may use a hydrophilizing agent individually by 1 type or in combination of 2 or more types.

  Examples of the hydrophobizing agent include known surface treating agents other than the above-described hydrophilizing agents. For example, a compound represented by the following general formula (2); a compound represented by the following general formula (3): Silicone oils such as dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, chloroalkyl-modified silicone oil, chlorophenyl-modified silicone oil, fatty acid-modified silicone oil, alkoxy-modified silicone oil (hereinafter, hydrophobic silicone) Sometimes used as oil); use of siloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, etc. Kill. In addition, fluorine-modified silicone oil can be used as the silicone oil.

Si [-B] _(m) [-Y] _(4-m) (2)
[In the formula (2), B is an alkyl group having 1 to 20 carbon atoms which may be substituted with halogen, an alkoxy group having 1 to 20 carbon atoms which may be substituted with halogen, or halogen. Represents an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 3 carbon atoms which may be substituted with halogen, or an aryl group having 6 to 12 carbon atoms which may be substituted with halogen; Represents a monovalent hydrolyzable group, and m represents an integer of 1 to 3. When m is 2 or more, the plurality of B may be the same or different. ]

  Examples of the monovalent hydrolyzable group include an alkoxy group having 1 to 3 carbon atoms and a halogen group.

［式（３）中、Ｒ^１〜Ｒ^６はそれぞれ独立に、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基又はフェニル基を表す。］

[In Formula (3), R < ¹ > -R < ⁶ > represents a C1-C6 alkyl group, a C2-C6 alkenyl group, or a phenyl group each independently. ]

  The hydrophobizing agent is represented by the compound represented by the general formula (2) and / or the general formula (3) from the viewpoint of water repellency, dispersibility of the water repellent composition in an aqueous medium and ease of treatment. It is preferable to use a compound represented by formula (3), more preferably hexamethyldisilazane, and even more preferably hexamethyldisilazane.

  You may use a hydrophobizing agent individually by 1 type or in combination of 2 or more types.

  The component (I) can have a hydrophilic group and a hydrophobic group on the silica surface by treatment with a hydrophilizing agent and a hydrophobizing agent.

  The hydrophilic group is a hydrophilic group represented by the following general formula (4) derived from the compound represented by the general formula (1) from the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium. It is preferably a functional group-containing silyl group. Among these, the hydrophilic group is preferably an ionic hydrophilic group, preferably a cationic hydrophilic group, and at least selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group. More preferably, it is a single amino group.

［式（４）中、Ａは、１級アミノ基、２級アミノ基、３級アミノ基、アミノ基の酸中和基、４級アンモニウム塩基、スルホ基、スルホ基の塩基中和基、カルボキシル基、カルボキシル基の塩基中和基、メルカプト基及びグリシジル基からなる群から選ばれる少なくとも１種の官能基を含有する１価の炭化水素基を表し、ｎは１〜３の整数を表し、結合手のｓ及びｔは０又は１を表し、ｎ、ｓ及びｔの合計は３である。］

[In Formula (4), A is a primary amino group, secondary amino group, tertiary amino group, amino acid neutralizing group, quaternary ammonium base, sulfo group, sulfo group base neutralizing group, carboxyl Represents a monovalent hydrocarbon group containing at least one functional group selected from the group consisting of a group, a base neutralizing group of a carboxyl group, a mercapto group and a glycidyl group, n represents an integer of 1 to 3, S and t of the hand represent 0 or 1, and the sum of n, s and t is 3. ]

  The hydrophobic group includes a compound represented by the general formula (2) and / or the general formula (3) from the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium and ease of treatment. It is preferably a substituted silyl group derived from the compound represented, more preferably a substituted silyl group derived from the compound represented by the general formula (3), even more preferably a trialkylsilyl group, Even more preferred is a trimethylsilyl group.

  Examples of the substituted silyl group derived from the compound represented by the general formula (2) include a hydrophobic group-containing silyl group represented by the following general formula (5).

［式（５）中、Ｂは、ハロゲンで置換されていてもよい炭素数１〜２０のアルキル基、ハロゲンで置換されていてもよい炭素数１〜２０のアルコキシ基、ハロゲンで置換されていてもよい炭素数２〜２０のアルケニル基、又はハロゲンで置換されていてもよい炭素数１〜３のアルキル基若しくはハロゲンで置換されていてもよい炭素数６〜１２のアリール基を表し、ｍは１〜３の整数を表し、結合手のｕ及びｖは０又は１を表し、ｍ、ｕ及びｖの合計は３である。］

[In the formula (5), B is an alkyl group having 1 to 20 carbon atoms which may be substituted with halogen, an alkoxy group having 1 to 20 carbon atoms which may be substituted with halogen, or halogen. Represents an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 3 carbon atoms which may be substituted with halogen, or an aryl group having 6 to 12 carbon atoms which may be substituted with halogen; Represents an integer of 1 to 3, the bonds u and v represent 0 or 1, and the sum of m, u and v is 3. ]

  Examples of the substituted silyl group derived from the compound represented by the general formula (3) include a hydrophobic group-containing silyl group represented by the following general formula (6).

［式（６）中、Ｒ^７〜Ｒ^９はそれぞれ独立に、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基又はフェニル基を表す。］

[In Formula (6), R < ⁷ > -R < ⁹ > represents a C1-C6 alkyl group, a C2-C6 alkenyl group, or a phenyl group each independently. ]

  The hydrophobic group-containing silyl group represented by the general formula (6) can also be derived from the compound represented by the general formula (2). That is, B in the general formula (5) may be a C 1-6 alkyl group, a C 2-6 alkenyl group or a phenyl group, and m may be a hydrophobic group-containing silyl group.

  The bond in the hydrophilic group-containing silyl group represented by the general formula (4) and the hydrophobic group-containing silyl group represented by the general formula (5) may be bonded to silica. It may be bonded to the hydrophilic group-containing silyl group represented by 4) and / or the hydrophobic group-containing silyl group represented by the general formula (5), and may be bonded to another hydrophilizing agent or hydrophobizing agent. It may have a hydrolyzable group (for example, a group represented by the above X and Y) or may have an OH group generated by hydrolysis. When combined with other hydrophilic group-containing silyl groups represented by the general formula (4) and / or hydrophobic group-containing silyl groups represented by the general formula (5), other hydrophilizing agents or hydrophobizing agents Is a Si—O—Si bond, and when it has an OH group produced by hydrolysis, it is Si—OH.

The component (I) preferably has a BET specific surface area of 30 to 500 m ² / g, preferably 50 to 400 m ² / g, from the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium. Is more preferable. Moreover, it is preferable that an average primary particle diameter is 5-500 nm.

  In addition, the component (I) preferably has a carbon content of 0.5 to 5.5% by mass from the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium. More preferably, it is 4.5 mass%. The carbon content can be measured by a Sumigraph NC-22F manufactured by Sumika Chemical Analysis Co., Ltd.

  The component (I) preferably has a hydrophobicity (M value) of 10 to 50 from the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium. The M value is obtained by adding 0.2 g of a sample to 50 ml of water, adding methanol with stirring thereto, and setting the time when the total amount of the sample powder is wetted with the solvent as the end point, in the methanol-water mixed solvent at the end point. The volume% of methanol can be measured as the hydrophobicity (M value).

  Moreover, when (I) component has an amino group as a hydrophilic group, it is preferable that nitrogen content is 0.1-0.5 mass%. The nitrogen content can be measured by a Sumigraph NC-22F manufactured by Sumika Chemical Analysis Co., Ltd.

  The component (I) can be obtained as a commercial product. For example, Leorosil HG-09 (trade name, manufactured by Tokuyama Co., Ltd.), AEROSIL NA50H, RA200H, RA200HS (above, manufactured by Nippon Aerosil Co., Ltd.) Product name).

  As the component (I), one type may be used alone, or two or more types may be used in combination.

<(II) resin>
The component (II) is not particularly limited, and examples thereof include silicone resins, acrylic resins, vinyl acetate resins, polyurethane resins, epoxy resins, melamine resins, glyoxal resins, alkylphenol resins, rosin ester resins, polyolefins, and the like. One of them may be used alone, or two or more may be used in combination. Among these, silicone resin, acrylic resin, polyurethane resin, and epoxy resin are preferable from the viewpoint of water repellency.

Examples of the silicone resin include silicone resin and silicone oil. The silicone resin is an organopolysiloxane that contains MQ, MDQ, MT, MTQ, MDT, or MDTQ as a component, is solid at 25 ° C., and has a three-dimensional structure. Here, M, D, T, and Q represent (R ″) ₃ SiO _0.5 unit, (R ″) ₂ SiO unit, R ″ SiO _1.5 unit, and SiO ₂ unit, respectively. R ″ represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

  Silicone resins are commonly known as MQ resins, MT resins, or MDT resins, and may have portions designated as MDQ, MTQ, or MDTQ.

  The silicone resin can also be obtained as a solution in which it is dissolved in an appropriate solvent. Examples of the solvent include relatively low molecular weight methylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and a mixture of these solvents. Etc.

  Examples of the silicone resin solution include KF7312J (trimethylsilyl group-containing polysiloxane: decamethylcyclopentasiloxane = 50: 50 mixture) and KF7312F (trimethylsilyl group-containing polysiloxane: octamethyl) commercially available from Shin-Etsu Chemical Co., Ltd. Cyclotetrasiloxane), KF9021L (trimethylsilyl group-containing polysiloxane: low-viscosity methylpolysiloxane = 50: 50 mixture), KF7312L (trimethylsilyl group-containing polysiloxane: low-viscosity methylpolysiloxane = 50: 50 mixture), and the like.

  As the silicone resin alone, for example, MQ-1600 solid Resin (trimethylsilyl group-containing polysiloxane), MQ-1640 Flask Resin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane) commercially available from Toray Dow Corning Co., Ltd. Etc. The said commercial item contains trimethylsilyl group containing polysiloxane, and contains MQ, MDQ, MT, MTQ, MDT, or MDTQ.

  Silicone oil is a linear organopolysiloxane and may have an organic group in at least one of the side chain and terminal of the organopolysiloxane. As such silicone oil, the same hydrophobized silicone oil and functionalized silicone oil can be used, for example, straight silicone such as dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, etc. Oil: Amino modified silicone oil, epoxy modified silicone oil, carbinol modified silicone oil, mercapto modified silicone oil, carboxyl modified silicone oil, polyether modified silicone oil, alkyl modified silicone oil, aralkyl modified silicone oil, alkyl aralkyl modified silicone oil, List of modified silicone oils such as higher fatty acid ester-modified silicone oil and higher aliphatic amide-modified silicone oil Door can be.

  Among these silicone resins, silicone oil is preferred from the viewpoint of water repellency and dispersibility of the water repellent composition in an aqueous medium, methyl hydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carbinol. Modified silicone oil, carboxyl-modified silicone oil, and mercapto-modified silicone oil are more preferable.

Examples of the amino-modified silicone oil include compounds having an organic group containing an amino group and / or an imino group in at least one of the side chain and terminal of the organopolysiloxane. Examples of such an organic group include an organic group represented by —R—NH ₂ and an organic group represented by —R—NH—R′—NH ₂ . Examples of R and R ′ include divalent groups such as an ethylene group and a propylene group. A part or all of the amino group and / or imino group may be a blocked amino group and / or imino group. The blocked amino group and / or imino group can be obtained, for example, by treating the amino group and / or imino group with a blocking agent. Examples of the blocking agent include fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms. Can be mentioned.

  The functional group equivalent of the amino-modified silicone oil is preferably 100 to 20000 g / mol, more preferably 150 to 12000 g / mol, and more preferably 200 to 4000 g / mol from the viewpoint of water repellency.

The amino-modified silicone oil is preferably liquid at 25 ° C. Kinematic viscosity at 25 ° C. of amino-modified silicone oil is preferably 10~100,000mm ² / s, more preferably 10~30,000mm ² / s, at 10~5,000mm ² / s More preferably it is. When the kinematic viscosity at 25 ° C. is greater than 100,000 mm ² / s, the viscosity is too high and the workability tends to deteriorate. The kinematic viscosity at 25 ° C. means a value measured by the method described in JIS K 2283: 2000 (Ubbelohde viscometer).

  The amino-modified silicone oil can be easily obtained as a commercial product. Examples of commercially available products include KF8005, KF-868, KF-864, KF-393, KF-8021 (all trade names manufactured by Shin-Etsu Chemical Co., Ltd.), TSF-4709, and XF42-B1989 (Momentive Performance Materials Japan (commercial name, trade name), BY16-872, SF-8417, BY16-853U, BY16-892 (all are trade names, manufactured by Toray Dow Corning Co., Ltd.), etc. .

  Similarly, silicone oils other than amino-modified silicone oils can be easily obtained as commercial products. Examples of commercially available products include KF-101 (trade name, epoxy-modified silicone oil manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-3701E (trade name, carboxyl-modified silicone oil manufactured by Shin-Etsu Chemical Co., Ltd.). SF 8428 (trade name, carbinol-modified silicone oil, manufactured by Toray Dow Corning Co., Ltd.), KF-9901 (trade name, methyl hydrogen silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-715 ( Shin-Etsu Chemical Co., Ltd., trade name, higher fatty acid ester-modified silicone oil), KF-96-3000 cp (Shin-Etsu Chemical Co., Ltd., trade name, dimethyl silicone oil), SF8416 (Toray Dow Corning Co., Ltd.) Manufactured, trade name, alkyl-modified silicone oil), SH203 (manufactured by Toray Dow Corning Co., Ltd.) Alkyl aralkyl-modified silicone oil), SF8410 (manufactured by Dow Corning Toray Co., Ltd., trade name, polyether-modified silicone oil), and the like.

  Silicone resins may be used alone or in combination of two or more.

  Examples of the acrylic resin include a non-fluorinated acrylic polymer containing a structural unit derived from a (meth) acrylic acid ester monomer.

From the viewpoint of water repellency, the (meth) acrylic acid ester constituting such a non-fluorinated acrylic polymer preferably has 12 to 24 carbon atoms in the hydrocarbon group present via the ester bond. The hydrocarbon group may be linear or branched, and may be a saturated hydrocarbon or an unsaturated hydrocarbon, and has an alicyclic or aromatic ring. May be. Among these, those that are linear are preferable, and those that are linear saturated hydrocarbon groups are more preferable. These hydrocarbon groups may have a functional group such as —OH, —NCO, and —NH ₂ .

  The proportion of the (meth) acrylic acid ester monomer in the polymer is preferably 80 to 100% by mass with respect to the total amount of monomer units constituting the polymer. Moreover, it is preferable that the weight average molecular weight of this polymer is 500,000 or more.

  The monomer other than (meth) acrylic acid ester is not particularly limited as long as it is a monomer copolymerizable with (meth) acrylic acid ester. For example, acrylic acid, methacrylic acid, angelic acid, tiglic acid, Examples thereof include maleic acid, fumaric acid, itaconic acid, α-hydroxyacrylic acid, ethylene, styrene, methylstyrene, vinyl chloride, vinyl acetate, and acrylamide. These copolymerizable monomers may be used alone or in combination of two or more.

  Such an acrylic resin is also available as a commercial product, and examples thereof include Neoseed NR-90 (manufactured by Nikka Chemical Co., Ltd., trade name, acrylic resin emulsion).

  As the polyurethane resin, a urethane prepolymer having an isocyanate group at the terminal obtained by reacting (a) an organic polyisocyanate and (b) a polyol is emulsified and dispersed in water, and (c) an amino group and / or An aqueous polyurethane resin obtained by a chain extension reaction using a polyamine compound having two or more imino groups is preferred.

  Such a polyurethane resin is also available as a commercial product, and examples thereof include Evaphanol AE-12 (manufactured by Nikka Chemical Co., Ltd., trade name, polyurethane resin emulsion).

  The epoxy resin is preferably a polymer that is cured by crosslinking with an epoxy group remaining in the polymer. Such an epoxy resin is also available as a commercial product, and examples thereof include Territic GC-100B (trade name, epoxy resin emulsion, manufactured by Glow Chemical Co., Ltd.).

  In the present embodiment, a fluorine-based silicone oil such as a fluoroalkyl-modified silicone oil or a fluororesin can be blended as the component (II).

  Examples of the fluororesin include a fluoroacrylic polymer containing a structural unit derived from a fluorinated (meth) acrylic acid ester monomer. The fluorinated (meth) acrylic acid ester constituting the fluoroacrylic polymer has 2 to 6 carbon atoms in the fluorinated hydrocarbon group present through an ester bond from the viewpoint of water repellency and decomposability of the fluororesin. It is preferable. The fluorinated hydrocarbon group is preferably a perfluoroalkyl group from the viewpoint of water repellency.

  Such a fluororesin is also available as a commercial product, and examples thereof include NK guard S-33 (manufactured by Nikka Chemical Co., Ltd., trade name, fluororesin emulsion).

  Component (II) may be used alone or in combination of two or more.

  In the water repellent composition of this embodiment, in addition to the components (I) and (II) described above, as the component (III), a surfactant, an antifoaming agent, a pH adjuster, an antibacterial agent, and an antifungal agent , Coloring agents, antioxidants, deodorants, various organic solvents, chelating agents, antistatic agents, crosslinking agents, catalysts, and the like may further be contained.

  As the surfactant, known nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used. Surfactant can be used individually by 1 type or in combination of 2 or more types.

  Examples of the antifoaming agent include fat-based antifoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; fatty acid-based antifoaming agents such as stearic acid, oleic acid, and palmitic acid; isoamyl stearate, distearyl succinate Fatty acid ester antifoaming agents such as ethylene glycol distearate and butyl stearate; alcohol defoaming agents such as polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3-heptanol and 2-ethylhexanol; -T-amylphenoxyethanol 3-heptyl cellosolvonyl cellosolve 3-heptyl carbitol and other ether-based antifoaming agents; tributyl osphate, tris (butoxyethyl) phosphatate and other phosphate ester-based antifoaming agents; diamylamine and other amine-based defoaming agents Foaming agent Sulfate-based defoaming agents such as sodium lauryl sulfate; alkylene amide, amide-based defoaming agent such as acylate polyamine mineral oil, and the like. An antifoamer can be used individually by 1 type or in combination of 2 or more types.

  Examples of pH adjusters include lactic acid, acetic acid, propionic acid, maleic acid, oxalic acid, formic acid, citric acid, malic acid, sulfonic acid, methanesulfonic acid, toluenesulfonic acid and other organic acids; hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Inorganic acids such as boric acid; bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonia, alkanolamine, pyridine, morpholine and the like. A pH adjuster can be used individually by 1 type or in combination of 2 or more types.

  Examples of the organic solvent include aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, hexyl alcohol, and 2-ethylhexyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, Ketones such as diacetone alcohol; esters such as ethyl acetate, methyl acetate, butyl acetate, methyl lactate, and ethyl lactate; diethyl ether, diisopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, methyl tertiary butyl ether, butylcarbi Ethers such as tall; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol Glycols such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol and the like; ethylene glycol monomethyl ether Examples include glycol esters such as acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; amides such as formamide, acetamide, benzamide, N, N-dimethylformamide, and acetanilide. An organic solvent can be used individually by 1 type or in combination of 2 or more types.

  As the antistatic agent, it is preferable to use an antistatic agent that does not easily impair water repellency. Examples of the antistatic agent include cationic surfactants such as higher alcohol sulfates, sulfated oils, sulfonates, quaternary ammonium salts, imidazoline type quaternary salts, polyethylene glycol types, polyhydric alcohol ester types. Nonionic surfactants such as, imidazoline type quaternary salts, amphoteric surfactants such as alanine type and betaine type, polymer compound type antistatic polymer, polyalkylamine and the like. An antistatic agent can be used individually by 1 type or in combination of 2 or more types.

  Examples of the crosslinking agent include melamine resins, glyoxal resins, and compounds having at least one isocyanate group or blocked isocyanate group. When the melamine resin and / or glyoxal resin is used as the component (II), the component (III) other than the melamine resin and / or glyoxal resin can be used as the component (III).

  As the melamine resin, a compound having a melamine skeleton can be used. For example, polymethylol melamine such as trimethylol melamine and hexamethylol melamine; a part or all of the methylol groups of polymethylol melamine have 1 to 6 carbon atoms. An alkoxymethyl melamine having an alkoxymethyl group having an alkyl group; an acyloxymethyl melamine in which a part or all of the methylol group of the polymethylolmelamine is an acyloxymethyl group having an acyl group having 2 to 6 carbon atoms, etc. Can be mentioned. These melamine resins may be either a monomer or a dimer or higher multimer, or a mixture thereof. Furthermore, what co-condensed urea etc. to a part of melamine can also be used. Examples of such a melamine resin include Becamine APM, Becamine M-3, Becamine M-3 (60), Becamine MA-S, Becamine J-101, and Becamine J-101LF manufactured by DIC Corporation, Union Chemical Industries Examples include UNIKA RESIN 380K manufactured by Riken Resin MM series manufactured by Miki Riken Kogyo Co., Ltd.

  A conventionally well-known thing can be used as a glioxal resin. Examples of the glyoxal resin include 1,3-dimethylglyoxal urea resin, dimethylol dihydroxyethylene urea resin, dimethylol dihydroxypropylene urea resin, and the like. The functional groups of these resins may be substituted with other functional groups. Examples of such glyoxal resins include Becamine N-80, Becamine NS-11, Becamine LF-K, Becamine NS-19, Becamine LF-55P Conch, Becamine NS-210L, Becamine NS-200 manufactured by DIC Corporation. And Becamine NF-3, Union Resin GS-20E manufactured by Union Chemical Industry Co., Ltd., Riken Resin RG Series, Riken Resin MS Series manufactured by Miki Riken Kogyo Co., Ltd., and the like.

  It is preferable to use a catalyst for the melamine resin and the glyoxal resin from the viewpoint of promoting the reaction. Such a catalyst is not particularly limited as long as it is a commonly used catalyst. For example, borofluorinated compounds such as ammonium borofluoride and borofluorinated subsalt; neutral metal salt catalysts such as magnesium chloride and magnesium sulfate An inorganic acid such as phosphoric acid, hydrochloric acid or boric acid. If necessary, these catalysts may be used in combination with an organic acid such as citric acid, tartaric acid, malic acid, maleic acid, and lactic acid. As such a catalyst, for example, Catalyst ACX, Catalyst 376, Catalyst O, Catalyst M, Catalyst G (GT), Catalyst X-110, Catalyst GT-3 manufactured by DIC Corporation, and Catalyst NFC-1, Unika Catalyst 3-P manufactured by Union Chemical Industries, Ltd., and Unica Catalyst MC-109, RIKENFIXER RC series, RIKENFIXER MX series, and RIKENFIXER RZ- manufactured by Miki Riken Kogyo Co., Ltd. 5 etc. are mentioned.

  As the compound having one or more isocyanate groups or blocked isocyanate groups, monofunctional (mono) isocyanate compounds such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate, and polyfunctional isocyanate compounds can be used.

  As a polyfunctional isocyanate compound, if it is a compound which has two or more isocyanate groups in a molecule | numerator, it will not specifically limit, A well-known polyisocyanate compound can be used. Examples of the polyfunctional isocyanate compound include diisocyanate compounds such as alkylene diisocyanate, aryl diisocyanate and cycloalkyl diisocyanate, and modified polyisocyanate compounds such as dimers or trimers of these diisocyanate compounds. The alkylene diisocyanate preferably has 1 to 12 carbon atoms.

  Examples of the diisocyanate compound include 2,4 or 2,6-tolylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, dodeca. Methylene diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, phenylene diisocyanate, tolylene or naphthylene diisocyanate, 4,4'-methylene-bis (phenylisocyanate), 2,4'-methylene-bis ( Phenyl isocyanate), 3,4′-methylene-bis (phenyl isocyanate), 4,4′-ethylene-bis (phenyl isocyanate) Nate), ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylcyclohexane, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′- Diisocyanate-1,3-dimethylcyclohexane, 1-methyl-2,4-diisocyanate cyclohexane, 4,4′-methylene-bis (cyclohexyl isocyanate), 3-isocyanate-methyl-3,5,5-trimethylcyclohexyl isocyanate, acid Diisocyanate dimer, ω, ω′-diisocyanate diethylbenzene, ω, ω′-diisocyanate dimethyltoluene, ω, ω′-diisocyanate diethyltoluene, fumaric acid bis (2-isocyanatoethyl) ester, 1,4-bis (2 -Isocyanate group 2-yl) benzene, and 1,3-bis (2-isocyanate - prop-2-yl), and benzene.

  Examples of the triisocyanate compound include triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, tris (isocyanatophenyl) -thiophosphate, and the like.

  The modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups. For example, biuret structure, isocyanurate structure, urethane structure, uretdione structure, allophanate structure, trimer Examples thereof include polyisocyanates having a body structure and the like, adducts of trimethylolpropane aliphatic isocyanates, and the like. Polymeric MDI (MDI = diphenylmethane diisocyanate) can also be used as the polyfunctional isocyanate compound.

  A polyfunctional isocyanate compound can be used individually by 1 type or in combination of 2 or more types.

  The isocyanate group which the polyfunctional isocyanate compound has may be as it is, or may be a blocked isocyanate group blocked with a blocking agent. Examples of the blocking agent include pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, and pyrazole; phenol, methylphenol, Phenols such as chlorophenol, iso-butylphenol, tert-butylphenol, iso-amylphenol, octylphenol, nonylphenol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam; malonic acid dimethyl ester, malonic acid diethyl ester , Active methylene compounds such as acetylacetone, methyl acetoacetate, ethyl acetoacetate; formaldoxime, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone Oxime, acetophenone oxime, oxime such as benzophenone oxime; imidazole, imidazole compounds such as 2-methylimidazole; and sodium bisulfite and the like. Among these, pyrazoles and oximes are preferable from the viewpoint of water repellency.

  As the polyfunctional isocyanate compound, water-dispersible isocyanate obtained by imparting water-dispersibility to polyisocyanate by introducing a hydrophilic group into the polyisocyanate structure to have a surface-active effect can also be used. Moreover, in order to accelerate | stimulate reaction, well-known catalysts, such as organic tin and organic zinc, can also be used together.

  A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

  The component (III) is preferably a crosslinking agent from the viewpoint of improving water repellency.

  In the water repellent composition of the present embodiment, from the viewpoint of water repellency, the mass ratio (I: II) of the component (I) to the component (II) is preferably 99: 1 to 30:70, More preferably, it is 95: 5 to 50:50, and still more preferably 90:10 to 60:40.

  From the viewpoint of water repellency, the water repellent composition of the present embodiment preferably contains a crosslinking agent as the component (III) in addition to the components (I) and (II). In this case, the content of the crosslinking agent in the water repellent composition of the present embodiment is 1 to 200 with respect to 100 parts by mass in total of the (I) component and the (II) component from the viewpoint of water repellency and texture. It is preferable that it is a mass part, It is more preferable that it is 1-100 mass parts, It is still more preferable that it is 5-70 mass parts.

  The water repellent composition according to this embodiment described above can be suitably used for applications such as a textile product processing agent, a paper product processing agent, and a leather product processing agent.

  A method for producing the water repellent composition of the present embodiment will be described.

  The water repellent composition of this embodiment can be obtained by mixing (I) component, (II) component, and (III) component as needed.

  The water repellent composition of the present embodiment may be a one-component type in which the component (I) and the component (II) are mixed in advance, or a two-component type in which the two components are separated from each other. May be. In the water repellent composition of this embodiment, from the viewpoint of easy handling, the two components are preferably dispersed (including emulsification and dissolution) in an aqueous medium.

  The component (III) may be in a single dosage form with at least one of the component (I) and the component (II) or may be separate.

  In the case of a one-component type in which the component (I) and the component (II) are mixed in advance, the water repellent composition of this embodiment simultaneously disperses the component (I) and the component (II) in an aqueous medium. Or by mixing the respective dispersions of component (I) and component (II).

  Examples of the method of dispersing each of the above components in an aqueous medium include mixing and stirring each component, the aqueous medium, and, if necessary, a dispersant. When mixing and stirring, known emulsifiers and dispersers such as milders, high-speed stirrers, homogenizers, ultrasonic homogenizers, homomixers, bead mills, pearl mills, dyno mills, Aspec mills, basket mills, ball mills, nanomizers, optimizers, starbursts, etc. May be used. These emulsification dispersers can be used alone or in combination of two or more.

  The aqueous medium is preferably water or a mixed solvent of water and a hydrophilic solvent miscible with water. Examples of the hydrophilic solvent include methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, hexylene glycol, glycerin (1, butyl glycol, butyl diglycol, solfit, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, etc. Is mentioned.

  The dispersion preferably further contains a surfactant from the viewpoint of dispersion stability. From the viewpoint of water repellency, it is preferable not to contain a surfactant.

  Such a surfactant is not particularly limited as long as it can improve the dispersion stability, and the same surfactants as those described in the component (III) can be used.

  The dispersion liquid may be used as a treatment liquid as it is, or may be used as a treatment liquid by further diluting with an aqueous medium or a hydrophobic organic solvent.

  The water-repellent fiber product and the method for producing the water-repellent fiber product of this embodiment will be described.

The water repellent fiber product of this embodiment is a fiber product treated with a treatment liquid containing the water repellent composition of this embodiment described above.

  The method of this embodiment includes a step of treating a fiber with a treatment liquid containing the water repellent composition of this embodiment described above. A water-repellent fiber product is obtained through this process.

  The fiber material is not particularly limited, and natural fibers such as cotton, hemp, silk and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as nylon, polyester, polyurethane and polypropylene, and composite fibers and blended fibers thereof. Etc. The form of the fiber may be any form such as yarn, cloth, non-woven fabric, and paper. The fiber may be a textile product.

  As a method of treating fibers with a treatment liquid containing the water repellent composition of the present embodiment, for example, a method of treating in one step using a treatment liquid containing the components (I) and (II), the above The method of processing in 2 steps | paragraphs using the 2 types of dispersion liquid which contains 2 components separately can be mentioned. When processing by two processes, the order which processes each component may be what kind of order.

  In the case of using the component (III), a method in which the treatment liquid containing the components (I), (II) and (III) is used in one step, the above three components are separated into two steps or three. The method of processing at a process can be mentioned.

  Examples of a method for treating the fiber with the treatment liquid include processing methods such as dipping, spraying, and coating. Further, when the water repellent composition contains water, it is preferably dried to remove the water after adhering to the fiber.

  The amount of the water repellent composition of the present embodiment attached to the fibers can be appropriately adjusted according to the required degree of water repellency, but from the viewpoint of water repellency and economy, the amount of water repellency is 100 g. It is preferable to adjust so that the adhesion amount of a liquid agent composition may be 0.1-5 g, and it is more preferable to adjust so that it may become 0.1-3 g.

  Moreover, after making the water repellent composition of this embodiment adhere to a fiber, it is preferable to heat-process suitably. Although there is no restriction | limiting in particular in temperature conditions, It is preferable to carry out for 1 to 5 minutes at 110-180 degreeC from a water-repellent viewpoint.

  Since the water-repellent fiber product of the present embodiment exhibits excellent initial water repellency, the down side, the coat, the blouson, the windbreaker, the blouse, the dress shirt, the skirt, the slacks, the gloves, the hat, the duvet side, and the futon It is suitably used for textile applications such as clothes and non-clothing products such as dried covers, curtains, tents and umbrellas.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

<Preparation of dispersion containing (I) component>
(Preparation Example A1)
(I) 10 parts by mass of Leolosil HG-09 (silica having amino group and trimethylsilyl group, manufactured by Tokuyama Corporation) as component, 1 part by mass of 90% acetic acid as acid component, and 44.5 parts by mass of butyl diglycol as organic solvent And 44.5 parts by mass of water were mixed. Subsequently, it was dispersed for 10 minutes while maintaining 60 ° C. using an ultrasonic emulsifier US-600E (Nippon Seiki Seisakusho Co., Ltd.). Thereafter, the mixture was cooled to obtain a dispersion containing 10% by mass of component (I).

(Preparation Examples A2 to A10)
In the same manner as in Preparation Example A1, except that the type of component (I), presence or absence of acid component, type and amount of organic solvent, and amount of water used were changed as shown in Table 1, component (I) A dispersion containing 10% by mass was obtained.

<Preparation of dispersion containing other silica>
(Preparation Examples A11 to A12)
The component (I) was changed to other silica, and the type and amount of organic solvent used, and the amount of water used were changed as shown in Table 1, in the same manner as in Preparation Example A1, and 10 masses of other silica. % Dispersion was obtained.

(Preparation Example A13)
As other silica, Leoroseal ZD-30ST (silica modified with hexamethyldisilazane, manufactured by Tokuyama Co., Ltd.) 4.2 parts by mass, MEK 25.8 parts by mass as an organic solvent, stearyltrimethylammonium chloride 0 as a surfactant .14 parts by mass and 69.86 parts by mass of water were mixed. Subsequently, it was dispersed for 10 minutes while maintaining 60 ° C. using an ultrasonic emulsifier US-600E (Nippon Seiki Seisakusho Co., Ltd.). Thereafter, the mixture was cooled to obtain a dispersion containing 4.2% by mass of other silica.

Details of the compounds shown in Table 1 are as follows.
Leolosil HG-09: Silica having amino group and trimethylsilyl group, manufactured by Tokuyama Corporation, trade name, BET specific surface area 65 m ² / g, nitrogen content 0.25 mass%, carbon content 1.5 mass%
AEROSIL NA50H: Silica having amino group and trimethylsilyl group, manufactured by Nippon Aerosil Co., Ltd., trade name, BET specific surface area 50 m ² / g
AEROSIL RA200H: Silica having an amino group and a trimethylsilyl group, manufactured by Nippon Aerosil Co., Ltd., trade name, BET specific surface area of 150 m ² / g, carbon content of 2.0 to 4.5% by mass
AEROSIL RA200HS: Silica having amino group and trimethylsilyl group, manufactured by Nippon Aerosil Co., Ltd., trade name, BET specific surface area 140 m ² / g, carbon content 3.5% by mass
Leolosil QS-40: Silica, manufactured by Tokuyama Corporation, trade name, BET specific surface area 65 m ² / g, average primary particle size 7 nm
Leolosil ZD-30ST: Silica modified with hexamethyldisilazane, manufactured by Tokuyama Corporation, trade name, carbon content 2.8% by mass, average primary particle size 7 nm
BDG: butyl diglycol IPA: isopropyl alcohol MEK: methyl ethyl ketone DMF: dimethylformamide

<Preparation of dispersion containing component (II)>
(Preparation Example B1)
(II) 20 parts by mass of TSF-4709 (amino-modified silicone oil, manufactured by Momentive Performance Materials Japan G.K., trade name), 0.3 parts by mass of glycolic acid, and a branch having 12 to 14 carbon atoms 4 parts by mass of an alcohol ethylene oxide 5 mol adduct and 5 parts by mass of butyl diglycol were mixed. Next, 70.7 parts by mass of water was added to the obtained mixture while being mixed little by little to obtain a dispersion containing 20% by mass of the component (II).

(Preparation Examples B2 to B12)
A dispersion containing 20% by mass of the component (II) was obtained in the same manner as in Preparation Example B1, except that the following resin was used as the component (II).
(Preparation Example B2) BY 16-872 (amino silicone, manufactured by Toray Dow Corning Co., Ltd., trade name)
(Preparation Example B3) KF-8021 (Aminosilicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name)
(Preparation Example B4) KF-101 (epoxy silicone, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
(Preparation Example B5) X-22-3701E (Carboxyryl silicone, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
(Preparation Example B6) SF 8428 (Carbinol silicone, manufactured by Toray Dow Corning Co., Ltd., trade name)
(Preparation Example B7) KF-9901 (methyl hydrogen silicone, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
(Preparation Example B8) X-22-715 (higher fatty acid ester silicone, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
(Preparation example B9) KF-96-3000cs (dimethylsilicone, manufactured by Shin-Etsu Chemical Co., Ltd., trade name)
(Preparation Example B10) SF 8416 (alkyl silicone, manufactured by Toray Dow Corning Co., Ltd., trade name)
(Preparation Example B11) SH 203 (alkyl aralkyl silicone, manufactured by Toray Dow Corning Co., Ltd., trade name)
(Preparation example B12) SF 8410 (polyether silicone, manufactured by Toray Dow Corning Co., Ltd., trade name)

(Preparation Example B13)
KF8005 (amino-modified silicone, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 18.5 parts by mass, 0.15 parts by mass of formic acid and ethylene oxide 5 mol adduct of branched alcohol having 12 to 14 carbon atoms 0.5 The mass part was mixed. Next, 80.85 parts by mass of water was added to the obtained mixture while mixing little by little to obtain a dispersion containing 18.5% by mass of amino-modified silicone.

  MQ-1600 (silicone resin = trimethylsilyl group-containing polysiloxane, manufactured by Toray Dow Corning Co., Ltd., trade name) and 15 parts by weight of dimethyl silicone (6 cs, manufactured by Toray Dow Corning Co., Ltd., trade name) And mixed until the silicone resin was dissolved to obtain a mixture. 18.5 parts by mass of the obtained mixture was mixed with 0.5 parts by mass of an ethylene oxide 5 mol adduct of a branched alcohol having 12 to 14 carbon atoms. Next, 81 parts by mass of water was added while being mixed little by little to obtain a dispersion containing 18.5% by mass of silicone resin and dimethyl silicone in total.

  The amino-modified silicone dispersion and a dispersion containing a silicone resin and dimethyl silicone are mixed at a ratio of 100: 117, and the amino-modified silicone, silicone resin, and dimethyl silicone are mixed in a mass ratio of 9 as component (II). .2: 5.4: 5.4 to obtain a 20 mass% dispersion.

(Preparation Example B14)
11.5 parts by mass of amino-modified silicone BY16-892 (trade name, manufactured by Toray Dow Corning Co., Ltd.) having both ends silanol-modified as amino-modified silicone and 0.5 part by mass of acetic anhydride in a nitrogen atmosphere The mixture is allowed to react at 100 ° C. for 1 hour, and then added with 3.0 parts by mass of an ethylene oxide 9 mol adduct of a branched alcohol having 12 to 14 carbon atoms, 5.0 parts by mass of isopropanol, and 0.1 parts by mass of formic acid and mixed. did. Next, 79.9 parts by mass of water was added to the obtained mixture while mixing little by little, and a dispersion containing 11.7% by mass of amino-modified silicone in which 85% of amino groups were blocked with acetyl groups as component (II) Got.

(Preparation Example B15)
In a 500 mL pressure-resistant flask, stearyl acrylate 30 g, lauryl acrylate 10 g, chloroethylene 20 g, 3 styrenated phenol 30 mol ethylene oxide adduct 5 g, ARCARD T-28 (manufactured by Lion Corporation, trade name, stearyltrimethylammonium chloride) 3 g Then, 25 g of tripropylene glycol and 206.7 g of water were added and mixed and stirred at 45 ° C. to obtain a mixed solution. This mixture was irradiated with ultrasonic waves to emulsify and disperse all the monomers. Next, 0.3 g 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. As a component (II), 20% by mass of a non-fluorinated acrylic polymer is contained. A dispersion was obtained.

(Preparation Example B16)
Water was added to Evaphanol AE-12 (trade name, manufactured by Nikka Chemical Co., Ltd.), a urethane resin emulsion, to obtain a dispersion containing 20% by mass of urethane resin as component (II).

(Preparation Example B17)
Water was added to an epoxy resin emulsion, Territic GC-100B (trade name, manufactured by Glow Chemical Co., Ltd.) to obtain a dispersion containing 20% by mass of an epoxy resin as a component (II).

(Preparation Example B18)
Water was added to a melamine resin solution, Unica Resin 380-K (trade name, manufactured by Union Chemical Industry Co., Ltd.) to obtain a dispersion containing 20% by mass of melamine resin as component (II).

(Preparation Example B19)
Water is added to NK guard S-33 (trade name, manufactured by Nikka Chemical Co., Ltd.), a fluororesin emulsion having a fluorocarbon group with 6 fluorocarbon groups and a perfluoroalkyl group. A dispersion containing 20% by mass of a fluororesin was obtained.

(Preparation Example B20)
Water was added to Neoseed NR-90 (trade name, manufactured by Nikka Chemical Co., Ltd.) of acrylic resin emulsion to obtain a dispersion containing 20% by mass of acrylic resin as component (II).

<Preparation of Dispersion Containing Component (I) and Component (II)>
(Preparation Example C1)
The silica fine particle dispersion of Preparation Example A1 as the component (I) and the amino-modified silicone resin dispersion of Preparation Example B1 as the component (II) are mixed at a mass ratio of 8: 1, and the components (I) and (II ) Component at a mass ratio of 80:20 was obtained.

<Preparation of component (III)>
(Preparation Example D1)
As a reaction product of trimethylolpropane and toluene diisocyanate, reaction product of Polurene AD (trimethylolpropane and toluene diisocyanate (mass ratio of 2,4 isomer and 2,6 isomer is 80:20)) An amount of 75% by mass, a solvent: ethyl acetate, manufactured by SAPCI, trade name) was prepared.

  1 mol of the reaction product of trimethylolpropane prepared above and toluene diisocyanate was heated to 60 to 70 ° C. Next, 3 moles of methyl ethyl ketoxime was slowly charged, reacted at 60 to 70 ° C. until the isocyanate content confirmed by an infrared spectrophotometer was zero, ethyl acetate was added, and a methyl ethyl ketoxime block polyisocyanate compound was added. A colorless and transparent viscous liquid composition containing 98.7% by mass was obtained.

  180 parts by mass of the composition obtained above and 20 parts by mass of an adduct of 30 mol of ethylene oxide of 3 styrenated phenol as a nonionic surfactant were mixed and homogenized. After gradually adding water with stirring, homogenizer treatment was performed at 30 MPa to obtain a dispersion containing 40% by mass of methyl ethyl ketoxime blocked product of the reaction product of trimethylolpropane and toluene diisocyanate as component (III). .

(Preparation Example D2)
As the component (III), becamine M-3 (melamine / formaldehyde, manufactured by DIC Corporation, trade name) was prepared.

(Preparation Example D3)
As component (III), becamine ACX (organic amine catalyst, manufactured by DIC Corporation, trade name) was prepared.

<Production of water-repellent fiber products>
Example 1
The silica fine particle dispersion obtained in Preparation Example A1 as component (I) is 9.6% by mass, the amino-modified silicone resin dispersion obtained in Preparation Example B1 as component (II) is 1.2% by mass, (III ) 0.5% by mass of the dispersion obtained in Preparation Example D1 as components, 0.5% by mass of Nicepol FE-26 (antistatic agent, manufactured by Nikka Chemical Co., Ltd., trade name) and Textport BG- Dyeing treatment of dyed 100% polyester cloth or 100% nylon cloth in a treatment solution diluted with water so that 290 (penetrating agent, Nikka Chemical Co., Ltd., trade name) is 0.5% by mass (Pickup rate 60% by mass), and then dried at 130 ° C. for 1 minute. Further, a 100% polyester cloth was heat treated at 180 ° C. for 30 seconds, and a 100% nylon cloth was heat treated at 170 ° C. for 30 seconds to obtain a water-repellent fiber product. In Table 3, the mass ratio between the blending amount of component (I) and the blending amount of component (II), and the total blending amount of component (I) and component (II) and blending amount of component (III). And the mass ratio.

(Examples 2-32, 34-37, Comparative Examples 1-5, Reference Example 1)
(I) Component types and amounts used, other silica types and amounts used, (II) component types and amounts used, and (III) component types and amounts used as shown in Tables 3-7. Except for the above, operations were performed in the same manner as in Example 1 to obtain water-repellent fiber products of Examples 2-32, 34-36, Comparative Examples 1-5, and Reference Example 1, respectively. In Comparative Example 4, since other silica floated and a uniform treatment bath could not be prepared, a water-repellent fiber product could not be obtained.

(Example 33)
Instead of the dispersion obtained in Preparation Example A1 and the dispersion obtained in Preparation Example B1, the dispersion containing the components (I) and (II) obtained in Preparation Example C1 was used for 10.9% by mass. A water-repellent fiber product of Example 33 was obtained in the same manner as Example 1 except that.

  About the water-repellent fiber product obtained above, the water repellency and the falling angle of water droplets were measured by the following methods. The results are shown in Tables 3-7.

(Evaluation of water repellency of textile products)
The test was conducted at a shower water temperature of 20 ° C. according to the spray method of JIS L 1092 (2009). The results were visually evaluated according to the following grade. When the characteristics were slightly good, “+” was assigned to the grade, and when the characteristics were slightly inferior, “−” was assigned to the grade.
Water repellency: State 5: No adhesion or wetness on the surface 4: A slight adhesion or wetness on the surface 3: A partial wetness on the surface 2: A wetness on the surface 1: A wetness on the entire surface Things 0: Both front and back surfaces are completely wet

(Water drop falling angle)
The textile product was placed so as to be horizontal, and 100 μL of water droplets were placed on the surface. Next, the fiber product was tilted, the angle (°) at which the water droplets rolled was measured, and this was defined as the water drop falling angle (°). In addition, it shows that water repellency is excellent, so that a waterdrop fall angle is small.

  According to the water repellent compositions of Examples 1 to 37, it was confirmed that better water repellency was obtained compared to conventional non-fluorinated water repellents. In addition, according to the present invention, the water repellency of the fluorine-based water repellent can be further improved, and as shown by the comparison between Example 32 and Reference Example 1, it is good while reducing the amount of fluororesin used. It becomes possible to obtain excellent water repellency.

  According to the present invention, a water repellent composition capable of imparting better water repellency to a fiber product or the like compared to a conventional non-fluorinated water repellent, a water repellent fiber product treated with the composition, and the fiber product The manufacturing method of can be provided.

Claims (7)

  A water repellent composition comprising (I) silica modified with a hydrophilizing agent and a hydrophobizing agent, and (II) a resin. The repellent according to claim 1, wherein the silica has a hydrophilic group-containing silyl group represented by the following general formula (4) and a hydrophobic group-containing silyl group represented by the following general formula (5). Liquid medication composition.

[In Formula (4), A is a primary amino group, secondary amino group, tertiary amino group, amino acid neutralizing group, quaternary ammonium base, sulfo group, sulfo group base neutralizing group, carboxyl Represents a monovalent hydrocarbon group containing at least one functional group selected from the group consisting of a group, a base neutralizing group of a carboxyl group, a mercapto group and a glycidyl group, n represents an integer of 1 to 3, S and t of the hand represent 0 or 1, and the sum of n, s and t is 3. ]

[In the formula (5), B is an alkyl group having 1 to 20 carbon atoms which may be substituted with halogen, an alkoxy group having 1 to 20 carbon atoms which may be substituted with halogen, or halogen. Represents an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 3 carbon atoms which may be substituted with halogen, or an aryl group having 6 to 12 carbon atoms which may be substituted with halogen; Represents an integer of 1 to 3, the bonds u and v represent 0 or 1, and the sum of m, u and v is 3. ] The silica is at least one amino group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group as the hydrophilic group-containing silyl group represented by the general formula (4). An amino group-containing silyl group which is a monovalent hydrocarbon group containing
The water repellent composition according to claim 2, comprising a trimethylsilyl group as the hydrophobic group-containing silyl group represented by the general formula (5).   The water repellent composition according to any one of claims 1 to 3, comprising at least one resin selected from the group consisting of a silicone resin, an acrylic resin, a urethane resin, and an epoxy resin as the resin.   The water repellent composition according to any one of claims 1 to 3, comprising a silicone resin as the resin.   A water-repellent fiber product treated with a treatment liquid containing the water-repellent composition according to any one of claims 1 to 5.   The process of processing a fiber with the process liquid in which the water repellent composition as described in any one of Claims 1-5 is contained, The manufacturing method of a water-repellent fiber product.