JP5200403B2 - Liquid repellent composition, liquid repellent processing method, article having liquid repellent film - Google Patents

Description

  The present invention relates to a liquid repellent composition, a liquid repellent processing method, and an article having a liquid repellent film.

As a technique for simultaneously imparting water repellency and oil repellency to a surface, a copolymer containing a structural unit of a polymerizable monomer containing a polyfluoroalkyl group (hereinafter referred to as ^Rf group) in the molecule is used. Treating an article with a polymer or a copolymer of this and another monomer (also collectively referred to as an ^Rf group-containing polymer) as an organic solvent solution or an aqueous dispersion. Has been done.

This expression of water and oil repellency is attributed to the formation of a “low surface energy surface” having a low critical surface tension on the surface due to the surface orientation of the R ^f group in the coating film. In order to achieve both water repellency and oil repellency are the important orientation of ^the R ^f group on the surface, in order to realize the surface orientation of ^the R ^f group, the melting point of fine crystals derived from R ^f groups in the polymer Has been required to exist. Therefore, in the homopolymer, ^the R ^f group-containing monomer having a melting point of fine crystals derived from R ^f groups (crystalline R ^f group-containing monomer) has been used.

A composition comprising a copolymer containing a structural unit of the crystalline ^Rf group-containing monomer (hereinafter also referred to as a crystalline polymer) as an active ingredient achieves the object in terms of water and oil repellency. Improvements have been made to other practical functions. For example, in order to improve durability against washing, dry cleaning, friction, etc., improvement such as using a monomer having high hardness or a monomer having a crosslinking reactive group together with a crystalline R ^f group-containing monomer Has been done.

In addition, studies have been made to soften the hard texture and to lower the melting point of the R ^f group in order to develop water repellency under low temperature curing conditions. For example, broad chain length range of the perfluoroalkyl group (hereinafter a perfluoroalkyl group described as R ^F group.) Examples for containing monomer to be copolymerized with the alkyl group-containing monomer are known.

Further, a method of using a silicone containing R ^F group of similar broad chain length ranging is known.
For example, a cosmetic composition containing a fluorine-based compound and a wax having a specific melting point (see, for example, Patent Document 1), R ^F group (meth) acrylate, stearyl (meth) acrylate, and other two monomers 4 terpolymer as essential components (e.g., see Patent Document 2.), fluorine-based identification and water and oil repellent chain length of R ^F group-containing alcohol, or perfluoropolyether group-containing alcohol of the formulation (e.g., patent Reference 3)), a reaction product of an amino group-containing silicone and an R ^f group-containing ester compound (for example, see Patent Document 4), and the like are known examples. On the other hand, an example of limiting the chain length of the R ^f group-containing monomer to be used is an acrylic seven-element copolymer (for example, see Patent Document 5) that defines the chain length distribution of the R ^F group. However, it contains at least 40% of a monomer containing a crystalline R ^f group. Techniques in this field, represented by these known examples, have improved physical properties in terms of other required functions without impairing the water and oil repellency inherent to the R ^f group. However, since the crystalline polymer containing the R ^f group is the main component, the drawbacks described later have not been improved fundamentally.
JP-A-7-173025 Japanese Patent Laid-Open No. 10-237133 Japanese Patent Laid-Open No. 10-81873 JP-A-8-109580 Japanese Patent Laid-Open No. 62-179517

In conventional water and oil repellents (liquid repellents), in order to impart water and oil repellency, among crystalline R ^f group-containing monomers, the melting point derived from the R ^f group microcrystals is high ( It was indispensable to use a crystalline R ^f group-containing monomer (normally 70 ° C. or higher). However, when a crystalline ^Rf group-containing monomer is used, the entire polymer has high crystallinity derived from it, and thus an article coated and processed with such a polymer becomes very hard. For example, in the case of textile products that should be flexible, the soft texture is impaired, and the coating film is hard and brittle. In some cases, it may occur in the original fabric.

  In addition, textile products such as cloth and nonwoven fabric processed with water and oil repellents exhibit high water and oil repellency at the beginning, but their performance decreases extremely due to wear during use or repeated washing. There was a drawback. That is, a water / oil repellent capable of stably maintaining the initial performance has been desired. Furthermore, there is a problem in that the adhesiveness on the surface of the coating film is insufficient, and cracks, cracks, and the like that deteriorate the quality of the article tend to occur, and improvement has been desired.

When a crystalline polymer containing an ^Rf group is a main component, in order to obtain a uniform coating film having high water and oil repellency, the polymer is usually subjected to high-temperature treatment at a temperature equal to or higher than the melting point of the microcrystal after coating. After melting, cooling and forming a film was indispensable. However, when such a high temperature treatment is performed, in the case of fiber products made of materials such as ultrafine fibers and atypical cross-section yarns, problems such as a decrease in dyeing fastness, hardening of the texture, and discoloration occur, and the quality of the processed article There was a further damage.

Conventionally, techniques for lowering the crystallinity of a polymer or making a polymer flexible are known in order to solve the problems of crystalline polymers containing an R ^f group. In addition, for the purpose of forming a film at a low temperature, a film forming aid is used, or a technique for copolymerizing a polymerizable monomer containing a branched alkyl group having an internal plastic effect with a crystalline R ^f group-containing monomer. Is known. However, in these cases, the crystal derived from the ^Rf group that should exhibit water and oil repellency is partially destroyed, so that the water and oil repellency is not exhibited, the strength of the film is insufficient, and the adhesion to the substrate. There are problems such as inadequate and durability.

In addition, there is a problem in that the adhesion and the texture are not compatible on the surface processed using a water / oil repellent containing an R ^f group-containing crystalline polymer as an active ingredient. That is, adhesive processing for imparting various functions to the surface of a fiber product processed using a water / oil repellent containing a crystalline polymer, for example, processing for bonding a film laminate or a seam tape to provide waterproof performance In order to provide moisture permeability and waterproof performance, even if processing such as coating with urethane or acrylic resin is applied, the crystalline R ^f group inhibits adhesion, so that sufficient adhesion can be secured. was difficult. Adhesion is improved by using a copolymer of a crystalline ^Rf group-containing monomer and a specific monomer such as vinyl chloride. In this method, the texture of the fiber is further increased. Therefore, the adhesiveness and the texture were not compatible.

  In recent years, as a medium for water and oil repellents, there is an influence on the ozone layer of a medium mainly composed of water (hereinafter referred to as an aqueous medium), an alcohol solvent, a petroleum solvent called a weak solvent, or a hydrofluorocarbon. There is a demand for the use of media that are friendly to the work environment and the global environment, such as small fluorine-based solvents. However, in the case of a conventional water- and oil-repellent agent having a crystalline polymer as an active ingredient, in terms of solubility, dispersibility, etc., so-called strong solvents such as aromatics, ketones and esters, chlorinated solvents, chlorofluorocarbons It was necessary to use a fluorine-based solvent that had a great impact on the ozone layer, etc., and the work environment and the global environment were not considered.

  An object of the present invention is to provide a liquid repellent composition capable of imparting excellent liquid repellency and durability to a substrate, and an article having a liquid repellent film using the liquid repellent composition.

The present invention comprises a copolymer (I) and a copolymer (II), which are separate particles, or a copolymer (I) and a copolymer (II) present in the same particle. It is a liquid agent composition, Comprising: Copolymer (I) is a mass ratio with respect to copolymer (I). The copolymer (II) contains a structural unit (a) having a mass ratio of 25 to 80% by mass and a structural unit (c) having 1 to 50% by mass relative to the copolymer (II). The mass ratio of the structural unit (a) contained in the copolymer (I) to the copolymer (I) is [a ₁ ], and the structural unit contained in the copolymer (II) (a ) With respect to the copolymer (II) as [a ₂ ], [a ₁ ] − [a ₂ ] ≧ 16 ( Mass%), and the copolymer (I) and the copolymer (II) are [mass ratio of the copolymer (I)] / [mass ratio of the copolymer (II)] = 10 / 90- Provided is a liquid repellent composition characterized by being contained at 95/5.

The structural unit (a) _is a structural unit derived from a monomer represented by _{(Z A -Y A) n X} A. However, Z _A is a polyfluoroalkyl group having 6 or less carbon atoms. n is 1 or 2, and when n is 2, (Z _A -Y _A ) may be the same or different. X _A is, -CR ₌ CH 2 when n _is 1, -COOCR = CH 2, -OCOCR = CH 2, a -OCH ₂ -φ-CR = CH ₂ or -OCH = CH _2, n is 2 for the _{= CH (CH 2) m CR} = CH 2, = CH (CH 2) m COOCR = CH 2, = CH (CH 2) m OCOCR = CH 2 or -OCOCH = CHCOO- (R is a hydrogen atom, A methyl group or a halogen atom, φ is a phenylene group, and m is an integer of 0 to 4. Y _A is a divalent organic group or a single bond.
The structural unit (b) _is a structural unit derived from a monomer represented by Z B -X _B. However, Z _B is a hydrocarbon group having 14 or more carbon atoms. X _B is the same as X _A described above.
The structural unit (c) is a structural unit derived from a monomer that does not have a polyfluoroalkyl group and has a crosslinkable functional group.

  In addition, the liquid repellent composition of the present invention comprises a copolymer (I) and / or a copolymer (II) having a polymerizable group other than the structural units (a), (b) and (c). It is preferable to contain the structural unit (d) derived from a monomer.

Moreover, it is preferable that the liquid repellent composition of this invention contains surfactant (III) further. Surfactant (III) consists of the following surfactant (e1) and / or surfactant (e2) and surfactant (e3).
The surfactant (e1) is at least one selected from polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monoalkapolyenyl ether, and polyoxyalkylene monopolyfluoroalkyl ether.
The surfactant (e2) is a nonionic surfactant composed of a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule.
Surfactant (e3) is a cationic surfactant represented by the following formula s ^71.
[(R ²¹ ) ₄ N ⁺ ] · X ⁻ (formula s ⁷¹ )
(However, R ²¹ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a polyoxyalkylene chain having a hydroxyl group at the end. The four R ^{21 s} may be the same or different, but the four R ²¹ are not simultaneously hydrogen atoms . X ⁻ is a counter ion.)

  Also provided are a liquid repellent processing method using the liquid repellent composition and an article having a liquid repellent film formed using the liquid repellent composition.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid repellent composition which can provide the water repellency excellent in durability to articles | goods can be provided. Further, an article having a liquid repellent film having excellent liquid repellency and high durability can be provided by using the liquid repellent composition of the present invention.

  The liquid repellent composition of the present invention contains a copolymer (I) and a copolymer (II), and the copolymer (I) and the copolymer (II) are structural units (a) to (d). ) Can be contained. However, the copolymer (I) contains the structural unit (a) and the structural unit (b), and the copolymer (II) contains the structural unit (a) and the structural unit (c). The copolymer (I) mainly contributes to the expression of the liquid repellency of the liquid repellent composition, and the copolymer (II) mainly contributes to the durability of the liquid repellent composition.

In the present invention, the structural unit (a) _is a structural unit derived from a monomer having a represented, ^{R f} group _{(Z A -Y A) n X} A. However, Z _A is an R ^f group having 6 or less carbon atoms, n is 1 or 2, and when n is 2, (Z _A -Y _A ) may be the same or different. Also good. X _A is, -CR ₌ CH 2 when n _is 1, -COOCR = CH 2, -OCOCR = CH 2, a -OCH ₂ -φ-CR = CH ₂ or -OCH = CH _2, n is 2 for the _{= CH (CH 2) m CR} = CH 2, = CH (CH 2) m COOCR = CH 2, = CH (CH 2) m OCOCR = CH 2 or -OCOCH = CHCOO- (R is a hydrogen atom, A methyl group or a halogen atom, φ is a phenylene group, and m is an integer of 0 to 4. Y _A is a divalent organic group or a single bond.
The structural unit (a) of the present invention may be derived from a mixture of two or more monomers having the above R ^f group. The structural unit (a) mainly contributes to the development of water repellency of the liquid repellent composition.

The R ^f group is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and has 1 to 6 carbon atoms. However, when ^Rf group has ether type oxygen, the number of carbon atoms may be 1-20. The R ^f group is preferably a group in which at least 20 to 80% of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Further, some or all of the remaining hydrogen atoms may be substituted with chlorine atoms. Further, the R ^f group may be linear or branched. In the case of a branched shape, those having a short branch at the end far from the bond or in the vicinity thereof are preferable. Further, among the preferable R ^f groups described above, a linear R ^F group represented by F (CF ₂ ) _h — (h is an integer of 1 to 6) or C ₂ F ₅ (CM ¹ M ² CM ³ M ⁴ ) ₂ — (M ¹ , M ² , M ³ and M ⁴ each independently represents a hydrogen atom, a fluorine atom or a chlorine atom, and one of them is a fluorine atom). Is more preferable. Those having a small number of carbon atoms are preferable because, when a homopolymer is formed, microcrystals derived from the R ^f group hardly appear, and the copolymer can form a flexible film. The R ^f group may be a chain polyfluorohydrocarbon group having one or more unsaturated groups such as a carbon-carbon unsaturated double bond.

Specific R ^F groups include, but are not limited to, the following R ^f groups:
_{F (CF 2) 4 -,} F (CF 2) 5 -, F (CF 2) 6 -, (CF 3) 2 CF (CF 2) 2 -, H (CF 2) 6 -, HCF 2 CF 2 - _{, Cl (CF 2) 4 -} , F (CF 2) 4 (CH 2 CF 2) 3 -, F (CF 2) 6 (CH 2 CF 2) 3 -, F (CF 2) 4 (CFClCF 2) 2 _{-, CF 3 CF = CFCF 2} CF = CF-.
Examples of the R ^F group containing ether-based oxygen include C _k F _{2k + 1} O [CF (CF ₃ ) CF ₂ O] _e —CF (CF ₃ ) —, C ₃ F ₇ O [CF (CF _{3 ) CF 2 O] e (CF} 2) k - (k is an integer of 3 to 6, e is include integer) of 0-3..

The R ^f group and the polymerizable unsaturated group may be bonded by a single bond or may be bonded through a divalent organic group. The divalent organic group is preferably a group containing an alkylene group. The alkylene group may be linear or branched. In addition, the divalent organic group includes —O—, —NH—, —CO—, —SO ₂ —, —CD ¹ ═CD ² — (D ¹ and D ² are each independently a hydrogen atom or methyl Group may be included). As the divalent organic group, an alkylene group is preferable.

Y _A is a divalent organic group represented by —R ^M —QR ^N — (R ^M and R ^N are each independently a single bond, carbon that may contain one or more oxygen atoms. A saturated or unsaturated hydrocarbon group having 1 to 22 atoms, and Q is preferably a single bond, —OCONH—, —CONH—, —SO ₂ NH— or —NHCONH—. The _{Y A, -CH 2 -, -} CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - (CH 2) 11 -, - CH 2 CH 2 CH (CH 3) -, - CH = CHCH _2- , — (CH ₂ CHR ² O) _p CH ₂ CH ₂ — (p represents an integer of 1 to 10, R ² represents a hydrogen atom or a methyl group), —C ₂ H ₄ OCONHC ₂ H ₄ —, _{-C 2 H 4 OCOOC 2 H 4} -, - COOC 2 H 4 - , and the like preferably.

The X _A, ethylenic polymerizable unsaturated group, i.e., residues of olefins, residues of a vinyl ether, residues of vinyl esters, (meth) residues of acrylate, residual maleate esters Preferred are groups, residues of fumaric acid esters, and the like. Here, the residue of olefins is -CR = CH ₂ , the residue of vinyl esters is -COOCR = CH ₂ , the residue of vinyl ethers is -OCR = CH ₂ , the residue of (meth) acrylates And —OCOCR═CH ₂ and the residue of maleic acid or fumaric acid ester represent a group represented by —OCOCH═CHCOO—. In addition, —OCH ₂ —φ—CR═CH ₂ , —OCH═CH _{2 and the} like can be mentioned (φ represents a phenylene group). However, R is preferably a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, etc.) or a short-chain alkyl group having 1 to 3 carbon atoms (particularly a methyl group) in order not to disturb the polymerizability. Considering the polymerization of the copolymer, as the X _A, (meth) residues of acrylates, preferably residues of maleic acid or fumaric acid ester, from the viewpoint of easiness of solubility or emulsion polymerization in the solvent Residues of (meth) acrylates are particularly preferred, and in particular, methacrylate residues are preferred.

As R ^f is monomer, particularly preferred (meth) acrylates having R ^f group, especially methacrylate having ^the R ^f group is preferred. As such R ^f monomer, various monomers such as the following monomers can be used. As these monomers, known monomers can be used. As the monomer for forming the structural unit (a) used in the present invention, polymerizability with other monomers, flexibility of a formed film, adhesion to a substrate, solubility in a solvent, ease of emulsion polymerization In view of the above, (meth) acrylates are particularly preferable as described above, and methacrylates are particularly preferable.

^The R ^f group is an ^{R F} group, and _{Y A} is _{- (CH 2) -, -} (CH 2 CH 2) - or - _{(CH 2) 3} - if it is a is (meth) acrylate, ^{R F} When the number of carbon atoms in the group is 7 or more, the melting point of the microcrystal is higher than 55 ° C. and the intended function is not exhibited. The R ^f group of the monomer of the structural unit (a) of the present invention is an R ^F group having 6 or less carbon atoms, and is preferably a linear R ^F group having 4 to 6 carbon atoms.
Even when Y _A is —CH ₂ CH ₂ CH (CH ₃ ) — or —CH═CH—CH ₂ —, and X _A is (meth) acrylate, the number of carbon atoms in the R ^f group is 4 to 6. Is preferred.

The structural unit (b) in the present invention is a structural unit derived from a monomer represented by Z _B -X _B. Z _B is a hydrocarbon group having 14 or more carbon atoms, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be linear or branched. , Tetradecyl group, cetyl group, heptadecyl group, stearyl group, icosyl group, behenyl group, laurone group, tetracosyl group, montanyl group, stearone group.
X _B is ethylenic polymerizable unsaturated group, i.e., residues of olefins, residues of a vinyl ether, residues of vinyl esters, (meth) residues acrylates, residues of maleic acid esters The residue of fumaric acid esters is preferred. Here, the residue of olefins is -CR = CH ₂ , the residue of vinyl esters is -COOCR = CH ₂ , the residue of vinyl ethers is -OCR = CH ₂ , the residue of (meth) acrylates And —OCOCR═CH ₂ and the residue of maleic acid or fumaric acid ester represent a group represented by —OCOCH═CHCOO—. In addition, —OCH ₂ —φ—CR═CH ₂ , —OCH═CH _{2 and the} like can be mentioned (φ represents a phenylene group). However, R is preferably a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, etc.) or a short-chain alkyl group having 1 to 3 carbon atoms (particularly a methyl group) in order not to disturb the polymerizability. X _B is more preferably a residue of (meth) acrylates, vinyl ethers or vinyl esters. As the monomer forming the structural unit (b), a mixture of two or more kinds may be used.

  The monomer forming the structural unit (b) is preferably a monomer having a saturated hydrocarbon group having 16 to 40 carbon atoms, and contains an alkyl group having 16 to 40 carbon atoms (meta ) Acrylate is more preferable, and stearyl (meth) acrylate and behenyl (meth) acrylate are more preferable. The copolymer containing the structural unit (b) can impart excellent water and oil repellency to the fiber.

The structural unit (c) in the present invention is a monomer that does not have an R ^f group and is derived from a monomer having a crosslinkable functional group. The functional group capable of crosslinking is preferably a functional group having at least one of a covalent bond, an ionic bond and a hydrogen bond, or capable of forming a crosslinked structure by the interaction of the bonds. Examples of the functional group include isocyanate group, blocked isocyanate group, alkoxysilyl group, amino group, alkoxymethylamide group, silanol group, ammonium group, amide group, epoxy group, hydroxyl group, oxazoline group, carboxyl group, alkenyl group, sulfone. Acid groups and the like are preferable. Moreover, an epoxy group, a hydroxyl group, a blocked isocyanate group, an alkoxysilyl group, an amino group, and a carboxyl group are more preferable.

Preferred examples of the monomer that forms the structural unit (c) include (meth) acrylates, compounds having two or more copolymerizable groups, vinyl ethers, and vinyl esters. The structural unit (c) may be derived from a mixture of two or more. Preferred examples of the monomer that forms the structural unit (c) include the following compounds.
2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl (meth) acrylate, 2-isocyanate Pyrazole adduct of natoethyl (meth) acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, 3-methylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, 2-isocyanate Ε-Caprolactam adduct of natoethyl (meth) acrylate, 2-butanone oxime adduct of 3-isocyanatopropyl (meth) acrylate, pyrazole adduct of 3-isocyanatopropyl (meth) acrylate.
3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, 3-methylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, ε-caprolactam addition of 3-isocyanatopropyl (meth) acrylate 4-isocyanatobutyl (meth) acrylate 2-butanone oxime adduct, 4-isocyanatobutyl (meth) acrylate pyrazole adduct, 4-isocyanatobutyl (meth) acrylate 3,5-dimethylpyrazole addition 4-isocyanatobutyl (meth) acrylate 3-methylpyrazole adduct, 4-isocyanatobutyl (meth) acrylate ε-caprolactam adduct.
Methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, butoxymethyl (meth) acrylamide, diacetone acrylamide, γ-methacryloyloxypropyltrimethoxysilane, trimethoxyvinylsilane, vinyltrimethoxysilane, dimethylaminoethyl (meth) acrylate , Diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth) acryloylmorpholine, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium chloride, (meth) acrylamidoethyltrimethylammonium chloride , (Meth) acrylamidopropyltrimethylammonium chloride.
t-butyl (meth) acrylamide sulfonic acid, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl methacrylate, polyoxyalkylene glycol mono (meth) acrylate, (meth) acrylic acid, 2- (meth) ) Acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyhexahydrophthalic acid, 2- (meth) acryloyloxyethyl acid phosphate, allyl (meth) acrylate, 2-vinyl-2-oxazo Down, 2-vinyl-4-methyl - (2-vinyl oxazoline) polycaprolactone ester of hydroxyethyl (meth) acrylate.
Tri (meth) allyl isocyanurate (T (M) AIC), triallyl cyanurate (TAC), phenylglycidylethyl acrylate tolylene diisocyanate (AT-600), 3- (methylethylketoxime) isocyanatomethyl-3,5 , 5-Trimethylcyclohexyl (2-hydroxyethyl methacrylate) cyanate (HE-6P).
As the monomer (c), N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, diacetone acrylamide, Glycidyl methacrylate, polycaprolactone ester of hydroxyethyl (meth) acrylate, AT-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Techcoat HE-6P (manufactured by Kyokin Kasei Co., Ltd.) are preferred.
The structural unit (c) mainly affects the film-forming property of the liquid-repellent film and the adhesiveness and adhesion of the liquid-repellent composition to the base material, and contributes to enhancing the durability.

The structural unit (d) in the present invention is a structural unit derived from a monomer having a polymerizable group other than the structural units (a), (b) and (c). Moreover, it is preferable that it is derived from the monomer which has favorable film forming property and can obtain a uniform copolymer solution or dispersion. Examples of the monomer that forms the structural unit (d) include the following.
Methyl acrylate, ethyl acrylate, propyl acrylate, butyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl (meth) acrylate, butyl methacrylate, n-hexyl (meth) acrylate, cyclohexyl acrylate, vinyl acetate, vinyl propionate, vinylidene chloride, butene, isoprene , Butadiene, ethylene, propylene, vinylethylene, pentene, ethyl-2-propylene, butylethylene, cyclohexylpropylethylene, decylethylene, dodecylethylene, hexene, isohexylethylene, neopentylethylene, (1,2-diethoxycarbonyl) Ethylene, (1,2-dipropoxycarbonyl) ethylene, methoxyethylene, ethoxyethylene, butoxyethylene, 2 Methoxy propylene, pentyl polyoxyethylene, cycloalkyl pentanoyloxy ethylene, cyclopentyl acetoxystyrene ethylene, styrene, alpha-methyl styrene, p- methyl styrene, hexyl styrene, octyl styrene, nonyl styrene, chloroprene, vinyl chloride, vinylidene fluoride.
N, N-dimethyl (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butyl acrylate, propyl methacrylate, cyclohexyl methacrylate, benzyl (meth) acrylate, octyl (meth) acrylate, decyl methacrylate, dodecyl acrylate, Cyclododecyl acrylate, lauryl (meth) acrylate, 3-ethoxypropyl acrylate, methoxy-butyl acrylate, 2-ethylbutyl acrylate, 1,3-dimethylbutyl acrylate, 2-methylpentyl acrylate, aziridinylethyl (meth) acrylate, 2-ethylhexyl polyoxyalkylene (meth) acrylate, polyoxyalkylene di (meth) acrylate.
Crotonic acid alkyl ester, maleic acid alkyl ester, fumaric acid alkyl ester, citraconic acid alkyl ester, mesaconic acid alkyl ester, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, (meth) acrylate having silicone in the side chain (Meth) acrylate having a urethane bond, (meth) acrylate having a polyoxyalkylene chain whose terminal is an alkyl group having 1 to 4 carbon atoms, alkylene di (meth) acrylate, and the like.
The structural unit (d) is particularly preferably derived from vinyl chloride, vinylidene chloride, cyclohexyl methacrylate, polyoxyethylene di (meth) acrylate, alkyl ether of polyoxyethylene di (meth) acrylate, or dioctyl maleate. . The structural unit (d) can contribute to improving the adhesion of the composition to the substrate and improving the dispersibility.

The copolymer (I) and copolymer (II) of the liquid repellent composition of the present invention can contain the structural units (a) to (d) described above.
The copolymer (I) of the liquid repellent composition of the present invention contains 65 to 95% by mass of the structural unit (a) based on the mass of the copolymer (I). The content of the structural unit (a) in the copolymer (I) is preferably 70 to 95% by mass, and more preferably 70 to 90% by mass. If the structural unit (a) contained in the copolymer (I) is within this range, the liquid repellency can be sufficiently exhibited.
Copolymer (II) contains 25-80 mass% structural unit (a) on the basis of the mass of copolymer (II). The content of the structural unit (a) in the copolymer (II) is preferably 30 to 80% by mass, and more preferably 30 to 75% by mass. If the structural unit (II) in the copolymer (II) is within this range, the liquid repellency can be kept high.
The mass ratio of the structural unit (a) contained in the copolymer (I) to the copolymer (I) is [a ₁ ], and the copolymer weight of the structural unit (a) contained in the copolymer (II) When the mass ratio with respect to the union (II) is [a ₂ ], [a ₁ ] − [a ₂ ] ≧ 10 (mass%). Further, this relationship is preferably [a ₁ ] − [a ₂ ] ≧ 30.
Moreover, copolymer (I) contains 1-30 mass% structural unit (b). The structural unit (b) in the copolymer (I) is preferably 1 to 27% by mass, more preferably 3 to 27% by mass. If the structural unit (b) in the copolymer (I) is within this range, the liquid repellency can be sufficiently expressed.
Moreover, copolymer (II) contains 1-50 mass% structural unit (c). The structural unit (c) in the copolymer (II) is preferably 1 to 40% by mass, and more preferably 1 to 35% by mass. If the structural unit (c) in the copolymer (II) is within this range, the durability can be sufficiently exhibited.
Further, in the liquid repellent composition of the present invention, the copolymer (I) and the copolymer (II) are [the mass ratio of the copolymer (I)] / [the mass ratio of the copolymer (II)]. = 10/90 to 95/5.

In the liquid repellent composition of the present invention, the form of the copolymer (I) and the copolymer (II) is a form in which the copolymer (I) and the copolymer (II) are randomly mixed as separate particles. Alternatively, the copolymer (I) and the copolymer (II) may be present in the same particle (for example, a core-shell type).
When the particles of copolymer (I) and the particles of copolymer (II) of the present invention are randomly mixed in the liquid repellent composition, [mass ratio of copolymer (I)] / [ The mass ratio of the copolymer (II)] is mixed at 10/90 to 95/5. Moreover, it is preferable that [mass ratio of copolymer (I)] / [mass ratio of copolymer (II)] = 20/80 to 90/10. If the copolymer (I) and the copolymer (II) are contained in this ratio, the function relating to the liquid repellency of the copolymer (I) and the function relating to the adhesive adhesion of the copolymer (II) Can be expressed synergistically.
At this time, when the structural units (a), (b), (c) and (d) are contained as a whole, the structural unit (a) is 20 to 95% by mass in the entire copolymer. Preferably, it is 30-90 mass%. The structural unit (b) is preferably 0.1 to 80% by mass, and more preferably 0.5 to 70% by mass in the entire copolymer. The structural unit (c) is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15% by mass in the entire copolymer. The structural unit (d) is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass in the entire copolymer. When the composition is within this range, the resulting liquid repellent composition has more excellent liquid repellency and durability.

  In the form in which the copolymer (I) and the copolymer (II) are present in the same particle, the presence form of the copolymer (II) is the surface activity coexisting in the fine particle dispersion of the copolymer (I). The amount of agent, the hydrophobicity relationship between the monomers constituting the copolymer (I) and the copolymer (II), or the distribution coefficient of the monomers constituting the copolymer (II) to the aqueous phase However, it is preferable to use copolymer particles having a form in which the copolymer (II) is present on the surface of the fine particles of the copolymer (I) or inside thereof. In the copolymer particles, a core-shell type in which the copolymer (I) and the copolymer (II) are separated into layers is preferable in terms of performance, and the layer separation form is a sea-island structure or a copolymer. Some may be localized, or may be in a form in which other copolymer molecular chains are entangled. By adopting such a form, excellent water and oil repellency performance that cannot be obtained at all by the method of producing and mixing the dispersion of copolymer (I) and the dispersion of copolymer (II) ( It is estimated that liquid repellency is obtained.

When the copolymer (I) and the copolymer (II) are a core-shell type in which the layers are separated into layers, the core part is the copolymer (I) and the shell part is the copolymer (II). Is preferable. When this structure is adopted, the function relating to the adhesive adhesion of the copolymer (II) can be enhanced, the durability can be improved, and an effective sea-island structure can be formed on the film. Sex can be obtained.
The copolymer (I) of the present invention may contain the structural unit (c) and the structural unit (d) as long as it contains the structural unit (a) and the structural unit (b). The copolymer (II) of the present invention may contain the structural unit (b) and the structural unit (d) as long as it contains the structural unit (a) and the structural unit (c). When the copolymer (I) and the copolymer (II) of the present invention are of a core-shell type, the copolymer (I) and the copolymer (II) both have the structural unit (d). It is preferable to contain.
As a combination of the structural units of the core-shell type copolymer (I) and the copolymer (II), the copolymer (I) composed of the structural units (a) and (b) and the copolymer (a ) And (c), a copolymer (I) consisting of structural units (a) and (b), and copolymers (a) and (c) and (d) A copolymer (I) consisting of structural units (a) and (b) and (c), and a copolymer (a) and copolymers (a) and (c) and (b). A combination of polymers (II), a copolymer (I) comprising structural units (a) and (b) and (d), and a copolymer comprising structural units (a) and (c) and (d) ( II) in combination with the structural units (a) and (b) and (c) and (d) The body (I), include a combination of a copolymer (II) containing a structural unit (a) and (c) and (d).
When the copolymer (I) is a copolymer containing the structural units (a) and (b) and (c) and (d), the ratio of each structural unit in the copolymer (I) is: It is preferable that (a) :( b) :( c) :( d) = 65 to 95: 1 to 30: 0.1 to 20: 0.1 to 20 (mass%). When the copolymer (I) is a copolymer containing the structural units (a) and (b) and (d), the ratio of each structural unit in the copolymer (I) is ( It is preferable that a) :( b) :( d) = 65 to 95: 1 to 30: 0.1 to 20 (mass%). When the copolymer (II) is a copolymer containing the structural units (a) and (c) and (d), the ratio of each structural unit in the copolymer (II) is (a): (C) :( d) = 25-80: 1-50: 10-55 (mass%) is preferable.

  When the copolymer (I) and the copolymer (II) of the present invention are present in the same particle, and the structural unit (a), (b), (c) and (d) is included in the particle In the total copolymer, the structural unit (a) is preferably 55 to 95% by mass, more preferably 60 to 90% by mass. The structural unit (b) is preferably 0.1 to 30% by mass, and more preferably 0.5 to 15% by mass in the entire copolymer. The structural unit (c) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass in the entire copolymer. The structural unit (d) is preferably 0.1 to 30% by mass and more preferably 1 to 20% by mass in the copolymer. When the composition is within this range, the resulting liquid repellent composition has more excellent liquid repellency and durability.

The core-shell type copolymer (I) and the copolymer (II) are [mass ratio of the copolymer (I)] / [mass ratio of the copolymer (II)] = 60/40 to 90 / 10 is preferable. Moreover, the further copolymer can also be contained as needed. For example, the copolymer (I) and the copolymer (II) may be used as core-shell type particles and further mixed with another copolymer (II) ′.
In particular, when the copolymer (I) and the copolymer (II) are of a core-shell type, the structural unit (a) is preferably 55 to 95% by mass in the total copolymer, More preferably, it is -90 mass%. The structural unit (b) is preferably 0.1 to 30% by mass, and more preferably 0.5 to 15% by mass in the entire copolymer. The structural unit (c) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass in the entire copolymer. The structural unit (d) is preferably 0.1 to 30% by mass and more preferably 1 to 20% by mass in the copolymer. When the composition is within this range, the resulting liquid repellent composition has more excellent liquid repellency and durability.

  In the liquid repellent composition of the present invention, the method for preparing the copolymer (I) and the copolymer (II) as active ingredients is not particularly limited. For example, a dispersion weight containing water as a dispersion medium and containing a nonionic surfactant and / or a cationic surfactant, a nonionic surfactant and / or an amphoteric surfactant, a nonionic surfactant and / or an anionic surfactant Conventional polymerization reaction techniques such as a combination method, an emulsion polymerization method, and a suspension polymerization method can be employed. In particular, it is preferable to produce a copolymer by emulsion polymerization in a medium containing water. The obtained copolymer solution, dispersion, and emulsion may be used as they are, or may be used after dilution. Further, after the copolymer is separated, it may be dissolved, dispersed, or emulsified in a solvent, a dispersion medium, or an emulsion polymerization medium.

  It is preferable to pre-emulsify using a high-pressure emulsifier or the like before the start of the polymerization reaction. For example, it is preferable to mix and disperse a mixture comprising a monomer, a surfactant and an aqueous medium with a homomixer or a high-pressure emulsifier. It is preferable to mix and disperse the polymerization mixture in advance before the start of the polymerization because the yield of the finally obtained copolymer is improved.

When the copolymer (I) and the copolymer (II) are mixed separately, the copolymer (I) and the copolymer (II) are separately polymerized to produce a copolymer ( It is preferable to prepare the respective dispersions of I) and copolymer (II) and then mix the dispersions.
In the case where the copolymer (I) and the copolymer (II) are present in the same particle, a method in which a polymerizable monomer is reacted at a time may be used, or the copolymer (I) A method of polymerizing the monomer constituting the copolymer (II) in the presence thereof may also be used. The latter method is not particularly limited, but the monomer constituting the copolymer (II) is added to the emulsion or dispersion in which the copolymer (I) is present as fine particles in one step or several steps. A method (so-called seed emulsion polymerization method) in which a polymerization initiator is added and then polymerized by adding a polymerization initiator is preferable.
Before starting the polymerization of the monomer constituting the copolymer (II), it is preferable to thoroughly stir the mixture containing the copolymer (I) and the monomer constituting the copolymer (II). This can also improve the final yield.
The amount of the monomer constituting the copolymer (II) with respect to the copolymer (I) is [mass ratio of copolymer (I)] / [mass ratio of copolymer (II)] = 10/90. It is -95/5, and it is preferable that it is 20 / 80-90 / 10.

  In the liquid repellent composition of the present invention, the copolymer (I) and the copolymer (II) are preferably dispersed as particles in a medium. The number average particle size of the copolymer dispersed in the medium is preferably 10 to 1000 nm, particularly preferably 10 to 300 nm, and particularly preferably 10 to 200 nm. When the average particle size is in this range, it is not necessary to use a large amount of a surfactant, a dispersant, etc., water and oil repellency is good, and color fading occurs when processed into dyed fabrics. Furthermore, it is preferable because the dispersed particles can exist stably in the medium and do not settle. In the present invention, the average particle size can be measured with a dynamic light scattering device, an electron microscope, or the like.

  The liquid repellent composition of the present invention preferably uses a medium. As the medium, water, alcohol, glycol, glycol ether, halogen compound, hydrocarbon, ketone, ester, ether, nitrogen compound, sulfur compound, inorganic solvent, organic acid, etc. are preferable, and water, alcohol, glycol, glycol are particularly preferable. One or more media selected from the group consisting of ethers and glycol esters are preferred from the viewpoints of solubility and ease of handling. Specific examples of preferred media are given below.

  Examples of alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, and 3-pentanol. 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-butanol, 1,2-dimethylpropanol, 1-hexanol, 2-methyl-1-pen Preferred examples include butanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, and 3-heptanol.

  As glycol and glycol ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol As glycol ethers, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, triplicate Propylene glycol monomethyl ether, polypropylene glycol, hexylene glycol, and the like preferably.

Preferred examples of the halogen compound include halogenated hydrocarbons and halogenated ethers. Examples of the halogenated hydrocarbon include hydrochlorofluorocarbon, hydrofluorocarbon, hydrobromocarbon and the like.
Preferred examples of the hydrochlorofluorocarbon include CH ₃ CCl ₂ F, CHCl ₂ CF ₂ CF ₃ , and CHClFCF ₂ CClF.
Examples of the hydrofluorocarbon include CF ₃ CF ₂ CF ₂ CHF ₂ , CF ₃ CF ₂ CF ₂ CH ₂ F, CF ₃ CF ₂ CH ₂ CF ₃ , CHF ₂ CF ₂ CF ₂ CHF ₂ , and CHF ₂ CH ₂ CF ₂ CF _3. , CF ₃ CHFCH ₂ CF ₃ , CF ₃ CH ₂ CF ₂ CHF ₂ , CHF ₂ CHFCF ₂ CHF ₂ , CF ₃ CHFCF ₂ CH ₃ , CHF ₂ CHFCHFCHF ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CF ₂ CH ₂ CH ₃ , CHF ₂ CH ₂ CF ₂ CH ₃ , CHF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CHFCF ₃ , CHF ₂ CF ₂ CF ₂ CF ₂ CHF ₂ , CF ₃ CHFCHFCF ₂ CF _{3 , CF 3 CHFCF 2 CH 2 CF} 3, CF 3 CF (C _{3) CH 2 CHF 2, CF} 3 CH (CF 3) CH 2 CF 3, CF 3 CH 2 CF 2 CH 2 CF 3, CHF 2 CHFCF 2 CHFCHF 2, CHF 2 CF 2 CF 2 CHFCH 3, CF 3 CH 2 CH ₂ CH ₂ CF ₃ , CHF ₂ CH ₂ CF ₂ CH ₂ CHF ₂ , CF ₃ (CF ₂ ) ₄ CHF ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ F, CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CF _{3, CHF 2 CF 2 CF 2} CF 2 CF 2 CHF 2, CF 3 CH (CF 3) CHFCF 2 CF 3, CF 3 CF 2 CH 2 CH (CF 3) CF 3, CF 3 CH 2 CF 2 CF 2 CH _{2 CF 3, CF 3 CF 2} CH 2 CH 2 CF 2 CF 3, CF 3 CF 2 CF 2 CF 2 CH 2 CH 3, CF 3 C _{(CF 3)} or the like _{CH 2 CH 2 CF 3, CHF} 2 CF 2 CH 2 CH 2 CF 2 CHF 2, CF 3 CF 2 CF 2 CH 2 CH 2 CH 3 are preferred.
Preferred examples of the hydrobromocarbon include CH ₂ Br ₂ , CH ₂ BrCH ₂ CH ₃ , CH ₃ CHBrCH ₃ , and CH ₂ BrCHBrCH ₃ .
Preferred examples of the halogenated ether include hydrofluoroethers, and preferred examples of the hydrofluoroether include separated hydrofluoroethers and non-separable hydrofluoroethers. The separated hydrofluoroether is a compound in which a perfluoroalkyl group or a perfluoroalkylene group and an alkyl group or an alkylene group are bonded via an etheric oxygen atom. The non-separable hydrofluoroether is a hydrofluoroether containing a partially fluorinated alkyl group or alkylene group.
As the separation type hydrofluoroether, CF ₃ CF ₂ CF ₂ OCH ₃ , (CF ₃ ) ₂ CFOCH ₃ , CF ₃ CF ₂ CF ₂ OCH ₂ CH ₃ , CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ , (CF ₃ ) ₂ CFCF ₂ OCH ₃ , (CF ₃ ) ₃ COCH ₃ , CF ₃ CF ₂ CF ₂ CF ₂ OCH ₂ CH ₃ , (CF ₃ ) CFCF ₂ OCH ₂ CH ₃ , (CF ₃ ) ₃ COCH ₂ CH ₃ , CF ₃ CF (OCH ₃ ) CF (CF ₃ ) ₂ , CF ₃ CF (OCH ₂ CH ₃ ) CF (CF ₃ ) ₂ , C ₅ F ₁₁ OCH ₂ CH ₃ , CF ₃ CF ₂ CF ₂ CF (OCH ₂ CH _{3 ) CF (CF 3) 2,} CH 3 O (CF 2) 4 OCH 3, CH 3 OCF 2 CF 2 OCH 2 CH 3, C 3 H 7 OCF _{CF 3)} CF 2 OCH ₃ and the like _preferably.
Non-separable hydrofluoroethers include CHF ₂ OCF ₂ OCHF ₂ , CH ₂ FCF ₂ OCHF ₂ , CF ₃ CF ₂ CF ₂ OCH ₂ F, CF ₃ CF ₂ OCH ₂ CHF ₂ , CHF ₂ CF ₂ CH ₂ OCF ₃ , CF ₃ CF ₂ CH ₂ OCHF ₂ , CHF ₂ CF ₂ OCH ₂ CHF ₂ , CF ₃ CH ₂ OCF ₂ CH ₂ F, CF ₃ CH ₂ OCF ₂ CHF ₂ , CHF ₂ CF ₂ CF ₂ OCH ₃ , HF ₂ CF ₂ CH ₂ OCH ₃ , CF ₃ CF ₂ CF ₂ OCH ₂ CF ₃ , CF ₃ CF ₂ CH ₂ OCF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ OCH ₂ CHF ₂ , CF ₃ CF ₂ CH ₂ OCF ₂ CHF ₂ , CHF ₂ CF ₂ CH ₂ OCF ₂ CF ₃ , CHF ₂ CF ₂ CH ₂ OCF ₂ C _{HF 2, CF 3 CHFCF 2 CH} 2 OCF 3, CF 3 CHFCF 2 CH 2 OCHF 2, CF 3 CF 2 CF 2 CH 2 OCH 3, (CF 3) 2 CHCF 2 OCH 3, CF 3 CF 2 CF 2 OCH 2 CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ OCH ₂ CF ₂ CHF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ OCF ₂ CHF ₂ , CF ₃ (CF ₂ ) ₅ OCHF ₂ , CHF ₂ OCF ₂ CF ₂ OCHF ₂ , Preferred examples include CHF ₂ OCF ₂ OCF ₂ CF ₂ OCHF ₂ , CHF ₂ OCF ₂ OCF ₂ OCF ₂ OCHF _{2 and the} like.

Preferred examples of the hydrocarbon include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. As aliphatic hydrocarbons, pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,4-trimethylpentane, 2,2 , 3-trimethylhexane, decane, undecane, dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, tetradecane, hexadecane and the like are preferable.
Preferred examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane. Preferred examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like.

Preferred examples of the ketone include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, and methyl isobutyl ketone.
Preferred examples of the ester include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, and pentyl lactate.
Preferred examples of the ether include diisopropyl ether, dioxane, tetrahydrofuran and the like.
Preferred examples of the nitrogen compound include pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
Preferred examples of the sulfur compound include dimethyl sulfoxide and sulfolane.
As the inorganic solvent, liquid carbon dioxide is preferably mentioned.
Preferred examples of the organic acid include acetic acid, propionic acid, malic acid, and lactic acid.

  In the present invention, two or more kinds of media may be mixed and used, and when two or more kinds are mixed, it is preferable to use a mixture with water. By using a mixed medium, it is easy to control the solubility and dispersibility of the copolymer, and it is easy to control the permeability, wettability, solvent drying rate, etc. to the substrate during processing.

The liquid repellent composition of the present invention preferably contains a surfactant (III) in order to facilitate dispersion of the copolymer in the medium. In the present invention, a stable emulsion can be obtained even with a small amount of surfactant (for example, 4 parts or less), and by reducing the amount of surfactant, the influence of hydrophilicity is removed, thereby contributing to the development of performance. be able to.
As the surfactant (III), a hydrocarbon-based or fluorine-based surfactant can be used, and an anionic, nonionic, cationic or amphoteric surfactant can be used. From the viewpoint of dispersion stability, it is preferable to use a nonionic surfactant in combination with a cationic or amphoteric surfactant, or to use an anionic surfactant alone. In particular, the combined use of a nonionic surfactant and a cationic surfactant is preferable, and it is preferable to use them in a mass ratio of 97/3 to 40/60. In a specific combination of a nonionic surfactant and a cationic surfactant, the total amount used can be reduced to 5% by mass or less based on the polymer, so that hydrophilicity is reduced and excellent water repellency is imparted to the substrate. it can.
As the nonionic surfactant, one or more nonionic surfactants selected from the group consisting of the following surfactants s ^{1 to} s ⁶ are preferable.

Surfactant s ¹ : polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monoalkapolyenyl ether, or polyoxyalkylene monopolyfluoroalkyl ether.
Surfactant s ² : A nonionic surfactant comprising a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule.
Surfactant s ³ : A POE chain in which two or more oxyethylenes are continuously connected to a chain in which two or more oxyalkylenes having 3 or more carbon atoms are continuously connected, and both ends are hydroxyl groups A nonionic surfactant comprising a compound which is
Surfactant s ⁴ : Nonionic surfactant having an amine oxide moiety in the molecule,
Surfactant s ⁵ : Nonionic surfactant comprising polyoxyethylene mono (substituted phenyl) ether condensate or polyoxyethylene mono (substituted phenyl) ether,
Surfactant s ⁶ : Nonionic surfactant made of a fatty acid ester of polyol.

The alkyl group, alkenyl group, alkapolyenyl group or polyfluoroalkyl group (hereinafter referred to as R ^s group) in the surfactant s ¹ preferably has 4 to 26 carbon atoms.
The R ^s group may be linear or branched. As the branched structure, a secondary alkyl group, a secondary alkenyl group, or a secondary alkapolyenyl group is preferable. Further, some or all of the hydrogen atoms may be substituted with fluorine atoms.
Specific examples of the R ^s group include an octyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a hexadecyl group, a behenyl group (docosyl group), an oleyl group (9-octadecenyl group), and a heptadecylfluorooctyl group. Tridecylfluorohexyl group, 1H, 1H, 2H, 2H-tridecylfluorooctyl group, 1H, 1H, 2H, 2H-nonafluorohexyl group and the like.

The surfactant s ¹ is preferably polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether or polyoxyalkylene monopolyfluoroalkyl ether. R ¹ may be used alone or in combination of two or more.
The polyoxyalkylene (hereinafter referred to as POA) chain of the surfactant s ¹ is preferably a chain in which two or more polyoxyethylene (hereinafter referred to as POE) chains and / or polyoxypropylene (hereinafter referred to as POP) chains are connected. . A single POA chain or two or more POA chains may be used in combination. When it consists of two types, it is preferable that the way of connection is block shape.

The surfactant s ^1, a compound represented by the following formula S ¹¹ is more preferable.
_{^{R 10 O [CH 2 CH (}} CH 3) O] q - (CH 2 CH 2 O) r H ··· formula ^{S 11}
However, R ¹⁰ represents an alkyl group having 8 or more carbon atoms or an alkenyl group having 8 or more carbon atoms, q represents 0 or an integer of 1 to 20, and r represents an integer of 5 to 50. When q and r are at least 2, the POE chains and the POP chains in Formula ^{S 11} are linked to form blocks. R ¹⁰ is preferably a linear structure or a branched structure, q is 0 or an integer of 1 to 10, and r is an integer of 10 to 30. When r is 4 or less or q is 21 or more, it becomes hardly soluble in water and does not dissolve uniformly in the aqueous medium, so that the effect of penetrating the liquid repellent composition into the object to be treated is lowered. When r is 51 or more, hydrophilicity increases and water repellency is lowered.
The following compounds are specific examples of the compound represented by the formula s ^11. However, the POE chain and the POP chain are linked in a block shape.
_{C 18 H 37 O [CH 2} CH (CH 3) O] 2 - (CH 2 CH 2 O) 30 H, C 18 H 35 O [CH 2 CH (CH 3) O] 0 - (CH 2 CH 2 O _{) 30 H, C 16 H 33} O [CH 2 CH (CH 3) O] 5 - (CH 2 CH 2 O) 20 H, C 12 H 25 O [CH 2 CH (CH 3) O] 2 - (CH _{2 CH 2 O) 15 H,} (C 8 H 17) (C 6 H 13) CHO [CH 2 CH (CH 3) O] 0 - (CH 2 CH 2 O) 15 H, C 10 H 21 O [CH _{2 CH (CH 3) O]} 2 - (CH 2 CH 2 O) 15 H, C 6 F 13 CH 2 CH 2 [CH 2 CH (CH 3) O] 0 - (CH 2 CH 2 O) 15 H, _{C 6 F 13 CH 2 CH 2} [CH 2 CH (CH 3) O] 2 - (CH _{CH 2 O) 15 H, C} 4 F 9 CH 2 CH 2 [CH 2 CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H.

Surfactant s ^2, one of the carbons in the molecule - carbon triple bond, and one or nonionic surfactant which is a compound having two hydroxyl groups are preferred. Surfactant s ² may have a POA chain in the molecule. Examples of the POA chain include a POE chain, a POP chain, a chain in which a POE chain and a POP chain are connected in a random manner, or a chain in which a POE chain and a POP chain are connected in a block shape.

Specific examples of the surfactant s ² are preferably compounds represented by the following formula s ²¹ , the following formula s ²² , the following formula s ²³ or the following formula s ²⁴ .
^{HO-CR 11 R 12 -C≡C-} CR 13 R 14 -OH ··· formula ^{s 21}
HO— (A ¹ O) _u —CR ¹¹ R ¹² —C≡C—CR ¹³ R ¹⁴ — (OA ² ) _v —OH Formula S ²²
HO—CR ¹⁵ R ¹⁶ —C≡C—H Formula s ²³
HO— (A ³ O) _w —CR ¹⁵ R ¹⁶ —C≡C—H Formula s ²⁴ .
^However, A 1, ^{A 2} and ^{A 3} represents an alkylene group each independently, u and v are integers of 0 or more, (u + v) is an integer of 1 or more, w is shown integer of 1 or more, the. When u, v or w is 2 or more, each of A ¹ , A ² and A ³ may be used alone or in combination of two or more.
R ^{11 to} R ¹⁶ each independently represent a hydrogen atom or an alkyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group.
The POA chain is preferably a POE chain, a POP chain, or a chain containing a POE chain and a POP chain. The number of repeating units of the POA chain is preferably 1-50.
Surfactant s ^2, nonionic surfactant represented by the following formula s ²⁵ are preferred.
However, x and y show 0 or the integer of 1-100, respectively. Nonionic surface active agents represented by the formula s ²⁵ may be used in combination or alone or in combination.

As the nonionic surfactant of the formula s ²⁵ , nonionic surfactants are preferred in which x and y are 0, and the sum of x and y is 1 to 4 on average or the sum of x and y is 10 to 30 on average. .

The POA chain having 3 or more carbon atoms in the surfactant s ³ is preferably polyoxytetramethylene (hereinafter referred to as POT) and / or POP chain.
As the surfactant s ³ , a nonionic surfactant represented by the following formula s ³¹ or s ³² is preferable. Here, g1 is 0 or an integer of 1 to 200, t is an integer of 2 to 100, and g2 is 0 or an integer of 1 to 200. When g1 is 0, g2 is an integer of 2 or more, and when g2 is 0, g1 is an integer of 2 or more. The —C ₃ H ₆ O— unit may be —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH (CH ₃ ) CH ₂ — and —CH ₂ CH (CH ₃ ). -May be mixed. The POA chain is block-shaped.
HO (CH ₂ CH ₂ O) _{g 1} (C ₃ H ₆ O) _t (CH ₂ CH ₂ O) _{g 2} H... Formula S ³¹ , HO (CH ₂ CH ₂ O) _{g 1} (CH ₂ CH ₂ CH ₂ CH _{2 O) t (CH 2 CH} 2 O) g2 H ··· formula ^{s 32.}

Specific examples of the surfactant s ³ include the following compounds.
_{HO- (CH 2 CH 2 O)} 15 - (C 3 H 6 O) 35 - (CH 2 CH 2 O) 15 H, HO- (CH 2 CH 2 O) 8 - (C 3 H 6 O) 35 - (CH ₂ CH ₂ O) ₈ H, HO— (CH ₂ CH ₂ O) ₄₅ — (C ₃ H ₆ O) ₁₇ — (CH ₂ CH ₂ O) ₄₅ H, HO— (CH ₂ CH ₂ O) _{34 - (CH 2 CH 2 CH 2} CH 2 O) 28 - (CH 2 CH 2 O) 34 H.

As the surfactant s ⁴ , a nonionic surfactant represented by the following formula s ⁴¹ is preferable.
(R ¹⁷ ) (R ¹⁸ ) (R ¹⁹ ) N (→ O) Expression s ⁴¹
Here, R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a monovalent hydrocarbon group. In the present invention, a surfactant having amine oxide (N → O) is treated as a nonionic surfactant. Surfactant s ⁴ may be used in combination singly or two or more.
Surfactant s ^4, nonionic surfactant represented by the following formula s ⁴² is preferable from the viewpoint of dispersion stability of the copolymer.
(R ²⁰ ) (CH ₃ ) ₂ N (→ O) Formula s ⁴²
R ²⁰ is an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, a phenyl group or an alkenyl group to which an alkyl group (6 to 22 carbon atoms) is bonded (6 to 22 carbon atoms). Represents a phenyl group to which is bonded, a fluoroalkyl group having 6 to 13 carbon atoms, an alkyl group having 8 to 22 carbon atoms, an alkenyl group having 8 to 22 carbon atoms, or a polyfluoroalkyl group having 4 to 9 carbon atoms. preferable.
Specific examples of the nonionic surfactant represented by the formula s ^42, the following compounds may be mentioned.
[H (CH ₂ ) ₁₂ ] (CH ₃ ) ₂ N (→ O), [H (CH ₂ ) ₁₄ ] (CH ₃ ) ₂ N (→ O), [H (CH ₂ ) ₁₆ ] (CH ₃ ) _{2 N (→ O), [} H (CH 2) 18] (CH 3) 2 N (→ O), [F (CF 2) 6 (CH 2) 2] (CH 3) 2 N (→ O), [F (CF ₂ ) ₄ (CH ₂ ) ₂ ] (CH ₃ ) ₂ N (→ O).

The substituted phenyl group in the surfactant s ⁵ is preferably a phenyl group substituted with a monovalent hydrocarbon group, and more preferably a phenyl group substituted with an alkyl group, an alkenyl group or a styryl group.
Surfactant s ⁵ includes polyoxyethylene mono (alkylphenyl) ether condensate, polyoxyethylene mono (alkenylphenyl) ether condensate, polyoxyethylene mono (alkylphenyl) ether, polyoxyethylene mono (alkenyl). Phenyl) ether or polyoxyethylene mono [(alkyl) (styryl) phenyl] ether is preferred.
Specific examples of the polyoxyethylene mono (substituted phenyl) ether condensate or polyoxyethylene mono (substituted phenyl) ether include formaldehyde condensates of polyoxyethylene mono (nonylphenyl) ether, polyoxyethylene mono (nonylphenyl) Ether, polyoxyethylene mono (octylphenyl) ether, polyoxyethylenemono (oleylphenyl) ether, polyoxyethylenemono [(nonyl) (styryl) phenyl] ether, polyoxyethylenemono [(oleyl) (styryl) phenyl] Examples include ether.

The polyol in the surfactant s ⁶ represents glycerin, sorbitan, sorbit, polyglycerin, polyethylene glycol, polyoxyethylene glyceryl ether, polyoxyethylene sorbitan ether, or polyoxyethylene sorbit ether.
Surfactant s ⁶ includes a 1: 1 (molar ratio) ester of octadecanoic acid and polyethylene glycol, a 1: 4 (molar ratio) ester of ether of sorbite and polyethylene glycol and oleic acid, polyoxyethylene glycol, 1: 1 (molar ratio) ester of ether of sorbitan and octadecanoic acid, 1: 1 (molar ratio) of ether of polyethylene glycol and sorbitan and oleic acid, 1: 1 (molar ratio) of dodecanoic acid and sorbitan Ratio) ester, 1: 1 or 2: 1 (molar ratio) ester of oleic acid and decaglycerin, and 1: 1 or 2: 1 (molar ratio) ester of octadecanoic acid and decaglycerin.

In the present invention, when the surfactant includes a cationic Surfactant s ⁷ is preferred to use a cationic surfactant of a substituted ammonium salt form. The substituted ammonium salt type cationic surfactant is preferably an ammonium salt in which one or more hydrogen atoms bonded to a nitrogen atom are substituted with an alkyl group, an alkenyl group or a POA chain having a terminal hydroxyl group. The compound represented by s ⁷¹ is more preferred.
_{^{[(R 21) 4 N +}} ] · X - ··· formula ^{s 71}
R ²¹ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a POA chain having a hydroxyl group at the end, The four R ²¹ may be the same or different, but the four R ²¹ are not hydrogen atoms at the same time. X ⁻ represents a counter ion.
R ²¹ is preferably a long-chain alkyl group having 6 to 22 carbon atoms, a long-chain alkenyl group having 6 to 22 carbon atoms, or a fluoroalkyl group having 1 to 9 carbon atoms. When R ²¹ is an alkyl group other than a long-chain alkyl group, a methyl group or an ethyl group is preferable. When R ²¹ is a POA group, a POE group is preferred. X ⁻ is preferably chlorine ion, ethyl sulfate ion or acetate ion.
Examples of the compound represented by the formula s ^71, monooctadecyl trimethyl ammonium chloride, monooctadecyl dimethyl monoethyl ammonium ethyl sulfate, mono (octadecyl) monomethyldi (polyethylene glycol) ammonium chloride, mono-Na fluorohexyl trimethyl ammonium chloride, di (tallow alkyl ) Dimethylammonium chloride, dimethyl monococonut amine acetate and the like.

In the present invention, when the surfactant comprises an amphoteric Surfactant s ⁸ is alanine compounds, imidazolinium betaines, amide betaines or amphoteric surfactants acetate betaine forms are preferred. As the hydrophobic group, R ²¹ preferably contains a long-chain alkyl group having 6 to 22 carbon atoms, a long-chain alkenyl group having 6 to 22 carbon atoms, or a fluoroalkyl group having 1 to 9 carbon atoms. Specific examples of the amphoteric Surfactant s ⁸ is dodecyl betaine, octadecyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolinium betaine, dodecyl dimethylamino betaine, such as fatty acid amidopropyl dimethylamino acetic acid betaine.

  In the present invention, when the surfactant contains an anionic surfactant, examples thereof include carboxylic acid-containing surfactants, phosphoric acid-containing surfactants, sulfonic acid-containing surfactants, and fatty acid salts. Specifically, fatty acid sodium, fatty acid potassium, sodium linear alkylbenzene sulfonate, sodium alkyl ether sulfate, sodium alpha olefin sulfonate, sodium alkyl sulfonate, sodium lauryl sulfate, polyoxyethylene lauryl ether sodium phosphate, dipoly Examples include sodium oxyethylene alkyl ether phosphate, sodium polyoxyethylene alkyl ether acetate, sodium lauroylmethylenealanine, dialkyl sulfosuccinate, alkylamide sulfosuccinate, polyoxyethylene alkyl ether carboxylate, perfluoroalkyl carboxylate, etc. It is done.

As the surfactant (III), a block copolymer, random copolymer or hydrophilic copolymer of a hydrophilic monomer and a hydrocarbon-based hydrophobic monomer and / or a fluorine-based hydrophobic monomer It may be a polymer surfactant (s ⁹ ) composed of a hydrophobically modified product of
Specific examples of the surfactant (s ⁹ ) include a block or random copolymer of polyethylene glycol (meth) acrylate and long-chain alkyl acrylate, a block of polyethylene glycol (meth) acrylate and fluoro (meth) acrylate, or Random copolymer, block or random copolymer of vinyl acetate and long chain alkyl vinyl ether, block or random copolymer of vinyl acetate and long chain alkyl vinyl ester, polymer of styrene and maleic anhydride, polyvinyl alcohol Condensate of styrene and stearic acid, condensate of polyvinyl alcohol and stearyl mercaptan, condensate of polyallylamine and stearic acid, condensate of polyethyleneimine and stearyl alcohol, methylcellulose, hydroxypropylene Methylcellulose, hydroxyethyl cellulose, and the like.
Examples of the surfactant (s ⁹ ) include Kuraray MP polymer (product numbers: MP-103 and MP-203), Elf Atchem SMA resin, Shin-Etsu Chemical Co., Ltd., Nippon Shokubai Epomin RP, and Seimi Chemical. The company's Surflon (product numbers: S-381, S-393) and the like.

  In addition, when the medium is an organic solvent or the mixing ratio of the organic solvent is large, a block copolymer or a random copolymer of a lipophilic monomer and a fluorine-based monomer (its polyfluoroalkyl modified product) It is also possible to use a polymer surfactant comprising Specific examples include a copolymer of alkyl acrylate and fluoro (meth) acrylate, a copolymer of alkyl vinyl ether and fluoroalkyl vinyl ether, and the like, for example, Surflon (product number: S-383, SC-) of Seimi Chemical Co., Ltd. 100 series).

In particular, it is preferable to use a surfactant (III) comprising the following surfactant (e1) and / or surfactant (e2) and surfactant (e3), and a total of 5% by mass or less based on the polymer. A stable aqueous dispersion can be obtained with a small amount of use. In addition, it exhibits excellent water repellency and water repellency durability. Particularly preferably, it is effective to be 4% by mass or less.
Surfactant (e1): At least one of polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monoalkapolyenyl ether, and polyoxyalkylene monopolyfluoroalkyl ether. That is, the surfactant s ¹ .
Surfactant (e2): A nonionic surfactant comprising a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule. That is, the surfactant s ² .
Surfactant (e3): Cationic surfactant. In particular compounds of the formula ^{s 71.}

The liquid repellent composition of the present invention may contain an additive (IV). Additive (IV) has the effect of lowering the dynamic surface tension of the aqueous dispersion by adding it to the aqueous dispersion containing copolymer (I) and copolymer (II). Further, the temperature at which the weight attenuation in thermogravimetry of the additive (IV) is 30% by weight is 250 ° C. or less.
The dynamic surface tension is the surface tension of a moving gas-liquid interface, and is measured by a method called a maximum bubble pressure method or a bubble pressure differential pressure method. Journal of Chemical Society, 121, p858 (1922), Journal of Colloid and Interface Science, 166, p6 (1994), and the principles, measurement methods, and side examples are shown, and dedicated measurement devices are also commercially available. ing.
The thermogravimetric measurement can also be performed using a commercially available thermogravimetric measuring device (TG-DTA2000S manufactured by Bruker AXS, Pyris1TGA manufactured by PerkinElmer Co., Ltd.). It can be measured by weighing about 10 mg of sample in an aluminum sample cup, raising the temperature from room temperature to 400 ° C. at a temperature increase rate of 10.0 ° C./min, and examining the change in weight.

  The additive (IV) has the effect of reducing the dynamic surface tension when added to the aqueous dispersion containing the copolymer (I) and the copolymer (II). It can improve the permeability and wettability of the material, and can impart excellent water and oil repellency and durability. In particular, for a substrate having a polyester fiber surface, the adhesion rate during processing is improved, and a particularly excellent effect is obtained. The use of the additive (IV) is preferably 1% by mass or less with respect to the aqueous dispersion, and the dynamic surface tension is preferably lowered by 5 mN / m or more. In addition, the additive (IV) has a feature of high volatility since the weight attenuation is 30% by weight at 250 ° C. or less. When the water-dispersed composition of the liquid repellent composition is applied to a substrate by various methods such as coating, dipping, spraying, and the like, and when heated and dried under heating conditions of 40 ° C. or higher, it is difficult to remain on the substrate surface. It becomes easy to express liquid performance.

The additive (IV) may be a water-soluble solvent and is a compound having at least one hydrophilic group (for example, hydroxyl group, oxyalkylene group such as oxyethylene and oxypropylene), for example, alcohol or ether such as 2-propanol. Is preferred. In addition, it is represented by polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monopolyfluoroalkyl ether, or the following formula s ²⁵ (where x and y are each 0 or an integer of 1 to 100). 1 type of above-mentioned nonionic surfactant, or 2 or more types of combined use may be sufficient.

In particular, 2-propanol, polyoxyalkylene monoalkyl ether, of the nonionic surfactant of the formula s ^25, x and y are 0, that the sum of x and y are average 1-4 preferred.

  In starting the polymerization reaction, heat, light, radiation, a radical polymerization initiator, an ionic polymerization initiator, or the like is preferably used. In particular, a water-soluble or oil-soluble radical polymerization initiator is preferable, and general-purpose initiators such as an azo polymerization initiator, a peroxide polymerization initiator, and a redox initiator can be used depending on the polymerization temperature. As the polymerization initiator, an azo compound is particularly preferable, and when polymerization is performed in a medium using water, a salt of the azo compound is more preferable. The polymerization temperature is preferably 20 to 150 ° C.

In the polymerization reaction, a molecular weight modifier may be used. As the molecular weight regulator, aromatic compounds or mercaptans are preferable, and alkyl mercaptans are particularly preferable. Specific examples include n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan or α-methylstyrene dimer (CH ₂ = CPhCH ₂ C (CH ₃ ) ₂ Ph, Ph represents a phenyl group). Etc. are preferable.

If necessary, the liquid repellent composition of the present invention has a water-soluble polymer such as a penetrant, an antifoaming agent, a water absorbing agent, an antistatic agent, an antifungal agent, a texture adjusting agent, a film-forming aid, and polyacrylamide or polyvinyl alcohol. , Thermosetting agents such as melamine resin and urethane resin, isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1 , 1,1 ′, 1 ′,-Tetramethyl-4,4 ′-(methylene-di-para-phenylene) disemicarbazide, spiroglycol and other epoxy curing agents, compounds effective as synthetic resins and fiber stabilizers Etc., various additives may be added. Moreover, you may use a catalyst together in order to accelerate | stimulate thermosetting and bridge | crosslinking as needed.
These additives can be more effective by adjusting the addition amount, addition method, treatment conditions and the like according to the characteristics of the substrate. For example, in cloth treatment, it is common to use a melamine resin and a cross-linking catalyst for the purpose of improving the durability of performance, but the optimum amount varies depending on the kind of cloth. As a result of intensive studies, the composition of the present invention can achieve high performance when the amount of catalyst added to the polyester fabric is 1/20 to 1/5 that of nylon fibers.

  The liquid repellent composition of the present invention can be applied to an object to be processed by a known method. Usually, a method is adopted in which the liquid repellent composition is dispersed and diluted in an organic solvent or water, adhered to the surface of the object to be treated by dip coating, spray coating, foam coating, or the like, and dried. If necessary, a processing method by the Exhaust method in which the pH is adjusted to about 7 or less, the treatment liquid is attached to the object to be treated, and after the heat treatment is washed and dehydrated can be employed. In the case of dip coating, the concentration of the fluoropolymer in the treatment liquid is preferably 0.05 to 10% by mass. In the case of spray coating, the concentration of the fluoropolymer in the treatment liquid is preferably 0.1 to 5% by mass. In the case of the Exaust method, the concentration of the fluoropolymer in the treatment liquid is preferably 0.05 to 10% by mass.

The article having a liquid repellent film formed using the liquid repellent composition of the present invention is not particularly limited, and fibers, nonwoven fabrics, resins, papers, leathers, and metals made of natural fibers, synthetic fibers or blended fibers thereof, etc. And inorganic materials such as stone, concrete, gypsum, and glass.
When the article is treated with the liquid repellent composition of the present invention, since the film is flexible, the texture of the fiber product becomes flexible, and high quality water and oil repellency can be imparted to the article. In addition, it has excellent surface adhesion and can impart water and oil repellency even at low temperature curing. In addition, there is little deterioration in performance due to friction or washing, and the performance at the initial stage of processing can be stably maintained. Moreover, when processed to paper, excellent size, water repellency and oil resistance can be imparted to paper even under low temperature drying conditions. When treated on a resin, glass or metal surface, it is possible to form a water / oil repellent film having good adhesion to the substrate and excellent film forming properties.

Hereinafter, although this invention is demonstrated concretely, it is not limited to these.
[Production Example 1]
In a glass beaker, there was no C ₆ F ₁₃ C ₂ H ₄ OCOC (CH ₃ ) = CH ₂ (the melting point of the homopolymer crystallites (hereinafter referred to as T _m )), and the glass transition point of the homopolymer (hereinafter T _g and referred.) 51.5 ° C.. or less, 98.6 g of referred to as FMA.), alkyl methacrylate (Nippon emulsifier Co., VMA-70. However, the alkyl group is a linear, alkyl chain length GC area ratio C18: C20: C22 = 15/15/70 (hereinafter referred to as VMA) 5.5 g, surfactant polyoxyethylene oleyl ether (about 20 mol of ethylene oxide adduct, hereinafter referred to as PEO-) 2.19 g of acetylene glycol ethylene oxide adduct (ethylene oxide addition mole number 10 mol, hereinafter referred to as AGE-10) 1.0 g, 0.44 g of stearyltrimethylammonium chloride (hereinafter referred to as STMAC), 175 g of ion-exchanged water, 11 g of dipropylene glycol (hereinafter referred to as DPG), and stearyl mercaptan (hereinafter referred to as StSH). 0.5 g was added, heated at 60 ° C. for 30 minutes, and then mixed using a homomixer (manufactured by Nippon Seiki Seisakusho, Biomixer) to obtain a mixed solution.
The obtained liquid mixture was processed at 40 MPa using a high-pressure emulsifier (manufactured by APV Lanier Co., Ltd., Minilab) while maintaining the temperature at 60 ° C. to obtain an emulsion. 250 g of the obtained emulsion was put in a stainless steel reaction vessel, and 0.3 g of dimethyl 2,2′-azobis (2-methylpropionate) (hereinafter referred to as V601) as an initiator was added, and 30 Cooled below ℃. The gas phase was replaced with nitrogen, and 5.5 g of vinyl chloride monomer (referred to as VCM) was introduced, followed by polymerization reaction at 65 ° C. for 15 hours with stirring to obtain an emulsion having a solid content concentration of 34.0% by mass.

[Production Examples 2 and 3]
Except having the composition shown in Table 1, a polymerization reaction was carried out in the same manner as in Production Example 1 to obtain an emulsion. However, monomers other than VCM were charged before emulsification with a high-pressure emulsifier and mixed with a homomixer.

[Production Example 4]
A polymerization reaction was performed in the same manner as in Production Example 1 except that the surfactant was 3.27 g of AGE-10, to obtain an emulsion having a solid content concentration of 34.2% by mass. However, monomers other than VCM were charged before emulsification with a high-pressure emulsifier and mixed with a homomixer.

[Production Example 5]
Manufactured except that the surfactant is 1.09 g of acetylene glycol ethylene oxide adduct (30 mol of ethylene oxide addition, hereinafter referred to as AGE-30), 1.09 g of AGE-10 and 1.09 g of PEO-25. A polymerization reaction was carried out in the same manner as in Example 1 to obtain an emulsion having a solid content concentration of 34.2% by mass. However, monomers other than VCM were charged before emulsification with a high-pressure emulsifier and mixed with a homomixer.

[Production Examples 6 to 9]
A polymerization reaction was performed in the same manner as in Production Example 1 except that the composition shown in Table 1 was used to obtain an emulsion. However, monomers other than VCM were charged before emulsification with a high-pressure emulsifier and mixed with a homomixer.

The abbreviations in Table 1 have the following meanings.
_{C4FMA: C 4 F 9 C 2} H 4 OCOC (CH 3) = CH 2 ( no _{T m, T g 41 ℃.} )
STA: Stearyl acrylate
D-BI: 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl methacrylate (see Chemical Formula 3)
DAAM: diacetone acrylamide
DOM: Dioctyl maleate
GMA: Glycidyl methacrylate
CHMA: cyclohexyl methacrylate
PEO-30: Polyoxyethylene oleyl ether (ethylene oxide about 26 mol adduct)
FDMC: Coconut alkyldimethylamine acetate
EPO-40: ethylene oxide propylene oxide polymer (containing 40% ethylene oxide)
VA-061A: 2,2′-azobis [2- (2-imidazolin-2-yl) propane] acetate

[Production Example 10]
Using the copolymer composition produced in Production Example 1 as a copolymer (I) in a stainless steel autoclave, 203.0 g of an aqueous dispersion of the copolymer (I) (solid content concentration 34.0%), And 12.5 g of FMA, 8.28 g of CHMA, and 8.8 g of GMA, which are to be copolymer (II), were charged.
Further, 0.29 g of StSH, 2.7 g of DPG, and 44.4 g of water were added to prepare a total solid content of 35% by mass. The mixture was stirred at 60 ° C. for 1 hour, then cooled, 0.05 g of V-59 (2-2′-azobis (2-methylbutyronitrile)) was added, and after purging with nitrogen, at 65 ° C. for 15 hours. Polymerized. After cooling, 0.02 g of V-59 was added, and after purging with nitrogen, the reaction was aged at 65 ° C. for 4 hours. After cooling, the dispersion was taken out. The solid content concentration was 35.0% by mass. As a result of observation of the copolymer particles by a transmission electron microscope, the copolymer (I) exists as core-shell type fine particles existing inside the copolymer (II), and is partially polymerized in an aqueous phase. Something was done.

[Production Examples 11 to 14]
Regarding copolymer (II), the polymerization reactions of Production Examples 11 to 14 were carried out in the same manner as in Production Example 10 except that the compounds shown in Table 2 were used in the mass (unit: g) shown in Table 2 to obtain emulsions. However, VCM was introduced into the reactor after nitrogen substitution. In Table 2, C6FMA is _{C 6 F 13 C 2 H 4} OCOC (CH 3) = CH 2, PE350 is a polyethylene glycol methacrylate, M90G means methoxy polyethylene glycol methacrylate.

[Production Example 15]
A polymerization reaction was carried out in the same manner as in Production Example 10 except that the copolymer of Production Example 4 was used as the copolymer (I) to obtain an emulsion having a solid content concentration of 34.8% by mass.

[Production Example 16]
A polymerization reaction was carried out in the same manner as in Production Example 10 except that the copolymer of Production Example 5 was used as the copolymer (I) to obtain an emulsion having a solid content concentration of 34.8% by mass.

[Production Example 17]
In a stainless steel autoclave, using the copolymer produced in Production Example 5 as copolymer (I), 409.4 g of an aqueous dispersion of copolymer (I) (solid content concentration: 34.2% by mass), and copolymer As the polymer (II), 11.9 g of FMA, 7.7 g of CHMA, and 8.4 g of GMA were charged.
Further, 0.33 g of StSH, 3.15 g of DPG, and 52.2 g of water were added to prepare a total solid content of 35% by mass. The mixture was stirred at 60 ° C. for 1 hour, then cooled, 0.04 g of V-59 was added, and after nitrogen substitution, 7.0 g of VCM was added and polymerized at 65 ° C. for 15 hours. After cooling, 0.02 g of V-59 was added, and after purging with nitrogen, the reaction was aged at 65 ° C. for 4 hours. After cooling, the dispersion was taken out. The solid content concentration was 35.0% by mass.

[Production Example 18]
A polymerization reaction is carried out in the same manner as in Production Example 3 except that 5.78 g of PEO-30 and 0.66 g of STMAC are used in place of PEO-25 as a surfactant to obtain an emulsion having a solid content of 34.8% by mass. It was.
[Production Example 19]
Example 9 Similarly, a polymerization reaction was performed to obtain an emulsion having a solid content concentration of 34.8% by mass.
[Production Example 20]
A polymerization reaction was carried out in the same manner as in Production Example 10 except that the copolymer produced in Production Example 19 was used as copolymer (I) to obtain an emulsion having a solid content concentration of 35.2% by mass.
[Production Example 21]
The copolymer produced in Production Example 19 is referred to as Copolymer (I), and instead of 12.5 g of FMA to be copolymer (II) in Production Example 10, 12.2 g of FMA and 0.3 g of PFM3 are used. The polymerization reaction was carried out in the same manner as in Production Example 10 to obtain an emulsion having a solid content concentration of 35.1% by mass.

[Production Examples 22 to 26]
An emulsion was obtained by carrying out a polymerization reaction in the same manner as in Production Example 1 except that the compounds in Table 3 were used in the mass (unit: g) shown in Table 3. In Table 3, EPO-10 is an ethylene oxide propylene oxide polymer (containing 10% ethylene oxide), and DOSH is dodecyl mercaptan.

[Examples 1 to 24]
200 g of each test solution having a solid content concentration of 2% by mass shown in Examples 1 to 24 was prepared by diluting the aqueous dispersions obtained in Production Examples 1 to 21 with distilled water according to Tables 4 and 5. Examples 1-5 and Examples 22-24 are examples in which copolymer (I) and copolymer (II) were mixed as separate particles, and examples 6-13, 20, 21 and 21 were In this example, the polymer (I) and the copolymer (II) are used as a core-shell type. Example 14 is an example in which core-shell type particles and copolymer (II) were mixed. Examples 17 and 18 are comparative examples using only the copolymer (I), and Examples 19 and 20 are comparative examples using only the copolymer (II).
In Table 4 and Table 5, the mass ratio of the structural unit (a) and the structural unit (b) forming the copolymer (I) to the copolymer (I) is shown as [a ₁ ] and [b ₁ ]. It was. Moreover, the mass ratio with respect to copolymer (II) of structural unit (a) and structural unit (c) which forms copolymer (II) was shown as [a ₂ ] and [c ₂ ]. Copolymer (I) / copolymer (II) is [mass ratio of copolymer (I)] / [mass ratio of copolymer (II)]. Moreover, the mass ratio of each structural unit in all the copolymers (copolymer (I) + copolymer (II)) was shown as [a], [b], [c], [d].
The numbers in parentheses in Tables 4 and 5 represent the solid content ratio when mixing. In addition, 0.02 g of ADH was added to the test solution as an aqueous solution. About other additives, it prepared so that it might become the density | concentration in a table | surface. In the processing of nylon cloth, SMITEX Resin M-3 (hereinafter referred to as M-3) and SMITEX Accelerator ACX (hereinafter referred to as ACX) are added to each treatment bath so as to be 0.5% by mass, respectively. did. Moreover, in the processing of the polyester cloth, each treatment bath was prepared so as to be 0.5 mass% of M-3 and 0.05 mass% of ACX. The abbreviations in the table indicate the following, and the numbers in () represent the ratio of the solid content after mixing. Surfynol 104-PG50 (manufactured by Air Products Japan Co., Ltd., hereinafter referred to as AGE) used as an additive was diluted to 5% by mass with dipropylene glycol and added so as to be the mass% in the table with respect to the treatment bath. did. Surfynol 440 (manufactured by Air Products Japan, hereinafter referred to as AGE-4) and PEO-30 were added as a 5% by mass aqueous solution so that the mass% in the table was obtained.
M-3: Sumtex Resin M3 / Sumitomo Chemical Co., Ltd.
ACX: Sumitex Accelerator ACX / Sumitomo Chemical Co., Ltd.
MF: Meikanate MF / Madesei Chemical Industry Co., Ltd.
TP-10: Meikanate TP-10 / Maisei Chemical Industry Co., Ltd.
NBP: Meikanate NBP-211 / Maisei Chemical Industry Co., Ltd.
ADH: Adipic acid dihydrazide

[Preparation of test cloth]
Using the test solutions obtained in Examples 1 to 24, a dyed nylon cloth or a polyester cloth was dip-coated and squeezed so that the wet pick-up would be 70% by mass and 60% by mass, respectively. This was dried at 110 ° C. for 90 seconds and then dried at 170 ° C. for 60 seconds to obtain test cloth A.

[Evaluation method of water repellency]
The water repellency of the test cloth A was evaluated by a JIS-L1092 spray test (however, the amount of spray water was 0.25 liter or 1 liter. The water temperature was 27 ° C.). Expressed by grade. Those marked with + (−) in the water repellency grade indicate that the respective properties are slightly good (bad).

[Method for evaluating washing durability]
The washing durability of the test cloth A is determined by repeating washing 5 times (HL-5) 16 times (nylon cloth) or repeating HL-5 40 times (polyester cloth) according to the water washing method of JIS-L0217 Attached Table 103. The water repellency was evaluated after drying at 90 ° C. for 15 minutes.

[Evaluation method of rainfall test]
The evaluation of the rain test of the test cloth A is performed under the condition that the rainfall is 100 cc / min, the rain water temperature is 20 ° C., and the rain time is 10 minutes according to the method (Bundesmann test) described in the JIS-L-1092 (C) method. It was rained and expressed in 5 grades 1-5. The washing durability was evaluated by pressing for 15 seconds at 130 ° C. after repeated washing in the same manner as described above. The press used DKUSUN AF-43T. The larger the score, the better the water repellency. Those marked with + (−) indicate that each property is slightly good (bad).
The evaluation results of Examples 1 to 24 are shown in Tables 7 and 8.

[Examples 25-29]
The aqueous dispersions obtained in Production Examples 22 to 26 were prepared according to Table 9 so that the solid content concentration was 0.6% by mass for PET (polyethylene terephthalate) and 1.0% by mass for cotton. M-3 / ACX was prepared so that the solid concentration in the working fluid was 0.3% by mass, respectively. After processing the test cloth in the same manner as in Examples 1 to 24, the spray test of JIS-L1092 and the washing durability in HL-5 were evaluated. However, the cotton wet pick-up was squeezed to 65% by mass. Examples 25 to 28 are examples in which the copolymer (I) and the copolymer (II) were used as separate particles, and Example 29 was a single unit in which the structural units (a), (b) and ( It is a comparative example using the copolymer containing c).
In Table 9, the mass ratio of the structural unit (a) and the structural unit (b) forming the copolymer (I) to the copolymer (I) is indicated as [a ₁ ] and [b ₁ ]. Moreover, the mass ratio with respect to copolymer (II) of structural unit (a) and structural unit (c) which forms copolymer (II) was shown as [a ₂ ] and [c ₂ ]. Copolymer (I) / copolymer (II) is [mass ratio of copolymer (I)] / [mass ratio of copolymer (II)]. Moreover, the mass ratio of each structural unit in all the copolymers (copolymer (I) + copolymer (II)) was shown as [a], [b], [c], [d]. The numbers in parentheses in Table 9 represent the solid content ratio when mixing.

[Evaluation method of washing durability (HL-5)]
Washing was repeated 5 times according to the water washing method of JIS-L0217 Attached Table 103. After drying overnight in a room adjusted to a room temperature of 25 ° C. and a humidity of 55%, the water repellency was evaluated according to the evaluation method described above.
Table 10 shows the evaluation results.

[Evaluation method of friction durability test]
According to the method described in the JIS-L-1076 (C) method, a load of 28 gf per square centimeter was applied to conduct a friction durability test. The test was performed using the test solution prepared in the same manner as in Example 6 except that the nylon processed cloth of Examples 3, 6, and 11 (all are examples) and AG-415 (Asahi Glass Co., Ltd.) were used. Nylon processed cloth was used.
Thereafter, each processed cloth was repeatedly washed in the same manner as the above-mentioned washing durability, and then dried at 90 ° C. for 15 minutes to prepare a test cloth. The test cloth was subjected to elemental analysis on the cloth surface by X-ray photoelectron spectroscopy. The results for the fluorine element concentration are shown in Table 11.

  In Examples 17 and 18 in which only the copolymer (I) was used, the initial liquid repellency was very high, but the liquid repellency after washing was significantly reduced and the durability was low (Tables 7 and 8). ). Even in Examples 19 and 20 using only the copolymer (II), both liquid repellency and durability were not achieved. Further, even in Example 29 using the copolymer containing the structural units (a), (b) and (c) in one particle, sufficient liquid repellency was not obtained and the durability was low (Table 10). ).

On the other hand, in Examples 25 to 28, sufficient liquid repellency and high durability were obtained even though the total proportion of each structural unit contained in the entire copolymer was the same as in Example 29 (Table 10). ). Thus, when the copolymer (I) and the copolymer (II) were mixed and used as separate particles, sufficient liquid repellency and high durability could be confirmed. Similarly, in Examples 1 to 5 and 22 to 24, in which the copolymer (I) and the copolymer (II) were mixed and used as separate particles, high liquid repellency and durability were obtained. Further, when the copolymer (I) and the copolymer (II) are used in a core-shell type (Examples 6 to 13, 15, 16, 21), sufficient liquid repellency and high durability are obtained. It was.
Further, the liquid repellent film formed by the liquid repellent composition of the present invention has little surface change due to friction and high durability (Table 11).
As described above, the liquid repellent composition containing the copolymer (I) and the copolymer (II) of the present invention can form a liquid repellent film excellent in liquid repellency and durability.

The results of thermogravimetry for each additive used in the examples are shown in FIG. For measurement, TG-DTA2000S manufactured by Bruker AXS was used. 10 mg of the additive to be measured was weighed into a deep dish aluminum container having a height of φ5.2 mm and a height of 5.1 mm, and the weight change was measured when the temperature was raised from room temperature to 400 ° C. at 10 ° C./min.
FIG. 2 shows the change of the dynamic surface tension with and without the additive, taking Example 6 as an example. The measurement was performed using FACE BP-D3 manufactured by Kyowa Interface Science Co., Ltd.

The liquid repellent composition of the present invention exhibits practically necessary functions such as sufficient water and oil repellency and durability. It is estimated to be due to the synergistic effect of immobilization of promotion and ^the R ^f group on the surface orientation of ^the R ^f group.
A water / oil repellent (liquid repellent) based on this principle can form a coating film at a lower temperature than a conventional water / oil repellent, and the resulting coating film is flexible and tough and has excellent adhesion to a substrate. Therefore, it is possible to impart water and oil repellency to the article without lowering the quality such as hardening of the texture and embrittlement of the film, which are the conventional problems. Furthermore, the obtained article can impart sufficient water and oil repellency even in processing at a lower temperature than conventional. Furthermore, there is little decrease in performance due to wear or washing. In addition, adhesion during laminating and coating is also significantly improved over conventional water and oil repellents. Furthermore, the copolymer in the present invention has good solubility in a fluorine-based solvent having a small influence on the ozone layer, such as an alcohol solvent, a weak solvent, hydrofluorocarbon, etc., so that there are few problems in terms of environment and safety. A solvent can be used as a solvent.

  In addition, the liquid repellent composition of the present invention includes sportswear, coats, blousons, clothing articles such as work clothes or uniforms, textile products such as bags and industrial materials, nonwoven fabrics, leather products, stone materials, concrete building materials, etc. Used for water and oil repellent treatment. Moreover, it is used also for the use as a coating agent for filter materials used in the presence of an organic solvent liquid or its vapor, a surface protective agent, a coating agent for electronics, and an antifouling coating agent. Furthermore, it is also used for applications that impart water and oil repellency by mixing and molding with fiber such as polypropylene and nylon.

The figure which shows the thermogravimetric reduction (TG-DTA) of each additive. The figure which shows the change of dynamic surface tension.

Claims (5)

A liquid repellent composition containing copolymer (I) and copolymer (II) which are separate particles , or containing copolymer (I) and copolymer (II) present in the same particle. There,
The copolymer (I) contains 65 to 95% by mass of the structural unit (a) and 1 to 30% by mass of the structural unit (b) with respect to the copolymer (I).
The copolymer (II) contains a structural unit (a) of 25 to 80% by mass and a structural unit (c) of 1 to 50% by mass relative to the copolymer (II).
The mass ratio of the structural unit (a) contained in the copolymer (I) to the copolymer (I) is [a ₁ ], and the structural unit (a) contained in the copolymer (II) When the mass ratio to the polymer (II) is [a ₂ ], [a ₁ ] − [a ₂ ] ≧ 16 (mass%),
Copolymer (I) and copolymer (II) are contained at [mass ratio of copolymer (I)] / [mass ratio of copolymer (II)] = 10/90 to 95/5. A liquid repellent composition characterized by comprising:
The structural unit _{(a) :( Z A -Y A} ) n X A constituent unit derived from a monomer represented by. However, Z _A is a polyfluoroalkyl group having 6 or less carbon atoms. n is 1 or 2, and when n is 2, (Z _A -Y _A ) may be the same or different. X _A is, -CR ₌ CH 2 when n _is 1, -COOCR = CH 2, -OCOCR = CH 2, a -OCH ₂ -φ-CR = CH ₂ or -OCH = CH _2, n is 2 for the _{= CH (CH 2) m CR} = CH 2, = CH (CH 2) m COOCR = CH 2, = CH (CH 2) m OCOCR = CH 2 or -OCOCH = CHCOO- (R is a hydrogen atom, A methyl group or a halogen atom, φ is a phenylene group, and m is an integer of 0 to 4. Y _A is a divalent organic group or a single bond.
The structural unit _(b): Z B -X constituent unit derived from a monomer represented by _B. However, Z _B is a hydrocarbon group having 14 or more carbon atoms. X _B is the same as X _A described above.
Structural unit (c): a structural unit derived from a monomer having no polyfluoroalkyl group and having a crosslinkable functional group.   The copolymer (I) and / or the copolymer (II) is a structural unit (d) derived from a monomer having a polymerizable group other than the structural units (a), (b) and (c). The liquid repellent composition according to claim 1, which is contained. Furthermore, the liquid repellent composition of Claim 1 or 2 containing surfactant (III) which consists of surfactant (e1) and / or surfactant (e2), and surfactant (e3).
Surfactant (e1): At least one selected from the group consisting of polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monoalkapolyenyl ether, polyoxyalkylene monopolyfluoroalkyl ether.
Surfactant (e2): A nonionic surfactant comprising a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule.
Surfactant (e3): a cationic surfactant represented by the following formula ^{s 71.}
[(R ²¹ ) ₄ N ⁺ ] · X ⁻ (formula s ⁷¹ )
(However, R ²¹ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a polyoxyalkylene chain having a hydroxyl group at the end. The four R ^{21 s} may be the same or different, but the four R ²¹ are not simultaneously hydrogen atoms . X ⁻ is a counter ion.) The liquid repellent processing method using the liquid repellent composition as described in any one of Claims 1-3. An article having a liquid repellent film formed using the liquid repellent composition according to any one of claims 1 to 3.

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