JP2000160149A - Water dispersion-type composition for water- and oil- repellent agent, and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of manifesting properties such as excellent stability and color fastness to dyeing by carrying out the emulsion polymerization of a raw material composition comprising a specific polymerizable monomer, a surfactant and an aqueous medium to disperse the polymer in the aqueous medium. SOLUTION: This water-dispersion type composition having a polymer having the polymerization unit of (A) (i) a polymerizable monomer consisting of a (meth)acrylate having a polyfluoroalkyl group or (ii) polymerizable monomers comprising the component (i) and a polymerizable monomer without the component (i), dispersed in (C) an aqueous medium is obtained by emulsifying a raw material composition comprising the component A, (B) a surfactant selected from nonionic, cationic and amphoteric surfactants, and the component C under pressure, and polymerizing the obtained emulsion. The component (ii) is preferably a liquid or solid polymerizable monomer when carrying out the emulsification under the pressure, and preferably consists essentially of a 1-20C alkyl (meth)acrylate or a 5-8C cycloalkyl (meth)acrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a water-dispersible composition for a water / oil repellent and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a polymer having polymerized units of a polymerizable monomer having a polyfluoroalkyl group (hereinafter, referred to as an ^Rf group) is dispersed in an aqueous solvent to form an aqueous dispersion. What is dissolved in an organic solvent to form an organic solution, or what is dispersed in an organic solvent to form a solvent-based dispersion, is processed into a fiber product or the like to impart water and oil repellency to the surface thereof. The technology is known. Of these, in recent years, an aqueous dispersion has been recommended from the viewpoints of problems on the working environment and effects on the environment.

[0003] In producing the aqueous dispersion, in the case of producing a directly aqueous dispersion having ^the R ^f group is poorly soluble in water (meth) acrylate is polymerized in an aqueous medium, R ^f
In general, an organic solvent having high compatibility with a (meth) acrylate having a group and being water-soluble is added to an aqueous medium as a polymerization auxiliary solvent. However, the use of a polymerization auxiliary solvent has problems in work and environment.

To solve this problem, a raw material composition obtained by adding a (meth) acrylate having an R ^f group and an anionic surfactant to an aqueous medium containing no polymerization auxiliary solvent is first subjected to ultrasonic treatment, A method of producing an aqueous dispersion by a method of performing emulsion polymerization (JP-A-5-17538) has been proposed.

[0005]

However, the aqueous dispersion obtained by this method contains an anionic surfactant, and when this is treated with fibers, sufficient water and oil repellency is exhibited. However, the durability of the water- and oil-repellent performance was insufficient, and the stability of the aqueous dispersion was low. However, in order to solve this problem, it is necessary to remove the anionic surfactant, and there is a problem that extra work is required.

[0006] In addition, the proportion of polymerized units of (meth) acrylate having an ^Rf group in a polymer obtained by carrying out emulsion polymerization without using a polymerization auxiliary solvent is low. There is also a problem that sufficient water and oil repellency is not exhibited.
Furthermore, in order to solve the above-mentioned problem, even when emulsion polymerization is performed after subjecting the raw material composition to ultrasonic treatment, there is a problem that a stable aqueous dispersion cannot be obtained.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is intended to provide stability and color fastness without using a polymerization auxiliary solvent having environmental or working environment problems. Provided are a production method capable of providing a water-dispersible composition for a water- and oil-repellent agent having excellent performances such as degree and water pressure resistance, and a water-dispersed composition for a water- and oil-repellent agent produced by the method.

That is, according to the present invention, a raw material composition containing the following polymerizable monomer (A), the following surfactant (B), and an aqueous medium (C) is emulsified under pressure and then polymerized.
A water-dispersible composition for a water- and oil-repellent, wherein the polymer (X) containing the polymerized unit of the polymerizable monomer (A) is dispersed in an aqueous medium (C). Provided are a production method, and a water-dispersible composition for a water / oil repellent produced by the method. Polymerizable monomer (A): R ^f having a group (meth) acrylate (a ¹⁾ consisting of polymerizable monomer, or, having R ^f group and (meth) acrylate (a ¹⁾ R ^f group Having a polymerizable monomer (a) other than the (meth) acrylate (a ¹ )
² ) a polymerizable monomer comprising: Surfactant (B): a surfactant selected from a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, acrylate and methacrylate are collectively referred to as (meth) acrylate. The same applies to notations such as (meth) acrylamide. Polymerizable monomer (A) in the present invention, the polymerizable monomer consisting of having ^the R ^f group (meth) acrylate (a ^1), or, having R ^f group and (meth) acrylate (a ¹⁾ A polymerizable monomer comprising a polymerizable monomer other than (a ¹ ). Having ^the R ^f group and (meth) acrylate (a ¹⁾ refers to a compound ^the R ^f group is present in the alcohol residue portion of the (meth) acrylate.

The R ^f group is a group in which two or more hydrogen atoms of an alkyl group have been replaced by fluorine atoms. The ^Rf group preferably has 2 to 20 carbon atoms, and particularly preferably 6 to 16 carbon atoms. R ^f
The group may have a straight-chain structure or a branched structure, and a straight-chain structure is particularly preferred. In the case of a branched structure, the branched portion is preferably present at the terminal of the R ^f group, and is preferably a short chain having about 1 to 4 carbon atoms.

The R ^f group may contain a halogen atom other than a fluorine atom. As another halogen atom, a chlorine atom is preferable. An etheric oxygen atom or a thioetheric sulfur atom may be inserted between carbon-carbon bonds in the R ^f group. The structure of the terminal portion of the R ^f group includes -CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF
_{2 H, -CFH 2, -CF 2} Cl and the like, -CF
₂ CF ₃ is preferred.

[0012] The number of fluorine atoms in the R ^f groups, [(R ^f number of fluorine atoms in the group) / (R ^f number of hydrogen atoms contained in the alkyl group corresponding same carbon number and group)] × 100 (%)
When expressed by, it is preferably at least 60%, particularly preferably at least 80%. Further, the R ^f group is preferably a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (that is, a perfluoroalkyl group), or a group having a perfluoroalkyl group at a terminal portion.

The perfluoroalkyl group has 2 to 2 carbon atoms.
0 is preferable and 6 to 16 are particularly preferable. When the number of carbon atoms in the perfluoroalkyl group is small, water repellency and oil repellency tend to decrease, and when the number of carbon atoms in the perfluoroalkyl group is large, handling of the (meth) acrylate having an ^Rf group may be difficult. is there.

Specific examples of the R ^f group include the following groups. _{C 4 F 9 - [F (} CF 2) 4 -, (CF 3) 2
_{CFCF 2 -, (CF 3)} 3 C-, CF 3 CF 2 CF
(CF ₃₎ - structure may be any of the groups isomeric] such as, C ₅ F ₁₁ - [e.g. _{F (CF 2) 5 -]} , C 6
F ₁₃ - [e.g. _{F (CF 2) 6 -]} , C 7 F 15 - [ e.g. _{F (CF 2) 7 -]} , C 8 F 17 - [ such as F
_{(CF 2) 8 -],} C 9 F 19 - [ e.g. F (CF _2)
9 −], C ₁₀ F ₂₁ − [for example, F (CF ₂ ) ₁₀ −], C
₁₂ F ₂₅ - [e.g. _{F (CF 2) 12 -]} , C 14 F 29 -
[E.g. _{F (CF 2) 14 -]} , C 16 F 33 - [ e.g. _{F (CF 2) 16 -]} , H (CF 2) j - ( where, j is 1 to 16 integer), Cl (CF ₂ ) _k − (where k is an integer of 1 to 16), (CF ₃ ) ₂ CF (CF ₂ ) _m −
(Where m is an integer of 1 to 13) and the like.

When the R ^f group is a group in which an etheric oxygen atom or a thioetheric sulfur atom is inserted between carbon-carbon bonds, specific examples include the following groups. _{F (CF 2) 5 OCF (} CF 3) -, F [CF (C
_{F 3) CF 2 O] y} CF (CF 3) CF 2 CF 2 -, F
_{[CF (CF 3) CF 2} O] z CF (CF 3) -, F
_{[CF (CF 3) CF 2} O] u CF 2 CF 2 -, F (C
F ₂ CF ₂ CF ₂ O) _v CF ₂ CF _2- , F (CF ₂ C
F ₂ O) _w CF ₂ CF ₂ −, F (CF ₂ ) ₅ SCF (C
_{F 3) -, F [CF} (CF 3) CF 2 S] y CF (CF
_{3) CF 2 CF 2 -,} F [CF (CF 3) CF 2 S] z
_{CF (CF 3) -, F} [CF (CF 3) CF 2 S] u C
_{F 2 CF 2 -, F (} CF 2 CF 2 CF 2 S) v CF 2 C
F ₂ —, F (CF ₂ CF ₂ S) _w CF ₂ CF ₂ — (where y and z are each independently an integer of 1 to 10, u is an integer of 2 to 6, v is an integer of 1 to 11, w is Is an integer of 1 to 11).

(Meth) acrylate having an R ^f group (a
^{As 1} ), a compound represented by the following formula 1 is preferable. In the formula 1, R ^f is an R ^f group, Q is a divalent organic group, and R
¹ represents a hydrogen atom or a methyl group. R ^f -Q-OCOCR ¹ = CH ₂ Formula 1

The R ^f group in the formula 1 is preferably an R ^f group containing no etheric oxygen atom or thioetheric sulfur atom, particularly preferably a perfluoroalkyl group, especially — (CF ₂ ) _n F (where n is 1). An integer of from 16 to 16, preferably an integer of from 4 to 16, and particularly preferably an integer of from 6 to 12.

In the formula 1, Q is-(CH ₂ )
_{p + q -, - (CH} 2) p CONR a (CH 2) q -, -
(CH ₂ ) _p OCONR ^a (CH ₂ ) _q -,-(CH
^{_{2) p SO 2 NR a (}} CH 2) q -, - (CH 2) p N
_{HCONH (CH 2) q -,} - (CH 2) p CH (O
H) (CH ₂ ) _q -,-(CH ₂ ) _p CH (OCOR
^a ) (CH ₂ ) _q- and the like are preferable. Here, Ra represents ^a hydrogen atom or an alkyl group. p and q are independently 0
The above integers are shown, and p + q is an integer of 1 to 22.

In the compound (formula 1), Q is-(CH
_{2) p + q -, -} (CH 2) p CONR a (CH 2) q
-, or _{- (CH 2) p SO 2} NR a (CH 2) q -
And q is an integer of 2 or more, and p + q
Is preferably 2 to 6, and-(CH ₂ ) _{p + q} − when p + q is 2 to 6 (that is, ethylene group to
The compound (formula 1) in the case of a hexamethylene group) is particularly preferred. It is preferable that a fluorine atom is bonded to the carbon atom of R ^f bonded to Q in the compound (formula 1).

(Meth) acrylate having an R ^f group (a
Examples of ¹ ) include the following compounds. Where R ¹
Represents a hydrogen atom or a methyl group.

[0021]

Embedded image F (CF ₂ ) ₅ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , H (CF ₂ ) ₆ CH ₂ OCOCR ¹ = CH ₂ , H ( CF ₂ ) ₈ CH ₂ OCOCR ¹ = CH ₂ , H (CF ₂ ) ₁₀ CH ₂ OCOCR ¹ = CH ₂ , H (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₁₀ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₁₂ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₁₄ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₁₆ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₄ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₃ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OCOCH ₃ ) OCOR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH ( OH) CH ₂ OCOCR ¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₉ CH ₂ CH ₂ OCOCR ¹ = CH ₂ , F (CF ₂ ) ₉ CONHCH ₂ CH ₂ OCOCR ¹ = CH ₂ .

The polymerizable monomer (A) may contain two or more (meth) acrylates (a ¹ ) having an R ^f group. In that case, a mixture of (meth) acrylates (a ¹ ) having R ^f groups having different carbon numbers is preferable. Further, the polymerizable monomer (A) may be composed of only a (meth) acrylate (a ¹ ) having an R ^f group,
It may consist of (a ¹ ) and a polymerizable monomer (a ² ) other than (a ¹ ).

Examples of the polymerizable monomer (a ² ) include known or well-known polymerizable monomers.
Or two polymerizable monomers are preferred. further,
The polymerizable monomer (a ² ) is preferably a polymerizable monomer that is liquid or a solid polymerizable monomer under the conditions of emulsification under pressure. As the polymerizable monomer, the following polymerizable monomer (a ²¹ ) and / or the following polymerizable monomer (a ²² ) are preferable, and the polymerizable monomer (a ²¹ ) is particularly essential. Is preferred.

Polymerizable monomer (a ²¹ ): an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl (meth) acrylate having a cycloalkyl group having 5 to 8 carbon atoms . Polymerizable monomer (a ²² ): a polymerizable monomer other than (meth) acrylate (a ¹ ) having R ^f group and polymerizable monomer (a ²¹ ).

When the polymerizable monomer (a ²¹ ) is an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, the alkyl group may have a branched structure even if it has a linear structure. There may be. The polymerizable monomer (a ²¹ ) may be of two or more types, and in the case of two or more types, may be composed of two or more types having different structures of the alkyl group portion. The polymerizable monomer (a ²¹ ) has a cycloalkyl group having 5 carbon atoms.
In the case of a cycloalkyl (meth) acrylate having a molecular weight of from 8 to 8, the cycloalkyl group is preferably a cyclohexyl group.

The polymerizable monomer (a ²¹ ) is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms, such as methyl (meth) acrylate, octadecyl (meth) acrylate, or 2-ethylhexyl ( Meth) acrylates and the like are particularly preferred.

As the polymerizable monomer (a ²² ), monoolefin, vinyl halide, vinylidene halide, vinyl carboxylate, styrene, substituted styrene, (meth) acrylamide, N-substituted (meth) acrylamide, alkyl vinyl ether , (Substituted alkyl) vinyl ether, vinyl alkyl ketone, diolefin, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, aziridinyl alkyl (meth) acrylate, aralkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, poly Oxyalkylene mono (meth) acrylate, polyoxyalkylene mono (meth)
Acrylate monomethyl ether, polyoxyalkylene di (meth) acrylate, (meth) acrylate having a polydimethylsiloxane group, triallyl cyanurate, allyl glycidyl ether, allyl carboxylate, N
A polymerizable monomer selected from vinylcarbazole, N-methylmaleimide, maleic anhydride, monoalkyl maleate, dialkyl maleate, substituted aminoalkyl (meth) acrylate, and blocked isocyanate group-containing (meth) acrylate Is preferred.

Further, as the polymerizable monomer (a ²² ),
Ethylene, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth)
Acrylamide, alkyl vinyl ether, (halogenated alkyl) vinyl ether, vinyl alkyl ketone,
Butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, aziridinylethyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyoxyalkylene (meth) acrylate, Polyoxyalkylene mono (meth) acrylate monomethyl ether, polyoxyalkylene mono (meth) acrylate (2-ethylhexyl) ether, polyoxyalkylene di (meth) acrylate, (meth) acrylate having a polydimethylsiloxane group, triallyl cyanurate , Allyl glycidyl ether, allyl acetate, N-vinyl carbazole, maleimide, N-methylmaleimide, (2-dimethylamino) ethyl (meth) acrylate, etc. Preferred.

The (meth) acrylate having a blocked isocyanate group in the polymerizable monomer (a ²² ) is preferably a (meth) acrylate having at least one blocked isocyanate group. ) Compounds having a structure in which isocyanate groups of acrylate are blocked with a blocking agent are preferred.

Here, as the isocyanate group-containing (meth) acrylate, 2-isocyanateethyl (meth) acrylate or (meth) acrylate having a functional group capable of binding to an isocyanate group and one or more polyisocyanates are used. A reaction product obtained by allowing the isocyanate groups to react at a remaining ratio is preferable. As the (meth) acrylate having a functional group capable of binding to an isocyanate group, a (meth) acrylate having a hydroxyl group is preferable, and a mono- or diester of (meth) acrylic acid and a polyhydric alcohol is particularly preferable. Examples of the polyhydric alcohol include ethylene glycol, polyoxyethylene glycol, propylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane-alkylene oxide adduct, and pentaerythritol.

Further, as the polyisocyanate, 4,
Aromatic isocyanates such as 4'-diphenylmethane diisocyanate and tolylene diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate and norbornene diisocyanate, and polyisocyanate nurate Modified, prepolymer modified, modified such as buret modified is preferred, particularly aliphatic isocyanates, and its nullate modified,
Prepolymer modified products and buret modified products are preferred.

As the blocking agent, alkyl ketoximes, phenols, alcohols, β-diketones and lactams are preferable, and methyl ethyl ketoxime, ε-caprolactam, phenol, cresol, acetylacetone, diethyl malonate, isopropyl alcohol, Particularly preferred are t-butyl alcohol, maleimide and the like, particularly preferred are alkyl ketoximes such as methyl ethyl ketoxime, and lactams such as ε-caprolactam, and particularly preferred are blocking agents having a dissociation temperature of 120 to 180 ° C.

Blocked isocyanate group-containing (meth)
Specific examples of the acrylate include the following. Compound in which the isocyanate group of 2-isocyanatoethyl (meth) acrylate is blocked with methyl ethyl ketoxime, 2-isocyanatoethyl (meth)
Compound in which isocyanate group of acrylate is blocked with ε-caprolactam, 1: 1 of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate
(Molar ratio) a compound in which an isocyanate group of a reactant is blocked with methyl ethyl ketoxime, a compound in which an isocyanate group of a 1: 1 (molar ratio) of isophorone diisocyanate and 2-hydroxypropyl (meth) acrylate is blocked with methyl ethyl ketoxime, A compound in which a 1: 1 (molar ratio) reaction product of norbornene diisocyanate and 2-hydroxyethyl (meth) acrylate is blocked with methyl ethyl ketoxime.

The polymerizable monomer (a ²² ) may be a liquid or solid polymerizable monomer (hereinafter referred to as the polymerizable monomer (a ²² )) under the conditions of emulsification under pressure. , A polymerizable monomer (a ²³ )).
That is, as the polymerizable monomer contained in the raw material composition, a polymerizable monomer (a ²³ ) is employed, and a polymerizable monomer which is a gas under the conditions of emulsification under pressure [hereinafter, referred to as “ It is referred to as a polymerizable monomer (a ³ ). Is preferable to be introduced into the emulsion after emulsifying the raw material composition under pressure to form an emulsion.

As the polymerizable monomer (a ³ ), it is preferable to select a polymerizable monomer which is a gas under the conditions at the time of emulsification under pressure from among those listed as the polymerizable monomer (a ²² ). , Vinyl halide is preferable, vinyl chloride or vinyl fluoride is particularly preferable, and vinyl chloride is particularly preferable.

The polymer (X) in the present invention preferably contains a polymerized unit of the polymerizable monomer (a ²¹ ) or a polymerized unit of the polymerizable monomer (a ³ ). Heavy addition polymer (X) is having with polymerized units of the polymerizable monomer polymerized units or polymerizable monomer ^{(a 21) (a 3)} , the polymerizable monomer polymerized units of (a ²³⁾ It is preferred that they are united.

(Meth) having R ^f group in polymer (X)
The proportion of polymerized units of acrylate (a ¹⁾ is preferably 40 to 100 wt% from the viewpoint of water and oil repellency, especially 40-9
0% by weight is preferable, and particularly preferably 50 to 80% by weight. According to the method of the present invention, the ratio of the polymerization unit of (meth) acrylate (a ¹ ) having an R ^f group can be increased without using a polymerization auxiliary solvent. The proportion of the polymerizable monomer in the polymer (X) (a ²⁾ is preferably 0 to 60 wt%, especially 10 to 60% by weight.

The ratio of the polymerizable unit of the polymerizable monomer (a ²¹ ) in the polymerizable monomer (a ² ) is 10 to 10 in the polymer (X).
It is preferably 60% by weight, particularly preferably 20 to 50% by weight. The proportion of polymerized units of the polymerizable monomer (a ³⁾ 0.1 to 40% by weight is preferred in the polymer (X). The proportion of polymerized units of further polymerizable monomer (a ^23), the proportion of the polymerized units of the polymerizable monomer (a ³⁾ to the polymer (X) 0 to 20
% By weight is preferred. The molecular weight of the polymer (X) is from 1,000 to
200,000 is preferable, and 2000-100,000 is particularly preferable.

As the surfactant (B), a surfactant selected from a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant is used. Among them, a nonionic surfactant and / or a cationic surfactant is used. Nonionic surfactants are preferred. The surfactant (B) is selected from the following surfactant (b ¹ ), the following surfactant (b ² ), the following surfactant (b ³ ), and the following surfactant (b ⁴ ) Particularly preferred, and particularly preferred are surfactants (b ¹ ).

The surfactant (b ¹ ) is a nonionic surfactant comprising a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, or a polyoxyalkylene monoalkapolyenyl ether.

An alkyl group in the surfactant (b ¹ ),
The alkenyl group or alkapolyenyl group preferably has 4 to 26 carbon atoms. Further, the alkyl group, alkenyl group, or alkapolyenyl group may have a linear structure or a branched structure, respectively. In the case of a branched structure, it may be a secondary alkyl group, a secondary alkenyl group, or a secondary alkapolyenyl group.
Specific examples of the alkyl group, alkenyl group, or alkapolyenyl group include octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, hexadecyl, behenyl (docosyl), and oleyl (9-octadecenyl). ) And the like.

The surfactant (b ¹ ) is preferably a polyoxyalkylene monoalkyl ether or a polyoxyalkylene monoalkenyl ether. The polyoxyalkylene portion of the surfactant (b ¹ ) is preferably composed of one or two oxyalkylene groups, and when composed of two types, it is preferred that their connection is a block. The polyoxyalkylene portion preferably comprises a portion in which two or more oxyethylene groups and / or oxypropylene groups are linked.

As the surfactant (b ¹ ), a compound represented by the following formula 2 is preferable. However R ² in the formula 2 represents an alkyl group or the number 8 or more alkenyl groups of carbon atoms of 8 or more carbon atoms, s represents an integer of 5 to 50, g is an integer of 0 to 20. When g and s are 2 or more, the expression 2
The oxyethylene group and the oxypropylene group in the inside are connected in a block shape.

[0044]

R ² O [CH ₂ CH (CH ₃ ) O] _g- (CH ₂ CH ₂ O) _s H Formula 2

R ^{2 in} Formula 2 may have either a straight-chain structure or a branched structure. s is preferably an integer of 10 to 30, and g is preferably an integer of 0 to 10. When s is 4 or less, or g is 21 or more, it becomes hardly soluble in water and becomes difficult to be uniformly dissolved in the aqueous medium (C), so that the effect of improving permeability may decrease. When s is 51 or more, hydrophilicity is increased, and there is a possibility that water repellency is reduced.

Specific examples of the compound (Formula 2) include the following compounds. Where s and g are
It has the same meaning as described above, and the preferred embodiment is also the same. Further, the oxyethylene group and the oxypropylene group are connected in a block shape.

[0047]

Embedded image C ₁₈ H ₃₇ O [CH ₂ CH (CH ₃ ) O] _g −
(CH ₂ CH ₂ O) _s H, C ₁₈ H ₃₅ O [CH ₂ CH (C
_{H 3) O] g - (} CH 2 CH 2 O) s H, C 16 H 33 O
_{[CH 2 CH (CH 3)} O] g - (CH 2 CH 2 O) s
_{H, C 12 H 25 O [} CH 2 CH (CH 3) O] g - (CH
₂ CH ₂ O) _s H, (C ₈ H ₁₇ ) (C ₆ H ₁₃ ) CHO
[CH ₂ CH (CH ₃ ) O] _g- (CH ₂ CH ₂ O)
_{s H, C 10 H 21 O} [CH 2 CH (CH 3) O] g - (C
H ₂ CH ₂ O) _s H.

The surfactant (b ² ) has at least one carbon-carbon triple bond and at least one hydroxyl group in the molecule,
And a nonionic surfactant comprising a compound exhibiting surface activity.

The surfactant (b ² ) is preferably a nonionic surfactant comprising a compound having one carbon-carbon triple bond and one or two hydroxyl groups in the molecule. Further, the nonionic surfactant may have a polyoxyalkylene moiety as a partial structure. As the polyoxyalkylene portion, a polyoxyethylene portion, a polyoxypropylene portion, a portion in which oxyethylene groups and oxypropylene groups are connected in a random shape, or a portion in which polyoxyethylene and polyoxypropylene are connected in a block shape, Is mentioned. Surfactant (b
^As a specific example of ² ), a compound represented by the following formula 3, 4, 5, or 6 is preferable.

[0050]

Embedded image HO—CR ³ R ⁴ —C≡C—CR ⁵ R ⁶ —OH Formula 3 HO— (A ¹ O) _m —CR ³ R ⁴ —C≡C—CR ⁵ R ⁶ — ( OA ² ) _n -OH Formula 4 HO-CR ⁷ R ⁸ -C≡CH Formula 5 HO- (A ³ O) _k -CR ⁷ R ⁸ -C≡CH Equation 6

However, A ¹ , A ² and A ³ in Formulas 3 to 6 each independently represent an alkylene group, m and n each represent an integer of 0 or more, and (m + n) represents an integer of 1 or more. It is an integer. k represents an integer of 1 or more. When m, n, or k is 2 or more, A ¹ , A ² ,
And A ³ may each consist of only one kind of alkylene group or two or more kinds of alkylene groups.

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R
⁸ each independently represents a hydrogen atom or an alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 6 to 12 carbon atoms. Specific examples of these groups include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group.

The oxyalkylene portion preferably comprises an oxyethylene portion, an oxypropylene portion, or both an oxyethylene portion and an oxypropylene portion. The number of oxyalkylene groups of the surfactant (b ²⁾ in the 1-50 is preferred. Further, as the surfactant (b ² ), a nonionic surfactant represented by the following formula 7 is preferable. Here, x and y in Formula 7 each represent an integer of 0 or more. The nonionic surfactant (Formula 7) may be used alone or in combination of two or more.

[0054]

Embedded image

As the nonionic surfactant (formula 7),
A nonionic surfactant in which the average of the sum of x and y is 10, a nonionic surfactant in which x is 0 and y is 0, or an average of the sum of x and y in the formula 7 is 1. A nonionic surfactant of 3 is preferred.

The surfactant (b ³ ) comprises a polyoxyethylene portion in which two or more oxyethylenes are continuously connected,
It is a nonionic surfactant comprising a compound in which two or more oxyalkylenes having 3 or more carbon atoms are continuously linked and both terminals are hydroxyl groups. The oxyalkylene having 3 or more carbon atoms in the surfactant (b ³ ) is preferably oxytetramethylene and / or oxypropylene.

As the surfactant (b ³ ), a nonionic surfactant comprising a compound represented by the following formula 8 or 9 is preferable. Note that h in Equations 8 and 9 is 0 to 200.
And r is an integer of 2 to 100, t is an integer of 0 to 200, and when h is 0, t is an integer of 2 or more, and when t is 0, h is an integer of 2 or more. It is. Equation 8
The -C ₃ H ₆ O- moiety therein is -CH (CH ₃ ) CH _{2-
Even, -CH 2 CH (CH 3)} - be -
CH (CH ₃ ) CH ₂ — and —CH ₂ CH (CH ₃ ) — may be mixed. Further, the polyoxyalkylene moiety in the following formula is connected in a block shape.

[0058]

Embedded image _{HO- (CH 2 CH 2 O)} h - (C 3 H 6 O) r - (CH 2 CH 2 O) t H ··· formula _{8 HO- (CH 2 CH 2 O} ) h - ( CH ₂ CH ₂ CH ₂ CH ₂ O) _r − — (CH ₂ CH ₂ O) _t H Formula 9

Further, as the surfactant (b ³ ), a nonionic surfactant comprising any of the following compounds is preferable.

[0060]

Embedded image _{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 - (C
_{H 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.

The surfactant (b ⁴ ) is a cationic surfactant comprising a substituted ammonium salt. The surfactant (b ⁴ ) is a cationic compound comprising a compound in which at least one hydrogen atom bonded to a nitrogen atom of an ammonium salt is substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene group having a hydroxyl group at a terminal. Surfactants are preferred, and cationic surfactants composed of compounds represented by the following formula 10 are particularly preferred. _{^{[(R 9) 4 N +}} ] · X - ··· formula 10

However, the symbols in the expression 10 have the following meanings. R ⁹ : The four R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a polyoxyalkylene group having a terminal hydroxyl group. However, four R ⁹ are not simultaneously hydrogen atoms. X ^-: counter ion.

When R ⁹ is an alkyl group, a long-chain alkyl group having 6 to 22 carbon atoms is preferred. When R ⁹ is an alkyl group other than a long-chain alkyl group, a methyl group or an ethyl group is preferred. When R ⁹ is an alkenyl group, a long-chain alkenyl group having 6 to 22 carbon atoms is preferred.
When R ⁹ is a polyoxyalkylene group,
Polyoxyethylene groups are preferred. X ⁻ is preferably a chloride ion, an ethyl sulfate ion, or an acetate ion.

The compound (formula 10) includes mono (long-chain alkyl) amine hydrochloride, mono (long-chain alkyl) dimethylamine hydrochloride, mono (long-chain alkyl) dimethylamine acetate, mono (long-chain alkenyl) dimethyl Amine hydrochloride,
Mono (long chain alkyl) dimethylamine / ethyl sulfate,
Mono (long-chain alkyl) trimethylammonium chloride, di (long-chain alkyl) monomethylamine hydrochloride, di (long-chain alkyl) dimethylammonium chloride, mono (long-chain alkyl) monomethyldi (polyoxyethylene)
Ammonium chloride, di (long-chain alkyl) monomethylmono (polyoxyethylene) ammonium chloride and the like.

Further, as the compound (formula 10), monooctadecyltrimethylammonium chloride, monooctadecyldimethylmonoethylammonium ethyl sulfate, mono (long chain alkyl) monomethyldi (polyethylene glycol) ammonium chloride, di (tallowalkyl) dimethylammonium chloride And dimethylmonococonutamine acetate.

When a nonionic surfactant other than the above surfactants (b ¹ ) to (b ³ ) is used as the surfactant (B) (hereinafter referred to as other nonionic surfactant). Examples of other nonionic surfactants include polyoxyethylene mono (substituted phenyl) ether, polyoxyethylene mono (substituted phenyl) ether condensate, polyol fatty acid ester, and an amine oxide moiety in the molecule. Compounds or polyoxyalkylene fatty acid amides are preferred.

Among other nonionic surfactants, a condensate of polyoxyethylene mono (substituted phenyl) ether or a substituted phenyl group in polyoxyethylene mono (substituted phenyl) ether was substituted with a monovalent hydrocarbon group. A phenyl group is preferable, and a phenyl group substituted with an alkyl group, an alkenyl group, or a styryl group is more preferable.

Further, the polyoxyethylene mono (substituted phenyl) ether condensate or polyoxyethylene mono (substituted phenyl) ether includes polyoxyethylene mono (alkylphenyl) ether condensate, polyoxyethylene mono (alkenylphenyl) ether. ) Condensation product of ether, polyoxyethylene mono (alkylphenyl)
Ether, polyoxyethylene mono (alkenylphenyl) ether or polyoxyethylene mono [(alkyl) (styryl) phenyl] ether is preferred.

Polyoxyethylene mono (substituted phenyl)
Specific examples of the condensate of ether or polyoxyethylene mono (substituted phenyl) ether include formaldehyde condensate of polyoxyethylene mono (nonylphenyl) ether and polyoxyethylene mono (nonylphenyl)
Ether, polyoxyethylene mono (octylphenyl) ether, polyoxyethylene mono (oleylphenyl) ether, polyoxyethylene mono [(nonyl)
(Styryl) phenyl] ether, polyoxyethylene mono [(oleyl) (styryl) phenyl] ether and the like.

Examples of the polyol in the polyol fatty acid ester include polyethylene glycol, decaglycerin, and ethers of polyethylene glycol and a polyol (other than polyethylene glycol).

Among the other nonionic surfactants, the fatty acid esters of polyols include 1: 1 (molar ratio) esters of octadecanoic acid and polyethylene glycol, and 1: 1 of ethers of sorbitol and polyethylene glycol and oleic acid. 4 (molar ratio) ester, 1: 1 (molar ratio) ester of ether of polyoxyethylene glycol and sorbitan with octadecanoic acid, 1: 1 (molar ratio) of ether of polyethylene glycol and sorbitan and oleic acid ) Esters, 1: 1 (molar ratio) ester of dodecanoic acid and sorbitan, (1 or 2): 1 (molar ratio) ester of oleic acid and decaglycerin, (1 or 2) of octadecanoic acid and decaglycerin : 1
(Molar ratio) esters.

Among the other nonionic surfactants, compounds having an amine oxide moiety in the molecule include compounds represented by the following formula 11
The compound represented by is preferred. (R ¹⁰ ) (R ¹¹ ) (R ¹² ) N (→ O) Formula 11 In Formula 11, R ¹⁰ , R ¹¹ and R ¹² each independently represent a monovalent hydrocarbon group. Surfactants having an amine oxide moiety (N → O) in the molecule are sometimes classified as cationic surfactants, but are treated as nonionic surfactants in the present invention. The surfactant may be one kind or two or more kinds.

Among the other nonionic surfactants, nonionic surfactants comprising a compound having an amine oxide moiety in the molecule include nonionic surfactants represented by the following formula (12): This is preferable because the dispersion stability of (1) is improved. (R ¹³ ) (CH ₃ ) ₂ N (→ O) Formula 12 R ^{13 in} Formula 12 is an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, an alkyl group (having a carbon number of 6-2
A phenyl group to which 2) is bonded or a phenyl group to which an alkenyl group (having 6 to 22 carbon atoms) is bonded;
An alkyl group having 22 or an alkenyl group having 8 to 22 carbon atoms is preferable.

Specific examples of the nonionic surfactant (formula 12) include the following compounds. [H (CH ₂ ) ₁₂ ] (CH ₃ ) ₂ N (→ O), [H (C
H 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). As the polyoxyalkylene fatty acid amide among other nonionic surfactants, polyoxyethylene fatty acid amide is preferable.

When an amphoteric surfactant is used as the surfactant (B), the amphoteric surfactant may be
Alanines, imidazolinium betaines, amidobetaines, betaine acetate and the like are preferred. Specific examples thereof include dodecyl betaine, octadecyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolinium betaine, dodecyl dimethyl amino acetate betaine, and fatty acid amidopropyl dimethyl amino acetate betaine.

The surfactant (B) may be used alone or in combination of two or more. When surfactants having different ionic properties are used in combination, a combination of a nonionic surfactant and a cationic surfactant, or a combination of a nonionic surfactant and an amphoteric surfactant is preferable. The amount of the surfactant (B) is 0.1 to 10% by weight based on the total amount of the polymerizable monomer (A) because the water / oil repellency is enhanced.
Is preferred. However, when the polymerizable monomer (A) contains a self-emulsifying polymerizable monomer, the surfactant (B)
The amount may be reduced.

The aqueous medium (C) in the present invention consists essentially of water only and does not contain a solvent such as a polymerization auxiliary solvent. In the present invention, by using the specific surfactant (B), the polymerization can be efficiently carried out even when the aqueous medium (C) is used, and the obtained water-dispersed composition is excellent. Demonstrate water and oil repellency. Water medium (C)
Is 100 to 500 with respect to the total amount of the polymerizable monomer (A).
% By weight is preferred.

The raw material composition of the present invention contains a polymerizable monomer (A), a surfactant (B), and an aqueous medium (C).
(Hereinafter, referred to as other components). Other components are components other than the solvent, and include a chain transfer agent, a radical initiator, an organic acid, an inorganic acid, and an inorganic salt. In the present invention, it is preferable to add a chain transfer agent, and as the chain transfer agent, a compound represented by the following formula 13 is particularly preferable. Here, R ¹⁴ in the following formula 13 represents an alkyl group having 6 to 18 carbon atoms. R ¹⁴ -SH ... Equation 13

When the compound (Formula 13) is used as the chain transfer agent, the molecular weight can be controlled efficiently even when the aqueous medium (C) is used, and the molecular weight distribution of the produced polymer (X) is narrow. There is an advantage that it is easy to control the molecular weight to exhibit the performance according to the purpose. Although the amount of the chain transfer agent depends on the molecular weight of the polymer (X), it is 0.1% based on the total amount of the polymerizable monomer (A).
1-2% by weight is preferred.

The raw material composition prepared as described above is emulsified under pressure. For emulsification under pressure, it is preferable to use a high-pressure emulsifier, whereby an emulsion of the polymerizable monomer (A) can be produced. The pressure at the time of pressurization is preferably 1.5 kg / cm ² or more, particularly 10 to 5 kg / cm ^2.
00 kg / cm ² is preferable, and especially 100 to 500
kg / cm ² is preferred. In addition, if necessary, preliminary dispersion before pressure emulsification enhances the efficiency of high pressure emulsification. The temperature of the raw material composition during pressurization is preferably 30 to 70 ° C. The emulsification under pressure can be carried out simply by applying the raw material composition under pressurized conditions, but stirring may be performed as necessary. Examples of the high-pressure emulsifier include Manton-Gaulin, hydroshear, and microfluidizer.

The emulsion produced by emulsifying the raw material composition under pressure has a low viscosity, a small particle size, and is thermodynamically stable. The particle size of the polymerizable monomer (A) in the emulsion is preferably from 0.01 to 0.5 μm, particularly preferably from 0.05 to 0.25 μm.

In the present invention, the raw material composition after pressure emulsification is polymerized by an emulsion polymerization method. As the polymerization method,
It is preferable to employ a general emulsification method, and more specifically, a method in which a polymerization initiator is added to the raw material composition after pressure emulsification to carry out polymerization. The polymerization initiator is not particularly limited, and ordinary polymerization initiators such as organic peroxides, azo compounds, and persulfates, or ionizing radiation such as γ-rays can be used.

When it is desired that the polymer (X) contains polymerized units based on the polymerizable monomer (a ³ ) which is a gas under the emulsifying conditions, the polymerizable monomer (a ³ ) is emulsified under pressure. a
^It is preferable to carry out the polymerization reaction after introducing ³ ) into the raw material composition. The reaction temperature of the polymerization reaction is preferably from 30 to 80C. The reaction time of the polymerization reaction is preferably 4 to 70 hours.

The reaction product obtained by the polymerization reaction may be used as it is as the composition of the present invention, or may be diluted with water and / or an organic solvent, if necessary. Preferred examples of the organic solvent include propylene glycol, dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, and isopropyl alcohol.

In the production method of the present invention, a water-dispersed composition in which the polymer (X) is dispersed in the aqueous medium (C) is obtained. The polymer (X) dispersed in the aqueous medium (C) is preferably dispersed in the form of particles, and the average particle diameter of the polymer (X) is
0.03 to 0.25 because of high dispersion stability during storage
μm is preferred.

The water-dispersible composition for a water- and oil-repellent agent of the present invention is diluted to an arbitrary concentration depending on the purpose and application, and applied to a material to be treated. As a method of applying to the object to be treated, any method can be adopted according to the type of the object to be treated, the preparation form of the water-dispersible composition, and the like. For example, a method is employed in which the material is adhered to the surface of the object to be processed by a coating method such as dip coating and dried. If necessary, the composition may be applied together with a suitable crosslinking agent to perform curing.

The water-dispersed composition for a water / oil repellent of the present invention is
Even if additives or contaminants are present, they exhibit excellent stability and excellent wet / friction durability with excellent water / oil repellency, so if necessary, other polymers, other water repellents, etc. Additives such as oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers, and anti-wrinkle agents.

The object to be treated with the water- and oil-repellent agent of the present invention is not particularly limited.
Examples include wood, leather, fur, asbestos, brick, cement, metal and its oxides, ceramic products, plastics, and the like, and textile fabrics are preferred. As textile fabrics, cotton, hemp, wool,
Animal and plant natural fibers such as silk, polyamide, polyester,
Examples include synthetic fibers such as polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers and carbon fibers; and woven fabrics of mixed fibers thereof.

[0089]

EXAMPLES Next, the present invention will be described specifically with reference to Examples (Examples 1 to 10) and Comparative Examples (Examples 11 to 12), but the present invention is not limited thereto.

Example 1 (Example) 2- (perfluoroalkyl) ethyl acrylate [F
(CF ₂ ) _n CH ₂ CH ₂ OCOCH = CH ₂ ,
The average value of n is 9 in a mixture in which n is 6 to 16. Hereinafter, it is referred to as FA. ] (154 g), octadecyl acrylate (St
A, 90 g), cyclohexyl methacrylate (CHM
A, 12.8 g), octadecyl mercaptan (StS
H, 0.77 g), polyoxyethylene monooleyl ether (PEOOE, 15.4 g), trimethyloctadecyl ammonium chloride (StTMAC, 5.1)
g) and a raw material composition containing ion-exchanged water (410 g)
Stirred at 0 ° C. for 30 minutes. The raw material composition is heated at 40 to 50 ° C.
While emulsifying at 200 kg / cm ² using a high-pressure emulsifier (Manton Gorin). The average particle size of the polymerizable monomer in the emulsion after emulsification was 0.23 μm.

Next, this was transferred to a 1-liter glass autoclave, to which 2,2'-azobis (2-amidinopropane) dihydrochloride (V-50, 0.5 g) was added. did. 60 with stirring
C., and the polymerization was carried out for 6 hours.
A milky-white emulsion containing a polymer having a molecular weight of 0 was obtained. The solid content concentration of the emulsion was 37.6% by weight, and the average particle size of the polymer contained in the emulsion was 0.11 μm.

The emulsion was diluted with water so as to have a solid concentration of 20% by weight, and this was used as a stock solution. Further, water was added so that the amount of the stock solution was 5% by weight. Then, 5% by weight of a glyoxal resin (trade name "Sumitec Resin MS-11" manufactured by Sumitomo Chemical Co., Ltd.) and a catalyst (trade name of Sumitomo Chemical Co., Ltd.) "Sumitex accelerator") was added to give a treatment liquid of 2% by weight. Hereinafter the process solution is called T ^1.

Example 2 (Example) FA (167 g), StA (46.2 g), N-methylolacrylamide (NMAA, 5.1 g), StSH
(0.77 g), PEOOE (15.4 g), a triple bond-containing surfactant (a compound in which the sum of x and y in the formula 7 is 10, hereinafter referred to as B ¹ , 5.1 g), polyoxyethylene mono ( 1-methylundecyl) ether (PEO
LE, 5.1 g) and a raw material composition containing ion-exchanged water (410 g) were stirred at 50 ° C. for 30 minutes. The raw material composition was emulsified at 300 kg / cm ² using a high-pressure emulsifier (Manton-Gaulin) while maintaining the temperature at 40 to 50 ° C. The average particle size of the polymerizable monomer in the emulsion after emulsification is 0.17.
μm.

Next, this was transferred to a 1-liter glass autoclave, and V-50 (0.5 g) was added.
The autoclave was purged with nitrogen. Then vinyl chloride (V
CL, 38.5 g) was added thereto, and the mixture was heated to 60 ° C. with stirring and polymerized for 15 hours to obtain a milky white emulsion containing a polymer having an average molecular weight of 101,000. The solid content concentration of the emulsion was 37.8% by weight, and the average particle size of the polymer contained in the emulsion was 0.08 μm.
Next, a treatment liquid was obtained from the emulsion in the same procedure as in Example 1. Hereinafter the process solution is called T ^2.

Example 3 (Example) FA (154 g), dioctyl maleate (DOM, 1
6.7 g), NMAA (6.4 g), n-dodecyl mercaptan (DSH, 0.5 g), PEOOE (15.4)
g), a polyoxyethylene polyoxypropylene block polymer (h is 15, t is 15, and r is 35 in the formula 8)
A compound that is Hereinafter, referred to as PEOPPO, 2.5 g),
StTMAC (5.1 g), ion-exchanged water (410 g)
Was stirred at 50 ° C. for 30 minutes. The raw material composition was emulsified at 300 kg / cm ² using a high-pressure emulsifier (Manton-Gaulin) while maintaining the temperature at 40 to 50 ° C.
The average particle size of the polymerizable monomer in the emulsion after emulsification was 0.16 μm.

Next, this was transferred to a 1-liter glass autoclave, and V-50 (0.5 g) was added.
The autoclave was purged with nitrogen. Then, VCL (53.
9g), and the mixture was heated to 60 ° C. with stirring and polymerized for 15 hours to obtain a milky white emulsion containing a polymer having an average molecular weight of 141,000. The solid content of the emulsion was 37.6% by weight, and the average particle size of the polymer contained in the emulsion was 0.08 μm. Next, a treatment liquid was obtained from the emulsion in the same procedure as in Example 1. Hereinafter the process solution is called T ^3.

Example 4 (Example) FA (154 g), StA (95 g), 2-hydroxyethyl acrylate (HEA, 7.7 g), StSH
(0.77 g), dodecyldimethylamine oxide (L
DMAO, 5.1 g), polyoxyethylene mono (octylphenyl) ether (PEOOPE, 15.4)
g), StTMAC (5.1 g), ion-exchanged water (41
0g) was thoroughly stirred at 50 ° C for 30 minutes. The raw material composition was emulsified at 200 kg / cm ² using a high-pressure emulsifier (Manton-Gaulin) while maintaining the temperature at 40 to 50 ° C. The average particle size of the polymerizable monomer in the emulsion after emulsification was 0.21 μm.

Next, this was transferred to a 1-liter glass autoclave, and V-50 (0.5 g) was added.
The autoclave was purged with nitrogen. The temperature was raised to 60 ° C. with stirring, polymerization was carried out for 6 hours, and the average molecular weight was 105,000.
A milky white emulsion containing a polymer was obtained. The solid content of the emulsion was 38% by weight, and the average particle size of the polymer contained in the emulsion was 0.12 μm. Next, a treatment liquid was obtained from the emulsion in the same procedure as in Example 1. Hereinafter the process solution is called T ^4.

[Examples 5 to 10] (Examples) Using the polymerizable monomers and surfactants shown in Table 1,
With respect to 7 and 8, in the same manner as in Example 1, Examples 6, 9, 10
Was subjected to polymerization in the same manner as in Example 3 to obtain an emulsion, and treatment liquids T ^{5 to} T ¹⁰ were obtained from the emulsion in the same procedure as in Example 1.

Example 11 (Comparative Example) FA (154 g), StA (90 g), CHMA (1
A raw material composition containing 2.8 g), StSH (0.77 g), sodium n-dodecylbenzenesulfonate (7.7 g), and ion-exchanged water (410 g) was sufficiently stirred at 50 ° C. for 30 minutes. While maintaining the raw material composition at 40 to 50 ° C., 200 kg /
Emulsified in cm ² . The average particle size of the polymerizable monomer in the emulsion after emulsification was 0.25 μm.

Next, this was transferred to a 1-liter glass autoclave, and ammonium persulfate (0.54 g) was used.
After the addition, the autoclave was purged with nitrogen. The temperature was raised to 60 ° C. with stirring, and polymerization was carried out for 15 hours to obtain a milky white emulsion containing a polymer having an average molecular weight of 99000. The solid content concentration of the emulsion was 37.0% by weight, and the average particle size of the polymer contained in the emulsion was 0.13.
μm. Next, a treatment liquid was obtained from the emulsion in the same procedure as in Example 1. Hereinafter the process solution is called T ^11.

Example 12 (Comparative Example) FA (154) was placed in a 1-liter glass autoclave.
g), StA (90 g), CHMA (12.8 g), S
tSH (0.77 g), PEOOE (15.4 g), S
tTMAC (5.1 g) and ion-exchanged water (410 g) were charged and sufficiently stirred at 50 ° C. for 1 hour. Here V-5
After adding 0 (0.5 g), the autoclave was purged with nitrogen. The temperature was raised to 60 ° C. with stirring, and polymerization was carried out for 6 hours. However, a large amount of solids settled out, and an emulsion corresponding to the preparation was not obtained.

[0103]

[Table 1]

The abbreviations in Table 1 are as follows.

EHMA: 2-ethylhexyl methacrylate, GMA: glycidyl methacrylate, CHPMA: 3-chloro-2-hydroxypropyl methacrylate, DMAA: dimethylacrylamide, HE6P: isophorone diisocyanate in which one of the isocyanate groups is blocked with methyl ethyl ketone oxime Reaction product with 2-hydroxyethyl methacrylate, PEPA: polyoxyethylene polyoxypropylene methacrylate, tDSH: 2,4,6-trimethylnonylmercaptan (= t-dodecylmercaptan), DTDMAC: di (tallow alkyl) dimethylammonium chloride .

[Method of Treating Cloth] The treatment liquids T ^{1 to} T ¹¹ obtained as described above are dipped in a cotton broad cloth and
The cloth was squeezed between the rubber rollers to adjust the wet pickup to 60% by weight. Then, it was dried at 110 ° C. for 90 seconds and heat-treated at 170 ° C. for 60 seconds. The water repellency, oil repellency and wet friction durability of the treated cotton broad cloth were evaluated, and the results are summarized in Table 5.

The water repellency is represented by a water repellency number (see Table 2) by the spray method of JIS L1092, and the oil repellency is obtained by dropping a test solution shown in Table 3 below at several places on a sample cloth (approximately 4 mm in diameter). To determine the permeation state after 30 seconds (AATCC-TM118-196).
6). Those with a “-” after the oil-repellent number,
Indicates slightly inferior performance.

Further, the durability of wet friction with a Gakushin type friction tester is performed in accordance with JIS L0849-1967. One drop of an aqueous solution of isopropyl alcohol (IPA) having a different concentration is placed on the surface of a cotton broad cloth before and after friction. 1
Minutes, the highest concentration of IPA that can hold droplets
The water repellency values of the aqueous solution kit (Table 4) are shown. The smaller the difference between the water repellency values, the better the wet friction durability.

[0109]

[Table 2]

[0110]

[Table 3]

[0111]

[Table 4]

[0112]

[Table 5]

[0113]

The water-dispersed composition for a water / oil repellent obtained by the method of the present invention is an environmentally and operationally advantageous composition produced without using an organic solvent as a polymerization auxiliary solvent. is there. Further, the water-dispersible composition for water- and oil-repellent of the present invention, by selecting and using a specific surfactant,
Shows excellent water and oil repellency and wet friction durability even without using the co-solvent, even if co-agents and impurities are present,
There is no decrease in the stability of the emulsion, and it has water- and oil-repellent performance with excellent practicality.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H020 BA13 4J002 BB071 BC071 BD091 BG071 CH052 DE027 EC036 EC046 EC066 EN046 EN136 ES006 EV186 FD312 FD316 GH00 HA07 4J011 KA02 KA03 KA08 KA10 KA23 KA24 KB03 AC03 AC03 AB03 AC03 AC24Q AE44Q AG04Q AL03Q AL04Q AL08P AL08Q AL09Q AL10Q AM15Q AM17Q AM19Q AM21Q AM43Q AQ20Q AQ26Q AS02Q AS03Q AS07Q BA03P BA03Q BA07Q BA11Q BA20P BA34P BA59P BB12P BB13P BC54Q BC65CA FA05

Claims (12)

[Claims] 1. A raw material composition comprising the following polymerizable monomer (A), the following surfactant (B), and an aqueous medium (C) is emulsified under pressure, and then polymerized to obtain a polymerizable monomer. A method for producing a water-dispersible composition for a water- and oil-repellent, wherein the polymer (X) containing the polymerized unit of the monomer (A) is dispersed in an aqueous medium (C). Polymerizable monomer (A): a polymerizable monomer comprising a (meth) acrylate (a ¹ ) having a polyfluoroalkyl group,
Or, having a polyfluoroalkyl group-containing (meth) acrylate (a ¹⁾ and having a polyfluoroalkyl group-containing (meth) acrylate (a ¹⁾ other than the polymerizable monomer (a
² ) a polymerizable monomer comprising: Surfactant (B): a surfactant selected from nonionic surfactants, cationic surfactants, and amphoteric surfactants. 2. The method according to claim 1, wherein the polymerizable monomer (a ² ) is a liquid or solid polymerizable monomer under the conditions of emulsification under pressure. 3. The method according to claim 2, wherein the polymerizable monomer (a ² ) essentially comprises the following polymerizable monomer (a ²¹ ). Polymerizable monomer (a ²¹ ): an alkyl group having 1 to 20 carbon atoms
Or a cycloalkyl (meth) acrylate in which the cycloalkyl group has 5 to 8 carbon atoms. 4. The production method according to claim 2, wherein after emulsification under pressure, a gaseous polymerizable monomer (a ³ ) is introduced under emulsification conditions and then polymerized. 5. The surfactant (B) is a nonionic surfactant and / or a cationic surfactant.
5. The production method according to any one of items 1 to 4. 6. The surfactant (B) comprises the following surfactant (b)
¹ ), the following surfactant (b ² ), surfactant (b ³ ),
6. The method according to claim 5, wherein the method is selected from the following and surfactants (b ⁴ ). Surfactant (b ¹ ): a nonionic surfactant composed of polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, or polyoxyalkylene monoalkapolyenyl ether. Surfactant (b ² ): a nonionic surfactant comprising a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule and exhibiting surface activity. Surfactant (b ³ ): a polyoxyethylene portion in which two or more oxyethylenes are continuously connected, and a portion in which two or more oxyalkylenes having 3 or more carbon atoms are continuously connected, and both A nonionic surfactant comprising a compound having a terminal hydroxyl group. Surfactant (b ⁴ ): a cationic surfactant comprising a substituted ammonium salt. 7. The method according to claim 1, wherein the amount of the surfactant (B) is 0.1 to 10% by weight based on the total amount of the polymerizable monomer (A). 8. The method according to claim 1, wherein the raw material composition further contains a compound represented by the following formula 13. Here, R ^{14 in} Formula 13 represents an alkyl group having 6 to 18 carbon atoms. R ¹⁴ -SH ... Equation 13 9. (Meth) having a polyfluoroalkyl group
The method according to the amount of acrylate (a ¹⁾ is any one of claims 1 to 8, 40 to 100% by weight relative to the total amount of the polymerizable monomer (A). 10. The polymer (X) having an average particle size of 0.03 to 0.03.
The method according to claim 1, wherein the thickness is 0.25 μm. 11. A water-dispersible composition for a water / oil repellent produced by the method according to claim 1. Description: 12. A treated product obtained by treating an object to be treated with the composition according to claim 11.