JP2000087014A - Water- and oil-repellent agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in water- and oil-repelling property and dry stain resistance by compounding a fluorine atom-containing polymer and an ester obtained from a hydroxy compound and a carboxylic acid free from a polymerizable unsaturated group. SOLUTION: This composition comprises (A) a fluorine atom-containing polymer and (B) an ester obtained from a hydroxy compound represented by the formula: Rf1(CH2)2OH (wherein Rf1 is a polyfluoroalkyl) and a carboxylic acid free from a polymerizable unsaturated group. As the component A is preferable a polymer containing a polymer unit of a (meth)acrylate ester bearing a polyfluoroalkyl group. As the component B is preferable, for example, a compound represented by the formula: Rf2-Q1-(CH2)2OCOCHR1CH2O(CH2)2Rf3. In the formula, Rf2 and Rf3 can be the same or different and are independently a polyfluoroalkyl group. R1 is H or methyl; and Q1 is a single bond, COO or the like. Preferably, the compounding ratio of the component B is 0.5-20 wt.% based on the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a water / oil repellent composition. More specifically, the present invention relates to a water / oil repellent composition capable of exhibiting excellent water / oil repellency and dry stain resistance when treated into interior fabrics, fiber woven fabrics such as carpets and wool.

[0002]

2. Description of the Related Art (Meth) having a polyfluoroalkyl group (hereinafter, a polyfluoroalkyl group is referred to as an ^Rf group).
2. Description of the Related Art A technique for imparting water / oil repellency by treating a fiber with a water / oil repellent containing a polymer having a fluorine atom such as acrylate as an active ingredient has been conventionally performed. The following examples are known as a technique for blending another fluorine-containing compound with the water / oil repellent.

(1) A method of blending a water-insoluble compound containing a fluoroaliphatic group selected from a carbonylimino compound and an imine compound (JP-A-58-1341)
43). (2) A hydrocarbon compound having an ^Rf group is blended as a compatibilizer of a monomer when copolymerizing an ^Rf group-containing polymerizable compound with another copolymerizable compound that is incompatible with the compound. Method (JP-A-6-166705). (3) A method of blending a fluorinated alcohol that is liquid at normal temperature (Japanese Patent Laid-Open No. Hei 10-81873). (4) A method of blending a fluorine-based surfactant such as a carboxylic acid having an ^Rf group (JP-A-10-8041).

[0004]

However, the conventional method has the following drawbacks. That is, in the method (1), a carbonylimino compound and an imine compound, which have a complicated structure, are difficult to obtain and are difficult to synthesize, are used as the main components, and the content of the (meth) acrylate containing an ^Rf group is essential. And there is a drawback in that dry stain resistance and shower water repellency are low. Further, the methods (2) and (3) have a drawback that the dry stain resistance is low. Furthermore, the method (4) requires the use of a large amount of expensive fluorine-containing surfactant, which is disadvantageous in that it is not economical and also has the disadvantage of low dry stain resistance.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is a novel water and water repellent having excellent water and oil repellency and dry stain resistance, particularly excellent oil repellency. Provided are an oil agent composition and an object to be treated treated with the water / oil repellent composition.

That is, the present invention provides a polymer (A) having a fluorine atom and R ^f1 (CH ₂ ) ₂ OH (provided that
R ^f1 has the same meaning as described above. ) And an ester (B) of a carboxylic acid containing no polymerizable unsaturated group.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, an R ^f group refers to a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The ^Rf group preferably has 2 to 20 carbon atoms, particularly preferably 6 to 16 carbon atoms.

The R ^f group is preferably a linear or branched group, and particularly preferably a linear group. In the case of a branched group, the branched portion is present at the terminal of the R ^f group, and
It is preferably a short chain having about 1 to 4 carbon atoms. The R ^f group may contain another halogen atom other than a fluorine atom. As another halogen atom, a chlorine atom is preferable. An etheric oxygen atom or a thioetheric oxygen atom may be inserted between carbon-carbon bonds in the R ^f group. The structure of the terminal portion of the ^Rf group is -CF
_{2 CF 3, -CF (CF 3} ) 2, -CF 2 H, -CFH
_2, include -CF ₂ Cl and the like, -CF ₂ CF ₃ are preferred.

[0009] 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 60% or more, particularly 80%
The above is preferred.

Further, the R ^f group is preferably a group in which all of the hydrogen atoms of the alkyl group have been replaced by fluorine atoms (ie, a perfluoroalkyl group) or a group having a perfluoroalkyl group at the terminal.

The carbon number of the perfluoroalkyl group is from 2 to
20 is preferable, and especially 6 to 16 is preferable. 6 carbon atoms
If it is less than 16, the water repellency and oil repellency tend to decrease, and if it is more than 16, the compound containing it is not economical and may be difficult to handle.

Specific examples of the R ^f group include the following groups. _{C 4 F 9 - [CF 3} (CF 2) 3 -, (CF
₃ ) ₂ CFCF _2- , (CF ₃ ) ₃ C-, and CF ₃
CF ₂ (CF ₃ ) CF— and the like;
₅ F ₁₁ - [example _{CF 3 (CF 2) 4 -} ], C 6 F 13
- [example _{CF 3 (CF 2) 5 -} ], C 7 F 15 - [ example _{CF 3 (CF 2) 6 -} ], C 8 F 17 - [ example _{CF 3 (CF 2) 7 -} ], C 9 F _19- [for example CF ₃
(CF ₂ ) ₈ −], C ₁₀ F ₂₁ − [for example, CF ₃ (CF
₂ ) _9- ], C ₁₂ F _25- [for example, CF ₃ (CF ₂ ) ₁₁
−], C ₁₄ F ₂₉ − [for example, CF ₃ (CF ₂ ) ₁₃ −],
C ₁₆ F ₃₃ - [example _{CF 3 (CF 2) 15 -} ], CHF
₂ (CF ₂ ) _j- (where j is an integer of 1 to 15), C
_{F 2 Cl (CF 2) k} - ( wherein, k is from 1 to 15 _{integer), (CF 3) 2 CF} (CF 2) m - ( wherein, m is an integer of 1 to 14), and the like.

The R ^f group may be a group having an etheric oxygen atom or a thioetheric sulfur atom inserted between carbon-carbon bonds. Specific examples of the group include the following groups. _{CF 3 (CF 2) 4 OCF} (CF 3) -,
F [CF (CF 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 (CF ₂ CF ₂ CF ₂ O) _v CF ₂ CF ₂ −, F
(CF ₂ CF ₂ O) _w CF ₂ CF _2- (y and z are 1 to 1
An integer of 0, u is an integer of 2 to 6, v is an integer of 1 to 11, w
Is an integer of 1 to 11).

CF ₃ (CF ₂ ) ₄ SCF (CF 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 CF 2 CF 2
−, F (CF ₂ CF ₂ CF ₂ S) _v CF ₂ CF ₂ −, F
(CF ₂ CF ₂ S) _w CF ₂ CF _2- (y and z are 1 to 1
An integer of 0, u is an integer of 2 to 6, v is an integer of 1 to 11, w
Is an integer of 1 to 11).

The polymer (A) having a fluorine atom in the present invention is a polymer containing polymerized units of a polymerizable monomer having a fluorine atom. Examples of the polymerizable monomer having a fluorine atom include tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene, vinyl fluoride, and (meth) acrylate having an ^Rf group. In this specification, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid esters, and the description of (meth) acrylate and the like has the same meaning. Here, the (meth) acrylic acid ester having ^the R ^f group means a compound ^the R ^f group is (meth) present in the alcohol residue portion of the acrylic acid ester.

The polymer (A) has an R ^f group-containing (meth)
A polymer essentially including a polymerization unit of an acrylate ester is preferable, and a polymer including a polymerization unit of a (meth) acrylate ester having an R ^f group and a polymerizable monomer other than the ester is preferable. .

As the (meth) acrylate having an R ^f group, a compound represented by the following formula a is preferable. However, in Formula 1, Q ¹⁰ represents a divalent organic group, and R ¹⁰ represents a hydrogen atom or a methyl group. R ^f8 in ^{R f8 -Q 10 -OCOCR 10 = CH} 2 ··· formula a formula a can, R ^f group is preferably free of ether oxygen atoms or thioether sulfur atoms, particularly a perfluoroalkyl group are preferred, especially - (CF ₂ )
_n CF ₃ (where n is an integer of 1 to 16, 4 to 1
An integer of 6 is preferred, and an integer of 6 to 12 is particularly preferred. ) Is preferred.

In formula a, Q ¹⁰ is-(CH ₂ )
_{p + q -, - (CH} 2) p CONH (CH 2) q -, -
(CH ₂ ) _p OCONH (CH ₂ ) _q -,-(CH ₂ )
_{^{p SO 2 NR 11 (CH 2}} ) q -, - (CH 2) p NHC
_{ONH (CH 2) q -,} - (CH 2) p CH (OH) -
(CH ₂ ) _q- and the like are preferable. Here, R ¹¹ represents a hydrogen atom or an alkyl group. P and q each represent an integer of 0 or more, and p + q is an integer of 1 to 22. Among these, Q ¹⁰ is _{- (CH 2) p + q} -, - (CH 2) p CO
_{NH (CH 2) q -,} - (CH 2) p SO 2 NR 11 (C
H ₂ ) _q −, q is an integer of 2 or more, and p + q is preferably 2 to 6, particularly — (CH ₂ ) _{p + q} − when p + q is 2 to 6, that is, And an ethylene group to a hexamethylene group. It is preferable that a fluorine atom is bonded to the carbon atom of R ^f bonded to Q ¹⁰ .

As the (meth) acrylic ester having an R ^f group, the following compounds can be mentioned. Here, R ¹¹ represents a hydrogen atom or a methyl group.

CF ₃ (CF ₂ ) ₄ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₂ H (CF ₂ ) ₅ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₂ H (CF ₂ ) ₇ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₂ H (CF ₂ ) ₉ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₂ H (CF ₂ ) ₇ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₁₃ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₁₅ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₄ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₇ CONHCH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₃ OCOCR ¹¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OCOCH ₃ ) OCR ¹¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ OCOCR ¹¹ = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR ¹¹ = CH ₂ , CF ₃ (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOCR ¹¹ = CH ₂ .

The polymer (A) has an R ^f group-containing (meth)
A polymer containing one or more polymer units of an acrylate ester is preferable. When two or more polymer units are contained, a polymer unit of a (meth) acrylate ester having a ^Rf group having a different number of carbon atoms is preferably used. It is preferable to include two or more types.

The polymer (A) in the present invention includes a (meth) polymer obtained by only polymerizing acrylic acid ester, having ^the R ^f group (meth) acrylic acid ester and the ^the R ^f group having ^the R ^f group A copolymer obtained by polymerizing a polymerizable monomer other than the (meth) acrylic acid ester (hereinafter, referred to as another monomer) is preferable. Examples of the other monomer include a known or well-known polymerizable monomer, and a polymerizable monomer having one or two polymerizable unsaturated groups is preferable. As the other monomer, the following polymerizable monomer (a ¹ ) and / or the following polymerizable monomer (a ² ) are particularly essential.
Further, as the other monomer, when both the polymerizable monomer (a ¹ ) and the following polymerizable monomer (a ² ) are essential, or only the polymerizable monomer (a ² ) Is preferred.

Polymerizable monomer (a ¹ ): One or more polymerizable monomers selected from alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group.

Polymerizable monomer (a ² ): olefin, 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, diene, glycidyl (meth) acrylate, aziridinyl (meth) acrylate, substituted alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, hydroxyl-terminated polyoxyalkylene (meth)
Acrylate, alkoxy group-terminated polyoxyalkylene (meth) acrylate, polyoxyalkylene di (meth) acrylate, polysiloxane group-containing (meth) acrylate, triallyl cyanurate, allyl glycidyl ether, allyl carboxylate, N-vinyl carbazole, N One or more polymerizable monomers selected from methylmaleimide, maleic anhydride, monoalkyl maleate, dialkyl maleate, and (meth) acrylates containing blocked isocyanate groups.

The alkyl group in the polymerizable monomer (a ¹ ) has 1 to 20 carbon atoms. An alkyl group is a straight-chain,
The structure may be either a branched structure or a ring structure, or may be a structure partially having a ring structure. The polymerizable monomer (a ¹ ) 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 alkyl group structures.

The polymerizable monomer (a ¹ ) is preferably an alkyl (meth) acrylate having a linear or branched alkyl group portion and 1 to 18 carbon atoms.
Especially methyl (meth) acrylate, stearyl (meth)
Acrylate or 2-ethylhexyl (meth) acrylate is preferred.

Examples of the polymerizable monomer (a ² ) include ethylene, vinyl chloride, vinylidene chloride, vinylidene fluoride,
Vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, glycidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N-methylolated (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, aziridinylethyl (meth) acrylate, benzyl (meth) acrylate, aziridinyl (meth) acrylate, 2 -Hydroxyethyl (meth) acrylate, hydroxyl-terminated polyoxyalkylene (meth) acrylate, methoxy-terminated polyoxyalkylene (meth) acrylate, 2-ethylhexyl Polyoxyalkylene (meth)
Acrylate, polyoxyalkylene di (meth) acrylate, (meth) acrylate having polysiloxane, triallyl cyanurate, allyl glycidyl ether, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, (2-dimethylamino) Ethyl (meth) acrylate and the like are preferred.

Here, the (meth) acrylate having a blocked isocyanate group is a (meth) acrylate having at least one blocked isocyanate group, and a (meth) acrylic acid having an isocyanate group. A compound having a structure in which an isocyanate group of an ester is blocked by a blocking agent is preferable.

(Meth) having an isocyanate group
As the acrylate, 2-isocyanateethyl (meth) acrylate or a (meth) acrylate having a functional group capable of binding to an isocyanate group is reacted with polyisocyanate in such a ratio that one or more isocyanate groups remain. The reaction product obtained by the reaction is preferred.

The (meth) acrylate having a functional group capable of binding to an isocyanate group is preferably a (meth) acrylate having a hydroxyl group, and particularly a monoester or diester of (meth) acrylic acid and a polyhydric alcohol. Is preferred. Examples of the polyhydric alcohol include ethylene glycol, polyoxyethylene glycol, propylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane-alkylene oxide adduct, and pentaerythritol.

As the polyisocyanate, 4,4'-
Aromatic isocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,
Aliphatic isocyanates or cycloaliphatic isocyanates such as 4'-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, norbornene diisocyanate, and their nullate-modified, prepolymer-modified, and buret-modified products are particularly preferable. Aliphatic isocyanates, cycloaliphatic isocyanates, and their nurate-modified, prepolymer-modified, and burette-modified products are preferred.

As the blocking agent, alkyl ketoximes, phenols, alcohols, β-diketones and lactams are preferred, and methyl ethyl ketoxime, ε-caprolactam, phenol, cresol, acetylacetone, diethyl malonate, isopropanol, t -Butyl alcohol, maleic imide and the like are particularly preferred, and a blocking agent comprising a compound having a dissociation temperature of 120 to 180 ° C, such as an alkyl ketoxime such as methyl ethyl ketoxime and a lactam such as ε-caprolactam, is particularly preferred.

Specific examples of the (meth) acrylate having a blocked isocyanate group include a compound in which the isocyanate group of 2-isocyanatoethyl (meth) acrylate is blocked with methyl ethyl ketoxime, and a compound of 2-isocyanatoethyl (meth) acrylate. A compound in which an isocyanate group is blocked with ε-caprolactam, a compound in which a 1: 1 (molar ratio) reaction product of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate is blocked with methyl ethyl ketoxime,
1: 1 with hydroxypropyl (meth) acrylate
(Molar ratio) Compounds in which the isocyanate group of the reactant is blocked with methyl ethyl ketoxime, compounds in which a 1: 1 (molar ratio) reactant of norbornene diisocyanate and 2-hydroxyethyl (meth) acrylate is blocked with methyl ethyl ketoxime, and the like. . Two or more polymerizable monomers (a ² ) may be used.

As a method for obtaining the polymer (A), a known or well-known polymerization method, that is, bulk polymerization, suspension polymerization, emulsion polymerization, radiation polymerization, photopolymerization, solution polymerization, or the like can be employed. Solvents in solution polymerization, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, diethylene glycol dimethyl ether, tetrahydrofuran, methyl-t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, ethers such as tridipropylene glycol,
Ethanol, isopropyl alcohol, alcohols such as n-butanol, mineral spirit, undecane,
Hydrocarbons such as toluene, xylene and hexane, amides such as formamide, dimethylformamide, acetamide and dimethylacetamide, carboxylic acid esters such as ethyl acetate, butyl acetate, diethyl malonate and diethyl succinate, pentafluorodichloropropane, Halogenated hydrocarbons such as tridecafluorohexane and methylene chloride are exemplified.

In emulsion polymerization and suspension polymerization,
In a medium consisting of water or a mixed solvent of water and a water-soluble solvent,
A method in which a polymerizable monomer and an emulsifier are added and the polymerizable monomer is emulsified and then polymerized, or a method in which the polymerizable monomer is dissolved and dispersed in a medium comprising a solvent and polymerized, can be employed. As the water-soluble solvent, a water-soluble solvent having a solubility of 10 g or more in 100 g of water is preferable, and examples thereof include acetone, propylene glycol, dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl ether, and ethylene glycol monomethyl ether. Two or more water-soluble solvents may be used. Further, the amount of the water-soluble solvent is preferably from 0 to 80% by weight based on the polymer (A).

The polymerization is usually carried out by acting a polymerization initiation source. The polymerization initiation source is not particularly limited, and a usual polymerization initiator such as an organic peroxide, an azo compound, a persulfate, or an ionizing radiation such as γ-ray can be employed. The amount of the polymer (A) in the water / oil repellent composition is preferably from 10 to 30% by weight, particularly preferably from 15 to 30% by weight.

The water / oil repellent composition of the present invention preferably contains a surfactant (C). The surfactant (C) may be added to the system during the polymerization, or may be added after the polymerization, and the former is preferable. As the surfactant (C), a known or known nonionic surfactant having an amine oxide moiety in a molecule, other nonionic surfactants, cationic surfactants, amphoteric surfactants, polymers Surfactants and the like can be mentioned, and these can be used alone or in combination. It is preferable to use a surfactant containing no fluorine atom as the surfactant (C). Further, as the surfactant, it is preferable to use any of the following surfactants (C ¹ ) to (C ⁶ ).

Nonionic surfactant (c ¹ ) comprising a polyoxyalkylene alkyl ether; nonionic surfactant comprising a compound containing at least one triple bond, at least one hydroxyl group, and at least two oxyalkylene moieties in the molecule. Agent (c ² ), a nonionic surfactant (c ³ ) composed of a block polymer having a polyoxyethylene portion and a portion in which two or more oxyalkylenes having 3 or more carbon atoms are continuously connected, and an amine in the molecule Nonionic surfactant having an oxide moiety (c ⁴ ), nonionic surfactant comprising polyoxyethylene alkyl phenyl ether (c
⁵ ) A nonionic surfactant (c ⁶ ) comprising a fatty acid ester of polyethylene glycol.

The amount of the surfactant is preferably 3 to 10% by weight based on the polymer (A). When the amount of the surfactant is 10% by weight or more, the water / oil repellency may decrease, and when the amount is 3% by weight or less, the stability of the emulsion may decrease. However, there may be exceptions when a polymerizable monomer having self-emulsifiability is used.

The ester (B) in the present invention is represented by R
^f1 (CH ₂ ) ₂ OH (where R ^f1 represents an R ^f group)
Of a hydroxy compound with a carboxylic acid containing no polymerizable unsaturated group. R ^f1 (CH ₂ ) ₂ OH
R ^f1 in the hydroxy compound is an R ^f group,
It may be the same as or different from the R ^f group in the polymer (A). R ^f1 is preferably the same group as the above-mentioned perfluoroalkyl group.

The carboxylic acid containing no polymerizable unsaturated group is preferably a monocarboxylic acid containing no polymerizable unsaturated group or a dicarboxylic acid containing no polymerizable unsaturated group.

The carboxylic acid containing no polymerizable unsaturated group is preferably a monocarboxylic acid represented by R ¹² COOH or a dicarboxylic acid represented by HOOC-R ¹³ -COOH. Here, R ¹² is an alkyl group or a substituted alkyl group. As the substituted alkyl group, a group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom or a phenyl group and / or a group in which an etheric oxygen atom is inserted between carbon-carbon bonds of the alkyl group is preferable. R ¹³ is an alkylene group or a substituted alkylene group. Examples of the substituted alkylene group include a substituted alkylene group in which at least one hydrogen atom of the alkylene group is substituted with a halogen atom or a phenyl group and / or a group having an etheric oxygen atom inserted between carbon-carbon bonds of the alkylene group. preferable. As preferred specific examples of the monocarboxylic acid and the dicarboxylic acid, a carboxylic acid compound having a group corresponding to an ester residue in the ester compounds represented by the following formulas 1 to 4 is preferable.

The ester (B) is an ester (B ¹ ) composed of an ester formed from 1 mol of a hydroxy compound and 1 mol of a monocarboxylic acid, or an ester (B ¹ ) formed from 2 mol of a hydroxy compound and 1 mol of a dicarboxylic acid. The diester (B ² ) consisting of an ester is preferred, and the ester (B ² ) is particularly preferred.

Further, the ester (B ¹ ) is preferably a compound represented by the following formula 2 or 3, and the ester (B ² ) is a compound represented by the following formula 1 or 4 Is preferred. Further, as the ester (B), a compound represented by the following formula 1 or 4 is preferable.

[0045]

Embedded image R ^f2 -Q ^1- (CH ₂ ) ₂ OCOCHR ¹ CH ₂ O (CH ₂ ) ₂ R ^f3 Formula 1 R ^f4 -Q ^2- (CH ₂ ) ₂ OCOCR ² ClCH ₃ Formula 2 R ^{f5 _{-Q 3 - (CH 2) 2}} OCOR 3 ... formula ^{3 R f6 -Q 4 - (CH} 2) 2 OCO-Q 5 -COO (CH 2) 2 R f7 ... equation 4

However, the symbols in the formula have the following meanings. R ^f2 , R ^f3 , R ^f4 , R ^f5 , R ^f6 , R ^f7 : each independently is a polyfluoroalkyl group, and R ^f2 and R
^f3 may be the same or different, and R ^f6 and R ^{f7 in} Formula 4 may be the same or different. R ¹ and R ² : a hydrogen atom or a methyl group. R ^3: a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a phenyl group or a benzyl group. Q ^{1 to} Q ⁴ : a single bond, —COO—, or —
SO ₂ NR ¹⁰ - (provided that, R ¹⁰ is a hydrogen atom or a lower alkyl group). Q ^{1 to} Q ⁴ are preferably single bonds. Q ⁵ : a single bond, an alkylene group having 1 to 8 carbon atoms, or a phenylene group. Specific examples of the ester compound represented by Formula 1 include the following compounds.

[0047]

Embedded image C ₈ F ₁₇ (CH ₂ ) ₂ OCOCH ₂ CH ₂ O
(CH ₂ ) ₂ C ₈ F ₁₇ , C ₁₀ F ₂₁ (CH ₂ ) ₂ OCOC
H ₂ CH ₂ O (CH ₂ ) ₂ C ₈ F ₁₇ , C ₁₀ F ₂₁ (CH
₂ ) ₂ OCOCH ₂ CH ₂ O (CH ₂ ) ₂ C ₁₀ F ₂₁ , C
_{8 F 17 SO 2 N (CH} 3) (CH 2) 2 O - COCH
_{2 CH 2 O (CH 2)} 2 N (CH 3) SO 2 C 8 F 17.

Specific examples of the ester compound represented by Formula 2 include the following compounds.

[0049]

Embedded image C ₈ F ₁₇ (CH ₂ ) ₂ OCOC (CH ₃ ) ClCH ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCOCHCH ₃ , C ₁₀ F ₂₁ (CH ₂ ) ₂ OCOC (CH ₃ ) ClCH ₃ , _{C 10 F 21 (CH 2)} 2 OCOCHClCH 3.

Specific examples of the ester compound represented by the formula 3 include the following compounds.

[0051]

Embedded image C ₈ F ₁₇ (CH ₂ ) ₂ OCOH, C ₈ F ₁₇ (C
H ₂ ) ₂ OCOCH ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCOC
_{17 H 35, C 8 F 17} (CH 2) 2 OCOC 6 H 5, C 10 F
_{21 (CH 2) 2 OCOC 7} H 15.

Specific examples of the ester compound represented by the formula 4 include the following compounds.

[0053]

Embedded image C ₈ F ₁₇ (CH ₂ ) ₂ OCOCOO (CH ₂ )
₂ C ₈ F ₁₇ , C ₈ F ₁₇ (CH ₂ ) ₂ OCO (CH ₂ ) ₂
COO (CH ₂ ) ₂ C ₈ F ₁₇ , C ₈ F ₁₇ (CH ₂ ) ₂ O
CO (CH ₂ ) ₂ COO (CH ₂ ) ₂ C ₁₀ F ₂₁ , C ₁₀ F
₂₁ (CH ₂ ) ₂ OCO (CH ₂ ) ₂ COO (CH ₂ ) ₂
C ₁₀ F ₂₁ , C ₈ F ₁₇ (CH ₂ ) ₂ OCO (CH ₂ ) ₄ C
OO (CH ₂ ) ₂ C ₈ F ₁₇ , C ₈ F ₁₇ (CH ₂ ) ₂ OC
O (CH ₂ ) ₈ COO (CH ₂ ) ₂ C ₈ F ₁₇ , C ₈ F ₁₇
(CH ₂ ) ₂ OCOC ₆ H ₄ COO (CH ₂ ) ₂ C ₈ F
₁₇ .

The compounds represented by the above formulas 1 to 4 can be respectively synthesized by the following methods. The method for synthesizing the compound is not limited to the following method.

[Method for producing compound represented by formula 1] R ^f2
-Q ^1- (CH ₂ ) ₂ OCOCR ¹ = CH ₂ and R ^f3 (C
H ₂ ) ₂ OH is reacted at about 100 to 150 ° C. in the presence of an acid catalyst such as paratoluenesulfonic acid to obtain R ^f2 -Q ^1- (CH ₂ ) ₂ OCOCHR ¹ CH ₂ O
A method of (CH ₂ ) ₂ R ^f3 .

[Method for producing compound represented by formula 2] R ^{f4
_{-Q 2 - (CH 2) 2}} OCOCR 2 = CH 2 and by reacting hydrogen chloride _{^{R f4 -Q 2 - (CH 2}} ) 2 O
A method of producing COCR ² ClCH ₃ .

[Method for producing compound represented by formula 3] R ³
COOH and R ^f5 -Q ^3- (CH ₂ ) ₂ OH are reacted at 50 to 150 ° C. in the presence of an acid catalyst such as paratoluenesulfonic acid.
To about R ^f5 -Q ^3- (CH
₂ ) ₂ OCOR ³ method. Or, R ³ COX (X
Is a halogen atom) and R ^f5 -Q ^3- (CH ₂ ) ₂ OH to obtain R ^f5 -Q ^3- (CH ₂ ) ₂ OCOR ³ .

[Method for producing compound represented by formula 4] HO
COQCOOH and _{^{R f6 -Q 4 - (CH 2}} ) 50~15 and ₂ OH in the presence of an acid catalyst such as p-toluenesulfonic acid
By ^performing a dehydration esterification reaction at about 0 ° C, R ^f6 −
^{_{Q 4 - (CH 2) 2}} OCOQ 5 COO (CH 2) 2 R f7
And how. Alternatively, by reacting XCOQ ⁴ COX (X is a halogen atom) with R ^f6 (CH ₂ ) ₂ OH, R ^f6 (CH ₂ ) ₂ OCOQ ⁴ COO (CH ₂ ) ₂ R
Method to be ^f7 .

The ester (B) contained in the water / oil repellent composition of the present invention may be a mixture of two or more kinds.
In the case of a mixture of two or more esters, the mixture may be a mixture of two or more esters differing only in the chain length of the R ^f group, or a mixture of two or more esters having different structures.

The total amount of the ester (B) contained in the water- and oil-repellent composition of the present invention is 0.5 to 0.5 with respect to the polymer (A).
It is preferably 20% by weight, particularly preferably 5 to 20% by weight.

The timing of incorporating the ester (B) into the composition is not particularly limited, and examples thereof include a method in which the ester (B) is charged and emulsified at the same time with the monomer prior to polymerization, followed by emulsification and then a method of mixing and stirring after polymerization. The former method is preferred. Further, the water / oil repellent composition of the present invention may contain additives other than the polymer (A) and the ester (B). Examples of the additives include other polymer blenders, other water repellents, oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents, stain blockers, and the like.

The water- and oil-repellent composition of the present invention is diluted to an arbitrary concentration depending on the purpose and application, and applied to the object to be treated. As an application method to the object to be treated, any method can be adopted depending on the type of the object to be treated, the preparation form of the 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 / oil repellent composition of the present invention imparts excellent dry stain resistance to the object to be treated in addition to excellent water / oil repellency. The object to be treated with the water / oil repellent composition of the present invention is not particularly limited, and fibers, fiber fabrics, glass,
Examples include paper, wood, leather, fur, asbestos, brick, cement, metal and its oxides, ceramic products, plastics, and the like, and textile fabrics are preferred.

Examples of the textile fabric include animal and plant natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; and semi-synthetic fibers such as rayon and acetate. , Glass fibers, carbon fibers, inorganic fibers such as asbestos fibers, or a woven fabric of these mixed fibers. The water- and oil-repellent composition of the present invention is particularly suitable for animal and plant natural fibers, synthetic fibers, semi-synthetic fibers, or fiber woven fabrics formed from these fibers. Therefore, it is particularly useful as a water / oil repellent composition for carpets and interior interiors.

[0065]

EXAMPLES Next, the present invention will be specifically described with reference to Examples (Examples 1 to 5) and Comparative Examples (Examples 6 to 8), but the present invention is not limited thereto. In addition, the notation of a perfluoroalkyl group and an alkyl group in Examples shows a linear structure.

Reference Example 1 C ₈ F ₁₇ (CH ₂ ) ₂ OCO
Example of synthesis of CH ₂ CH ₂ O (CH ₂ ) ₂ C ₈ F ₁₇ C ₈ F ₁₇ (CH ₂ ) ₂ OCOCH was placed in a 500 ml glass three-necked flask equipped with a stirrer, a thermometer and a reflux condenser.
= CH ₂ of _{311g, C 8 F 17 (CH} 2) 2 OH 2 78
g, 10 g of p-toluenesulfonic acid, 130 g
The reaction was performed at 10 ° C. for 10 hours. Cas chromatography (G
C) The analysis showed that the reaction had progressed to 28%. After washing the reaction mixture with warm water of 80 ° C., 5 m
The starting material was distilled off at a pressure of mHg, and 141 g of the title compound was recovered as a residue. Hereinafter, the compound is referred to as ester compound 1.

Reference Example 2 C ₈ F ₁₇ (CH ₂ ) ₂ OCO
Example of synthesis of C (CH ₃ ) ClCH _{3 In} a 1-liter glass autoclave equipped with a stirrer and a thermometer, C ₈ F ₁₇ (CH ₂ ) ₂ OCOC (CH ₃ ) = C
311 g of H ₂ was charged, and 23 g of hydrogen chloride was slowly introduced at 50 ° C. After everything was charged, the mixture was further stirred for 2 hours. GC analysis confirmed that the reaction rate was 100%. The product was washed with warm water at 50 ° C. to obtain 330 g of the title compound. Hereinafter, the compound is referred to as ester compound 2.

Reference Example 3 C ₈ F ₁₇ (CH ₂ ) ₂ OCO
Synthesis Example of C ₁₇ H ₃₅ C ₈ F ₁₇ (CH ₂ ) was placed in a 1-liter glass four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser.
₂ OH 278 g, triethylamine 67 g, acetone 1
50 g was charged, and the internal temperature of the reactor was adjusted to 30 ° C. There C
A mixture of 182 g of ₁₇ H ₃₅ COCl and 100 g of acetone was added dropwise over 3 hours. After the completion of the dropwise addition, the mixture was heated under reflux for 2 hours. Washing with warm water at 80 ° C. gave 420 g of the title compound. Hereinafter, the compound is referred to as ester compound 3.

Reference Example 4 C ₈ F ₁₇ (CH ₂ ) ₂ OCO
_{(CH 2) 2 COO (CH} 2) 2 C 8 Synthesis Example stirrer F _17, a thermometer, a dropping funnel, C ₈ F ₁₇ four-neck glass flask of one liter equipped with a reflux condenser (CH ₂ )
278 g of ₂ OH, 67 g of triethylamine, 100 g of pentafluorodichloropropane and 100 g of acetone
And the temperature inside the reactor was adjusted to 30 ° C. There (CH ₂
A mixture of 46.5 g of (COCl) ₂ and 100 g of acetone was added dropwise over 3 hours. After the completion of the dropwise addition, the mixture was heated under reflux for 2 hours. Washing with warm water at 80 ° C. provided 290 g of the title compound. Hereinafter, the compound is referred to as ester compound 4.

Reference Example 5 C ₈ F ₁₇ (CH ₂ ) ₂ OCO
PhCOO (CH ₂ ) ₂ C ₈ F ₁₇ (where Ph is 1,
Shows a 4-phenylene group. Example of the synthesis of) C ₈ F ₁₇ (CH ₂ ) was placed in a 1-liter glass four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser.
278 g of ₂ OH, 67 g of triethylamine, 100 g of pentafluorodichloropropane and 100 g of acetone were charged, and the temperature inside the reactor was set to 30 ° C. A mixture of 61 g of phthaloyl dichloride and 100 g of acetone was added dropwise thereto over 3 hours. After the completion of the dropwise addition, the mixture was heated under reflux for 2 hours. 80 ℃
Was washed with warm water to obtain 300 g of the title compound. Less than,
This compound is referred to as ester compound 5.

Example 1 (Example) Perfluoroalkylethyl acrylate [CF ₃ (C
F ₂ ) _n CH ₂ CH ₂ OCOCH = CH ₂ and n is 5 to 15
The average value of n is 8 in the mixture. ] (167 g), ester compound 1 (30 g), stearyl acrylate (46.
2 g), N-methylolacrylamide (5.1 g),
Stearyl mercaptan (0.77 g), hydroxyl-terminated (polyoxyethylene) oleyl ether (PE
OOE, 10.3 g), a surfactant represented by the following formula 5 (where x is an integer of 0 to 10, y is an integer of 0 to 10, and the average value of (x + y) is 10; Write,
5.1 g), (polyoxyethylene) -2-dodecyl ether (PEOLE, 5.1) having a hydroxyl group at a terminal
g), a composition containing tripropylene glycol (130 g) and ion-exchanged water (350 g) were stirred at 50 ° C. for 30 minutes. While maintaining the composition at 40 to 50 ° C., 400 kg / cm ² using a high-pressure emulsifier manufactured by Manton Gorin Co., Ltd.
And emulsified. The particle size of the emulsion after emulsification is 0.18
μm.

[0072]

Embedded image

Next, this was transferred to a 1-liter glass autoclave, to which azobis (dimethyleneisobutyramide) hydrochloride (0.5 g) was added, and then the autoclave was replaced with nitrogen. Thereafter, vinyl chloride (38.5 g) was added, the temperature was raised to 60 ° C. while stirring, and polymerization was carried out for 15 hours to obtain a milky white emulsion containing a polymer having an average molecular weight of 70,000. Solid content of emulsion 38.
The content was 5% by weight and the particle size was 0.09 μm. The emulsion was adjusted with water so that the solid content concentration became 20% by weight, and this was used as an emulsion stock solution.

[Examples 2 to 5] (Examples) Ester compound using ester compound 2 instead of ester compound 1 (Example 2), using ester compound 3 (Example 3), using ester compound 4 (Example 4) Except that 5 was used (Example 5), an emulsion stock solution was obtained in the same manner as in Example 1.

[Examples 6 and 7] (Comparative Example) Instead of the ester compound 1, C ₃ F ₇ O [CF (CF
₃ ) CF ₂ O] ₂ CF (CF ₃ ) COOC ₁₂ H ₂₅ is used (Example 6), and C ₃ F ₇ O (C ₃ F ₆ O) ₂ CF (CF
₃ ) An emulsion stock solution was obtained in the same manner as in Example 1 except that CH ₂ OH was used (Example 7).

Example 8 (Comparative Example) C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ was used, without adding the ester compound 1 in Example 1 and replacing PEOOE, B1 and PEOLE as emulsifiers used in Example 1. N ⁺ (CH ₃ ) ₃
An emulsion stock solution was obtained by the same operation except that 17.9 g of Cl ^- was used.

[Evaluation Method] Water-repellent and oil-repellent properties and dry soil resistance properties were measured by using the undiluted emulsion obtained by the above method as a treatment liquid diluted to a ratio of 2% by weight to water. .

The performance was evaluated by immersing the test cloth in the treatment liquid prepared for the nylon knit cloth, squeezing the cloth between two rubber rollers, and adjusting the wet pickup to 60% by weight. Then dried at 110 ° C. for 90 seconds,
A cloth heat-treated at 60 ° C. for 60 seconds was obtained, and this cloth was evaluated according to the following criteria. The results are summarized in Table 4.

(1) Evaluation Method for Dry Soil Resistance The dry soil shown in Table 1 was adjusted at the ratio shown in Table 1. 1.25 g of this dry soil mixture, 10 treated nylon knit cloths (5 cm × 5 cm) and a diameter of 1.
Ten 5 cm rubber balls were put in a 30 cm × 40 cm plastic bag and sealed with nitrogen. After shaking the bag vigorously for 5 minutes, the excess dry soil mixture on the surface of the test cloth is suctioned with a vacuum cleaner, then the lightness of the surface is measured with a colorimeter, and the contamination rate is calculated by the following equation to determine the dryness. The soil contamination was evaluated. In this evaluation, smaller numbers indicate higher performance.

Contamination rate = L ⁰ −L (where L ⁰ : lightness before contamination, L: lightness after contamination)

[0081]

[Table 1]

(2) Evaluation method of water repellency A spray test according to JIS-L1092 was carried out, and represented by the water repellency numbers shown in Table 2.

[0083]

[Table 2]

(3) Evaluation method of oil repellency The oil repellency was evaluated according to AATCC-TM118-1966 and represented by the oil repellency numbers shown in Table 3.

[0085]

[Table 3]

[0086]

[Table 4]

[0087]

The water / oil repellent composition of the present invention is a water / oil repellent composition excellent in water / oil repellency and dry stain resistance. The water- and oil-repellent agent of the present invention can impart particularly excellent water- and oil-repellent performance and dry stain resistance to a textile fabric, and thus is used for treating a textile fabric for carpet and a textile fabric for interior interior. It is useful as an oil repellent composition.

Claims (8)

[Claims] 1. A polymer (A) having a fluorine atom, a hydroxy compound represented by R ^f1 (CH ₂ ) ₂ OH (where R ^f1 represents a polyfluoroalkyl group) and a polymerizable unsaturated compound. A water / oil repellent composition containing an ester (B) with a carboxylic acid having no group. 2. The ester (B) is one of the hydroxy compounds
A monoester formed from 1 mol of a monocarboxylic acid having no polymerizable unsaturated group or a diester formed from 2 mol of a hydroxy compound and 1 mol of a dicarboxylic acid having no polymerizable unsaturated group. The water / oil repellent composition according to claim 1. 3. The water / oil repellent composition according to claim 2, wherein the ester (B) is a compound represented by the following formula 1, 2, 3, or 4. Embedded image R ^f2 -Q ^1- (CH ₂ ) ₂ OCOCHR ¹ CH ₂ O (CH ₂ ) ₂ R ^f3 Formula 1 R ^f4 -Q ^2- (CH ₂ ) ₂ OCOCR ² ClCH ₃ Formula 2 R ^{f5 _{-Q 3 - (CH 2) 2}} OCOR 3 ... formula ^{3 R f6 -Q 4 - (CH} 2) 2 OCO-Q 5 -COO (CH 2) 2 R f7 ... equation 4 provided that the symbols in the formula have the following Indicates the meaning of R ^f2 , R ^f3 , R ^f4 , R ^f5 , R ^f6 , R ^f7 : each independently is a polyfluoroalkyl group, and R ^f2 and R
^f3 may be the same or different, and R ^f6 and R ^{f7 in} Formula 4 may be the same or different. R ¹ and R ² : a hydrogen atom or a methyl group. R ^3: a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a phenyl group or a benzyl group. Q ^{1 to} Q ⁴ : a single bond, —COO—, or —
SO ₂ NR ¹⁰ - (provided that, R ¹⁰ is a hydrogen atom or a lower alkyl group). Q ⁵ : a single bond, an alkylene group having 1 to 8 carbon atoms, or a phenylene group. 4. ^Rf2 , ^Rf3 , ^Rf4 , ^Rf5 , ^Rf6 , ^Rf7 are:
4. The water / oil repellent composition according to claim 3, wherein each of the water / oil repellents is independently a perfluoroalkyl group having 4 to 12 carbon atoms. 5. The water / oil repellent composition according to claim 1, wherein the ester (B) is contained in an amount of 0.5 to 20% by weight based on the polymer (A). 6. The water and water repellency according to claim 1, wherein the polymer (A) is a polymer containing polymerized units of a (meth) acrylate having a polyfluoroalkyl group. Oil composition. 7. The water / oil repellent composition according to claim 1, which is used for treating fibers. 8. A textile fabric treated with the water / oil repellent composition according to any one of claims 1 to 6.