JP2002249630A - Water-dispersion type fluoric copolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-dispersion type fluoric copolymer composition which exhibits stable water/oil repellency even in the processing conditions at low temperatures and high speeds and which in addition is excellent in adhesiveness after the processing of imparting the water/oil repellency. SOLUTION: A water-dispersion type fluoric copolymer composition comprising a copolymer that contains the polymeric unit of a monomer having a polyfluoroalkyl group and one polymerizable unsaturated group, an ammonium salt and an aqueous medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-dispersed fluorine-based copolymer composition which imparts water / oil repellency to an object to be treated.

[0002]

2. Description of the Related Art There is known a technique for treating a fiber product or paper with a water / oil repellent using a polymer containing a polyfluoroalkyl group as an aqueous medium dispersion and imparting water / oil repellency to the surface thereof. Have been. In addition, a process such as adhesion may be performed on a surface on which water / oil repellency is further applied after water / oil repellency. For example, in the field of textile products, water-repellent and oil-repellent fabrics are subjected to processing such as film lamination, seam tape bonding, or resin coating to increase waterproofness.

[0003] Therefore, for example, when processing into a textile fabric, the amount of the water-repellent and oil-repellent applied is reduced, or the heat treatment temperature during the water-repellent and oil-repellent processing is reduced, so that the water-repellent and oil-repellent properties or the releasability are improved. Attempts have been made to improve the adhesiveness by reducing the particle size. However, in this case, the water or oil repellency on the cloth is reduced, so that the cloth is coarsely cured by the impregnation of the adhesive or the coating resin, or the adhesive or the coating resin is stained on the opposite side of the cloth. There was a problem such as taking out and contaminating. Further, in order to impart sufficient water / oil repellency, it was necessary to perform a second water / oil repellency process.

[0004]

SUMMARY OF THE INVENTION The present invention can exhibit stable water and oil repellency even under low-temperature, high-speed processing conditions.
It is another object of the present invention to provide a water-dispersed fluorine-based copolymer composition having excellent adhesion to a water- and oil-repellent surface.

[0005]

According to the present invention, a water-dispersible fluorine-based copolymer composition comprising a combination of a specific fluorine-containing polymer and an ammonium salt is used, whereby the composition is stable even at low-temperature and high-speed processing conditions. Expressed water and oil repellency,
Water- and oil-repellent treated products and coating resins, which were difficult in the past
It was possible to achieve both adhesiveness with a film or cloth and water / oil repellency.

That is, the present invention provides the following (1) to
The present invention provides a water-dispersed fluorine-based copolymer composition shown in (4). (1) A water-dispersed fluorine-based copolymer including a polymer containing a polymerized unit of a monomer having a polyfluoroalkyl group and one polymerizable unsaturated group, an ammonium salt, and an aqueous medium Composition. (2) A water-dispersed fluorine-based copolymer composition wherein the ammonium salt has a molecular weight of 300 or less. (3) A water-dispersed fluorine-based copolymer composition further containing a cyclic azoamidine compound. (4) An object to be treated which has been treated with the water-dispersed fluorine-based copolymer composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The water-dispersed fluorine-based copolymer composition of the present invention (hereinafter, also referred to as the composition of the present invention) has a polyfluoroalkyl group (hereinafter, also referred to as ^Rf group) and 1 It is characterized by containing a copolymer containing a polymerized unit of a monomer having two polymerizable unsaturated groups (hereinafter, also referred to as polymer A), an ammonium salt, and an aqueous medium. In addition,
In the present specification, acrylate and methacrylate are collectively referred to as (meth) acrylate. The same applies to notations such as (meth) acrylamide.

The polymer A used in the present invention is a copolymer containing a polymerized unit of a monomer having an R ^f group and one polymerizable unsaturated group (hereinafter, also referred to as monomer (a)). A polymer,
It is a copolymer containing a polymerized unit of a monomer (a) and a monomer not containing an R ^f group (hereinafter, also referred to as a monomer (b)).

In the present invention, the 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, especially 4 to 1 carbon atoms.
6 is preferred. The R ^f group may have a straight-chain structure or a branched structure, and preferably has a straight-chain structure. In the case of a branched structure, the branched portion is present at the terminal portion of the R ^f group and has 1 to 4 carbon atoms.
Is preferred.

The R ^f group may contain a halogen atom other than a fluorine atom. Other halogen atoms include
A chlorine atom is preferred. Further, an etheric oxygen atom, an ester group, a sulfonamide group or a thioetheric sulfur atom may be inserted between the carbon-carbon bonds in the R ^f group. The structure of the terminal portion of the R ^f group is -CF ₂ C
F ₃ , —CF (CF ₃ ) ₂ , —CF ₂ H, —CFH ₂ ,
—CF ₂ Cl and the like, among which —CF ₂ CF ₃ is preferable.

[0011] 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 are substituted with fluorine atoms (that is, a perfluoroalkyl group), or a group having a perfluoroalkyl group at the terminal portion.

The carbon number of the perfluoroalkyl group is from 2 to
20 is preferable, and especially 4-16 is preferable. 2 carbon atoms
If it is less than 20, the water repellency and oil repellency tend to decrease, and if it is more than 20, the monomer having an ^Rf group becomes a solid at room temperature, has high sublimability, and is difficult to handle. Could be.

R^fSpecific examples of the group include the following groups
Can be C_FourF₉− [CF_Three(CF_Two)_Three−, (C
F_Three)_TwoCFCF_Two−, (CF_Three) _ThreeC- and CF
_ThreeCF_Two(CF_Three) CF- and other structurally isomer groups],
C_FiveF₁₁-[For example, CF_Three(CF_Two)_Four−], C₆F
₁₃-[For example, CF_Three(CF _Two)_Five−], C₇F₁₅−
[For example, CF_Three(CF_Two)₆−], C₈F₁₇− [
For example, CF_Three(CF_Two)₇−], C₉F₁₉-[For example C
F_Three(CF_Two)₈−], C_TenF_{twenty one}-[For example, CF
_Three(CF_Two)₉−], C₁₂F_{twenty five}-[For example, CF_Three(C
F_Two)₁₁−], C₁₄F₂₉-[For example, CF_Three(CF_Two)
₁₃−], C₁₆F₃₃-[For example, CF_Three(CF_Two)
₁₅−], CHF_Two(CF_Two)_d− (D is an integer of 1 to 15
Number), CF_TwoCl (CF_Two)_e− (E is an integer of 1 to 15
Number), (CF_Three)_TwoCF (CF_Two)_f− (F is 1 to 14
Integer).

Further, etheric oxygen is present between carbon-carbon bonds.
Atom, ester group, sulfonamide group or thioate
R with a neutral sulfur atom inserted^fBase Specific examples of
The following groups may be mentioned. CF_Three(CF_Two)_FourOCF (CF
_Three)-, F [CF (CF_Three) CF_TwoO]_sCF (C
F_Three) CF_TwoCF_Two−, F [CF (CF_Three) CF_TwoO]
_tCF (CF_Three)-, F [CF (CF_Three) CF_TwoO]_u
CF_TwoCF_Two−, F (CF_TwoCF_TwoCF_TwoO)_vCF_Two
CF_Two−, F (CF_TwoCF_TwoO)_wCF_TwoCF_Two-, C
₈F₁₇SO _TwoN (CH_Three)-, C₈F₁₇SO_TwoN (C_Two
H_Five)-(S, t are integers of 1 to 10, u is an integer of 2 to 6)
Number, v is an integer of 1 to 11, w is an integer of 1 to 11) and the like.

Examples of the polymerizable unsaturated group include residues of olefins, residues of vinyl ethers, residues of vinyl esters, residues of (meth) acrylates, and residues of styrenes. No.

The monomer (a) is not particularly limited as long as it has an R ^f group and one polymerizable unsaturated group. In the present invention, the (meth) acrylic monomer having an R ^f group is used. Acid esters are preferred. 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.

[0017] As (meth) acrylic acid ester having ^the R ^f group is a compound represented by the following formula a ¹¹ is preferred. _{^{R f -Q-OCOCR = CH 2}} ··· formula a ^11, where, Q is a divalent organic radical, R represents a hydrogen atom or a methyl group.

[0018] R ^f in formula a ¹¹ is described above R
^{Among the f} groups, an R ^f group containing no etheric oxygen atom, ester group, sulfonamide group, or thioetheric sulfur atom between carbon-carbon bonds is preferable, a perfluoroalkyl group is particularly preferable, and CF ₃ (CF ₂ ) is particularly preferable.
A group represented by _n- (however, n is an integer of 1 to 19, preferably an integer of 3 to 15, and particularly preferably an integer of 6 to 12) is preferable.

[0019] Q in the formula a ¹¹ is, - (CH _{2)
p + q -, - (CH} 2) p O (CH 2) q -, - CF = C
_{H (CH 2) p -,} - (CH 2) p CONH (CH 2)
_q -,-(CH ₂ ) _p OCONH (CH ₂ ) _q -,-
(CH ₂ ) _p SO ₂ NR ′ (CH ₂ ) _q -,-(C
H ₂ ) _p NHCONH (CH ₂ ) _q -,-(CH ₂ ) _{p
CH (OH) - (CH 2} ) q - and the like are preferable. here,
R '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 them, Q is-(CH ₂ ) _{p + q} -,-
(CH ₂ ) _p CONH (CH ₂ ) _q- or-(CH
_{2) p SO 2 NR '(} CH 2) q - and may, and preferably when q is an integer of 2 or more, p + q is 2 to 6,
In particular,-(CH ₂ ) _{p + q} − when p + q is 2 to 6.
(That is, an ethylene group, a trimethylene group, a tetramethylene group, a heptamethylene group or a hexamethylene group) is preferable. Further, in the equation a ^11, the R ^f is carbon atoms attached is Q, preferably fluorine atoms are bonded.

Specific examples of the (meth) acrylate having an R ^f group include the following compounds. Here, R represents a hydrogen atom or a methyl group. CF ₃ (CF ₂ ) ₄ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₂ H (CF ₂ ) ₅ CH ₂ OCOCR = CH ₂ , CF ₂ H (CF ₂ ) ₇ CH ₂ OCOCR = CH ₂ , CF ₂ H (CF ₂ ) ₉ CH ₂ OCOCR = CH ₂ , CF ₂ H (CF ₂ ) ₇ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₁₃ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₁₅ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ CONHCH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OCOCH ₃ ) OCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOCR = CH ₂ .

The monomer (a) preferably contains one or more of the above (meth) acrylates having an R ^f group. When containing a R ^f group with (meth) acrylic acid ester more preferably comprises (meth) acrylic acid ester having different ^the R ^f group carbon numbers.

Examples of the monomer (b) constituting the polymer (A) together with the monomer (A) include known or well-known monomers that do not contain an R ^f group. Among them, a monomer having one or two polymerizable unsaturated groups is preferable. Examples of the polymerizable unsaturated group include those described above. These are 1
Species can be used alone or in combination of two or more.

The monomer (b) preferably contains the following monomer (b ¹ ) and / or the following monomer (b ² ). In particular, when the monomer (b) includes both of the following monomer (b ¹ ) and the following monomer (b ² ),
Alternatively, it is preferable to include only the monomer (b ² ) without including the monomer (b ¹ ). The monomer (b ¹ ) or the monomer (b ² ) may be used alone or in combination of two or more.

Monomer (b ¹ ): an alkyl (meth) acrylate having 1 to 20 carbon atoms in the alkyl group. Monomer (b ² ): olefin, vinyl halide, vinylidene halide, vinyl carboxylate, styrene, substituted styrene, (meth) acrylamide, N-substituted (meth)
Acrylamide, vinyl alkyl 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-vinylcarbazole, N-methylmaleimide, maleic anhydride, monoalkyl maleate, dialkyl maleate, and blocked At least one monomer selected from the group consisting of isocyanate group-containing (meth) acrylates.

The alkyl group in the monomer (b ¹ ) has 1 to 20 carbon atoms. The alkyl group may have any of a straight-chain structure, a branched structure, and a ring structure, and may have a structure partially having a ring structure. When two or more monomers (b ¹ ) are used, the structures of the alkyl groups may be the same or different. The monomer (b ¹ ) is preferably a (meth) acrylic acid alkyl ester having an alkyl group part having a linear or branched structure and having 1 to 18 carbon atoms, particularly methyl (meth) acrylate and stearyl. (Meth) acrylate or 2-ethylhexyl (meth) acrylate is preferred.

As the monomer (b ² ), 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-methylol (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, polyoxyalkylene (meth) acrylate, methylpolyoxyalkylene (meth) A) acrylate, 2-ethylhexyl polyoxyalkylene (meth) acrylate, polyoxyalkylene di (meth) acrylate, (meth) acrylate having polysiloxane, triallyl cyanurate, allyl glycidyl ether, allyl acetate, N-vinyl carbazole, maleimide , N-methylmaleimide, or (2-dimethylamino) ethyl (meth) acrylate;
Dioctyl malate, dibutyl malate, diethyl malate and the like are preferred. As the monomer (b ² ), a blocked isocyanate group-containing (meth) acrylic acid ester is also preferable.

The blocked isocyanate group-containing (meth) acrylate is a (meth) acrylate having at least one blocked isocyanate group, and isocyanate group of the (meth) acrylate having an isocyanate group. Compounds having a structure in which is blocked by a blocking agent are preferred. Examples of the (meth) acrylate having an isocyanate group include 2-isocyanateethyl (meth) acrylate or a (meth) acrylate having a functional group capable of binding to an isocyanate group and a polyisocyanate having at least one isocyanate group. A reaction product obtained by reacting at a ratio where remains 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 mono- or diester of (meth) acrylic acid and a polyhydric alcohol. preferable. Examples of the polyhydric alcohol include ethylene glycol, polyoxyethylene glycol, propylene glycol, polyoxypropylene glycol, glycerin, an adduct of trimethylolpropane-alkylene oxide, and pentaerythritol.

As the polyisocyanate, 4,4'-
Diphenylmethane diisocyanate, aromatic isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
4,4′-dicyclohexylmethane diisocyanate,
Aliphatic isocyanates or cycloaliphatic isocyanates such as cyclohexylene diisocyanate and norbornene diisocyanate, and modified products thereof such as a nullate-modified product, a prepolymer-modified product, and a burette-modified product are preferable. Aromatic isocyanates and their nullate-modified, prepolymer-modified or burette-modified products are preferred.

Examples of the blocking agent for the isocyanate group of the isocyanate group-containing (meth) acrylate include:
Alkyl ketoximes, phenols, alcohols, β-diketones or lactams are preferred, and methyl ethyl ketoxime, ε-caprolactam, phenol, cresol, acetylacetone, diethyl malonate, isopropanol, t-butyl alcohol, maleic imide, etc. More preferred. Above all, the dissociation temperature of alkyl ketoximes such as methyl ethyl ketoxime and lactams such as ε-caprolactam is 120 to 180.
Particular preference is given to blocking agents consisting of compounds at 0 ° C.

Specific examples of the blocked isocyanate group-containing (meth) acrylate include compounds in which the isocyanate group of 2-isocyanatoethyl (meth) acrylate is blocked with methyl ethyl ketoxime.
A compound in which the isocyanate group of 2-isocyanate ethyl (meth) acrylate is blocked with ε-caprolactam, and the isocyanate group of a 1: 1 (molar ratio) reaction product of isophorone diisocyanate and 2-hydroxyethyl (meth) acrylate is blocked with methyl ethyl ketoxime. Or a compound in which the isocyanate group of a 1: 1 (molar ratio) reaction product of isophorone diisocyanate and 2-hydroxypropyl (meth) acrylate is blocked with methyl ethyl ketoxime, or a mixture of norbornene diisocyanate and 2-hydroxyethyl (meth) acrylate Compounds in which a 1: 1 (molar ratio) reaction product is blocked with methyl ethyl ketoxime are exemplified. Monomer (b
^{When two} or more kinds of ² ) are used, those having the same structure may be used, or two or more kinds having completely different structures may be used in combination.

The polymer A comprises a monomer (a) and a monomer (b)
And obtained by polymerizing The monomer (b) is used in an amount of preferably 1 to 90% by mass, more preferably 5 to 60% by mass, and still more preferably 20 to 50% by mass, based on the monomer (a). When used in this ratio, the monomer (b)
Effectively improves the water and oil repellency or the durability thereof, which is effective from an economic viewpoint.

The composition of the present invention comprises, together with the polymer A,
It is characterized by containing an ammonium salt. Ammonium salts include ammonium chloride, ethanolamine hydrochloride, N, N-dimethylethanolamine hydrochloride, N, N
In addition to ordinary amine hydrochlorides such as -diethylethanolamine hydrochloride, N, N-dibutylethanolamine hydrochloride, and N-methyldiethanolamine hydrochloride, ammonium salts having the following structure and a molecular weight of 300 or less can be used.

[0034]

Embedded image

Of these, ammonium chloride, monoethanolamine hydrochloride, and 2,2'-azobis (2-methylpropionamidine) dihydrochloride are preferred. The ammonium salts may be used alone or in combination of two or more.

The content of the ammonium salt in the composition of the present invention is preferably from 0.1 to 5% by mass, particularly preferably from 0.5 to 3.0% by mass, based on the polymer A. When the content of the ammonium salt is too small, the effect of improving the water / oil repellency and the effect of improving the adhesiveness are poor. If the amount is too large, the stability of the dispersion of the aqueous dispersion may be impaired. The composition of the present invention, by including an ammonium salt, has an effect of improving the adhesiveness when a coating resin or a laminate film is adhered to a surface having water / oil repellency.

The aqueous medium used in the composition of the present invention includes:
It consists of water and an organic solvent soluble in water. As the organic solvent in the aqueous medium, the solubility in 100 g of water is 10 g.
Although not particularly limited as long as it is above, for example, acetone,
Isopropyl alcohol, saturated polyhydric alcohols, (mono- or poly) alkyl ethers of saturated polyhydric alcohols,
Alternatively, at least one selected from alkylene oxide adducts of saturated polyhydric alcohols is preferred.

As the saturated polyhydric alcohol, a compound having 2 to 4 hydroxyl groups is preferable, and particularly, ethylene glycol, propylene glycol, glycerin, trimethylolethane or trimethylolpropane is preferable. As the (mono or poly) alkyl ether of the saturated polyhydric alcohol, a monoalkyl ether of a diol or a dialkyl ether of a diol is preferable, for example, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether is preferable, and diethylene glycol is particularly preferable. Monomethyl ether or dipropylene glycol monomethyl ether is preferred.

Examples of the alkylene oxide adduct of a saturated polyhydric alcohol include a reaction product of a saturated polyhydric alcohol with ethylene oxide and / or propylene oxide. As a reaction product between the saturated polyhydric alcohol and ethylene oxide and / or propylene oxide,
Dipropylene glycol, tripropylene glycol,
Tetrapropylene glycol or polypropylene glycol having five or more oxypropylene groups connected is preferred.

Examples of the organic solvent in the aqueous medium include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, glycerin, dipropylene glycol, and the like. One or more selected from the group consisting of tripropylene glycol, tetrapropylene glycol, and polypropylene glycol is preferred.

The amount of the organic solvent in the aqueous medium is preferably from 2 to 50% by mass, more preferably from 10 to 40% by mass, based on the polymer A. If the amount of the organic solvent is too small, the effect of improving the stability of the emulsion may not be recognized,
If the amount of the organic solvent is too large, the washing durability of the water- and oil-repellent property may be reduced. The amount of the aqueous medium is preferably 1 to 5 times the mass of the polymer A.

The composition of the present invention is not particularly limited as long as it contains the polymer A, an ammonium salt, and an aqueous medium. Preferably, the polymer A is present as particles in the aqueous medium. Is good.

The average particle size of the polymer A is 10 to 1000 n
m is preferable, 10 to 300 nm is more preferable, and 10
~ 200 nm is particularly preferred. If the average particle diameter is less than 10 nm, a large amount of surfactant is required to obtain a stable dispersion, the water / oil repellency is reduced, and furthermore, discoloration occurs when treated with dyed fabrics. If the average particle size exceeds 1000 nm, the particles settle out in the aqueous medium. The average particle diameter can be measured by a dynamic light scattering device, an electron microscope, or the like. When the polymerization is carried out in the presence of a surfactant by the ordinary emulsion polymerization method described below, the average particle size falls within the above range.

The method for causing the polymer A to be present as particles in the aqueous medium is not particularly limited, but the polymer A is simply mixed with the monomer (a) in the aqueous medium in the presence of the surfactant (c). The monomer (b) is preferably polymerized by a known method, for example, an emulsion polymerization method or a dispersion polymerization method.

When the polymerization is carried out by an emulsion polymerization method or a dispersion polymerization method, a method in which a polymerization initiator and a chain transfer agent are added, if necessary, in the presence of a surfactant (c) and a polymerization medium can be exemplified. . Therefore, it is one of the preferable embodiments that the composition of the present invention contains a surfactant, a polymerization initiator and a chain transfer agent in addition to the above essential components.

The surfactant (c) may be used alone or in combination of two or more. Further, the surfactant (c) may use only a nonionic surfactant,
A surfactant other than the nonionic surfactant may be used together with the nonionic surfactant. As the surfactant other than the nonionic surfactant, a cationic surfactant or an amphoteric surfactant is preferable.

As the nonionic surfactant in the surfactant (c), one or more nonionic surfactants selected from the following surfactants (c ¹ ) to (c ⁶ ) are preferable. The surfactant (c ¹ ) is a nonionic surfactant composed of a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, or a polyoxyalkylene monoalkapolyenyl ether. The alkyl group, alkenyl group or alkapolyenyl group in the surfactant (c ¹ ) has 4 to 4 carbon atoms each.
26 is preferred. 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, a secondary alkyl group, a secondary alkenyl group, or a secondary alkapolyenyl group is preferred. Specific examples of the alkyl group, alkenyl group or alkapolyenyl group include octyl group, dodecyl group, tetradecyl group, hexadecyl group,
Examples thereof include an octadecyl group, a behenyl group (a docosyl group), and an oleyl group (a 9-octadecenyl group).

The surfactant (c ¹ ) is preferably a polyoxyalkylene monoalkyl ether or a polyoxyalkylene monoalkenyl ether. The polyoxyalkylene portion of the surfactant (c ¹ ) preferably comprises one or two oxyalkylene groups,
When they are composed of seeds, it is preferable that their connection be block-shaped. The polyoxyalkylene portion preferably comprises a portion in which two or more oxyethylene groups and / or oxypropylene groups are linked.

[0049] The surfactant (c ^1), a compound represented by the following formula c ¹¹ are preferred. However, R ¹⁰ in the formula c ¹¹ represents an alkyl group having 8 or more carbon atoms or an alkenyl group having 8 or more carbon atoms, g represents an integer of 0 to 20, and h represents 5 to 5
Indicates an integer of 0. When g and h are 2 or more,
Is connected becomes blocky The oxyethylene group and oxypropylene group in the formula c ^{11. _{R 10 O [CH 2 CH (}} CH 3) O] g - (CH 2 CH 2 O) R 10 in _h H · · · formula c ¹¹ formula c ¹¹ is either a linear structure or a branched structure Is also good. h is preferably an integer of 10 to 30, and g is preferably an integer of 0 to 10. h is 4 or less, or g is 2
If it is 1 or more, it becomes poorly soluble in water and does not dissolve uniformly in an aqueous medium, so that the effect of improving permeability may be reduced. When h is 51 or more, the hydrophilicity increases, and the water repellency may decrease.

Specific examples of the compound (formula c ¹¹ ) include the following compounds. However, in the following formula, g and h have the same meaning as described above, and the preferred embodiments are also the same. Further, the oxyethylene group and the oxypropylene group are connected in a block shape. C ₁₈ H ₃₇ O [CH ₂ CH (CH ₃ ) O] _g- (CH ₂ CH ₂ O) _h H, C ₁₈ H ₃₅ O [CH ₂ CH (CH ₃ ) O] _g- (CH ₂ CH ₂ O ) _h H, C ₁₆ H ₃₃ O [CH ₂ CH (CH ₃ ) O] _g- (CH ₂ CH ₂ O) _h H, C ₁₂ H ₂₅ O [CH ₂ CH (CH ₃ ) O] _g- (CH ₂ CH ₂ O) _h H, (C ₈ H ₁₇ ) (C ₆ H ₁₃ CHO [CH ₂ CH (CH ₃ ) O] _g )-(CH ₂ CH ₂ O) _h H, C ₁₀ H ₂₁ O [CH ₂ CH (CH ₃ ) O] _g- (CH ₂ CH ₂ O) _h H.

The surfactant (c 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. Surfactant (c ²⁾ has one carbon in the molecule - carbon triple bond, and one or nonionic surfactant made of a compound having two hydroxyl groups are preferred. 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.

As the surfactant (c ² ), the following formula c ²¹ ,
Compounds of the formula c ²² , c ²³ or c ²⁴ are preferred. ^{HO-CR 11 R 12 -C≡C-} CR 13 R 14 -OH ··· formula ^{c 21 HO- (A 1 O)} i -CR 11 R 12 -C≡C-CR 13 R 14 - (OA 2) _j -OH ・ ・ ・ Formula c ²² HO-CR ¹⁵ R ¹⁶ -C≡CH ・ ・ ・ Formula c ²³ HO- (A ³ O) _k -CR ¹⁵ R ¹⁶ -C≡CH ・ ・ ・ Formula c ²⁴

However, A ¹ , A ² and A ³ in the formulas c ²¹ to c ²⁴ each independently represent an alkylene group;
And j each represent an integer of 0 or more, and (i + j) represents 1
Is an integer greater than or equal to. k represents an integer of 1 or more. When i, j or k is 2 or more, A ¹ , A ² and A ³ may each consist of only one kind of alkylene group or may consist of two or more kinds of alkylene groups. . R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent 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 include a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group. Further, the oxyalkylene moiety preferably comprises an oxyethylene moiety, an oxypropylene moiety or both an oxyethylene moiety and an oxypropylene moiety. In addition, the surfactant (c
The number of oxyalkylene groups in ² ) is preferably from 1 to 50.

Further, as the surfactant (c ² ), a nonionic surfactant comprising a compound represented by the following formula c ²⁵ is preferable. Here, x and z in the formula c ²⁵ are each 0.
The following integers are shown. One or more nonionic surfactants (formula c ²⁵ ) may be used in combination.

[0055]

Embedded image

As the nonionic surfactant (formula c ²⁵ ), a nonionic surfactant in which the average of the sum of x and z is 10 and a nonionic surfactant in which x is 0 and z is 0 Or a nonionic surfactant in which the average of the sum of x and z is 1.3.

The surfactant (c 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 (c ³ ) is preferably oxytetramethylene and / or oxypropylene.

[0058] As the surfactant (c ^3), a compound represented by the following formula c ³¹ or the formula c ³² are preferred. Equation c ³¹
And a is 0 to 200 integer wherein c ^32, b is 2 to 10
Integer of 0, c represents an integer of 0 to 200, and when a is 0, c is an integer of 2 or more, and when c is 0, a is an integer of 2 or more. Further, -C in the formula c ³¹ ₃ H ₆ O-
_{Moiety, -CH (CH 3) CH 2} - even, -CH
₂ CH (CH ₃₎ - even, -CH (CH ₃₎ CH
₂ - and -CH ₂ CH (CH ₃₎ - and it may be mixed. Further, the polyoxyalkylene moiety in the formula c ³¹ or the formula c ³² is linked in a block form. HO- (CH ₂ CH ₂ O) _a- (C ₃ H ₆ O) _b- (CH ₂ CH ₂ O) _c H ・ ・ ・ Formula c ³¹ HO- (CH ₂ CH ₂ O) _a- (CH ₂ CH ₂ CH ₂ CH ₂ O) _b- (CH ₂ CH ₂ O) _c H ・ ・ ・ Formula c ³²

The following compounds are preferred as specific examples of the surfactant (c ³ ). _{HO- (CH 2 CH 2 O)} 15 - (C 3 H 6 O) 35 - (CH 2 CH 2 O) 15 H, HO- (CH 2 CH 2 O) 8 - (C 3 H 6 O) 35 - _{(CH 2 CH 2 O) 8} H, HO- (CH 2 CH 2 O) 45 - (C 3 H 6 O) 17 - (CH 2 CH 2 O) 45 H, HO- (CH 2 CH 2 O) 34 -(CH ₂ CH ₂ CH ₂ CH ₂ O) _28- (CH ₂ CH ₂ O) ₃₄ H.

[0060] Surfactant (c ⁴⁾ is a nonionic surfactant having an amine oxide moiety in its molecule, a nonionic surfactant made of a compound represented by the following formula c ⁴¹ are preferred. (R ¹⁷ ) (R ¹⁸ ) (R ¹⁹ ) N (→ O) formula c ⁴¹ R ¹⁷ , R ¹⁸ and R ^{19 in} formula c ⁴¹ are each independently 1
Represents 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. These surfactants can be used alone or in combination of two or more. As the surfactant (c ⁴ ), a nonionic surfactant represented by the following formula c ⁴² is particularly preferred because it improves the dispersion stability of the polymer A. _{^{(R 20) (CH 3)}} 2 N (→ O) ··· formula c ⁴² formula c R ²⁰ in ⁴² represents an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, an alkyl group ( 6 to 2 carbon atoms
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.

The following compounds are preferred as specific examples of the nonionic surfactant (formula c ⁴² ). [H (CH ₂ ) ₁₂ ] (CH ₃ ) ₂ N (→ O), [H (CH ₂ ) ₁₄ ] (CH ₃ ) ₂ N (→ O), [H (CH ₂ ) ₁₆ ] (CH ₃ ) ₂ N (→ O), [H (CH ₂ ) ₁₈ ] (CH ₃ ) ₂ N (→ O).

The surfactant (c ⁵ ) is a condensate of polyoxyethylene mono (substituted phenyl) ether or a nonionic surfactant composed of polyoxyethylene mono (substituted phenyl) ether. The substituted phenyl group in the surfactant (c ⁵ ) is preferably a phenyl group substituted with a monovalent hydrocarbon group, and particularly preferably a phenyl group substituted with an alkyl group, an alkenyl group or a styryl group.

As the surfactant (c ⁵ ), a condensate of polyoxyethylene mono (alkylphenyl) ether,
A condensate of polyoxyethylene mono (alkenylphenyl) ether, polyoxyethylene mono (alkylphenyl) ether, polyoxyethylene mono (alkenylphenyl) ether, or polyoxyethylene mono [(alkyl) (styryl) phenyl] ether is preferable. .

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, polyoxyethylene mono (nonylphenyl) ether, polyoxyethylene mono ( Octylphenyl) ether, polyoxyethylene mono (oleylphenyl) ether, polyoxyethylene mono [(nonyl) (styryl) phenyl] ether, or polyoxyethylene mono [(oleyl) (styryl) phenyl]
Ether and the like.

The surfactant (c ⁶ ) is a nonionic surfactant comprising a fatty acid ester of a polyol. Examples of the polyol in the surfactant (c ⁶ ) include polyethylene glycol, decaglycerin, and ethers of polyethylene glycol and a polyol (other than polyethylene glycol).

As the surfactant (c ⁶ ), 1: 1 (molar ratio) ester of octadecanoic acid and polyethylene glycol, 1: 4 (molar ratio) ester of ether of sorbitol and polyethylene glycol and oleic acid A 1: 1 (molar ratio) ester of polyoxyethylene glycol and sorbitan with octadecanoic acid, a 1: 1 (molar ratio) ester of polyethylene glycol and sorbitan with oleic acid, and dodecanoic acid 1: 1 (molar ratio) ester with sorbitan, (1 or 2): 1 (molar ratio) ester of oleic acid and decaglycerin, (1 or 2): 1 (molar ratio) of octadecanoic acid and decaglycerin Esters are mentioned.

When the surfactant (c) contains a cationic surfactant, it is preferable to use a cationic surfactant comprising a substituted ammonium salt. Cationic surfactants comprising a substituted ammonium salt are compounds in which at least one of the hydrogen atoms bonded to the nitrogen atom of the ammonium salt is substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene group having a terminal hydroxyl group. cationic surfactants are preferred made, in particular compounds represented by the following formula c ⁵¹ are preferred.

[0068] _{^{[(R 21) 4 N +}} ] · Y - ··· formula c ⁵¹ provided that the symbols in the formula c ⁵¹ indicates the following meanings. R ²¹ : The four R ²¹ are each independently a hydrogen atom, an alkyl group having 1 to 26 carbon atoms, an alkenyl group having 2 to 26 carbon atoms, or a polyoxyalkylene group having a terminal hydroxyl group. However, four R ²¹ are not simultaneously hydrogen atoms. Y ^-: counter-ion. When R ²¹ is an alkyl group, a long-chain alkyl group having 6 to 26 carbon atoms is preferred. When R ²¹ is an alkyl group other than a long-chain alkyl group, a methyl group or an ethyl group is preferred. When R ²¹ is an alkenyl group, a long-chain alkenyl group having 6 to 26 carbon atoms is preferred. When R ²¹ is a polyoxyalkylene group, a polyoxyethylene group is preferred. As Y ⁻ , a chlorine ion, an ethyl sulfate ion or an acetate ion is preferable.

As the compound (formula c ⁵¹ ), mono (long-chain alkyl) amine hydrochloride, mono (long-chain alkyl) dimethylamine hydrochloride, mono (long-chain alkyl) dimethylamine acetate, mono (long-chain alkenyl) Dimethylamine 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 are preferred.

Further, as the compound (formula c ⁵¹ ), monooctadecyltrimethylammonium chloride, monooctadecyldimethylmonoethylammonium ethyl sulfate, mono (long-chain alkyl) monomethyldi (polyethylene glycol) ammonium chloride, di (tallowalkyl) dimethyl Ammonium chloride or dimethyl monococonut amine acetate is preferred.

Examples of the cationic surfactant include amine salts, quaternary ammonium salts, and oxyethylene addition type ammonium salts. Specific examples include alkyldimethylamine hydrochloride, dialkylmethylamine hydrochloride, and alkyltrimethylammonium. Chloride, dialkyldimethylammonium chloride, monoalkylamine acetate,
Alkyl methyl dipolyoxyethylene ammonium chloride and the like can be mentioned. The alkyl moiety has 4 carbon atoms.
To 26 saturated aliphatic groups, which may be a straight-chain or branched chain, and specifically include octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, behenyl, and secondary alkyl groups. Can be

When the surfactant (c) contains an amphoteric surfactant, an amphoteric surfactant comprising an alanine, an imidazolinium betaine, an amidobetaine or a betaine acetate is preferred. Specific examples of the amphoteric surfactant include dodecyl betaine, octadecyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolinium betaine, dodecyl dimethylamino acetate betaine,
Fatty acid amidopropyldimethylaminoacetic acid betaine and the like.

The amount of the surfactant (c) is preferably from 1 to 12% by mass, more preferably from 3 to 10% by mass, based on the polymer A. If the amount of the surfactant (c) is too small, the stability of the emulsion may be reduced. If the amount is too large, the water / oil repellency and wet friction durability may be reduced. However, when the monomer in the raw material contains a self-emulsifying monomer, the amount of the surfactant (c) may be reduced.

When a cationic surfactant and / or an amphoteric surfactant is used as the surfactant (c), it is preferable to use the surfactant together with a nonionic surfactant.
The amount of the cationic surfactant and / or the amphoteric surfactant is preferably 1% by mass or less based on the polymer A. If the amount is too large, the concomitant use with the dyeing assistant used in combination may be impaired.

Examples of the polymerization initiator include known water-soluble or oil-soluble polymerization initiators, and general-purpose polymerization initiators such as azo-based, peroxide-based, and redox-based polymerization initiators are used depending on the polymerization temperature. Can be used. Among them, a water-soluble polymerization initiator is preferable, and a salt of an azo compound is more preferable. In the present invention, it is particularly preferable to use a cyclic azomidine compound. Therefore, it is a preferable embodiment that the composition of the present invention further contains a cyclic azoamidine compound.

The cyclic azoamidine compound used in the present invention includes, for example, 2,2′-azobis [2- (2-
Imidazolin-2-yl) propane], 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2,2'-azobis [2- (3,4,
5,6-tetrahydropyrimidin-2-yl) propane], 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}.
And their hydrochlorides, sulfates, acetates, malates and the like.

The cyclic azoamidine compound is preferably a water-soluble salt. This is because the dispersibility in an aqueous medium is good, and the stability of the composition of the present invention is excellent. In the case where a salt of the above compound is used as the cyclic azoamidine compound, the compound may be added after forming a salt in advance using an organic acid such as hydrochloric acid, sulfuric acid, acetic acid, or malic acid, The compound and the organic acid may be added separately. These cyclic azoamidine compounds may be used alone or in combination of two or more. As the cyclic azoamidine compound used in the present invention, in particular, 2,2 ′
-Azobis [2- (2-imidazolin-2-yl) propane] and its hydrochloride and acetate are preferred.

By containing a cyclic azoamidine compound, there is an advantage that excellent water and oil repellency can be obtained even under low-temperature and high-speed processing conditions. The content of the polymerization initiator is preferably from 0.1 to 2.0% by mass, more preferably from 0.5 to 1.0% by mass, based on the polymer A.

In the polymerization reaction, a chain transfer agent may be used for controlling the molecular weight. As the chain transfer agent, an aromatic compound or a mercaptan is preferable, and an alkyl mercaptan is particularly preferable. Specific examples of the chain transfer agent include n-octyl mercaptan,
Preferred examples include n-dodecyl mercaptan, t-dodecyl mercaptan, stearyl mercaptan, and α-methylstyrene dimer CH ₂ ＣＰCPhCH ₂ C (CH ₃ ) ₂ Ph, where Ph is a phenyl group.

The polymerization temperature of the polymer A is not particularly limited, but is preferably from 20 to 150 ° C. Further, as a pre-stage for starting the emulsion polymerization, a mixture comprising the monomers (a) and (b), the surfactant (c) and the aqueous medium may be pre-dispersed in advance using a homomixer or a high-pressure emulsifier. Good. By thoroughly stirring the mixture before the start of the polymerization, the yield of the polymer finally obtained can be improved.

In the present invention, the ammonium salt may be added later to the emulsion containing the polymer A obtained by the above-mentioned emulsion polymerization method, and when the polymer A is emulsion-polymerized, the ammonium salt is added in advance. In addition, an emulsion containing the polymer A and an ammonium salt can be produced.

Further, the composition of the present invention may contain other additives. Other additives include other polymer extenders, other water repellents, other oil repellents, insect repellants, flame retardants, antistatic agents, dye stabilizers, anti-wrinkles, stain blockers, and the like. The timing of adding these additives is not particularly limited.

The solid content of the composition of the present invention is 10 to 4
0 mass% is preferable, and especially 15 to 30 mass% is preferable. In addition, the solid content concentration is considered to be substantially equal to the concentration of the polymer A in the composition of the present invention.

The present invention also provides an article to be treated which has been treated with the above-mentioned composition of the present invention. The composition of the present invention can be diluted to an arbitrary concentration according to the purpose and use. Then, it can be applied to an object to be processed. 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 carry out curing.

Examples of the crosslinking agent include blocked isocyanate compounds, melamine resin compounds, glyoxal resin compounds, urea resin compounds, and crosslinkable monomers (such as N-methylol acrylamide and 2-isocyanate ethyl methacrylate). And the like, and a blocked isocyanate compound or a melamine resin compound is preferred.

The object to be treated with the composition of the present invention is:
The material is not particularly limited, and examples thereof include fiber, fiber fabric, glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxides thereof, ceramic products, plastics, and the like, and fiber fabric is particularly preferable. 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; semi-synthetic fibers such as rayon and acetate; and glass fibers. , A carbon fiber, an inorganic fiber such as an asbestos fiber, or a woven fabric of a mixed fiber thereof.

By treating with the composition of the present invention, stable water and oil repellency can be imparted without variation in water and oil repellency even under low-temperature and high-speed processing conditions. Further, the adhesiveness of the water- and oil-repellent processed surface is excellent, and no adhesion failure or interface peeling occurs. Therefore, the composition of the present invention is suitable as a water- and oil-repellent agent, and when used as a pretreatment agent for coating, a pretreatment agent for bonding, and a pretreatment agent for lamination, penetration of the adhesive into the object to be treated and backside Dropout can be effectively prevented.

[0088]

Next, the present invention will be described specifically with reference to examples.
However, the present invention is not limited to these. [Polymerization example of polymer A] Perflu in a 1 L glass beaker
Oroalkyl ethyl acrylate [F (CF _Two)_nCH
_TwoCH_TwoOCOCH = CH_TwoAnd n is a mixture of 6 to 16.
The average value of n in the compound is 9. Purity 93.6 mass%] 200.
9 g, dioctyl malate (DOM) 17.5 g, N-
6.7 g of methylol acrylamide (NMAA), n-
0.8 g of dodecyl mercaptan (DoSH), polyoxo
Cyethylene oleyl ether (ethylene oxide flat
(Average number of moles added: 30) (Nonion E manufactured by NOF Corporation)
230 ") 16.1 g, dipropylene glycol (DP
G) Add 107.4 g and 389.3 g of ion-exchanged water.
Was. Subsequently, the mixture is heated in a water bath to 50 ° C.
Momixer (Toki Homomixer MK manufactured by Tokushu Kika Co., Ltd.)
2 "). Next, the emulsion is brought to 50 ° C.
While maintaining the high pressure emulsifier (LAB60-10TBS AP)
Emulsified under the conditions of 40 MPa
Was. Take 647.2 g of this emulsion and add 1 L of autoclaved
1.9 g of acetic acid and 2,2′-azobis
[2- (2-imidazolin-2-yl) propane] 2.
After adding 5 g, the inside was replaced with nitrogen. Next,
49.3 g of Nyl was injected and the temperature was reduced to 55 ° C. while stirring.
Raised and polymerized for 10 hours to obtain a milky white emulsion. this
The solution was filtered under pressure using Advantech C-63 filter paper.
I have. Solids concentration in the emulsion after filtration
Is 33.6% by mass, a dynamic light scattering particle size measuring device (Otsuka Electric
Average particle size of polymer measured by "ELS-800" manufactured by Koshiro Co., Ltd.)
The diameter was 110 nm. Emulsion solids concentration
Diluted with ion-exchanged water so that the concentration becomes 20% by mass
Was used as stock solution A.

[Preparation of Evaluation Sample] (Example 1) A stock solution A was prepared by adding 0.5% by mass of ammonium chloride to stock solution A. (Example 2) 0.5% of monoethanolamine hydrochloride was added to stock solution A.
The solution added by mass% was used as stock solution A2. (Example 3) Stock solution A was prepared by adding 0.2% by mass of 2,2'-azobis (2-methylpropionamidine) dihydrochloride to stock solution A. (Example 4) Only stock solution A.

[Evaluation of Water / Oil Repellency] The water / oil repellency was measured using the stock solution obtained by the above method prepared so that the ratio to water was 6% by mass. The performance was evaluated under two conditions. An undyed polyester (100%) tropical cloth was used as a test cloth, immersed in the prepared treatment solution, and squeezed between two rubber rollers to obtain a wet pickup of 85% by mass. Then
The test cloth dried at 100 ° C. for 60 seconds and further heat-treated at 130 ° C. for 30 seconds was used as an evaluation cloth under low-temperature and high-speed heat treatment conditions. For comparison, the same sample was subjected to the same immersion treatment, and then dried at 110 ° C. for 90 seconds.
A test cloth heat-treated at 0 ° C. for 60 seconds was evaluated as an evaluation cloth under normal conditions.

[Evaluation of water repellency] JIS-L1092 1
The test was conducted by a spray test of No. 992, and represented by the water repellency numbers shown in Table 1.

[0092]

[Table 1]

[Evaluation of Oil Repellency] The oil repellency was evaluated by AAT.
Performed according to CC-Test Method 118-1997, and represented by oil repellency numbers shown in Table 2. In Table 2, “parts” indicates “parts by mass”.

[0094]

[Table 2]

[0095] The evaluation of adhesiveness was carried out in the following manner: 6% by mass of the stock solution obtained by the above method, 0.3% by mass of melamine resin ("Sumitec Resin M3" manufactured by Sumitomo Chemical Co., Ltd.), and a catalyst (Sumitomo Chemical Co., Ltd.). “Sumitex Accelerator ACX”) 0.
A treatment liquid was prepared by diluting and mixing with water so as to have a concentration of 3% by mass, and a dyed and fixed nylon taslan cloth was used as a test cloth.

The processing conditions were as follows: the test cloth was immersed in the processing liquid, and the test cloth was squeezed between two rubber rollers. This was repeated twice to obtain a wet pickup of 90% by mass. Then, it is dried at 100 ° C. for 60 seconds and further dried at 150 ° C.
C. for 30 seconds to obtain a water / oil repellent cloth. A polyester-type polyurethane resin (resin concentration 30%, DM
F solution) 100 parts and hexamethylene diisocyanate 1
Of the mixture was applied with a bar coater so as to be 100 g / m ^2, and then the cloth was immersed in water at 25 ° C. for 1 minute to coagulate the resin and then washed with water at 50 ° C. for 5 minutes. This fabric was heat-treated at 130 ° C. for 2 minutes to obtain a coated fabric. Further, a hot melt tape (“MELCO tape” manufactured by San Kasei Co., Ltd.) having a width of 2.5 cm and a length of 15 cm was applied to the coating resin surface of the coated fabric at 150 ° C. and 30 ° C. using a transfer press (manufactured by Okuno Electric Co., Ltd.). Bonded for seconds.

These cloths were left for 72 hours at 25 ° C. and a humidity of 60%, and the adhesion (peel strength) between the nylon cloth and the coating resin was measured by a tensile tester.
The results are summarized in Table 3.

[0098]

[Table 3]

[0099]

The water-dispersed fluorine-based copolymer composition of the present invention exhibits excellent water and oil repellency even under low-temperature and high-speed processing conditions, so that stable production is expected even in actual on-site processing. It is. Further, since the water-repellent and oil-repellent surfaces have excellent adhesiveness, peeling troubles are reduced, and durability of the coated product can be improved. Therefore, the range of processing and application is expanded more than before, and more functional finishing can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C09K 3/18 102 C09K 3/18 102 103 103 103

Claims (4)

[Claims] 1. A copolymer containing a polymerized unit of a monomer having a polyfluoroalkyl group and one polymerizable unsaturated group,
A water-dispersed fluorine-based copolymer composition comprising an ammonium salt and an aqueous medium. 2. The water-dispersed fluorine-based copolymer composition according to claim 1, wherein the ammonium salt has a molecular weight of 300 or less. 3. The water-dispersed fluorinated copolymer composition according to claim 1, further comprising a cyclic azoamidine compound. 4. An article to be treated which has been treated with the water-dispersed fluorine-based copolymer composition according to claim 1, 2 or 3.