JP5223385B2 - Water-repellent oil-repellent antifouling composition and articles treated with the same - Google Patents

Description

  The present invention relates to a water-repellent oil-repellent antifouling composition, and an article treated with the water-repellent oil-repellent antifouling composition.

Conventionally, for example, various compositions according to the purpose have been provided as processing agents for water repellent and antifouling processing of clothing. Water repellent and oil-repellent to make it difficult to get dirt on workwear such as work clothes and linen such as rental sheets, and antifouling property that makes it easy to remove dirt that has once adhered by wiping or washing ( A water-repellent oil-repellent antifouling composition having both a soil release property and an SR property is often used.
For example, in Patent Document 1 below, a water-repellent and oil-repellent fluoroalkyl compound that imparts a good antifouling property and a water-repellent oil-repellent and facilitating removal of attached dirt by washing treatment or the like. A method of using a mixture of a hydrophilic group-containing fluoroalkyl compound is described.
JP 60-104576 A

A polyfluoroalkyl group in a conventionally used fluoroalkyl compound (hereinafter, the polyfluoroalkyl group may be referred to as an R ^f group) mainly has 8 or more carbon atoms.
Recently, however, the EPA (US Environmental Protection Agency) pointed out that a compound having an ^RF group having 8 or more carbon atoms decomposes in the environment and in the living body and accumulates decomposition products, that is, has a high environmental load. Has been. Therefore, it is recommended that the ^Rf group in the compound be a short chain having 6 or less carbon atoms, and the water repellency is excellent in both oil repellency and antifouling properties while the ^Rf group is a short chain. There is a need for a water-repellent oil-repellent antifouling composition.

The present invention was made in view of the above circumstances, and the water repellency is excellent in both oil repellency and antifouling properties, and the R ^f group in the compound is a short chain and the load on the environment is reduced. An object of the present invention is to provide a coconut oil antifouling composition.
Another object of the present invention is to provide an article treated with the water-repellent oil-repellent antifouling agent composition.

In order to solve the above problems, the water-repellent oil-repellent antifouling agent composition of the present invention comprises a structural unit based on the following monomer (a), a structural unit based on the following monomer (b), A polymer (A) having a constitutional unit based on the monomer (c), wherein the proportion of fluorine atoms in the polymer (A) (100% by mass) is 15% by mass or more and less than 45% by mass; A structural unit based on the body (a), a structural unit based on the following monomer (b), and a structural unit based on the following monomer (c), and in the polymer (B) (100% by mass) Polymer (B) having a fluorine atom ratio of 45% by mass or more; and a polymer (C) having a structural unit based on the following monomer (a) and a structural unit based on the following monomer (d): The mass ratio ((A) / (B)) between the polymer (A) and the polymer (B) is 10/90 to 95/5, The mass ratio ({(A) + (B)} / (C) of the sum of the polymer (A) and the polymer (B) {(A) + (B)} to the polymer (C) )) Is 5/95 to 95/5.
Monomer (a): a polyfluoroalkyl group having 4 to 6 carbon atoms to which fluorine atoms are bonded (however, the polyfluoroalkyl group may contain an etheric oxygen atom). Having monomer.
Monomer (b): a monomer having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer (c): Vinyl chloride or vinylidene chloride.
Monomer (d): one or more hydrophilic groups that do not have a polyfluoroalkyl group and are selected from the group consisting of alkylene oxide groups, amino groups, hydroxy groups, acrylamide groups, carboxy groups, phosphoric acid groups, and sulfone groups A monomer having

It is preferable that at least one polymer among the polymer (A), the polymer (B), and the polymer (C) further has a structural unit based on the following monomer (e).
Monomer (e): a monomer having no polyfluoroalkyl group and having a functional group capable of crosslinking.

It is preferable that the polymer (C) has a structural unit based on the monomer (d ′) having an alkylene oxide group without having a polyfluoroalkyl group.
The monomer (d ′) is a monomer (d1) having an alkylene oxide group without a polyfluoroalkyl group, and the alkylene oxide group being an ethylene oxide group, and represented by the following formula (2): Or a monomer (d2) in which the alkylene oxide group is an ethylene oxide group and tetramethylene oxide present in the same side chain, and is preferably a compound represented by the following formula (3) .
^{_{CH 2 = CR 1 -G 1 -}} (C 2 H 4 O) q1 -R 2 ... (2).
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and q 1 represents an integer of ¹ to 50. G ¹ represents —COO (CH ₂ ) _{r 1} — or —COO (CH ₂ ). _t1- NHCOO- (r1 represents an integer of 0 to 4, t1 represents an integer of 1 to 4)
^{_{CH 2 = CR 3 -G 2 -}} (C 2 H 4 O) q2 - (C 4 H 8 O) q3 -R 4 ... (3).
^(Wherein, R 3, ^{R 4} are each independently a hydrogen atom or a methyl group, q2, q3 is an integer of 1 to 50 .G ² is -COO _{(CH 2) r2} - or -COO (CH ₂ ) _t2- NHCOO- (wherein r2 is an integer of 0-4, t2 is an integer of 1-4).)
The polymer (C) preferably has a structural unit based on the monomer (d3) having no amino group but no polyfluoroalkyl group.
The polymer (C) preferably has an anionic group at the end of the main chain.

The water-repellent oil-repellent antifouling agent composition of the present invention further contains at least one crosslinking agent selected from the group consisting of isocyanate-based crosslinking agents, melamine-based crosslinking agents, carbodiimide-based crosslinking agents, and oxazoline-based crosslinking agents. It is preferable to do.
Articles treated with the water-repellent oil-repellent antifouling agent composition according to Item.

The water-repellent oil-repellent antifouling agent composition of the present invention can impart excellent water-repellent oil-repellency and antifouling properties to the surface of the article, and the R ^f group in the compound has a short chain, which is an environmental load. Is low.
The article of the present invention is treated with a water-repellent oil-repellent antifouling agent composition having a low environmental load, and the surface water-repellent is excellent in oil-repellent and antifouling properties.

In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas. Moreover, in this specification, group represented by Formula (2) is described as group (2). Groups represented by other formulas are also described in the same manner.
(Meth) acrylate in this specification means acrylate or methacrylate.
The monomer in the present specification means a compound having a polymerizable unsaturated group.
In the present specification, the R ^f group is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the R ^F group is a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. It is.

In the present invention, the proportion of fluorine atoms in each of the polymers (A) and (B) is determined by analytical chemistry Vol. 26, no. 10, pages 721 to 723, the following method based on the quartz tube oxygen combustion gas collection method described in “Quantitative determination of fluorine in fluorine-containing organic compounds” (1977, published by the Analytical Society of Japan) It is a value obtained by measuring with.
FIG. 1 is a schematic configuration diagram schematically showing a disassembly / absorption device used in this measurement method. In the figure, reference numeral 1 is an oxygen cylinder, 2 is a flow meter, 3 is water, 3a is a steam supply flask, 4 is a steam supply furnace, 5 is a thermometer, 7 is a quartz tube, 8 is a sample boat, 9a is a sample furnace, 9b Indicates a decomposition furnace, 10 is silica wool, 11 is a cooler, and 12 is an Erlenmeyer flask for absorption.
In the apparatus of this figure, the sample is combusted and decomposed in the sample furnace 9a, and the generated fluorine reacts with the silica wool 10 as a fluoride. It is expelled by pyrohydrolysis with water vapor supplied from the water 3 heated by the water vapor supply furnace 4 and collected in the water in the absorption Erlenmeyer flask 12.

First, 10 mg of the sample (polymer) is weighed into the sample boat 8 and inserted into the sample furnace 9 a in the quartz tube 7. A platinum boat is used as a sample boat. At this time, the sample furnace 9a is at room temperature.
Moreover, 50 ml of distilled water is put into the Erlenmeyer flask 12 for absorption and set. Water 3 is placed in the steam supply flask 3a and set, and heated in the steam supply furnace 4 so that the thermometer 5 in the steam supply flask 3a becomes 200 ° C. The cracking furnace 9b is set to 1140 ° C.
Next, while supplying oxygen from the oxygen cylinder 1 at a flow rate of 20 ml / min, the sample furnace 9a is heated from room temperature to 600 ° C. in 20 minutes and held at 600 ° C. for 30 minutes.
Thereafter, water (measurement aqueous solution) in the Erlenmeyer flask 12 for absorption is quantified by the following F electrode method.

For determination, a fluoride ion electrode (manufactured by HORIBA, product name: # 6561-10C F ⁻ ) and an ion / PH meter (manufactured by HORIBA, product name: F-23) are used.
A calibration curve is prepared by measuring in advance a diluted solution of a fluoride ion standard solution (manufactured by Kanto Chemical Co., Inc., for chemical analysis, F ⁻ : 1000 ppm) as appropriate.
For the measurement aqueous solution and the fluoride ion standard aqueous solution, the same amount of TISAB aqueous solution (manufactured by Kanto Chemical Co., Inc., for fluorine ion electrode) is added to adjust the ionic strength, and the measurement is performed with the fluoride ion electrode and the ion / PH meter. The F recovery of fluorobenzoic acid by this method is 84%. The measured values of the fluoride ion electrode and the ion / PH meter are corrected by the recovery rate of the fluorobenzoic acid, and the ratio of fluorine atoms is calculated.

<Water repellent oil oil antifouling agent composition>
The water repellent oil composition of the present invention contains the polymer (A), the polymer (B), and the polymer (C) as essential components.

<Polymer (A)>
The polymer (A) is a copolymer having a structural unit based on the monomer (a), a structural unit based on the monomer (b), and a structural unit based on the monomer (c). The polymer (A) does not have a structural unit based on the monomer (d) described later.
The ratio of the fluorine atom in a polymer (A) (100 mass%) is 15 mass% or more and less than 45 mass%. 25 mass% or more is preferable and, as for the ratio of the fluorine atom in a polymer (A) (100 mass%), 30 mass% or more is more preferable.
The ratio of the fluorine atom in a polymer (A) (100 mass%) can be adjusted with the composition of the monomer used for manufacture of a polymer (A).

[Monomer (a)]
The monomer (a) has an R ^f group having 4 to 6 carbon atoms to which fluorine atoms are bonded (however, the R ^f group may contain an etheric oxygen atom). It is a monomer.
As a monomer (a), a compound (1) is mentioned, for example.
(ZY) _n X (1).

Z is an R ^f group having 4 to 6 carbon atoms (provided that the R ^f group may contain an etheric oxygen atom) or a group (2).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each independently a fluorine atom or a trifluoromethyl group.
The R ^f group is preferably an R ^F group. The R ^f group may be linear or branched, and is preferably linear.
Examples of Z include the following groups.
F (CF ₂ ) ₄ −,
F (CF ₂ ) _5- ,
F (CF ₂ ) _6- ,
(CF ₃ ) ₂ CF (CF ₂ ) _2- ,
_{C k F 2k + 1 O [} CF (CF 3) CF 2 O] h -CF (CF 3) - and the like.
However, k is an integer of 1-6 and h is an integer of 0-10.

Y is a divalent organic group or a single bond. In Equation (1), the boundary between Z and Y is determined so that the number of carbon atoms in Z is minimized.
As the divalent organic group, an alkylene group is preferable. The alkylene group may be linear or branched. The alkylene group is —O—, —NH—, —CO—, —SO ₂ —, —S—, —CD ¹ = CD ² — (wherein D ¹ and D ² are each independently a hydrogen atom or a methyl group. Or the like.

Examples of Y include the following groups.
-CH ₂ -,
—CH ₂ CH ₂ —
- _{(CH 2)} 3 -,
_{-CH 2 CH 2 CH (CH 3} ) -,
-CH = CH-CH ₂ - and the like.

n is 1 or 2.
X is any one of groups (3-1) to (3-5) when n is 1, and when n is 2, X is any of groups (4-1) to (4-4). Either.

-CR = CH ₂ (3-1),
-COOCR = CH ₂ (3-2),
-OCOCR = CH ₂ (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group.

_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} COOCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OCOCR = CH 2] - ··· (4-3),
-OCOCH = CHCOO- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4.

As compound (1), the number of carbon atoms in terms of polymerizability with other monomers, flexibility of the polymer film, adhesion of the polymer to the article, solubility in the medium, ease of emulsion polymerization, etc. There preferably (meth) acrylate having a ^{R F} group 4-6.
As the compound (1), Z is an ^{R F} group having 4 to 6 carbon atoms, Y is an alkylene group having 1 to 4 carbon atoms, n is 1, X is a group (3-3) Compounds are preferred.

[Monomer (b)]
The monomer (b) is a monomer having no R ^f group and having an alkyl group having 12 or more carbon atoms. The monomer (b) does not have a hydrophilic group. When the alkyl group has 12 or more carbon atoms, water repellency and adhesion to the substrate are improved.
Examples of the monomer (b) include (meth) acrylates, vinyl ethers, and vinyl esters.

  The monomer (b) is preferably a monomer having an alkyl group having 12 to 36 carbon atoms, more preferably a (meth) acrylate having an alkyl group having 12 to 24 carbon atoms, and stearyl (meth) acrylate. Or behenyl (meth) acrylate is particularly preferable.

[Monomer (c)]
The monomer (c) is vinyl chloride or vinylidene chloride. Either one or both may be used as the monomer (c). The monomer (c) contributes to good oil repellency, washing durability and antifouling properties.

[Monomer (e)]
The polymer (A) may further have a monomer (e) that does not have an R ^f group and has a functional group capable of crosslinking.
When the polymer (A) has a structural unit based on the monomer (e), the washing durability is further improved.
What is contained in the monomer (d) described later is not included in the monomer (e).

The functional group capable of crosslinking is preferably a functional group capable of forming a self-crosslinking structure in a polymer, a cross-linking structure between molecules of one polymer and another polymer, or a cross-linking structure with a reactive group present on a substrate. .
The functional group is preferably an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, an alkoxymethylamide group, an epoxy group, an oxazoline group, a carbodiimide group, etc., and an epoxy group, a blocked isocyanate group, an alkoxysilyl group or an alkoxymethylamide. The group is particularly preferred.

As the monomer (e), (meth) acrylates, acrylamides, vinyl ethers, or vinyl esters are preferable.
As the monomer (e), the following compounds may be mentioned.

  2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl (meth) acrylate, 2-isocyanate Pyrazole adduct of natoethyl (meth) acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, 3-methylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, 2-isocyanate Ε-Caprolactam adduct of natoethyl (meth) acrylate, 2-butanone oxime adduct of 3-isocyanatopropyl (meth) acrylate, pyrazole adduct of 3-isocyanatopropyl (meth) acrylate.

  3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, 3-methylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, ε-caprolactam addition of 3-isocyanatopropyl (meth) acrylate 4-isocyanatobutyl (meth) acrylate 2-butanone oxime adduct, 4-isocyanatobutyl (meth) acrylate pyrazole adduct, 4-isocyanatobutyl (meth) acrylate 3,5-dimethylpyrazole addition 4-isocyanatobutyl (meth) acrylate 3-methylpyrazole adduct, 4-isocyanatobutyl (meth) acrylate ε-caprolactam adduct.

Methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, butoxymethyl (meth) acrylamide, diacetone acrylamide, γ-methacryloyloxypropyltrimethoxysilane, trimethoxyvinylsilane, vinyltrimethoxysilane.
Glycidyl (meth) acrylate, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl- (2-vinyloxazoline).

  Tri (meth) allyl isocyanurate (T (M) AIC, manufactured by Nippon Kasei Co., Ltd.), triallyl cyanurate (TAC, manufactured by Nippon Kasei Co., Ltd.), 3- (methylethylketoxime) isocyanatomethyl-3,5,5-trimethyl Cyclohexyl (2-hydroxyethyl methacrylate) cyanate (Tech Coat HE-6P, manufactured by Kyo Silk Chemical Co., Ltd.).

  As monomer (e), N-methylol (meth) acrylamide, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, glycidyl methacrylate, Techcoat HE-6P (manufactured by Kyoto Silk Chemical Co., Ltd.) ) Is preferred.

[Other monomer (f)]
The polymer (A) may have a structural unit based on the monomer (f) other than the monomers (a) to (e). The monomer (f) preferably does not have a polyfluoroalkyl group having 7 or more carbon atoms to which fluorine atoms are bonded.
As the monomer (f), the following compounds may be mentioned.
Methyl acrylate, ethyl acrylate, propyl acrylate, butyl methacrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, vinyl acetate, vinyl propionate, butene, isoprene, butadiene, ethylene, propylene , Vinylethylene, pentene, ethyl-2-propylene, butylethylene, cyclohexylpropylethylene, decylethylene, dodecylethylene, hexene, isohexylethylene, neopentylethylene, (1,2-diethoxycarbonyl) ethylene, (1,2 -Dipropoxycarbonyl) ethylene, methoxyethylene, ethoxyethylene, butoxyethylene, 2-methoxypropylene, pentyloxyethylene, cyclopenta Yl oxyethylene, cyclopentyl acetoxystyrene ethylene, styrene, alpha-methyl styrene, p- methyl styrene, hexyl styrene, octyl styrene, nonyl styrene, chloroprene, tetrafluoroethylene, vinylidene fluoride.

  Vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, benzyl (meth) acrylate, octyl (meth) acrylate, decyl methacrylate, cyclododecyl acrylate, 3-ethoxypropyl acrylate, methoxy-butyl acrylate, 2-ethylbutyl acrylate, 1 3-dimethylbutyl acrylate, 2-methylpentyl acrylate.

[Production Method of Polymer (A)]
The polymer (A) can be produced, for example, by the following method.
Monomer component (X) containing monomers (a) to (c) and optionally monomers (e) and / or (f) in the medium in the presence of a surfactant and a polymerization initiator ) To obtain a solution, dispersion or emulsion of the polymer (A).
Examples of the polymerization method include a dispersion polymerization method, an emulsion polymerization method, and a suspension polymerization method. Moreover, batch polymerization may be sufficient and multistage polymerization may be sufficient.

As a method for producing the polymer (A), a method of obtaining an emulsion of the polymer (A) by emulsion polymerization of the monomer component (X) in an aqueous medium in the presence of a surfactant and a polymerization initiator is preferable. .
From the viewpoint of improving the yield of the polymer (A), it is preferable to pre-emulsify a mixture comprising a monomer, a surfactant and an aqueous medium before emulsion polymerization. For example, a mixture comprising a monomer, a surfactant and an aqueous medium is mixed and dispersed with a homomixer or a high-pressure emulsifier.

Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, an ionic polymerization initiator, and the like, and a water-soluble or oil-soluble radical polymerization initiator is preferable.
As the radical polymerization initiator, a general-purpose initiator such as an azo polymerization initiator, a peroxide polymerization initiator, or a redox initiator is used depending on the polymerization temperature. As the radical polymerization initiator, an azo compound is particularly preferable, and when polymerization is performed in an aqueous medium, a salt of the azo compound is more preferable. The polymerization temperature is preferably 20 to 150 ° C.
0.1-5 mass parts is preferable with respect to 100 mass parts of monomer components (X), and, as for the addition amount of a polymerization initiator, 0.1-3 mass parts is more preferable.

In the polymerization of the monomer component (X), a molecular weight modifier may be used. As the molecular weight regulator, aromatic compounds, mercapto alcohols, mercapto carboxylic acids or mercaptans are preferable, and mercapto carboxylic acids or alkyl mercaptans are particularly preferable. Examples of the molecular weight modifier include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, stearyl mercaptan, α-methylstyrene dimer (CH ₂ = C (Ph) CH ₂ C (CH ₃ ) ₂ Ph and Ph are phenyl groups.
0.01-5 mass parts is preferable with respect to 100 mass parts of monomer components (X), and, as for the addition amount of a molecular weight regulator, 0.1-3 mass parts is more preferable.

The proportion of the monomer (a) is preferably 30 to 80% by mass, and preferably 40 to 80% by mass in the monomer component (X) (100% by mass) from the viewpoint of water repellency and oil repellency and antifouling properties. Is more preferable.
The proportion of the monomer (b) is preferably 2 to 30% by mass in the monomer component (X) (100% by mass) from the viewpoint of water repellency and oil repellency and antifouling properties, and 5 to 20% by mass. Is more preferable.
The proportion of the monomer (c) is preferably 2 to 30% by mass in the monomer component (X) (100% by mass) from the viewpoint of water repellency and oil repellency and antifouling properties, and 5 to 20% by mass. Is more preferable.
The proportion of the monomer (e) is preferably 0 to 20% by mass in the monomer component (X) (100% by mass) from the viewpoint of water repellency, oil repellency and washing durability. The mass% is more preferable.

The number average molecular weight determined by gel permeation chromatography (GPC) of the polymer (A) is preferably from 5,000 to 150,000, more preferably from 8,000 to 40,000. The mass average molecular weight is preferably 10,000 to 300,000, more preferably 15,000 to 80,000.
When the molecular weight of the polymer (A) is not more than the upper limit of the above range, the dispersion stability is excellent, and when it is not less than the lower limit, the adhesion to the substrate is excellent.

<Polymer (B)>
The polymer (B) is a copolymer having a structural unit based on the monomer (a), a structural unit based on the monomer (b), and a structural unit based on the monomer (c). The polymer (B) does not have a structural unit based on the monomer (d) described later.
The proportion of fluorine atoms in the polymer (B) (100% by mass) is 45% by mass or more, and more preferably 49% by mass or more. Moreover, 60 mass% or less is preferable and, as for the upper limit of the ratio of the fluorine atom in a polymer (B) (100 mass%), 58 mass% or less is more preferable.
The ratio of the fluorine atom in a polymer (B) (100 mass%) can be adjusted with the composition of the monomer used for manufacture of a polymer (B).

[Monomer (a)]
The monomer (a) has an R ^f group having 4 to 6 carbon atoms to which fluorine atoms are bonded (however, the R ^f group may contain an etheric oxygen atom). It is a monomer.
Examples of the monomer (a) include those similar to the monomer (a) constituting the polymer (A) (for example, the compound (1)).

As compound (1), the number of carbon atoms in terms of polymerizability with other monomers, flexibility of the polymer film, adhesion of the polymer to the article, solubility in the medium, ease of emulsion polymerization, etc. There preferably (meth) acrylate having a ^{R F} group 4-6.
As the compound (1), Z is an ^{R F} group having 4 to 6 carbon atoms, Y is an alkylene group having 1 to 4 carbon atoms, n is 1, X is a group (3-3) Compounds are preferred.

[Monomer (b)]
The monomer (b) is a monomer having no R ^f group and having an alkyl group having 12 or more carbon atoms. The monomer (b) contributes to good water repellency and friction durability. The monomer (b) does not have a hydrophilic group.
Examples of the monomer (b) include the same monomers (b) that constitute the polymer (A).

[Monomer (c)]
The monomer (c) is vinyl chloride or vinylidene chloride. Either one or both may be used as the monomer (c). The monomer (c) contributes to good oil repellency, washing durability and antifouling properties.

[Monomer (e)]
The polymer (B) may further have a monomer (e) having no ^Rf group and having a functional group capable of crosslinking. When the polymer (B) has a structural unit based on the monomer (e), the washing durability is further improved.
Examples of the monomer (e) include the same monomers (e) that constitute the polymer (A).

[Other monomer (f)]
The polymer (B) may have a structural unit based on the monomer (f) other than the monomers (a) to (e). Examples of the monomer (f) include the same monomer (f) as that in the polymer (A).

[Production method of polymer (B)]
The polymer (B) can be produced, for example, by the following method.
Monomer component (Y) containing monomers (a) to (c) and, if necessary, monomers (e) and / or (f) in the presence of a surfactant and a polymerization initiator ) To obtain a solution, dispersion or emulsion of the polymer (B).
Examples of the polymerization method include a dispersion polymerization method, an emulsion polymerization method, and a suspension polymerization method. Moreover, batch polymerization may be sufficient and multistage polymerization may be sufficient.

As a method for producing the polymer (B), a method of obtaining an emulsion of the polymer (B) by emulsion polymerization of the monomer component (Y) in an aqueous medium in the presence of a surfactant and a polymerization initiator is preferable. .
From the viewpoint of improving the yield of the polymer (B), it is preferable to pre-emulsify a mixture comprising a monomer, a surfactant and an aqueous medium before emulsion polymerization. For example, a mixture comprising a monomer, a surfactant and an aqueous medium is mixed and dispersed with a homomixer or a high-pressure emulsifier.

As a polymerization initiator, the thing similar to what was used for manufacture of a polymer (A) is mentioned.
0.1-5 mass parts is preferable with respect to 100 mass parts of monomer components (Y), and, as for the addition amount of a polymerization initiator, 0.1-3 mass parts is more preferable.

In the polymerization of the monomer component (Y), a molecular weight modifier may be used. Examples of the molecular weight regulator include the same ones used for the production of the polymer (A).
0.01-5 mass parts is preferable with respect to 100 mass parts of monomer components (Y), and, as for the addition amount of a molecular weight modifier, 0.1-3 mass parts is more preferable.

The proportion of the monomer (a) is preferably 70 to 100% by mass, and 75 to 100% by mass in the monomer component (Y) (100% by mass) from the viewpoint of water repellency and oil repellency and antifouling properties. Is more preferable.
The proportion of the monomer (b) is preferably 1 to 15% by mass in the monomer component (Y) (100% by mass) from the viewpoint of water repellency and oil repellency and antifouling properties, and 1 to 10% by mass. Is more preferable.
The proportion of the monomer (c) is preferably 1 to 15% by mass in the monomer component (Y) (100% by mass) from the viewpoint of water repellency and oil repellency and antifouling properties, and 1 to 10% by mass. Is more preferable.
The proportion of the monomer (e) is preferably 0 to 10% by mass, preferably 0 to 5% by mass in the monomer component (Y) (100% by mass) from the viewpoint of water repellency and oil durability. Is more preferable.

The number average molecular weight by GPC of the polymer (B) is preferably 5,000 to 300,000, and more preferably 10,000 to 50,000. The mass average molecular weight is preferably 10,000 to 600,000, more preferably 15,000 to 100,000.
When the molecular weight of the polymer (B) is not more than the upper limit of the above range, the dispersion stability is excellent, and when it is not less than the lower limit, the adhesion to the substrate is excellent.

[Medium]
As a medium used for the production of the polymer (A) and the polymer (B), water, alcohol, glycol, glycol ether, halogen compound, hydrocarbon, ketone, ester, ether, nitrogen compound, sulfur compound, inorganic solvent, organic An acid etc. are mentioned. Of these, one or more media selected from the group consisting of water, alcohol, glycol, glycol ether and glycol ester are preferred from the viewpoints of solubility and ease of handling.

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

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

Examples of the halogen compound include halogenated hydrocarbons and halogenated ethers.
Examples of the halogenated hydrocarbon include hydrochlorofluorocarbon, hydrofluorocarbon, hydrobromocarbon and the like.

Examples of the halogenated ether include hydrofluoroether.
Examples of hydrofluoroethers include separated hydrofluoroethers and non-separable hydrofluoroethers. The separated hydrofluoroether is a compound in which an R ^F group or a perfluoroalkylene group and an alkyl group or an alkylene group are bonded via an etheric oxygen atom. The non-separable hydrofluoroether is a hydrofluoroether containing a partially fluorinated alkyl group or alkylene group.

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

Examples of the ketone include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, and methyl isobutyl ketone.
Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, and pentyl lactate.
Examples of the ether include diisopropyl ether, dioxane, tetrahydrofuran and the like.

Examples of the nitrogen compound include pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
Examples of the sulfur compound include dimethyl sulfoxide (DMSO) and sulfolane.
Examples of the inorganic solvent include liquid carbon dioxide.
Examples of the organic acid include acetic acid, propionic acid, malic acid, and lactic acid.

  A medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. When two or more media are used in combination, it is preferable to use a mixture with water. By using a mixed medium, it is easy to control the solubility and dispersibility of the copolymer, and it is easy to control the permeability, wettability, solvent drying rate and the like of the article during processing.

(Surfactant)
Examples of the surfactant used for the production of the polymer (A) and the polymer (B) include hydrocarbon surfactants and fluorine surfactants, which are anionic surfactant and nonionic surfactant, respectively. , Cationic surfactants, or amphoteric surfactants.
As the surfactant, from the viewpoint of dispersion stability, a combination of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant, or an anionic surfactant alone is preferable, and a nonionic surfactant is preferable. And a cationic surfactant are preferred.
The ratio of the nonionic surfactant to the cationic surfactant (nonionic surfactant / cationic surfactant) is preferably 97/3 to 40/60 (mass ratio).
In a specific combination of a nonionic surfactant and a cationic surfactant, the total amount with respect to the copolymer (100% by mass) can be reduced to 5% by mass or less, thereby reducing the adverse effect on the water repellency of the article. .

The nonionic surfactant, at least one member selected from the group consisting of surfactants s ¹ ~s ⁶ are preferred.

Surfactant s ¹ :
The surfactant s ¹ is a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, a polyoxyalkylene monoalkapolyenyl ether, or a polyoxyalkylene monopolyfluoroalkyl ether.
The surfactant s ¹ is preferably polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, or polyoxyalkylene monopolyfluoroalkyl ether. Surfactant s ¹ may be used alone or in combination of two or more thereof.

The alkyl group, alkenyl group, alkapolyenyl group or polyfluoroalkyl group (hereinafter, the alkyl group, alkenyl group, alkapolyenyl group and polyfluoroalkyl group are collectively referred to as R ^s group) has 4 carbon atoms. A group of ~ 26 is preferred. The R ^s group may be linear or branched. The branched R ^s group is preferably a secondary alkyl group, a secondary alkenyl group, or a secondary alkapolyenyl group. In the R ^s group, part or all of the hydrogen atoms may be substituted with fluorine atoms.

Specific examples of R ^s group include octyl group, dodecyl group, tetradecyl group, hexadecyl group, stearyl group (octadecyl group), behenyl group (docosyl group), oleyl group (9-octadecenyl group), heptadecylfluorooctyl group, Examples include tridecylfluorohexyl group, 1H, 1H, 2H, 2H-tridecylfluorooctyl group, 1H, 1H, 2H, 2H-nonafluorohexyl group and the like.

  The polyoxyalkylene (hereinafter referred to as POA) chain includes a chain in which two or more polyoxyethylene (hereinafter referred to as POE) chains and / or polyoxypropylene (hereinafter referred to as POP) chains are connected. preferable. The POA chain may be a chain composed of one kind of POA chain or a chain composed of two or more kinds of POA chains. When composed of two or more POA chains, each POA chain is preferably linked in a block form.

The surfactant ^{s 1,} compound ^{(s 11)} more preferred.
_{^{R 10 O [CH 2 CH (}} CH 3) O] s - (CH 2 CH 2 O) r H ··· (s 11).
However, R ¹⁰ is an alkyl group having 8 or more carbon atoms or an alkenyl group having 8 or more carbon atoms, r is an integer of 5 to 50, and s is an integer of 0 to 20. In R ¹⁰ , a part of hydrogen atoms may be substituted with fluorine atoms.

If r is 5 or more, it becomes soluble in water and is uniformly dissolved in an aqueous medium, so that the water-repellent oil-repellent composition has good penetrability into the article. When r is 50 or less, hydrophilicity is suppressed and water repellency is improved.
If s is 20 or less, it is soluble in water and is uniformly dissolved in an aqueous medium, so that the water-repellent oil-repellent composition has good permeability to articles.

When r and s are 2 or more, the POE chain and the POP chain are linked in a block shape.
R ¹⁰ is preferably linear or branched.
r is preferably an integer of 10 to 30.
s is preferably an integer of 0 to 10.

Examples of the compound (s ¹¹ ) include the following compounds. However, the POE chain and the POP chain are linked in a block shape.
_{C 18 H 37 O [CH 2} CH (CH 3) O] 2 - (CH 2 CH 2 O) 30 H,
_{C 18 H 35 O- (CH 2} CH 2 O) 30 H,
_{C 16 H 33 O [CH 2} CH (CH 3) O] 5 - (CH 2 CH 2 O) 20 H,
_{C 12 H 25 O [CH 2} CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H,
_{(C 8 H 17) (C} 6 H 13) CHO- (CH 2 CH 2 O) 15 H,
_{C 10 H 21 O [CH 2} CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H,
_{C 6 F 13 CH 2 CH 2} O- (CH 2 CH 2 O) 15 H,
_{C 6 F 13 CH 2 CH 2} O [CH 2 CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H,
_{C 4 F 9 CH 2 CH 2} O [CH 2 CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H.

Surfactant s ² :
Surfactant s ^2, one or more carbons in the molecule - is a nonionic surfactant made of a compound having a carbon triple bond and at least one hydroxy group.
Surfactant s ^2, one of the carbons in the molecule - carbon triple bond, and one or nonionic surfactant made of a compound having two hydroxyl groups are preferred.
Surfactant s ² may have a POA chain in the molecule. Examples of the POA chain include a POE chain, a POP chain, a chain in which a POE chain and a POP chain are connected randomly, or a chain in which a POE chain and a POP chain are connected in a block form.

Surfactant ^{s 2,} compound ^{(s 21) ~ (s 24} ) is preferably.
HO—C (R ¹¹ ) (R ¹² ) —C≡C—C (R ¹³ ) (R ¹⁴ ) —OH... (S ²¹ )
_{^{HO- (A 1 O) u -C}} (R 11) (R 12) -C≡C-C (R 13) (R 14) - (OA 2) v -OH
··· ^(s 22),
HO—C (R ¹⁵ ) (R ¹⁶ ) —C≡C—H (s ²³ ),
_{^{HO- (A 3 O) w -C}} (R 15) (R 16) -C≡C-H ··· (s 24).

A ^{1 to} A ³ are each an alkylene group.
u and v are each an integer of 0 or more, and (u + v) is an integer of 1 or more.
w is an integer of 1 or more.
When u, v, and w are each 2 or more, A ^{1 to} A ³ may be the same or different.
The POA chain is preferably a POE chain, a POP chain, or a chain containing a POE chain and a POP chain. The number of repeating units of the POA chain is preferably 1-50.

R ^{11 to} R ¹⁶ are each a hydrogen atom or an alkyl group.
As an alkyl group, a C1-C12 alkyl group is preferable and a C1-C4 alkyl group is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group.

As the compound (s ²² ), the compound (s ²⁵ ) is preferable.

However, x and y are integers of 0-100, respectively.
Compound (s ²⁵⁾ may be used alone or in combination of two or more thereof.
As the compound (s ²⁵ ), a compound in which x and y are 0, a compound in which the sum of x and y is 1 to 4 on average, or a compound in which the sum of x and y is on average 10 to 30 is preferable.

Surfactant s ³ :
Surfactant s ³ is a nonionic surfactant composed of a compound in which a POE chain is linked to a POA chain in which two or more oxyalkylenes having 3 or more carbon atoms are continuously linked, and both ends are hydroxyl groups. It is an agent.
The POA chain is preferably polyoxytetramethylene (hereinafter referred to as POT) and / or POP chain.

Surfactant ^{s 3,} compound ^{(s 31)} or compound ^{(s 32)} is preferably.
_{HO (CH 2 CH 2 O)} g1 (C 3 H 6 O) t (CH 2 CH 2 O) g2 H ··· (s 31),
_{HO (CH 2 CH 2 O)} g1 (CH 2 CH 2 CH 2 CH 2 O) t (CH 2 CH 2 O) g2 H ··· (s 32).

g1 is an integer of 0-200.
t is an integer of 2 to 100.
g2 is an integer of 0-200.
When g1 is 0, g2 is an integer of 2 or more. When g2 is 0, g1 is an integer of 2 or more.
-C ₃ H ₆ O- _{may, -CH (CH 3) CH 2} - is a even _{better, -CH 2 CH (CH 3)} - is a even _{better, -CH (CH 3) CH 2} - and - A mixture of CH ₂ CH (CH ₃ ) — may be used.
The POA chain is block-shaped.

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

Surfactant s ⁴ :
Surfactant s ⁴ is a nonionic surfactant having an amine oxide moiety in the molecule.
Surfactant ^{s 4,} compound ^{(s 41)} is preferably.
(R ¹⁷ ) (R ¹⁸ ) (R ¹⁹ ) N (→ O) (s ⁴¹ ).

R ^{17 to} R ¹⁹ are each a monovalent hydrocarbon group.
In the present invention, a surfactant having amine oxide (N → O) is treated as a nonionic surfactant.
Compound (s ⁴¹⁾ may be used alone or in combination of two or more thereof.

As the compound (s ⁴¹ ), the compound (s ⁴² ) is preferable from the viewpoint of dispersion stability of the copolymer.
(R ²⁰ ) (CH ₃ ) ₂ N (→ O) (s ⁴² ).

R ²⁰ is an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, a phenyl group to which an alkyl group having 6 to 22 carbon atoms is bonded, or an alkenyl group having 6 to 22 carbon atoms bonded thereto. Or a fluoroalkyl group having 6 to 13 carbon atoms. R ²⁰ is preferably an alkyl group having 8 to 22 carbon atoms, an alkenyl group having 8 to 22 carbon atoms, or a polyfluoroalkyl group having 4 to 9 carbon atoms.

Examples of the compound (s ⁴² ) include the following compounds.
[H (CH ₂ ) ₁₂ ] (CH ₃ ) ₂ N (→ O),
[H (CH ₂ ) ₁₄ ] (CH ₃ ) ₂ N (→ O),
[H (CH ₂ ) ₁₆ ] (CH ₃ ) ₂ N (→ O),
[H (CH ₂ ) ₁₈ ] (CH ₃ ) ₂ N (→ O),
[F (CF ₂ ) ₆ (CH ₂ ) ₂ ] (CH ₃ ) ₂ N (→ O),
[F (CF ₂ ) ₄ (CH ₂ ) ₂ ] (CH ₃ ) ₂ N (→ O).

Surfactant s ⁵ :
Surfactant s ⁵ is a nonionic surfactant made of a polyoxyethylene mono (substituted phenyl) ether condensate or polyoxyethylene mono (substituted phenyl) ether.
The substituted phenyl group is preferably a phenyl group substituted with a monovalent hydrocarbon group, and more preferably a phenyl group substituted with an alkyl group, an alkenyl group or a styryl group.

Surfactant s ⁵ includes polyoxyethylene mono (alkylphenyl) ether condensate, polyoxyethylene mono (alkenylphenyl) ether condensate, polyoxyethylene mono (alkylphenyl) ether, polyoxyethylene mono (alkenyl). Phenyl) ether or polyoxyethylene mono [(alkyl) (styryl) phenyl] ether is preferred.

  Polyoxyethylene mono (substituted phenyl) ether condensate or polyoxyethylene mono (substituted phenyl) ether includes formaldehyde condensate of polyoxyethylene mono (nonylphenyl) ether, polyoxyethylene mono (nonylphenyl) ether, poly Oxyethylene mono (octylphenyl) ether, polyoxyethylenemono (oleylphenyl) ether, polyoxyethylenemono [(nonyl) (styryl) phenyl] ether, polyoxyethylenemono [(oleyl) (styryl) phenyl] ether, etc. Can be mentioned.

Surfactant s ⁶ :
Surfactant s ⁶ is a nonionic surfactant made of a fatty acid ester of a polyol.
The polyol represents glycerin, sorbitan, sorbit, polyglycerin, polyethylene glycol, polyoxyethylene glyceryl ether, polyoxyethylene sorbitan ether, polyoxyethylene sorbit ether.

Surfactant s ⁶ includes a 1: 1 (molar ratio) ester of stearic acid and polyethylene glycol, a 1: 4 (molar ratio) ester of ether of sorbite and polyethylene glycol and oleic acid, and polyoxyethylene glycol. 1: 1 (molar ratio) ester of ether of sorbitan and stearic acid, 1: 1 (molar ratio) ester of ether of polyethylene glycol and sorbitan and oleic acid, 1: 1 (molar ratio) of dodecanoic acid and sorbitan Ratio) ester, 1: 1 or 2: 1 (molar ratio) ester of oleic acid and decaglycerin, and 1: 1 or 2: 1 (molar ratio) ester of stearic acid and decaglycerin.

Surfactant s ⁷ :
When the surfactant includes a cationic surfactant, the surfactant s ⁷ is preferable as the cationic surfactant.
Surfactant s ⁷ is a cationic surfactant in the form of a substituted ammonium salt.

The surfactant s ⁷ is preferably an ammonium salt in which one or more hydrogen atoms bonded to a nitrogen atom are substituted with an alkyl group, an alkenyl group, or a POA chain having a terminal hydroxyl group, and the compound (s ⁷¹ ) is more preferable. preferable.
[(R ²¹ ) ₄ N ⁺ ] · X ⁻ (s ⁷¹ ).

R ²¹ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a POA chain having a terminal hydroxyl group.
The four R ²¹ may be the same or different, but the four R ²¹ are not hydrogen atoms at the same time.
R ²¹ is preferably a long-chain alkyl group having 6 to 22 carbon atoms, a long-chain alkenyl group having 6 to 22 carbon atoms, or a fluoroalkyl group having 1 to 9 carbon atoms.
When R ²¹ is an alkyl group other than a long-chain alkyl group, R ²¹ is preferably a methyl group or an ethyl group.
When R ²¹ is a POA chain having a hydroxyl group at the end, the POA chain is preferably a POE chain.

X ⁻ is a counter ion.
X ⁻ is preferably a chlorine ion, an ethyl sulfate ion, or an acetate ion.

Examples of the compound (s ⁷¹ ) include monostearyl trimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono (stearyl) monomethyldi (polyethylene glycol) ammonium chloride, monofluorohexyltrimethylammonium chloride, di (tallow alkyl) dimethylammonium. Examples include chloride and dimethyl monococonut amine acetate.

Surfactant s ⁸ :
When the surfactant contains an amphoteric surfactant, the amphoteric surfactant, surfactant s ⁸ is preferred.
Surfactant s ⁸ is alanine compounds, imidazolinium betaines, amide betaines or betaine acetate.

The hydrophobic group is preferably a long chain alkyl group having 6 to 22 carbon atoms, a long chain alkenyl group having 6 to 22 carbon atoms, or a fluoroalkyl group having 1 to 9 carbon atoms.
Surfactant s ^8, dodecyl betaine, stearyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolinium betaine, dodecyl dimethylamino betaine, such as fatty acid amidopropyl dimethylamino acetic acid betaine.

Surfactant s ⁹ :
As surfactants, it may be used a surfactant s ^9.
Surfactant s ⁹ is a block copolymer, random copolymer, or hydrophilic copolymer of a hydrophilic monomer and a hydrocarbon-based hydrophobic monomer and / or a fluorine-based hydrophobic monomer. It is a polymer surfactant comprising a hydrophobic modified product.

Surfactant s ^9, a block or random copolymer derived from polyethylene glycol (meth) acrylate with a long chain alkyl acrylate, a block or random copolymer derived from polyethylene glycol (meth) acrylate and fluoro (meth) acrylate, acetate Block or random copolymer of vinyl and long chain alkyl vinyl ether, block or random copolymer of vinyl acetate and long chain alkyl vinyl ester, polymer of styrene and maleic anhydride, condensation of polyvinyl alcohol and stearic acid Products, condensation products of polyvinyl alcohol and stearyl mercaptan, condensation products of polyallylamine and stearic acid, condensation products of polyethyleneimine and stearyl alcohol, methyl cellulose, hydroxypropyl methylcellulose And hydroxyethyl methylcellulose.

Commercially available surfactant s ⁹ includes Kuraray's MP polymer (product numbers: MP-103, MP-203), Elf Atchem's SMA resin, Shin-Etsu Chemical's Metros, Nippon Shokubai's Epomin RP, and Seimi Chemical. The company's Surflon (product number: S-381, S-393), etc. are mentioned.

Surfactant s ^9, when the medium is often a mixing ratio in the case of an organic solvent or an organic solvent, is preferably surfactant s ^91.
Surfactant s ⁹¹ : a polymer surfactant comprising a block copolymer or a random copolymer (modified polyfluoroalkyl thereof) of a lipophilic monomer and a fluorine monomer.

Surfactant s ⁹¹ includes a copolymer of alkyl acrylate and fluoro (meth) acrylate, a copolymer of alkyl vinyl ether and fluoroalkyl vinyl ether, and the like.
Examples of a commercial product of surfactant ^{s 91,} Seimi Chemical Co. of Surflon (item code: S-383, SC-100 series) and the like.

As a combination of the surfactants, the surfactant s ¹ and the surfactant s ² are interfaced with the surfactant s ^{1 in} terms of the water repellency and the excellent water repellency and durability of the oil-repellent composition and the stability of the obtained emulsion. Combination with surfactant s ⁷ or combination of surfactant s ¹ , surfactant s ³ and surfactant s ⁷ , or surfactant s ¹ , surfactant s ² , surfactant s ³ and interface A combination with the active agent s ⁷ is preferable, and the above combination in which the surfactant s ⁷ is the compound (s ⁷¹ ) is more preferable.
As for the total amount of surfactant, 1-6 mass parts is more preferable with respect to a copolymer (100 mass parts).

<Polymer (C)>
The polymer (C) is a copolymer having a structural unit based on the monomer (a) and a structural unit based on the monomer (d).

[Monomer (a)]
The monomer (a) has an R ^f group having 4 to 6 carbon atoms to which fluorine atoms are bonded (however, the R ^f group may contain an etheric oxygen atom). It is a monomer.
Examples of the monomer (a) include those similar to the monomer (a) constituting the polymer (A) (for example, the compound (1)).

The compound (1) has a carbon number from the viewpoints of polymerizability with other monomers, flexibility of the polymer film, adhesion of the polymer to the article, solubility in the medium, ease of polymerization, and the like. having 4-6 ^{R F} group (meth) acrylate.
As the compound (1), Z is an ^{R F} group having 4 to 6 carbon atoms, Y is an alkylene group having 1 to 4 carbon atoms, n is 1, X is a group (3-3) Compounds are preferred.

[Monomer (d)]
The monomer (d) does not have a polyfluoroalkyl group, and has at least one group selected from the group consisting of an alkylene oxide group, an amino group, a hydroxy group, an acrylamide group, a carboxy group, a phosphoric acid group, and a sulfone group. It has a monomer. The amino group may be substituted with a hydrogen atom. These groups are all hydrophilic groups. Groups that can exist as a salt may form a salt.
The monomer (d) can impart an antifouling property (stain removal property by water washing) to the polymer (C). The monomer (d) is more preferably a (meth) acrylate having the above hydrophilic group.
Of the hydrophilic groups listed above, an alkylene oxide group, a hydroxy group, a carboxy group or an amino group is preferable, and an alkylene oxide group or an amino group is particularly preferable.

[Monomer (d ′)]
The monomer (d) is preferably a monomer (d ′) having an alkylene oxide group as a hydrophilic group. That is, it is preferable that the polymer (C) has a structural unit based on the monomer (d ′) having an alkylene oxide group without having a polyfluoroalkyl group.
As the alkylene oxide group, an ethylene oxide group (—C ₂ H ₄ O—), a propylene group (—C ₃ H ₆ O—), and a tetramethylene oxide group (—C ₄ H ₈ O—) are preferable.
As the monomer (d ′) having an alkylene oxide group, a monomer (d1) in which the alkylene oxide group is an ethylene oxide group, or a monomer having an ethylene oxide group and a tetramethylene oxide group present in the same side chain ( d2) is preferred.

[Monomer (d1)]
The monomer (d1) is a monomer which does not have a polyfluoroalkyl group but has an alkylene oxide group, and the alkylene oxide group is an ethylene oxide group, and is preferably the compound (2).
^{_{CH 2 = CR 1 -G 1 -}} (C 2 H 4 O) q1 -R 2 ... (2).
R ¹ and R ² in the formula are each independently a hydrogen atom or a methyl group, preferably a methyl group. q1 is an integer of 1-50, and 2-20 are preferable. G ¹ is —COO (CH ₂ ) _r1 — or —COO (CH ₂ ) _t1 —NHCOO— (wherein r1 is an integer of 0 to 4, t1 is an integer of 1 to 4), and —COO (CH ₂ ) _r1 -(R1 is an integer of 0 to 4) is preferable.

As the monomer (d1), polyethylene oxide monoacrylate (CH ₂ ═CHCOO (EO) _q1 H), polyethylene oxide monomethacrylate (CH ₂ ═C (CH ₃ ) COO (EO) _q1 H), methoxypolyethylene oxide mono acrylate _{(CH 2 = CHCOO (EO)} q1 CH 3), methoxypolyethylene oxide monomethacrylate _{(CH 2 = C (CH 3} ) COO (EO) q1 CH 3) are preferred, methoxy polyethylene oxide methacrylate is more preferable.

[Monomer (d2)]
The monomer (d2) has an ethylene oxide group and a tetramethylene oxide group present in the same side chain. The monomer (d2) may have a hydrophilic group (excluding an amino group) other than the ethylene oxide group and the tetramethylene oxide group present in the same side chain. The alkylene oxide group in the monomer (d2) is preferably composed of an ethylene oxide group and a tetramethylene oxide group present in the same side chain.
The monomer (d2) is preferably compound (3).
_{^{CH 2 = CR 3 -G 2 -}} (C 2 H 4 O) q2 - (C 4 H 8 O) q3 -R 4 ... (3).
In the formula, R ³ and R ⁴ are each independently a hydrogen atom or a methyl group. R ³ is preferably a methyl group, and R ⁴ is preferably a hydrogen atom. q2 is an integer of 1 to 50, preferably 2 to 20. q3 is an integer of 1 to 50, preferably 2 to 20. G ² is —COO (CH ₂ ) _{r 2} — or —COO (CH ₂ ) _{t 2} —NHCOO— (wherein r ₂ is an integer of 0 to 4, and t 2 is an integer of 1 to 4), and —COO (CH ₂ ) _{r 2} -(R2 is an integer of 0 to 4) is preferable.

In the monomer (d2), an ethylene oxide group (—C ₂ H ₄ O—, hereinafter sometimes referred to as EO) and a tetramethylene oxide group (—C ₄ H ₈ O—, hereinafter referred to as TO) The copolymer chain may be a random copolymer chain or a block copolymer chain.

As the monomer (d2), poly (ethylene oxide - tetramethylene oxide) monoacrylate _{(CH 2 = CHCOO - [(} EO) q2 - (TO) q3] -H), poly (ethylene oxide - tetramethylene oxide) Monometa acrylate _{(CH 2 = C (CH 3} ) COO - [(EO) q2 - (TO) q3] -H), methoxy poly (ethylene oxide - tetramethylene oxide) monoacrylate _{(CH 2 = CHCOO - [(} EO) q2 - ( _TO) q3] _{-CH 3),} methoxy poly (ethylene oxide - tetramethylene oxide) monomethacrylate _{(CH 2 = C (CH 3} ) COO - [(EO) q2 - (TO) q3] -CH 3), polytetramethylene oxide monoacrylate _{(CH 2 = CHCOO- (TO)} q3 H), polytetramethylene oxide methacrylate _{(CH 2 = C (CH 3} ) COO- (TO) q3 -H), methoxy polytetramethylene oxide monoacrylate _{(CH 2 = CHCOO- (TO)} q3 -CH 3), methoxy polytetramethylene oxide monomethacrylate _{(CH 2 = C (CH 3} ) COO- (TO) q3 -CH 3) is preferably a poly (ethylene oxide - tetramethylene oxide) monomethacrylate is more preferable.

[Monomer (d3)]
As the monomer (d), a monomer (d3) having no polyfluoroalkyl group and having an amino group (a hydrogen atom may be substituted) is also preferred. The monomer (d3) is preferably compound (4-1) or compound (4-2).
^{_{CH 2 = CR 5 -M-Q}} -NR 6 R 7 ... (4-1).
^{_{CH 2 = CR 5 -M-Q}} -N (O) R 6 R 7 ... (4-2).
In the formula, R ⁵ is a hydrogen atom or a methyl group, M is —COO— (ester bond) or —CONH— (amide bond), and Q is an alkylene group having 2 to 4 carbon atoms or a part of a hydrogen atom. Or an alkylene group having 2 to 3 carbon atoms, all of which are substituted with hydroxyl groups, and R ⁶ and R ⁷ are each independently a benzyl group, an alkyl group having 1 to 8 carbon atoms or a part of hydrogen atoms substituted with hydroxyl groups. And an alkyl group having 2 to 3 carbon atoms. R ⁶ , R ⁷ and the nitrogen atom may form a piperidino group or pyrrolidinyl group, and R ⁶ , R ⁷ , the oxygen atom and the nitrogen atom may form a morpholino group.
M is preferably —COO— (ester bond), Q is preferably an alkylene group having 2 to 4 carbon atoms, and R ⁶ and R ⁷ are preferably alkyl groups having 1 to 4 carbon atoms.

  As the monomer (d3), N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (Meth) acrylate, N, N-diisopropylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpepyridine, N, N- Dimethylaminooxide ethyl (meth) acrylate and N, N-diethylaminooxide ethyl (meth) acrylate are preferred, and N, N-dimethylaminoethyl methacrylate is more preferred.

In the polymer (C), it is preferable to use the monomer (d1) and the monomer (d2) in combination as the monomer (d). Furthermore, the monomer (d1) The body (d2) and the monomer (d3) are preferably used in combination.
In particular, by using a combination of the monomer (d1) and the monomer (d2), when only the monomer (d1) is used, or a single unit often used for conventional fluorine-based antifouling agents. Compared to the case where the monomer (d1) and a monomer containing a propylene oxide chain in the side chain are used in combination, the washing durability is improved, and the water / oil repellency and antifouling property are also improved. This is presumably because the use of the structural unit (d2) containing TO effectively improves the adhesion of the water-repellent oil-repellent antifouling agent composition to the substrate. The reason is that the monomer containing EO and TO has a lower Tg (glass transition point) than the monomer containing only EO and the monomer containing only propylene oxide, and as a result, the Tg of the polymer (C) is This is considered to be because the film forming property is further improved. Further, since the monomer (d2) containing EO and TO is more hydrophobic and oleophobic than the monomer containing propylene oxide, it is considered that water repellency does not inhibit the oil repellency.
Furthermore, by including a monomer (d3), it contributes to the improvement of the dispersibility to an aqueous medium. When the dispersibility in an aqueous medium is good, water repellency can suppress the content of the volatile organic solvent in the oil-repellent antifouling agent composition, which is environmentally preferable. In addition, due to the amino group of the monomer (d3), the polymer (C) has a cationic property, and the uniform adhesion to a fiber base material having a weak anionic surface charge is also improved.

[Monomer (e)]
The polymer (C) may further have a monomer (e) having no ^Rf group and having a functional group capable of crosslinking. When the polymer (C) has a structural unit based on the monomer (e), the washing durability is further improved.
Examples of the monomer (e) include the same monomers (e) that constitute the polymer (A).

[Other monomer (f)]
The polymer (C) may have a structural unit based on the monomer (f) other than the monomers (a), (d), and (e). The polymer (C) does not have the monomers (b) and (c).
Examples of the monomer (f) include the same monomer (f) as that in the polymer (A).

[Terminal anionic group]
The polymer (C) preferably has an anionic group at the end of the main chain. The main chain of the polymer (C) means an atomic chain formed by cleavage of the polymerizable unsaturated group of the monomer.
The amount of the anionic group present in the polymer (C) is preferably 0.1% by mass or more when the polymer (C) is 100% by mass in order to sufficiently obtain the effect of the anionic group. 3 mass% or more is more preferable. The upper limit of the amount of the anionic group is preferably determined in consideration of the ionic balance in the polymer (C). For example, 3.0 mass% or less is preferable and 2.0 mass% or less is more preferable.

The anionic group in the present invention is a group that can be ionized in water to become an anion, specifically, from the group consisting of a carboxy group, a sulfonic acid group, a phosphoric acid group, a chloric acid group, a nitric acid group, and a manganic acid group. One or more selected acid groups are preferred. A carboxy group is particularly preferable. These acid groups may form a salt or an ester. Two or more kinds of anionic groups may be present in one molecule of the polymer (C).
The method for introducing an anionic group at the end of the main chain of the polymer (C) is not particularly limited. A simple method includes a method of using a polymerization initiator having an anionic group and / or a chain transfer agent having an anionic group when the monomers are copolymerized. The anionic group contained in the polymerization initiator and / or chain transfer agent is preferably a carboxy group (which may form a salt or an ester) that is weakly acidic in view of acidity.
As the polymerization initiator having an anionic group, azo compounds having a carboxy group such as 4,4′-azobis (4-cyanovaleric acid), disuccinic acid peroxide, persulfate and the like are preferable. Among these, an azo compound having a carboxy group is more preferable, and 4,4′-azobis (4-cyanovaleric acid) is particularly preferable.
As the chain transfer agent having an anionic group, 3,3′-dithio-dipropionic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioglycolic acid and the like are preferable. Of these, 3-mercaptopropionic acid having a carboxy group is more preferable.

In particular, when the polymer (C) has a structural unit based on the monomer (d3), it preferably has an anionic group at the end of the main chain.
When a polymer (C) having a structural unit based on a monomer (d3) having an amino group is introduced, dispersibility of the polymer (C) in an aqueous medium and uniform adhesion to a fiber substrate can be obtained. improves. On the other hand, since an amino group is cationic, it easily adsorbs dirt components, and as a result, there is a tendency to reduce dirt removability (SR property). On the other hand, it is thought that by introducing an anionic group at the end of the main chain of the polymer (C), it is possible to suppress the adsorption of the soil component and improve the soil removability (SR property).
In addition, when a cross-linking agent having strong reactivity with a carboxy group is used in combination, the cross-linking site becomes the end of the main chain, so that the fluidity of the main chain is not hindered and the molecular mobility necessary for dirt removal is maintained. As a result, it is possible to achieve both good dirt removal performance and washing durability.

[Production Method of Polymer (C)]
The polymer (C) can be produced, for example, by the following method.
The polymer (C) is a monomer component (a) containing monomers (a) and (d) and optionally monomers (e) and (f) in a polymerization solvent using a known method. It is obtained by carrying out the polymerization reaction of Z).
As a polymerization solvent, the organic solvent mentioned as a medium used for manufacture of the said polymer (A) can be used. For example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone: alcohols such as methanol and 2-propyl alcohol; esters such as ethyl acetate and butyl acetate; ethers such as diisopropyl ether, tetrahydrofuran and dioxane; ethylene glycol and propylene Glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, or glycol ethers such as ethyl ether or methyl ether of dipropylene glycol and derivatives thereof, aliphatic hydrocarbons; aromatic hydrocarbons; perchloroethylene, trichloro-1 , 1,1-ethane, trichlorotrifluoroethane, dichloropentafluoropropane and the like halogenated hydrocarbons; dimethylformamide; N-methyl-2- Pyrrolidone; Buchiroaseton; dimethyl sulfoxide (DMSO) and the like are preferably used. Two or more polymerization solvents may be mixed and used.

In the polymerization reaction for obtaining the polymer (C), it is preferable to use a polymerization initiator. As the polymerization initiator, peroxides such as benzyl peroxide, lauryl peroxide, succinyl peroxide, tert-butyl perpivalate; azo compounds and the like are preferable. The concentration of the polymerization initiator in the solvent is preferably 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the monomer component (Z).
Specific examples of the polymerization initiator include 2,2′-azobis-2-methylbutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis [2- (2-imidazoline- 2-yl) propane], 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis (2cyclohexane-1-carbonitrile), 2,2′-azobis (2 4-dimethylvaleronitrile), 1,1′-azobis (1-acetoxy-1-phenylethane), dimethylazobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid) and the like are preferable.
Since 4,4′-azobis (4-cyanovaleric acid) has a carboxy group that can be an anionic group, anionicity can be introduced at the end of the main chain by using this as a polymerization initiator.

In order to adjust the degree of polymerization (molecular weight) of the polymer (C), it is preferable to use a chain transfer agent in the polymerization reaction. By using a chain transfer agent, there is also an effect of increasing the total concentration of monomers in the solvent. Examples of chain transfer agents include alkyl mercaptans such as tert-dodecyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan; aminoethanethiol, mercaptoethanol, 3-mercaptopropionic acid, 2-mercaptopropionic acid, thiomalic acid, thioglycolic acid, 3 , 3'-dithio-dipropionic acid, 2-ethylhexyl thioglycolate, n-butyl thioglycolate, methoxybutyl thioglycolate, ethyl thioglycolate, 2,4-diphenyl-4-methyl-1-pentene, four Carbon chloride and the like are preferable.
Among these, 3-mercaptopropionic acid, 2-mercaptopropionic acid, thiomalic acid, thioglycolic acid, and 3,3′-dithio-dipropionic acid are preferable because they have a carboxy group that can be an anionic group. 3-mercaptopropionic acid is particularly preferred. As for the usage-amount of a chain transfer agent, 0-2 mass parts is preferable with respect to 100 mass parts of monomer components (Z).

  The reaction temperature in the polymerization reaction is preferably in the range from room temperature to the boiling point of the reaction mixture. From the viewpoint of efficiently using the polymerization initiator, the vicinity of the half-life temperature of the polymerization initiator is preferable, and 30 to 90 ° C is more preferable.

When the water-repellent oil-repellent antifouling agent composition of the present invention is an aqueous dispersion in which the polymers (A) to (C) are dispersed in an aqueous medium, after the polymerization reaction of the polymer (C), An aqueous medium is added, and the polymerization solvent is removed as necessary. The polymerization solvent is removed by, for example, a stripping process. In addition, a small amount of an aqueous antifoaming agent may be used in order to shorten time efficiency in the step of performing the stripping process.
The aqueous medium in this specification means a liquid containing water and having a volatile organic solvent content of 1% by mass or less. Specifically, water or an azeotrope containing water is preferable.
When the water-repellent oil-repellent antifouling agent composition of the present invention is an aqueous dispersion, the content of the volatile organic solvent is preferably 1% by mass or less, and most preferably zero. In the present specification, the volatile organic solvent in the water-repellent oil-fouling antifouling agent composition means an organic solvent that volatilizes when the water-repellent oil-fouling antifouling agent composition is stored at room temperature. Specifically, it is an organic solvent having a boiling point at 1 × 10 ⁵ Pa (hereinafter simply referred to as “boiling point”) of 100 ° C. or less. Does not include dipropylene glycol or tripropylene glycol, which are high-boiling solvents. Note that the solvent that forms an azeotrope with water is not included in the volatile organic solvent.

  In order to disperse the polymer (C) in an aqueous medium, the polymer (C) preferably contains a structural unit having an amino group. As the polymerization solvent, from the viewpoint of good workability of the treatment after the polymerization reaction, an azeotropic composition with a solvent having a relatively low boiling point (for example, a boiling point of 80 ° C. or lower) or water among the polymerization solvents listed above. It is preferable to use a solvent having Examples of the solvent having a relatively low boiling point include acetone and methanol. Examples of the solvent having an azeotropic composition with water include methyl ethyl ketone, methyl isobutyl ketone, 2-propyl alcohol, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether. Acetone is more preferred.

When the polymer (c) contains a structural unit having an amino group, it is preferable to obtain the polymer (C) by a polymerization reaction of the monomer and then amine-treat the amino group in the polymer (C). . This improves the dispersibility of the polymer (C) in an aqueous medium.
An acid or the like is preferably used for amine chloride, and an acid having a dissociation constant or primary dissociation constant of 10 ⁻⁵ or more is more preferable. As the acid, hydrochloric acid, hydrobromic acid, sulfonic acid, nitric acid, phosphoric acid, acetic acid, formic acid, propionic acid, lactic acid and the like are preferable, and acetic acid is more preferable.
Further, instead of amine-treating the amino group of the polymer (C) with an acid, methyl iodide, ethyl iodide, dimethyl sulfate, diethyl sulfate, benzyl chloride, trityl phosphate, methyl p-toluene sulfonate, etc. are used. May be converted into a quaternary ammonium salt (also referred to as quaternary chloride).

The proportion of the monomer (a) is preferably 30 to 70% by mass, and preferably 40 to 60% by mass in the monomer component (Z) (100% by mass) from the viewpoint of water repellency and oil repellency and antifouling properties. Is more preferable.
The proportion of the monomer (d) is preferably 30 to 70% by mass, and 40 to 60% by mass in the monomer component (Z) (100% by mass) from the viewpoint of water repellency and oil repellency and antifouling properties. Is more preferable.
The proportion of the monomer (e) is preferably 0 to 5% by mass in the monomer component (Z) (100% by mass) from the viewpoint of water repellency and oil durability and washing durability, and 0.5 to 4%. The mass% is more preferable.

When the monomer (d) is composed of the monomer (d1) and the monomer (d2), the ratio of the monomer (d1) is the monomer component (Z) from the viewpoint of antifouling properties. In (100 mass%), 15-40 mass% is preferable and 20-35 mass% is more preferable.
The proportion of the monomer (d2) is preferably 15 to 30% by mass and more preferably 8 to 25% by mass in the monomer component (Z) (100% by mass) from the viewpoint of washing durability and antifouling properties. preferable.

When the monomer (d) is composed of the monomer (d1), the monomer (d2), and the monomer (d3), the ratio of the monomer (d1) is the point of antifouling property. Therefore, in the monomer component (Z) (100% by mass), 15 to 40% by mass is preferable, and 20 to 35% by mass is more preferable.
The proportion of the monomer (d2) is preferably 5 to 30% by mass and more preferably 10 to 20% by mass in the monomer component (Z) (100% by mass) from the viewpoint of washing durability and antifouling property. preferable.
The proportion of the monomer (d3) is preferably 0.5 to 6% by mass in the monomer component (Z) (100% by mass) from the viewpoint of dispersion stability and uniform adsorptivity to the substrate. 1-5 mass% is more preferable.

3000-30000 is preferable and, as for the number average molecular weight by GPC of a polymer (C), 6000-20000 is more preferable. The mass average molecular weight is preferably from 6000 to 60000, more preferably from 10000 to 40000.
When the molecular weight of the polymer (C) is not more than the upper limit of the above range, the dispersion stability is excellent, and when it is not less than the lower limit, the water repellency is excellent in oil repellency and adhesion to the substrate.

[Preparation of water-repellent oil-repellent antifouling agent composition]
The water-repellent oil-repellent antifouling agent composition of the present invention comprises, for example, a polymer (A) emulsion, a polymer (B) emulsion, and an aqueous dispersion of the polymer (C) at a predetermined ratio. It can be prepared by mixing.
It is preferable that at least one or more of the polymer (A), the polymer (B), and the polymer (C) to be mixed have a structural unit based on the monomer (e).
The mass ratio ((A) / (B)) of the polymer (A) (solid content) and the polymer (B) (solid content) is from the viewpoint of water repellency, oil repellency, antifouling properties and washing durability. 10/90 to 95/5 are preferable, and 10/90 to 70/30 are preferable.
Ratio of the total mass of the polymer (A) (solid content) and the polymer (B) (solid content) to the mass of the polymer (C) (solid content) ({(A) + (B)} / (C)) is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, from the viewpoint of water repellency and oil repellency.

The water-repellent oil repellent antifouling agent composition thus obtained can be used as a treatment liquid applied to the processing of the article as it is. Alternatively, the water-repellent oil-repellent antifouling agent composition diluted to an appropriate solid content concentration may be applied to the article.
The solid content concentration of the water-repellent oil-repellent antifouling agent composition (100% by mass) when applied to the processing of the article is preferably 0.2 to 5% by mass, and more preferably 0.5 to 3% by mass.
The solid content concentration in the emulsion, aqueous dispersion, or water repellent oil composition is calculated from the mass before heating and the mass after drying for 4 hours in a convection dryer at 120 ° C.

The water-repellent oil-repellent antifouling agent composition may contain a crosslinking agent, a catalyst and the like for improving the adhesion to the substrate by crosslinking with the substrate.
The crosslinking agent is preferably at least one crosslinking agent selected from the group consisting of isocyanate crosslinking agents, melamine crosslinking agents, carbodiimide crosslinking agents, and oxazoline crosslinking agents.
Specific examples of the isocyanate crosslinking agent include an aromatic block type isocyanate crosslinking agent, an aliphatic block type isocyanate crosslinking agent, an aromatic nonblocking isocyanate crosslinking agent, and an aliphatic nonblocking isocyanate crosslinking agent. It is done. These isocyanate-based crosslinking agents are preferably a water dispersion type emulsified with a surfactant or a self-water dispersion type having a hydrophilic group.
Specific examples of melamine-based crosslinking agents include condensates or precondensates of urea or melamine formaldehyde, methylol-dihydroxyethylene-urea and derivatives thereof, uron, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, dicyandiamide -Formaldehyde condensates, methylol-carbamates, methylol- (meth) acrylamides, and polymers thereof.
The carbodiimide-based crosslinking agent is a polymer having a carbodiimide group in the molecule, and the base material or the water repellent is a crosslinking agent having excellent reactivity with the carboxy group, amino group and active hydrogen group in the oil-repellent antifouling agent. is there.
The oxazoline-based cross-linking agent is a polymer having an oxazoline group in the molecule, and the base material or the water repellent is a cross-linking agent exhibiting excellent reactivity with the carboxy group in the oil-repellent antifouling agent.
Other crosslinking agents include divinylsulfone, polyamide and its cation derivative, epoxy derivatives such as diglycidylglycerol, (epoxy-2,3-propyl) trimethylammonium chloride, N-methyl-N- (epoxy-2, 3-propyl) morpholinium chloride halide derivatives, ethylene glycol chloromethyl ether pyridinium salts, polyamine-polyamide-epichlorohydrin resins, polyvinyl alcohol or derivatives thereof, polyacrylamide or derivatives thereof, glyoxal resin anti-wrinkle agents, etc. Can be mentioned.

  When the water-repellent oil-repellent antifouling agent composition contains a melamine-based crosslinking agent or glyoxal resin-based anti-wrinkle agent, it is preferable to contain a catalyst. Preferred catalysts include inorganic amine salts and organic amine salts. Examples of inorganic amine salts include ammonium chloride. Examples of the organic amine salts include amino alcohol hydrochloride and semicarbazide hydrochloride. Examples of amino alcohol hydrochloride include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanol hydrochloride, 2-amino-2-methylpropanol hydrochloride and the like.

  The water repellent and oil repellent antifouling agent composition may contain various known additives. Examples of the additive include fluorine polymers not included in the present invention, non-fluorine polymer blenders, water-soluble polymer resins (for example, hydrophilic polyester and derivatives thereof, or hydrophilic polyethylene glycol and derivatives thereof), penetration Agents (for example, nonionic surfactants having an acetylene group in the center and a symmetrical structure), antifoaming agents, film-forming aids, insecticides, flame retardants, antistatic agents, anti-wrinkle agents, softening agents , PH adjusting agents and the like.

<Article>
The article of the present invention is an article treated with the water-repellent oil-repellent antifouling agent composition of the present invention.
Examples of articles treated with the water-repellent oil-repellent antifouling agent composition of the present invention include fibers, fiber fabrics, fiber knitted fabrics, nonwoven fabrics, glass, paper, wood, leather, artificial leather, stone, concrete, and ceramics. , Metals and metal oxides, ceramic products, plastics and the like.
The treatment method is not particularly limited as long as it is a method capable of adhering the water-repellent oil-repellent antifouling agent composition to the article. For example, a method of attaching to the surface of the substrate and drying by a known coating method such as coating, impregnation, dipping, spraying, brushing, padding, size press, or roller is preferable. Drying may be performed at room temperature or heated, and is preferably heated. When heating, about 40-200 degreeC is preferable. Further, when the water-repellent oil-repellent antifouling agent composition contains a crosslinking agent, it is preferable to carry out curing by heating to a crosslinking temperature or higher of the crosslinking agent, if necessary.

According to the present invention, a polymer (A) having a specific structural unit and a small proportion of fluorine atoms, a polymer (B) having a specific structural unit and a large proportion of fluorine atoms, By blending the polymer (C) having a hydrophilic group, an excellent water repellency can impart both oil repellency and antifouling property to the surface of the article while the R ^f group in the composition is a short chain. A water-repellent oil-repellent antifouling agent composition is obtained.

Further, the article of the present invention has a water-repellent oil-repellent antifouling agent composition that can impart both excellent water-repellent and antifouling properties to the surface of the article while the ^Rf group in the composition is a short chain. Since the product is used, the environmental load is low, and good water repellency has oil repellency and antifouling properties.
Moreover, since the water-repellent oil-repellent antifouling agent composition of the present invention is mainly composed of a polymer having a structural unit based on a monomer having a polyfluoroalkyl group having 4 to 6 carbon atoms, The content of perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and their derivatives, which are concerned about the influence on the environment, can be made lower than the detection lower limit.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In the following, “%” is “% by mass” unless otherwise specified. Further, in the chemical formula representing a compound containing an alkylene oxide chain, the value of the alkylene oxide chain length is an average value.
In the present invention, the value of the proportion of fluorine atoms in each of the polymers (A) and (B) is a measured value obtained by the above-described measuring method. The calculated value was used. It was also confirmed that the error between the measured value and the calculated value was within ± 1%.

The performance evaluation was performed by the following method.
[Preparation of test cloth: Treatment method for base cloth]
After dipping the base fabric (unprocessed fabric) in 150 g of the treatment liquid (water repellent oil-repellent antifouling agent composition) obtained in each of the following examples, the substrate is squeezed with a mangle and the wet pickup is 60 to 90%. did. Next, it was dried at 110 ° C. for 90 seconds, and further subjected to curing heat treatment at 170 ° C. for 60 seconds to obtain a test cloth.
As the base fabric (unprocessed fabric), (1) a tropical fabric made of undyed polyester (hereinafter referred to as PET), and (2) a broad fabric in which undyed polyester / cotton is blended at a ratio of 65/35 ( (Hereinafter referred to as TC) and (3) broad cloth (hereinafter referred to as C) made of 100% undyed cotton was used.

[Evaluation method of water repellency: water repellency grade (WR)]
About the test cloth created by said method, the water repellency was evaluated in accordance with the spray method described in JIS L1092-98 6.2. The water repellency was represented by the grade shown in Table 1. The larger the water repellency rating, the higher the water repellency. However, those with + (−) in the water repellency grade indicate that the respective properties are slightly good (bad). Hereinafter, this water repellency rating is indicated as “WR”.

[Evaluation method of oil repellency: Oil repellency grade (OR)]
About the test cloth produced by said method, the oil repellency was evaluated by AATCC standard-TM118 method, and it represented with the oil repellency grade shown in Table 2. This oil repellency grade is based on the wettability of the eight types of hydrocarbon solvents (test solutions) having different surface tensions to the cloth. This indicates that the greater the oil repellency grade, the higher the oil repellency. However, those marked with + (−) in the oil repellency class indicate that the respective properties are slightly good (bad). Hereinafter, this oil repellency grade is indicated as “OR”.

[Evaluation method of dirt removal property (SR property)]
About the test cloth produced by said method, the stain | pollution | contamination removal property according to AATCC specification-TM130 method was evaluated. The specific evaluation method is as follows. Spread the test cloth on the blotting paper laid horizontally, drop 5 drops (about 0.2 ml) of the following two types of stains, and apply 7.6 cm x 7.6 cm glassine paper on top, Further, a 2.27 kg weight was placed thereon, and after 60 seconds, the weight and glassine paper were removed. After leaving at room temperature for 20 minutes, a ballast cloth was added to the test cloth to make 1.8 kg, and washing was performed at 100 g of AATCC standard detergent, a bath amount of 64 liters, and a bath temperature of 40 ° C. The soil removal property after washing was evaluated by the following method.
The determination was made by visually observing the degree of removal of the dirt liquid and using the grades shown in Table 3. The larger the grade, the higher the soil removal property. In addition, the thing which described + (-) to the grade of the removal degree of dirt liquid shows that each property is slightly good (bad).
The evaluation using a stain solution obtained by adding 0.1% by mass of carbon black to used engine oil as the stain solution in the above test is shown as “DMO” hereinafter. Evaluation using a soil solution obtained by adding 0.1% by mass of Sudan III (Solvent Red 23), which is an oily pigment, to corn oil is hereinafter referred to as “corn oil”.

[Washing durability]
Washing to confirm the durability was performed according to JIS 1092: 1998 5.2a) 3) method. Evaluation after washing was performed by air-drying the test cloth overnight in a constant temperature and humidity room at 25 ° C. and a humidity of 50 RH%. The evaluation results of those that have not been washed are shown in the "Initial" column, the evaluation results after repeating the same washing method 5 times are shown in the "HL5" column, and the evaluation after repeating the same washing method 20 times The results are shown in the “HL20” column.

<Synthesis Examples 1-5>
Polymers A to C were synthesized with the monomer composition (unit: parts by mass) shown in Table 4. Abbreviations of monomers in Table 4 represent the following compounds, respectively.
Monomer (a):
_{· C6FMA: C 6 F 13 C} 2 H 4 OCOC (CH 3) = CH 2 ( purity 99.7 wt%).
Monomer (b):
VMA: behenyl methacrylate.
STA: stearyl acrylate.
Monomer (c):
VCM: vinyl chloride.
Monomer (d1):
_{· MEO400M: CH 2 = C (} CH 3) COO (EO) 9 CH 3.
Monomer (d2):
_{· MEOTO800: CH 2 = C (} CH 3) COO - (- (EO) 10 - (TO) 5 -) - H (EO and TO are randomly contained.)
Monomer (d3):
DM: N, N-dimethylaminoethyl methacrylate.
Monomer (e):
Iso: 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl methacrylate (compound (5)).

The compounds used in the following synthesis examples are as follows.
Polymerization initiator:
ACP: 4,4′-azobis (4-cyanovaleric acid).
-VA-061A: 10 mass% aqueous solution of acetate of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA-061).
-2,2'-azobis (2-methylpropionate).
Chain transfer agent:
3MP: 3-mercaptopropionic acid.
StSH: Stearyl mercaptan.
DoSH: n-dodecyl mercaptan.

Surfactant s ¹ :
PEO-30: 10% by mass aqueous solution of polyoxyethylene oleyl ether (about 26 mol of ethylene oxide adduct).
Surfactant s ² :
AGE-10: 10 mass% aqueous solution of acetylene glycol ethylene oxide adduct (the number of moles of ethylene oxide addition is 10 mol).
Surfactant s ³ :
-EPO-40: 10 mass% aqueous solution of ethylene oxide propylene oxide polymer (the ratio of ethylene oxide is 40 mass%).
Surfactant s ⁷ :
ATMAC: 10% by mass aqueous solution of monostearyltrimethylammonium chloride.
Medium:
·acetone.
-Dipropylene glycol.
-Water: Ion exchange water.

[Synthesis Example 1: Synthesis of polymer (C) (SR-1)]
In a 100 mL glass container, 11.0 g (52 parts by mass) of C6FMA, 6.3 g (30 parts by mass) of MEO400M, 3.0 g (14 parts by mass) of MEOTO800, 0.6 g (3 parts by mass) of DM , 0.2 g (1 part by mass) of iso, 48.5 g of acetone, 0.2 g (1 part by mass) of ACP, and 0.1 g (0.5 part by mass) of 3MP were shaken under a nitrogen atmosphere. While performing polymerization at 65 ° C. for 20 hours, a pale yellow solution (polymer solution) having a solid content concentration of 30.4% by mass was obtained.
When the molecular weight of the obtained polymer was confirmed by GPC, the number-average molecular weight was 11,000 and the mass-average molecular weight was 24,000. Moreover, it was also confirmed by this measurement that there was no monomer-derived peak.
50 g of water and 0.26 g of acetic acid (1.5 times molar equivalent of DM) were added to 50 g of the resulting polymer solution, and the mixture was stirred for amine chloride treatment. Thereafter, acetone was removed at 60 ° C. under reduced pressure to obtain a pale yellow transparent aqueous dispersion, and then ion-exchanged water was added to adjust the solid content concentration to 20% by mass. When the obtained aqueous dispersion was measured by capillary gas chromatography, it was confirmed that the acetone content was 1% by mass or less.

[Synthesis Example 2: Synthesis of Polymer (C) (SR-2)]
In a 100 mL glass container, 13.5 g (54 parts by mass) of C6FMA, 6.5 g (26 parts by mass) of MEO400M, 3.7 g (15 parts by mass) of MEOTO800, 0.8 g (3 parts by mass) of DM , 0.5 g (2 parts by mass) of iso, 39.7 g of acetone as a polymerization solvent, 5.0 g of dipropylene glycol, 0.2 g (0.8 parts by mass) of ACP, and 0.15 g (0. 6 parts by mass) and polymerization was carried out at 65 ° C. for 15 hours while shaking in a nitrogen atmosphere to obtain a pale yellow solution (polymer solution) having a solid content concentration of 36.6% by mass.
When the molecular weight of the obtained polymer was confirmed by GPC, the number-average molecular weight was 14,000 and the mass-average molecular weight was 28,000. Moreover, it was also confirmed by this measurement that there was no monomer-derived peak.
The obtained polymer solution was treated in the same manner as in Synthesis Example 1 to obtain an aqueous dispersion having a solid concentration of 20% by mass. When the obtained aqueous dispersion was measured by capillary gas chromatography, it was confirmed that the acetone content was 1% by mass or less and the dipropylene glycol content was 4% by mass or less.

[Synthesis Example 3: Synthesis of Polymer (A) (WOR-1)]
In a glass beaker, 89.3 g (74 parts by mass) of C6FMA, 8.5 g (7 parts by mass) of STA, 4.8 g (4 parts by mass) of iso, 30.2 g of PEO-30, EPO-40 6.0 g, 6.0 g of ATMAC, 144.4 g of water, 36.2 g of dipropylene glycol, and 1.2 g of DoSH were added and heated at 60 ° C. for 30 minutes, and then a homomixer (manufactured by Nippon Seiki Seisakusho) , Biomixer) to obtain a mixed solution.
The obtained liquid mixture was processed at 40 MPa using a high-pressure emulsifier (manufactured by APV Lanier Co., Ltd., Minilab) while maintaining the temperature at 60 ° C. to obtain an emulsion. 300 g of the obtained emulsion was put in a stainless steel reaction vessel and cooled to 40 ° C. or lower. After adding 5.2 g of VA061A and replacing the gas phase with nitrogen, 18.1 g (15 parts by mass) of VCM was introduced, and the polymerization reaction was carried out at 60 ° C. for 15 hours with stirring to obtain a solid content concentration of 34.5. % Polymer emulsion was obtained. The proportion of fluorine atoms in this polymer solid (100% by mass) was 42.3% by mass.
Moreover, when the molecular weight of the obtained polymer was confirmed by GPC, it was number average molecular weight 16000 and mass average molecular weight 28000. Moreover, it was also confirmed by this measurement that there was no monomer-derived peak.

[Synthesis Example 4: Synthesis of Polymer (A) (WOR-2)]
In a glass beaker, 89.3 g (74 parts by mass) of C6FMA, 13.6 g (13 parts by mass) of STA, 4.8 g (4 parts by mass) of iso, 30.2 g of PEO-30, and EPO-40 Add 6.0 g, 6.0 g of ATMAC, 144.4 g of water, 36.2 g of dipropylene glycol, 1.2 g of DoSH, heat at 60 ° C. for 30 minutes, and then mix using a homomixer. A mixture was obtained.
The obtained mixed solution was treated at 40 MPa using a high-pressure emulsifier while maintaining the temperature at 60 ° C. to obtain an emulsion. 300 g of the obtained emulsion was put in a stainless steel reaction vessel and cooled to 40 ° C. or lower. After adding 5.2 g of VA061A and replacing the gas phase with nitrogen, 12.0 g (9 parts by mass) of VCM was introduced, and the polymerization reaction was carried out at 60 ° C. for 15 hours with stirring to obtain a solid content concentration of 34.7. % Polymer emulsion was obtained. The proportion of fluorine atoms in this polymer solid (100% by mass) was 42.3% by mass.
Moreover, when the molecular weight of the obtained polymer was confirmed by GPC, it was number average molecular weight 15000 and mass average molecular weight 27000. Moreover, it was also confirmed by this measurement that there was no monomer-derived peak.

[Synthesis Example 5: Polymer (B) (WOR-3)]
In a glass beaker, 98.6 g (90 parts by mass) of C6FMA, 5.5 g (5 parts by mass) of VMA, 32.8 g of AGE-10, 141.5 g of water, 11 g of dipropylene glycol, 0 of StSH 0.5 g was added and heated at 60 ° C. for 30 minutes, and then mixed using a homomixer to obtain a mixed solution.
The obtained mixed solution was treated at 40 MPa using a high-pressure emulsifier while maintaining the temperature at 60 ° C. to obtain an emulsion. 250 g of the obtained emulsion was put in a stainless steel reaction vessel, 0.3 g of 2,2′-azobis (2-methylpropionate) was added, and the mixture was cooled to 30 ° C. or lower. After replacing the gas phase with nitrogen, 5.5 g (5 parts by mass) of VCM was introduced, and the polymerization reaction was performed at 65 ° C. for 15 hours with stirring to obtain a polymer emulsion having a solid content concentration of 34.2% by mass. . The proportion of fluorine atoms in this polymer solid (100% by mass) was 51.5% by mass.
Moreover, when the molecular weight of the obtained polymer was confirmed by GPC, it was number average molecular weight 29000 and mass average molecular weight 65000. Moreover, it was also confirmed by this measurement that there was no monomer-derived peak.

[Examples and Comparative Examples]
An aqueous dispersion of the polymer (C) obtained in Synthesis Examples 1 and 2 above, an emulsion of the polymer (A) obtained in Synthesis Examples 3 and 4, and an emulsion of the polymer (B) obtained in Synthesis Example 5 The water-repellent oil-repellent antifouling agent composition was prepared using the combinations shown in the polymer compositions in Tables 5 to 8. To the water-repellent oil-repellent antifouling agent composition, a crosslinking agent shown in Tables 5 to 8 and, if necessary, a crosslinking catalyst were added in an addition amount (% by mass) shown in the table. Moreover, ion-exchange water was added as needed so that the solid content concentration of each polymer in the water-repellent oil-repellent antifouling agent composition (100% by mass) would be the concentration shown in Tables 5-8.
The crosslinking agents and crosslinking aids shown in Tables 5 to 8 are as follows.
Cross-linking agent:
M3: Melamine-based crosslinking agent, Becamine M-3 (product name), manufactured by Dainippon Ink & Chemicals, Inc.
TP10: Block type isocyanate-based crosslinking agent, Meikanate TP-10 (product name), manufactured by Meisei Chemical Industry Co., Ltd.
WEB: Block type isocyanate-based crosslinking agent, Meikanate WEB (product name), manufactured by Meisei Chemical Co., Ltd.
Cross-linking catalyst:
ACX: catalyst for melamine-based crosslinking agent M3, catalyst ACX (product name), manufactured by Dainippon Ink & Chemicals, Inc.
105: Non-blocking type isocyanate cross-linking agent, Aquanate 105 (product name), manufactured by Nippon Polyurethane Industry.
304: Non-blocking type isocyanate cross-linking agent, Vivijol 304 (product name), manufactured by Sumika Bayer Urethane Co., Ltd.
V02L2: Carbodiimide crosslinking agent, Carbodilite V02-L2 (product name), manufactured by Nisshinbo Industries, Inc.
WS700: Oxazoline-based crosslinking agent, Epocross WS-700 (product name), manufactured by Nippon Shokubai Co., Ltd.

Example 1
Of the aqueous dispersion of the polymer (SR-1) obtained in Synthesis Example 1, the emulsion of the polymer (WOR-1) obtained in Synthesis Example 3, and the polymer (WOR-3) obtained in Synthesis Example 5 The emulsion is mixed so that the solid content concentration of each polymer is the polymer composition (unit: mass%) shown in Table 5, and when the material of the test cloth is PET or TC, as a melamine-based crosslinking agent M3 was added to a concentration of 0.3% by mass, and ACX was added as a crosslinking aid to a concentration of 0.3% by mass. When the material of the test cloth was C, TP-10 was added as an isocyanate crosslinking agent so that the concentration became 1% by mass, and no crosslinking assistant was used.
The water-repellent oil repellant composition thus obtained was used to prepare a test cloth by the above method, and the water repellency, oil repellency and SR property were evaluated by the above evaluation methods. The results are shown in Table 5.

(Comparative Examples 1-3)
In Example 1, the polymer composition was changed as shown in Table 5 to prepare a water-repellent oil-repellent oil composition and evaluated in the same manner as in Example 1. The results are shown in Table 5.
In Comparative Examples 1 to 3, either the polymer (A) or the polymer (B) and the polymer (C) were used.

(Examples 2 to 4)
In Example 1, the polymer composition was changed as shown in Table 6 to prepare a water-repellent oil-repellent oil composition and evaluated in the same manner as in Example 1. The results are shown in Table 6.

(Example 5)
In Example 1, a polymer composition, a crosslinking agent and a catalyst were changed as shown in Table 6 to prepare a water-repellent oil-repellent oil composition.
That is, the solid content concentration of the polymer (SR-2) was 0.6% by mass, the solid content concentration of the polymer (WOR-1) was 0.5% by mass, and the solid content concentration of the polymer (WOR-3) was 0.5%. Contains 0.3% by mass of becamine M-3 as a melamine-based crosslinking agent, 0.3% by mass of ACX as a catalyst, 1% by mass of TP-10 as a block type isocyanate-based crosslinking agent, and ion-exchanged water A water-repellent oil repellent composition was prepared.
The water-repellent oil repellent composition thus obtained was evaluated in the same manner as in Example 1. However, in this example, only PET and TC were used as test cloths. The evaluation results are shown in Table 6.

(Example 6)
In Example 5, a water repellent oil-repellent composition was prepared in the same manner as in Example 5 except that the block type isocyanate-based crosslinking agent was changed to WEB, and evaluation was performed in the same manner as in Example 5. The results are shown in Table 6.

(Comparative Examples 4-6)
In Example 2, the polymer composition was changed as shown in Table 7 to prepare a water-repellent oil-repellent oil composition and evaluated in the same manner as in Example 2. The results are shown in Table 7.
In Comparative Examples 4 to 6, one of the polymer (A) and the polymer (B) and the polymer (C) were used.

(Comparative Example 7)
In Example 5, the polymer composition was changed as shown in Table 7 to prepare a water-repellent oil-repellent oil composition and evaluated in the same manner as in Example 5. The results are shown in Table 7.
In this example, the polymer (A) and the polymer (C) were used, and the polymer (B) was not used.

(Comparative Example 8)
In Example 6, the polymer composition was changed as shown in Table 7 to prepare a water-repellent oil-repellent oil composition and evaluated in the same manner as in Example 6. The results are shown in Table 7.
In this example, the polymer (A) and the polymer (C) were used, and the polymer (B) was not used.

(Example 7)
In Example 1, a water-repellent oil-repellent oil composition was prepared by changing the polymer composition, the crosslinking agent and the catalyst as shown in Table 8.
That is, the solid content concentration of the polymer (SR-2) was 0.6% by mass, the solid content concentration of the polymer (WOR-1) was 0.5% by mass, and the solid content concentration of the polymer (WOR-3) was 0.5%. A water-repellent oil repellent composition containing 10% by mass, 0.3% by mass of 105 as a non-blocking type isocyanate crosslinking agent, and ion-exchanged water was prepared.
The water-repellent oil repellent composition thus obtained was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 8.
(Example 8)
In Example 7, a water-repellent oil repellent composition was prepared in the same manner as in Example 7 except that the non-blocking type isocyanate crosslinking agent was changed to 304, and evaluation was performed in the same manner as in Example 7. The results are shown in Table 8.

Example 9
In Example 7, a water-repellent oil-repellent composition was prepared in the same manner as in Example 7 except that the crosslinking agent was changed to 1.0% by mass of V02L2, which is a carbodiimide-based crosslinking agent. And evaluated. The results are shown in Table 8.
(Example 10)
In Example 7, a water-repellent oil-repellent composition was prepared in the same manner as in Example 7 except that the crosslinking agent was changed to 1.0% by mass of WS700 which is an oxazoline-based crosslinking agent. And evaluated. The results are shown in Table 8.

From the results of Table 5, Example 1 using the polymers (A), (B), and (C) is Comparative Examples 1 to 1 that did not use either the polymer (A) or the polymer (B). Compared to 3, water repellency, oil repellency, and SR properties are all good. In particular, Comparative Examples 1 and 2 in which the polymer (B) was not used are inferior in SR property to Example 1. Moreover, the comparative example 3 which did not use a polymer (A) is inferior in washing durability compared with Example 1.
From the results of Tables 6 and 7, Example 2 using the polymers (A), (B), and (C) has good water repellency, oil repellency, and SR properties. In particular, compared with Example 2, Comparative Examples 4 and 5 in which the polymer (B) was not used were inferior in SR property, and Comparative Example 5 was also inferior in water repellency.
Further, compared to Example 2, Comparative Example 6 in which the polymer (A) was not used was slightly inferior in oil repellency, and in particular, the water repellency was greatly reduced with an increase in the number of washings.
In Example 5 using the polymers (A), (B), and (C), the water repellency, oil repellency, and SR properties were all better than those in Comparative Example 7 in which the polymer (B) was not used. It is.
In Example 6 using the polymers (A), (B), and (C), the water repellency, oil repellency, and SR properties were all better than those in Comparative Example 8 in which the polymer (B) was not used. It is.
Moreover, in Table 6, when Examples 2-4 are compared, in Example 3, 4 with a small content rate of a polymer (B), SR property tends to fall a little. Compared with Example 2, Example 5 using melamine-based crosslinking agent and isocyanate-based crosslinking agent TP-10 in combination as the crosslinking agent improved water repellency particularly when the test cloth was TC. In Example 6 in which a melamine-based crosslinking agent and an isocyanate-based crosslinking agent WEB are used in combination as the crosslinking agent, the oil repellency (OR) when the test cloth is TC is improved as compared with Example 2, and the test cloth is PET. There was a tendency for SR to be slightly inferior to corn oil.
In Table 8, in Examples 7 and 8 using a non-blocking type isocyanate crosslinking agent as a crosslinking agent, good washing durability and water repellency show oil repellency, but SR property tends to be slightly lowered. In Examples 9 and 10 in which a carbodiimide-based crosslinking agent or an oxazoline-based crosslinking agent was used as the crosslinking agent, good SR property was exhibited, but the water-repellent property of washing durability tended to decrease slightly.

It is a schematic block diagram which shows the apparatus used for the measurement of the ratio of the fluorine atom in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Oxygen cylinder 2 Flow meter 3 Water 3a Steam supply flask 4 Steam supply furnace 5 Thermometer 7 Quartz tube 8 Sample boat 9a Sample furnace 9b Decomposition furnace 10 Silica wool 11 Cooler 12 Triangle flask for absorption

Claims (9)

A structural unit based on the following monomer (a), a structural unit based on the following monomer (b), a structural unit based on the following monomer (c), and a polymer (A) (100 mass) %) Polymer (A) in which the proportion of fluorine atoms is 15% by mass or more and less than 45% by mass,
It has a structural unit based on the following monomer (a), a structural unit based on the following monomer (b), and a structural unit based on the following monomer (c), and the polymer (B) (100 mass) %)) Polymer having a fluorine atom ratio of 45% by mass or more, and a polymer having a structural unit based on the following monomer (a) and a structural unit based on the following monomer (d) Containing (C),
The mass ratio ((A) / (B)) between the polymer (A) and the polymer (B) is 10/90 to 95/5, and the polymer (A) and the polymer ( The mass ratio ({(A) + (B)} / (C)) of the total {(A) + (B)} of B) and the polymer (C) is 5/95 to 95/5. A water-repellent oil-repellent antifouling agent composition characterized by that.
Monomer (a): a polyfluoroalkyl group having 4 to 6 carbon atoms to which fluorine atoms are bonded (however, the polyfluoroalkyl group may contain an etheric oxygen atom). Having monomer.
Monomer (b): a monomer having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer (c): Vinyl chloride or vinylidene chloride.
Monomer (d): one or more hydrophilic groups that do not have a polyfluoroalkyl group and are selected from the group consisting of alkylene oxide groups, amino groups, hydroxy groups, acrylamide groups, carboxy groups, phosphoric acid groups, and sulfone groups A monomer having The polymer (A), the polymer (B), and the polymer (C), at least one polymer further has a structural unit based on the following monomer (e): Water repellent and oil-repellent antifouling composition.
Monomer (e): a monomer having no polyfluoroalkyl group and having a functional group capable of crosslinking.   The water-repellent oil-repellent antifouling agent according to claim 1 or 2, wherein the polymer (C) has a structural unit based on the monomer (d ') having no alkylene oxide group and having no polyfluoroalkyl group. Composition The monomer (d ′) is a monomer (d1) having an alkylene oxide group without a polyfluoroalkyl group, and the alkylene oxide group being an ethylene oxide group, and represented by the following formula (2): The water-repellent oil-repellent antifouling agent composition according to claim 3, which is a compound represented.
^{_{CH 2 = CR 1 -G 1 -}} (C 2 H 4 O) q1 -R 2 ... (2).
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and q 1 represents an integer of ¹ to 50. G ¹ represents —COO (CH ₂ ) _{r 1} — or —COO (CH ₂ ). _t1- NHCOO- (r1 represents an integer of 0 to 4, t1 represents an integer of 1 to 4) The monomer (d ′) does not have a polyfluoroalkyl group but has an alkylene oxide group, and the alkylene oxide group has an ethylene oxide group and a tetramethylene oxide group in the same side chain ( The water-repellent oil-repellent antifouling agent composition according to claim 3, which is d2) and is a compound represented by the following formula (3).
^{_{CH 2 = CR 3 -G 2 -}} (C 2 H 4 O) q2 - (C 4 H 8 O) q3 -R 4 ... (3).
^(Wherein, R 3, ^{R 4} are each independently a hydrogen atom or a methyl group, q2, q3 is an integer of 1 to 50 .G ² is -COO _{(CH 2) r2} - or -COO (CH ₂ ) _t2- NHCOO- (wherein r2 is an integer of 0-4, t2 is an integer of 1-4).)   The water-repellent repellency according to any one of claims 1 to 5, wherein the polymer (C) has a structural unit based on a monomer (d3) having no amino group but no polyfluoroalkyl group. Antifouling composition.   The water repellent oil-repellent antifouling agent composition according to any one of claims 1 to 6, wherein the polymer (C) has an anionic group at the end of the main chain.   Furthermore, at least 1 sort (s) of crosslinking agent chosen from the group which consists of an isocyanate type crosslinking agent, a melamine type crosslinking agent, a carbodiimide type crosslinking agent, and an oxazoline type crosslinking agent is contained. Water repellent and oil-repellent antifouling composition.   An article treated with the water-repellent oil-repellent antifouling agent composition according to any one of claims 1 to 8.

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