JPH11310685A - Water-dispersed water / oil repellent composition and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide a water-dispersed water / oil repellent composition capable of imparting a practical level of water / oil repellency to clothing requiring high water repellency. A water-dispersed water / oil repellent composition comprising an aqueous medium and composite particles containing a polyfluoroalkyl group-containing polymer and a methylolated polyamine dispersed in the aqueous medium as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-dispersible water-repellent material which has a soft feel during processing and which can impart practical water-repellent and oil-repellent properties which are excellent in durability against washing, dry cleaning and friction. The present invention relates to an oil composition and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a polymer having a polymerized unit of an addition-polymerizable monomer containing a polyfluoroalkyl group (hereinafter referred to as an ^Rf group) or a compound having an ^Rf group is dispersed in an organic solvent solution or an aqueous solvent. 2. Description of the Related Art There is known a technique in which a fiber product or the like is treated as a liquid to impart water / oil repellency to the surface thereof. Hereinafter, the addition-polymerizable monomer is simply referred to as a monomer.

[0003] water and oil repellency, for the purpose of improving the durability to laundering and dry cleaning, etc., or a monomer having an adhesive base in the copolymer composition for use with a monomer having R ^f group and having ^the R ^f group A certain level has been achieved by blending the polymer with a polymer having a high film strength or by changing the polymerization method.

Further, a water-soluble or water-dispersible crosslinking agent (melamine resin or blocked urethane resin) is added to an aqueous solvent dispersion to enhance the adhesion between the fiber and the polymer particles, thereby improving the durability. It is also known. However, in order to obtain a somewhat satisfactory durability, a large amount of a cross-linking agent needs to be added, and there has been a problem that the texture becomes hard.

On the other hand, in the field of paints, a thermosetting compound containing an amino resin such as a melamine resin has been blended into paints for the purpose of improving the physical properties of the coating film (US Pat. No. 4,853,422). A method for synthesizing a compound in which an oligomer having a perfluoroalkyl group is reacted with an amino resin for the same purpose is known, but it involves a complicated production process (US Pat. No. 5,292,796).

[0006]

In the conventional water and oil repellent compositions and water and oil repellent treatments, sports wear and water repellency of general clothing have a satisfactory level of durability against washing or dry cleaning. Washing or dry cleaning durability, friction durability and water pressure resistance of clothing requiring high water and oil repellency, such as mountain climbing clothing, were insufficient. In particular, water-repellent polyamide fibers having relatively high hydrophilicity, ultrafine synthetic fibers having a fiber diameter of 10 μm or less, fibers having a special surface shape of fibers using modified cross-section yarn or new synthetic fiber (split yarn), etc. In the case of oil treatment, the friction at the time of wearing and several washings and dry cleanings significantly reduce the water and oil repellency and the water pressure resistance, which is a practical problem. For this reason, there has been a demand for a water / oil repellent composition that does not require a cross-linking agent to be used in combination and has sufficient durability with a small amount of addition that does not impair the feeling.

An object of the present invention is to provide a water / oil repellent composition having excellent durability against washing, dry cleaning and friction, and practical water / oil repellency.

[0008]

SUMMARY OF THE INVENTION The present invention provides an aqueous medium,
A water-dispersed water / oil repellent composition comprising, as essential components, composite particles containing the following polymer A and the following methylolated polyamines C dispersed in an aqueous medium. Polymer A: a polymer containing a polymerized unit a of a monomer having a polyfluoroalkyl group and one polymerizable unsaturated group. Methylolated polyamines C: Methylolated polyamines which are reaction products of polyamines and formaldehyde, their initial condensates, or derivatives thereof.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer A is a polymer containing a polymerized unit a of a monomer having an R ^f group and only one polymerizable unsaturated group (hereinafter also referred to as an R ^f group-containing monomer).
The R ^f group is a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The carbon number of the R ^f group is preferably 4 to 20, more preferably 6 to 16, and particularly preferably 9 to 12. The R ^f group may have a linear or branched structure. In the case of a branched structure, it is preferred that the branched portion exists near the terminal of the R ^f group and the branched portion is a short chain having about 1 to 4 carbon atoms. The R ^f group may have an etheric oxygen atom or a thioetheric sulfur atom inserted between carbon-carbon bonds. The R ^f group may contain a halogen atom other than a fluorine atom, and the halogen atom other than the fluorine atom is preferably a chlorine atom.

The proportion of fluorine atoms in the R ^f group is [(R ^f
Number of fluorine atoms in the group) / (number of hydrogen atoms contained in the alkyl group having the same carbon number corresponding to the R ^f group)] × 100
When expressed in (%), 60% or more is preferable, and 80%
The above is particularly preferred. Further, the R ^f group is a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, that is, a perfluoroalkyl represented by the general formula C _m F _{2m + 1-} (where m is an integer of 4 to 20). Groups (hereinafter referred to as R ^F groups) are preferred.

The R ^f group-containing monomer having an R ^F group is represented by m
If it exceeds 20, it is solid at room temperature, has high sublimability, and is difficult to handle. If m is less than 4, water / oil repellency is low, and the intended function may not be exhibited. ^The R ^f group-containing monomer may be a mixture of two or more as will be described later, in which case the general formula C _m F _{2m + 1} - represented by the R ^F
R having a linear R ^F group having an average m of 6 to 12
Mixtures of monomers containing ^f groups are particularly preferred.

In the R ^f group-containing monomer, the R ^f group and the polymerizable unsaturated group are directly or indirectly bonded via a bonding group, and preferably indirectly bonded. Particularly, a compound having a structure in which the R ^f group is linked to a polymerizable unsaturated group via a divalent bonding group is preferable. As the R ^f group-containing monomer, a known compound is employed, and an R ^f group-containing alcohol,
It can be easily synthesized from a carboxylic acid containing an R ^f group or a sulfonic acid containing an R ^f group.

The R ^f group-containing monomer is preferably a compound represented by the following formula 1. R ^f -R ¹ -X Formula 1 In the formula 1, R ^f represents an R ^f group, R ¹ represents a single bond or a divalent bonding group, and X represents 1 having a polymerizable unsaturated group.
It shows a valent organic group. The R ^f group is preferably a group described in the following specific examples and examples.

The divalent linking group represented by R ¹ includes an alkylene group, an ester bond, an amide bond, an imino bond,
A urethane bond, an etheric oxygen atom, a phenyleneoxy group, a sulfonyl group, or a bonding group containing these structures is preferred. Specific _{examples, - (CH 2) n +} p -, -
(CH ₂ ) _n COONH (CH ₂ ) _p -,-(CH ₂ )
_n CONH (CH ₂ ) _p -,-(CH ₂ ) _n SO ₂ NH
_{(CH 2) p -, -} (CH 2) n NHCONH (CH
₂ ) _p- and the like. Here, n and p each represent an integer of 0 or more, and n + p represents an integer of 2 to 22.

R ¹ is-(CH ₂ ) _{n + p-} ,
-(CH ₂ ) _n CONH (CH ₂ ) _p- or-(CH
_{2) n SO 2 NH (CH} 2) p - (p is an integer of 2 or more,
n + p is preferably from 2 to 6), particularly-(CH ₂ ) _{n + p} −
(N + p is preferably 2 to 6).

[0016] As the X, -CR = residue of olefins CH ₂ etc., -OCR = residue of vinyl ethers CH ₂ etc., residues of vinyl esters such as -COOCR = CH _2, -OCOCR = residues of (meth) acrylates CH _{2 etc., -Ph-CH = CH 2,} -O-Ph-CH = C
A styrene residue such as H ₂ or —OCH ₂ —Ph—CR ＝ CH ₂ is preferred. Here, R is a hydrogen atom, a methyl group or a halogen atom, and Ph is a phenylene group. In this specification, acrylate and methacrylate are collectively referred to as (meth) acrylate, and (meth)
The same applies to other compounds such as acrylamide.

X is particularly preferred from the viewpoints of polymerizability with other monomers, flexibility of a film formed on the fiber, adhesion to textiles, etc., versatility, solubility in a solvent, and ease of emulsion polymerization. , (Meth) acrylates, and particularly preferred is —OCOCR ＝ CH ₂ when R is a hydrogen atom or a methyl group, that is, a (meth) acryloxy group.

As the R ^f group-containing monomer, one kind may be used alone, or two or more kinds having different carbon numbers of the R ^f group may be used in combination. Normally, R ^f groups having different carbon numbers
^It is used as a mixture of two or more ^f- group-containing monomers. Examples of the ^Rf group-containing monomer in the present invention are shown below, but are not limited thereto. Ph represents a phenylene group.

F (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOCH = CH ₂ , F (CF ₂ ) ₁₀ (C
H ₂ ) ₃ OCOCH = CH ₂ , F (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , F (CF
₂ ) ₁₀ (CH ₂ ) ₁₁ OCOCH = CH ₂ , F (CF ₂ ) ₁₀ O (CF ₂ ) ₂ (CH ₂ ) ₂ OCOCH = C
H ₂ , F (CF ₂ ) ₁₀ CH ₂ COOCH = CH ₂ , F (CF ₂ ) ₁₀ (CH ₂ ) ₂ COOCH = CH
₂ , F (CF ₂ ) ₁₀ CONH (CH ₂ ) ₂ CH = CH ₂ , F (CF ₂ ) ₁₀ CONH (CH ₂ ) ₅ OC
OCH = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ , Cl (CF ₂ )
₁₀ (CH ₂ ) ₃ OCOCH = CH ₂ , H (CF ₂ ) ₁₀ (CH ₂ ) ₂ OCOCH = CH ₂ , H (C
F ₂ ) ₁₀ CH = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₂ OCH = CH ₂ , F (CF ₂ ) ₈ CH ₂ CF ₂ (C
H ₂ ) ₂ OCOCH = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₄ OCOCH = CH ₂ , F (CF ₂ ) ₈ CONH
(CH ₂ ) ₃ CH = CH ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₂ OCH ₂ PhCH = CH ₂ , F (CF ₂ ) ₈
(CH ₂ ) ₂ OCH ₂ Ph (CH ₂ ) ₂ OCOCH = CH ₂ , F (CF ₂ ) ₈ SO ₂ N (C ₃ H ₇ ) (C
H ₂ ) ₂ OCOCH = CH ₂ , F (CF ₂ ) ₁₄ SO ₂ NH (CH ₂ ) ₂ CH = CH ₂ , F (CF ₂ )
₁₄ (CH ₂ ) ₆ OCOC (CH ₃ ) = CH ₂ .

The proportion of the polymerized unit a in the polymer A is from 50 to 99% by weight, particularly from 55 to 98% in order to exhibit water and oil repellency.
% By weight is preferred. The polymer A may be composed of only the above-mentioned polymerized unit a, but a copolymerizable monomer having at least one polymerizable unsaturated group other than the polymerized unit a and containing no R ^f group ( Hereinafter, it may include a polymerized unit of a copolymerizable monomer) (hereinafter, also referred to as a polymerized unit b).

The copolymerizable monomer is not particularly limited as long as it can be copolymerized with the ^Rf group-containing monomer. The copolymerizable monomer having one polymerizable unsaturated group and two polymerizable unsaturated groups are used. Preferred are the copolymerizable monomers having the above. Further, the copolymerizable monomer may be used alone or in combination of two or more kinds at an arbitrary ratio.

Examples of the copolymerizable monomer having one polymerizable unsaturated group include (meth) acrylates, (meth) acrylamides, vinyl ethers, vinyl esters,
Examples include fumarate and malate. These copolymerizable monomers preferably have an aliphatic hydrocarbon group or a benzene ring, and particularly preferably have an aliphatic hydrocarbon group. Also, vinyl chloride, ethylene,
Also preferred are vinylidene chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene, styrenes and the like.

When the copolymerizable monomer has an aliphatic hydrocarbon group, the aliphatic hydrocarbon group is preferably a long-chain aliphatic hydrocarbon group, more preferably has 8 or more carbon atoms, and preferably has 8 to 24 carbon atoms. Is particularly preferred. Further, the aliphatic hydrocarbon group may have any of a straight-chain structure, a branched structure and a ring-containing structure, but is preferably a straight-chain structure. As the straight-chain aliphatic hydrocarbon group, a saturated alkyl group is preferable. When a monomer having a long-chain aliphatic hydrocarbon group is used as the copolymerizable monomer, a copolymerizable monomer having a short-chain aliphatic hydrocarbon group having about 1 to 7 carbon atoms in the aliphatic hydrocarbon group is used. Although it can be used in combination, it is difficult to use a copolymerizable monomer having a short-chain aliphatic hydrocarbon group at a high ratio because it reduces water repellency.

The use of a copolymerizable monomer having a straight-chain saturated hydrocarbon group having 8 to 24 carbon atoms has a great effect of softening the texture of the treated fabric and an effect of improving the performance against friction. Further, a copolymerizable monomer having a cyclic saturated hydrocarbon group having 5 to 10 carbon atoms is also preferable because it improves friction durability. As the copolymerizable monomer having a long-chain aliphatic hydrocarbon group, (meth) acrylates having a linear monovalent aliphatic hydrocarbon group having 14 to 20 carbon atoms are preferable.

As the copolymerizable monomer having a benzene ring, (meth) acrylates having a benzene ring are preferable, and specific examples include phenyl (meth) acrylate and benzyl (meth) acrylate. Further, the benzene ring may have a substituent such as an alkyl group such as a methyl group or an ethyl group or a halogen atom.

The copolymerizable monomer may contain a reactive monomer having a reactive group in the molecule. As the reactive group, an epoxy group, a halogen atom, a hydroxyl group, a carbamoyl group, an amino group, a blocked isocyanate group,
Examples include an alkoxysilyl group, an N-methylol group, an N-alkyloxy group, and an imino group. The reactive monomer improves the adhesiveness to the fiber surface during fiber treatment, or forms a stronger film by reacting with the methylolated polyamines C described below, and forms a water- and oil-repellent agent during washing and dry cleaning. Prevent shedding.

The polymerizable unsaturated group in the copolymerizable monomer having two or more polymerizable unsaturated groups is preferably the unsaturated group contained in X. Specifically as the monomer,
α, ω-diolefins, divinylbenzenes, divinyl ethers, poly (meth) acrylates of polyhydric alcohols, and the like. In particular, divinylbenzene or polyhydric alcohol poly (meth) acrylates are preferred from the viewpoint of copolymerizability with the ^Rf group-containing monomer.

The polyhydric alcohols forming the poly (meth) acrylate include ethylene glycol, propylene glycol, butanediols, pentanediols,
Neopentyl glycol, hexanediols, nonanediols, benzenedimethanols, bisphenol A, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, dimethylolcyclohexane and the like, and modified products of these alcohols, etc., are mentioned. Further, a high molecular weight polyhydric alcohol obtained by ring-opening polymerization of ethylene oxide and / or propylene oxide with an optional initiator is also included.

The ratio of the polymerized unit b in the polymer A is 0.
-50% by weight, especially 5-40% by weight is preferred. When the copolymerizable monomer has a short-chain aliphatic hydrocarbon group having 11 or less carbon atoms, the proportion of the polymerized unit b in the polymer A is preferably 20% by weight or less. When the copolymerizable monomer has two or more polymerizable unsaturated groups, the content of the polymerized unit based on the monomer having two or more polymerizable unsaturated groups is 10% by weight or less in the polymer A. It is preferred that

The water / oil repellent composition of the present invention is formed from composite particles containing the polymer A and the methylolated polyamines C. The methylolated polyamines C are compounds having a methylol group obtained by reacting polyamines with formaldehyde and derivatives thereof, and are compounds that can be further cured. For example, when the polyamine is melamine, it is a methylolated melamine such as tetramethylolmelamine or hexamethylolmelamine, a precondensate thereof, or a mixture thereof. Examples of the derivative include butyl etherified methylol melamine obtained by butyl etherification of a part or all of a methylol group. These compounds are thermosetting resins, which are so-called uncured melamine resins, and can eventually be heat-cured to become cured melamine resins.

It is important that the methylolated polyamines C in the composite particles are in an uncured state. An object to be treated such as a cloth is treated with the water / oil repellent composition of the present invention, the object is loaded with the water / oil repellent, and heat treatment is performed. It is considered that the methylolated polyamines C are cured at the stage of the heat treatment, the water / oil repellent is firmly attached to the fabric, and the durability is exhibited.

Therefore, it is not preferable that the methylolated polyamines C be cured, for example, at the stage of forming composite particles (polymerization stage of monomers) (however, the condensation of the methylolated polyamines C may progress to some extent. Good). The polymerization of the monomer is usually less than 100 ° C,
The heat treatment is preferably performed at 80 ° C. or lower, and the heat treatment of the water / oil repellent-carrying fabric is usually performed at 100 ° C. or higher, preferably 130 ° C. or higher. Therefore, methylolated polyamines are 1
A material which does not sufficiently cure at a temperature lower than 00 ° C. but can sufficiently cure at a temperature of 100 ° C. or more, particularly 130 ° C. or more, is used.

As raw materials for the polyamines of the methylolated polyamines C, melamine, benzoguanamine, urea,
There are other compounds having two or more primary or secondary amino groups. Preferred polyamines include melamine, partially alkylated melamine, benzoguanamine, urea, partially alkylated urea and the like. The alkyl group in the partially alkylated melamine or partially alkylated urea preferably has 4 or less carbon atoms. The most preferred polyamines are melamine.

By reacting the polyamines with formaldehyde, methylolated polyamines C are produced. At this time, depending on the reaction conditions, partial condensation of the methylolated polyamines C occurs and the methylolated polyamines C
Is formed. Therefore, in many cases, the methylolated polyamines C are a mixture containing the precondensates thereof, and the precondensates of the polyamines and formaldehyde also include the uncondensed methylolated polyamines C. The methylolated polyamines C in the present invention also mean this precondensate. The average degree of condensation of the initial condensate (the average number of polyamine residues per molecule) is preferably 5 or less.

The methylolated polyamine derivative is a compound obtained by modifying the above methylolated polyamines C with an alcohol or a carboxylic acid. In particular, alkyl etherified methylolated polyamines C obtained by reacting an alcohol are preferable. As the alcohol, an alcohol having 6 or less carbon atoms, particularly an alcohol having 4 carbon atoms is preferable. Specific examples of the derivative include butyl etherified methylol melamine, isobutyl etherified methylol melamine, butyl etherified methylol urea, and butyl etherified methylol benzoguanamine.
N-methylolacrylamide contains a methylol group, but is included in the polymer A in the present invention.

The solubility of the methylolated polyamines C used in the present invention in water is not particularly limited. However, if the solubility is high, it is difficult to form composite particles, so the solubility in water is preferably 100 g or less per 100 g of water. In particular, 50 g or less is preferable.

The ratio of the polymer A in the composite particles is 80 to 9
It is preferably 9% by weight, particularly preferably 90 to 99% by weight. When the proportion of the polymer A is less than 80% by weight, no composite particles are formed or a stable aqueous dispersion cannot be obtained. If the proportion of the polymer A exceeds 90%, sufficient durability cannot be obtained. The proportion of the methylolated polyamines C in the composite particles is preferably from 1 to 20% by weight, particularly from 1 to 10% by weight.
% By weight is preferred.

It is important that the composite particles in the composition of the present invention contain both polymer A and methylolated polyamines C. A composition containing particles composed of only polymer A and methylolated polyamines C cannot achieve the object of the present invention. The individual composite particles in the composition of the present invention may be composed of a uniform mixture of the polymer A and the methylolated polyamines C, and may have a so-called sea-island structure in which the methylolated polyamines C are microscopically dispersed in the composite particles. Also, a so-called core / shell structure in which both are unevenly distributed may be used.

The location of the methylolated polyamines C relative to the polymer A in the composite particles depends on the amount of the emulsifier coexisting in the dispersion during the production of the polymer, and the magnitude of the hydrophobicity of the polymer A and the methylolated polyamines C. Or the distribution coefficient of the methylolated polyamines C to the aqueous phase. More preferred composite particles are a homogeneous mixture of polymer A and methylolated polyamines C.

The composite particles are preferably present as fine particles in the medium. The particle size is preferably from 0.001 to 1 μm, particularly preferably from 0.01 to 1 μm. Particle size 0.0
If it is less than 01 μm, a large amount of emulsifier is required to obtain a stable dispersion, the water / oil repellency is reduced, and furthermore, discoloration occurs when the dyed fabric is treated. If the particle diameter exceeds 1 μm, the fine particles settle in the medium. The particle size can be measured by a dynamic light scattering device, an electron microscope, or the like.
When polymerization is carried out in the presence of an emulsifier by the usual emulsion polymerization method described below, the average particle size falls within the above range.

The method for synthesizing the composite particles of the present invention is not particularly limited, and an ^Rf group-containing monomer (hereinafter also referred to as a monomer) is prepared in an aqueous medium in the presence of a methylolated polyamine C by a known method, for example, emulsification. The polymerization is preferably performed by a polymerization method or a dispersion polymerization method. In the case of performing polymerization by an emulsion polymerization method or a dispersion polymerization method, a method of performing polymerization by adding a polymerization initiator in the presence of an emulsifier and a polymerization medium can be exemplified. In this case, a method is preferable in which the monomers are added to the aqueous medium liquid of the methylolated polyamines C in a lump or divided into several steps, and then a polymerization initiator is added for polymerization. The methylolated polyamines C may be added in several stages during the progress of the polymerization.

The emulsifier is not particularly limited, and one or more of nonionic, cationic, anionic and amphoteric emulsifiers are employed. The amount of the emulsifier is preferably 0.5 to 20% by weight based on the ^Rf group-containing monomer, and particularly preferably 1 to 10% by weight from the viewpoint of water / oil repellency and dispersion stability. Specific examples of the emulsifier used in the present invention are shown below, but are not limited thereto.

Examples of the nonionic emulsifier include an alkylphenol-ethylene oxide adduct, an alkanol-ethylene oxide adduct, and an alkanol-ethylene oxide.
Propylene oxide adduct, fatty acid ester, alkylamine-ethylene oxide adduct, carboxylic acid amide
Examples include an ethylene oxide adduct, an alkylamine-ethylene oxide / propylene oxide adduct, and an alkylamine oxide.

Examples of the alkylphenol-ethylene oxide adduct include a nonylphenol-ethylene oxide adduct, an octylphenol-ethylene oxide adduct, and the like. Examples of the alkyl group in the alkanol-ethylene oxide adduct include a saturated or unsaturated aliphatic group having 4 to 26 carbon atoms, which is linear or branched, and specifically, an octyl group , Dodecyl, tetradecyl, hexadecyl, octadecyl, behenyl, oleyl, stearyl, secondary alkyl and the like.

Examples of the cationic emulsifier include amine salts, quaternary ammonium salts, and oxyethylene addition type ammonium hydrochloride. Specific examples include trimethylalkylammonium hydrochloride, dimethyldialkylammonium hydrochloride, and monoalkylamine acetate. And alkylmethyldipolyoxyethylene ammonium hydrochloride.
Examples of the alkyl group include the same as described above.

As anionic emulsifiers, fatty acid salts, α-
Olefin sulfonic acid salts, alkyl benzene sulfonic acids and salts thereof, alkyl sulfate salts, alkyl ether sulfate salts, alkyl phenyl ether sulfate salts, methyl taurate salts, alkyl sulfosuccinate salts, and the like.

Examples of the amphoteric emulsifier include alanines, imidazolinium betaines, amide betaines, betaine acetate and the like. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethyl amino acetate betaine, and fatty acid amidopropyl dimethyl amino acetate betaine.

The polymerization medium is preferably an aqueous medium containing water, and the aqueous medium may optionally contain an organic solvent. As the organic solvent, a water-soluble organic solvent is preferable, and an organic solvent such as an ester, a ketone, and an ether is preferable. The ratio between water and the organic solvent is not particularly limited.

Specific examples of the organic solvent include acetone, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether,
Propylene glycol monomethyl ether acetate,
Dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol butyl ether, ethyl 3-ethoxypropionate, 3-methoxy-3-methyl-1-butanol, 2-
Examples include tert-butoxyethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like.

The polymerization initiator is preferably a water-soluble or oil-soluble polymerization initiator, and general-purpose initiators such as azo, peroxide and redox can be used depending on the polymerization temperature. The polymerization initiator is particularly preferably a water-soluble initiator, and particularly preferably a salt of an azo compound. The polymerization temperature is not particularly limited.
0-130 ° C is preferred.

In the polymerization reaction of the monomer, a chain transfer agent may be included for the purpose of controlling the molecular weight.
As the chain transfer agent, aromatic or mercaptans are preferable, and alkyl mercaptan is particularly preferable. Specifically, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, stearyl mercaptan or α-methylstyrene dimer is preferred.

As a step before starting the polymerization, monomers,
A mixture comprising the methylolated polyamines C, water and an emulsifier may be predispersed by a homomixer or a high-pressure emulsifier. Stirring the mixture well before the start of polymerization has the effect of improving the yield of the finally obtained polymer.

The water / oil repellent composition produced by the method of the present invention has excellent water repellency which cannot be obtained by a method in which a dispersion of the particles of the polymer A and the methylolated polyamines C are produced and then mixed. Oil repellency, water pressure resistance and their durability are obtained.

The water-dispersed water / oil repellent composition of the present invention is a composition in which the above composite particles are dispersed in an aqueous medium. The composition may be prepared by dispersing the composite particles in a desired aqueous medium, but usually, in a polymerization reaction, the water-dispersed water / oil repellent composition is used as it is by using the desired medium as the polymerization medium. Can be prepared. As the aqueous medium, water or a medium containing water and an organic solvent is preferable. When the organic solvent is used, the amount is 0 to 40% by weight based on the composite particles.
The degree is preferred. Further, the amount of the composite particles is preferably about 1 to 50% by weight with respect to the aqueous medium, and it is preferable to adjust the concentration with water or an organic solvent to the concentration. The concentration can be appropriately changed depending on the purpose and the form of the composition.

The water-dispersed water / oil repellent composition of the present invention is applied to the article to be treated by any method according to the kind of the article to be treated and the preparation form of the composition. For example, a method is employed in which it is attached to the surface of the object to be treated by a coating method such as dip coating, dried, and heated to cure the methylolated polyamines C. The curing temperature is preferably from 100 to 250C, particularly preferably from 130 to 200C.

The water-dispersed water / oil repellent composition of the present invention may further contain other additional components, for example, other water repellents, oil repellents, cross-linking agents, insect repellents, flame retardants, antistatic agents, or anti-wrinkles. Agents and the like can be appropriately compounded. Examples of the object to be treated with the water-dispersed water- and oil-repellent composition of the present invention include fiber products composed of natural fibers, synthetic fibers, and blended fibers thereof. Metal, glass, resin and the like.

The mechanism by which the object treated with the water-dispersed water- and oil-repellent composition of the present invention has excellent durability and water- and oil-repellency is not clear, but when composite particles are used, methylolated polyamine Compared to the case where methylolated polyamines C are added later to fine particles containing no class C, the methylolated polyamines C present uniformly inside the composite particles
Because self-crosslinking and cross-linking with the fiber progress uniformly,
It is presumed that a strong film is easily formed on the surface of the workpiece.

[0058]

Examples 1 to 6 are examples of the preparation of a dispersion of composite particles, Example 7
To 8 are Comparative Production Examples, Examples 9 to 20 are Examples of the present invention, Example 2
1 to 24 are comparative examples.

[0059] [Example 1] glass container 1L, as a polymerizable monomer, perfluoroalkylethyl acrylate _{(C m F 2m + 1 CH} 2 CH 2 OCOCH = CH 2, m is 6, 8, 10, It is a mixture of 12, 14, and 16, and the average of m is 9. Hereinafter, it is described as FA.) 112 g (67% by weight), dioctyl maleate (hereinafter abbreviated as DOM)
8.8 g (5% by weight), 4.0 g (2% by weight) of N-methylolacrylamide (hereinafter abbreviated as NMAM), SM6
8.0 (5% by weight) of 53 (butyl etherified methylol melamine, manufactured by Sanwa Chemical Co., Ltd., 1.4), 0.8 g of n-dodecyl mercaptan, polyoxyethylene nonyl phenyl ether (hereinafter referred to as PP) as an emulsifier ) 10.4 g and alkyltrimethylammonium chloride (formula ^{_{RN + (CH 3) 3 ·}} Cl -; R is referred to as an alkyl group) (hereinafter AA of 16 to 18 carbon atoms) 0.8
g, 246.4 g of water and 48.0 g of dipropylene glycol monomethyl ether, pre-dispersed with a homogenizer, and then treated with a high-pressure homogenizer (emulsifier manufactured by Menton Goulin Co.) at 200 kg / cm ^{2 to} obtain an emulsion. I got

This emulsion was placed in a 1 L stainless steel autoclave and purged with nitrogen. 35.2 g (21% by weight) of a vinyl chloride monomer (hereinafter abbreviated as VCL)
After addition, VA-061 (azo initiator, manufactured by Wako Pure Chemical Industries, Ltd.,
1.6 g of disulfate) were added. After the temperature was raised to 50 ° C., polymerization was carried out for 15 hours to give a solid content of 35.5% and an average particle diameter of 0.155.
A μm dispersion of composite particles was obtained (465 g). The average particle diameter is measured by a laser light scattering method (manufactured by Otsuka Electronics Co., Ltd.)
Was performed. As a result of observing the dispersion liquid of the composite particles with a transmission electron microscope, it was confirmed that the polymer A was homopolymerized in a small amount of an aqueous phase in addition to the composite particles containing the polymer A and the condensate C.

[Examples 2 to 8] In the same manner as in Example 1, a dispersion of composite particles having a composition of monomers and the like shown in Table 1 was obtained.

[0062]

[Table 1]

[Examples 9 to 24] The solid content concentration of the dispersion of the obtained composite particles was adjusted to 20% by weight to prepare a latex stock solution, and this stock solution was used to prepare the processing formulations A to C shown in Table 2. A latex treatment solution was prepared. Nylon taffeta was prepared as a test cloth, immersed in a latex treatment liquid, squeezed with two rubber rollers, and the wet pickup was adjusted to 60% by weight.
Next, it is dried at 110 ° C. for 90 seconds, and further dried at 170 ° C. for 60 seconds.
Heat treated for seconds. The obtained test cloth was evaluated by the following method. In addition, durability test of test cloth (denoted as HL20)
Was washed 20 times by the water washing method shown in Appendix 103 of JIS-L0217, and air-dried to evaluate the performance. Table 5 shows the results.

[0064]

[Table 2]

[Evaluation of Water Repellency] A spray test according to JIS-L1092 was conducted, and the water repellency was shown in Table 3. Usually, the shower water temperature was 27 ° C. In addition, what indicated + (-) to a water-repellent grade shows that each evaluation was slightly good (bad).

[0066]

[Table 3]

[Evaluation of Oil Repellency] AATCC-TM118
The results are shown in Table 4. In addition, what indicated + (-) to oil repellency grade shows that each evaluation is slightly good (bad).

[0068]

[Table 4]

[Evaluation of Water Resistance] The water resistance was evaluated by the hydrostatic method (a) of the water resistance method A (low water pressure method) of JIS-L1092.

[0070]

[Table 5]

[0071]

The water-dispersed water / oil repellent composition of the present invention comprises:
It has excellent durability against washing, dry cleaning and rubbing, and practical water and oil repellency that could not be achieved conventionally.

Claims (7)

[Claims] A water-dispersed water / oil repellent composition comprising an aqueous medium and composite particles containing the following polymer A and the following methylolated polyamines C dispersed in the aqueous medium as essential components. Polymer A: a polymer containing a polymerized unit a of a monomer having a polyfluoroalkyl group and one polymerizable unsaturated group. Methylolated polyamines C: Methylolated polyamines which are reaction products of polyamines and formaldehyde, their initial condensates, or derivatives thereof. 2. The polymer A contains 50 to 99% by weight of polymer units a.
The water-dispersed water / oil repellent composition according to claim 1, which is a polymer containing the same. 3. The water-dispersed water / oil repellent composition according to claim 1, wherein the methylolated polyamine C is a formaldehyde precondensate of melamine, benzoguanamine or urea. 4. A polyfluoroalkyl group represented by the general formula C _m F
The water-dispersed water / oil repellent composition according to claim 1, 2 or 3, represented by _{2m + 1-} (where m is an integer of 4 to 20). 5. The water-dispersed water / oil repellent composition according to claim 1, wherein the composite particles contain 80 to 99% by weight of the polymer A and 1 to 20% by weight of the methylolated polyamines C. Stuff. 6. The water-dispersed water / oil repellent composition according to claim 1, wherein the composite particles have a particle size of 0.001 to 1 μm. 7. The process for producing a water-dispersed water- and oil-repellent composition according to claim 1, wherein the polyfluoroalkyl group and one of the polyolefins are present in an aqueous medium in the presence of a methylolated polyamine C. A method for producing a water-dispersed water / oil repellent composition, comprising emulsion-polymerizing a monomer having a polymerizable unsaturated group.