KR20150015535A - Moisture-permeable waterproof fabric - Google Patents

Abstract

The present invention is a fluorine-containing intermediate layer, and a moisture-permeable waterproof fabric has a moisture-permeable waterproof layer composed of a composite resin comprising a polymer, a fluorine-containing polymer, (a) _{formula: CH 2 = C (-X)} -C (= O) -YZ-Rf wherein X is a hydrogen atom or a methyl group, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 6 carbon atoms (B) a halogenated olefin monomer, and (c) a repeating unit derived from a non-fluorine monomer having no fluorine atom and having at least one carbon-carbon double bond, And has a dynamic viscoelasticity at 160 DEG C of 400 Pas or more, and is excellent in moisture permeability, water resistance and washing resistance.

Description

{MOISTURE-PERMEABLE WATERPROOF FABRIC}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a breathable waterproof cloth which can be used as a clothing material, a waterproof sheet, a shoe and a glove.

BACKGROUND ART Conventionally, various techniques have been proposed for moisture permeable waterproof cloths (for example, Japanese Patent Publication Nos. 60-47955 and 4-18066).

The fluorine-containing polymer not only imparts water- and oil-repellency and water-repellency to the fabric, but also is used as an antioxidant of the synthetic resin on the opposite side of the fabric substrate when the synthetic resin forming the moisture-permeable and waterproof layer is applied.

However, in a fluoroalkyl group-containing polymer having a fluoroalkyl group having 6 or less carbon atoms corresponding to environmental problems, the effect of preventing bleeding when the synthetic resin is applied is low, and the problem that the synthetic resin is apt to occur in the side opposite to the cloth substrate tends to occur Respectively.

In addition, in the case of attaching a film of a synthetic resin, since the adhesive penetrates into the fabric, the adhesive effect is weakened and the peel strength of the synthetic resin film is lowered.

Japanese Patent Publication No. 60-47955 Japanese Patent Publication No. 4-18066

An object of the present invention is to provide a moisture-permeable waterproof fabric which is excellent in moisture permeability, water resistance and washing resistance.

Another object of the present invention is to provide a breathable waterproof cloth which is free from the appearance of a synthetic resin on the opposite side surface of the cloth base when the synthetic resin forming the breathable waterproof layer is applied to the cloth base.

The inventors of the present invention have found that the above object can be achieved when an intermediate layer containing a specific fluorine-containing polymer is provided between the cloth base and the moisture-permeable and waterproof layer, and have completed the present invention.

According to the present invention,

A breathable waterproof fabric comprising an intermediate layer containing a fluorine-containing polymer and a breathable waterproof layer comprising a synthetic resin,

When the fluorine-

(a) Formula:

Wherein X is a hydrogen atom or a methyl group,

Y is -O- or -NH-,

Z is a direct bond or a divalent organic group,

And Rf is a fluoroalkyl group having 1 to 6 carbon atoms]

A fluorine-containing monomer represented by the formula

(b) a halogenated olefin monomer, and

(c) a non-fluorine monomer having no fluorine atom and having at least one carbon-carbon double bond,

Water-repellent, water-repellent fabric which is a fluorine-containing polymer having a dynamic viscoelasticity at 160 캜 of not lower than 400 Pa 占 퐏.

In the present invention, there is the following form.

A. (i) a step of applying a fluorine-containing treating agent comprising a fluorine-containing polymer to a fiber fabric to form an intermediate layer containing a fluorine-containing polymer, and

(Ii) a step of forming a moisture-permeable water-proof layer by applying a synthetic resin on the intermediate layer of the fluorine-containing polymer (for example, by applying a synthetic resin or attaching a film of a synthetic resin)

Wherein the waterproof fabric is fabricated by a method comprising the steps of:

B. A method for treating a fiber fabric, characterized in that a fluorine-containing treating agent comprising a fluorine-containing polymer is applied to a fiber fabric to form an intermediate layer of the fluorine-containing polymer.

C. (a) Formula:

Wherein X is a hydrogen atom or a methyl group,

Y is -O- or -NH-,

Z is a direct bond or a divalent organic group,

And Rf is a fluoroalkyl group having 1 to 6 carbon atoms]

A fluorine-containing monomer represented by the formula

(b) a halogenated olefin monomer, and

(c) a non-fluorine monomer having no fluorine atom and having at least one carbon-carbon double bond,

Containing fluorine-containing polymer having a dynamic viscoelasticity at 160 DEG C of 400 Pa-s or more.

D. A method for producing a fluorine-containing polymer in a moisture-permeable waterproof fabric,

In the manufacturing method,

(I) a step of polymerizing the fluorine-containing monomer (a) and, if necessary, the non-fluorine monomer (c) to obtain a first polymer, and

(II) a step of producing a fluorine-containing polymer by preparing a second polymer formed by the halogenated olefin monomer (b) by polymerizing the halogenated olefin monomer (b) in the presence of the first polymer

≪ / RTI >

The breathable waterproof fabric of the present invention is excellent in moisture permeability, water resistance and washability.

According to the present invention, when the synthetic resin forming the moisture permeable and waterproof layer is applied to the cloth base material, the synthetic resin does not leak into the opposite side surface of the cloth base material.

The breathable waterproof cloth has a cloth base, an intermediate layer comprising a fluorine-containing polymer on one surface of the cloth base, and a breathable waterproof layer on the intermediate layer. The intermediate layer may be formed inside the cloth base. A pattern layer for exposing a pattern or decoration may be formed on the moisture permeable waterproof layer. It is not necessary to form a layer on the other surface of the cloth base.

The fabric base is generally formed of natural fibers and / or synthetic fibers. The fabric of the fabric may be made of natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or leucel) or synthetic fibers (such as polyester, polyamide or acrylic fibers Etc.), or a mixture of fibers (e.g., a mixture of natural fibers and synthetic fibers, etc.). Examples of the form of the cloth base include a fabric, a knitted fabric, a nonwoven fabric, and a brushed cloth. The thickness of the fabric base is generally 0.05 to 10 mm, for example, 0.1 to 1 mm.

The breathable waterproof layer comprises a synthetic resin. The breathable waterproof layer is generally a microporous membrane. Specific examples of the synthetic resin include a polyurethane resin, a polyamino acid urethane resin, an acrylic resin, a polyester resin, and a polytetrafluoroethylene resin. The moisture permeable waterproof layer may be formed only of a synthetic resin, or may include an additive, for example, isocyanate. The thickness of the moisture permeable waterproof layer is generally 10 to 100 mu m, for example, 20 to 50 mu m.

The intermediate layer comprises a fluorine-containing polymer. The intermediate layer may be formed of only the fluorine-containing polymer, or may contain additives such as melamine resin and block isocyanate. The thickness of the intermediate layer is generally 0.1 to 1 占 퐉, for example, 0.2 to 0.3 占 퐉. The intermediate layer is excellent in solvent solubility and does not penetrate organic solvents such as dimethylformamide, toluene and methyl ethyl ketone.

The fluorine-containing polymer has a dynamic viscoelasticity at 160 ° C of 400 Pas · s or more.

The fluorine-containing polymer preferably has a dynamic viscoelasticity at 150 캜 of 500 Pas s or more, particularly 900 Pas s or more. The fluorine-containing polymer preferably has a dynamic viscoelasticity at 160 캜 of 400 Pas s or more, particularly 600 Pa s or more, for example 800 Pa s or more. It is preferable that the fluorine-containing polymer has a dynamic viscoelasticity at 170 캜 of 300 Pa s or more, particularly 700 Pa s or more.

The dynamic viscoelasticity of the fluorine-containing polymer at 150 ° C may be 2500 Pa · s or less, for example, 2200 Pa · s or less. The dynamic viscoelasticity of the fluorine-containing polymer at 160 ° C may be 2500 Pa · s or less, particularly 2300 Pa · s or less, for example, 2100 Pa · s or less. The dynamic viscoelasticity of the fluorine-containing polymer at 170 ° C may be 2300 Pa · s or less, for example, 2000 Pa · s or less.

When the dynamic viscoelasticity is too low (for example, the dynamic viscoelasticity at 160 캜 is less than 400 Pa s), the back side leakage occurs, and the moisture-permeable, waterproof layer tends to peel off. When the dynamic viscoelasticity is lower than a certain value, the moisture permeable and waterproof layer sufficiently adheres to the intermediate layer.

The manufacture of breathable waterproof fabric,

(I) a step of applying a fluorine-containing treating agent comprising a fluorine-containing polymer to a fiber fabric to form an intermediate layer of the fluorine-containing polymer, and

(Ii) a step of forming a moisture-permeable and waterproof layer of a synthetic resin on the intermediate layer of the fluorine-

As shown in FIG. The moisture permeable waterproof layer can be formed, for example, by applying a synthetic resin or by attaching a film of a synthetic resin.

The fluorine-containing polymer has, as an essential component, a repeating unit derived from a fluorine-containing monomer. The fluorine-containing polymer may further have a repeating unit derived from a non-fluorine monomer.

The fluorine-containing polymer having a fluorine-containing monomer and a repeating unit derived from a non-fluorine monomer can be produced by batch introduction (one-stage polymerization) or by partial introduction (multi-stage polymerization, especially two- Since the effect of preventing the leakage of the synthetic resin increases, it is preferable to carry out the split injection. The term "multistage polymerization (particularly, two-stage polymerization)" means that the introduction (polymerization initiation) of one or more monomers is delayed and the introduction of another monomer or monomers is initiated (polymerization initiation). The two-stage polymerization means that the polymerization of the second monomer containing at least one other monomer is carried out in the presence of the first polymer obtained by polymerizing the first monomer containing at least one monomer.

The multi-stage polymerization is two or more stages of polymerization, for example, two-stage polymerization, three-stage polymerization and four-stage polymerization. The three-stage polymerization uses a third polymer that is added later than the second polymer in addition to the first polymer and the second polymer. In the case of four or more stages polymerization, the fourth or higher monomer is further used.

Hereinafter, the two-step polymerization which is a representative of the multistage polymerization will be described.

In the case of a divided introduction (in particular, two-step polymerization), the fluorine-

A fluorine-containing polymer comprising a first polymer formed of a first monomer and a second polymer formed of a second monomer,

In the presence of the first polymer, the second monomer is polymerized,

At least one of the first monomer and the second monomer comprises a fluorine-containing monomer (a)

The first monomer does not include the halogenated olefin monomer (b)

The second monomer is a fluorine-containing polymer containing a halogenated olefin monomer (b).

The batch input (especially the two-stage polymerization)

A method for producing a fluorine-containing polymer comprising a first polymer formed with a first monomer and a second polymer formed with a second monomer,

In the manufacturing method,

(I) a step of polymerizing a first monomer to obtain a first polymer, and

(II) a step of obtaining a second polymer by polymerizing the second monomer in the presence of the first polymer

Respectively,

At least one of the first monomer and the second monomer includes a fluorine-containing monomer,

Wherein the first monomer comprises a non-fluorine-free cross-linking monomer and does not comprise a halogenated olefin monomer,

The second monomer is a production method comprising a halogenated olefin monomer.

In the present invention, the first monomer may or may not include a halogenated olefin monomer. It is preferred that the first monomer does not comprise halogenated olefin monomers.

The fluorine-containing polymer of the present invention has a repeating unit derived from the first monomer and a repeating unit derived from the second monomer. The first polymer and the second polymer may be copolymerized. That is, the first polymer and the second polymer may be chemically bonded. Alternatively, the first polymer and the second polymer may be physically bonded without forming a chemical bond. An example of physical bonding is a core / shell structure in which the first polymer forms the core and the second polymer forms the shell. In the core / shell structure, the first polymer and the second polymer may not chemically bond, but may be chemically bonded.

In the present invention, as the monomer, the fluorine-containing monomer (a) and the halogenated olefin monomer (b) are used. The non-fluorine monomer (c) may be used if necessary, and the non-fluorine ratio may be a cross-linkable monomer and / or a non-fluorine cross-linkable monomer. The non-fluorine monomer (c) is preferably a non-fluorine-free cross-linking monomer (c1) and / or a non-fluorine-crosslinking monomer (c2).

At least one of the first monomer and the second monomer includes a fluorine-containing monomer. It is preferred that the first monomer comprises a fluorine-containing monomer and the second monomer does not contain a fluorine-containing monomer.

It is preferred that the first monomer does not comprise a halogenated olefin monomer and the second monomer comprises a halogenated olefin monomer. The second monomer may comprise only halogenated olefin monomers.

The first monomer may contain a non-fluorine-free cross-linking monomer. It is preferred that the second monomer does not comprise non-fluorine-incompatible monomers. Since the second monomer does not contain a non-fluorine-free cross-linking monomer, it has excellent performance in preventing roll contamination due to adhesion of the polymer to the roll in the processing of the treatment agent containing the fluorine-containing polymer.

At least one of the first monomer and the second monomer may include a non-fluorine-crosslinkable monomer. When the fluorine-containing polymer comprises a non-fluorine-crosslinkable monomer, it is preferable that the first monomer does not include a non-fluorine-crosslinkable monomer, the second monomer may include a non-fluorine-crosslinkable monomer, Crosslinkable monomer, and the second monomer may not contain a non-fluorine-crosslinkable monomer.

Preferred types of monomers in the first and second monomers are as follows.

In the present invention, the second monomer (the first monomer is the fluorine-containing monomer and the non-fluorine-free monomer is the second monomer is the halogenated olefin monomer) is particularly preferable.

It is also preferable that each of the fluorine-containing monomer and the non-fluorine-crosslinkable monomer is present on both the first monomer and the second monomer. That is, in the same manner as in Forms 1 to 7 except that the fluorine-containing monomer is present on both the first monomer and the second monomer, Forms 1 to 7, except that the non-fluorine-crosslinkable monomer is present on both the first monomer and the second monomer, Is also preferable.

(a) a fluorine-containing monomer

The fluorine-containing monomer has the formula:

Wherein X is a hydrogen atom or a methyl group,

Y is -O- or -NH-,

Z is a direct bond or a divalent organic group,

And Rf is a fluoroalkyl group having 1 to 6 carbon atoms]

Is a fluorine-containing monomer. Z is for example C 1 -C 20 linear alkylene group or branched alkylene group, for example of formula - (CH _{2) x} - (wherein x is 1 to 10 Im) that group, or a group represented by the formula -SO ₂ represented by A group represented by N (R ¹ ) R ² - or a group represented by the formula -CON (R ¹ ) R ² wherein R ¹ is an alkyl group having 1 to 10 carbon atoms and R ² is a straight chain alkylene group having 1 to 10 carbon atoms, (Wherein R ³ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl)) or a group represented by the formula -CH ₂ CH (OR ³ ) CH ₂ - (CH ₂ ) _m -SO ₂ - (CH ₂ ) _n - group or a group represented by the formula -Ar-CH ₂ - (wherein Ar is an arylene group optionally having a substituent) - (CH ₂ ) _m -S- (CH ₂ ) _n - group (provided that m is 1 to 10 and n is 0 to 10).

The fluorine-containing monomer (a)

Wherein X is a hydrogen atom or a methyl group;

Y is -O- or -NH-;

Z represents an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,

-CH ₂ CH ₂ N (R ¹ ) SO ₂ - group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) or

-CH ₂ CH (OZ ¹ ) CH ₂ - group (provided that Z ¹ is a hydrogen atom or an acetyl group) or

- (CH ₂ ) _m --SO ₂ - (CH ₂ ) _n - group or - (CH ₂ ) _m -S- (CH ₂ ) _n- group wherein m is 1 to 10 and n is 0 to 10, ,

And Rf is a straight or branched fluoroalkyl group having 1 to 6 carbon atoms]

Is preferably an acrylate ester or acrylamide represented by the following formula

The fluorine-containing monomer (a) may be substituted with a halogen atom or the like at the α-position (of acrylate or methacrylate). Accordingly, in the formula (1), X represents a linear or branched alkyl group of 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (provided that X ¹ and X ² Is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a cyano group, a straight or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl Contributing.

In the above formula (1), it is preferable that the group Rf is a perfluoroalkyl group. The carbon number of the Rf group is 1 to 6, particularly 4 to 6. Examples of Rf groups _{include, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3) _{2, -C (CF 3) 3} , - (CF 2) 4 CF 3, - (CF 2) 2 CF (CF 3) 2, -CF 2 C (CF 3) 3, -CF (CF 3) CF 2 CF ₂ CF ₃ , - (CF ₂ ) ₅ CF ₃ , - (CF ₂ ) ₃ CF (CF ₃ ) ₂ , - (CF ₂ ) ₄ CF (CF ₃ ) ₂ and -C ₈ F ₁₇ .

Z represents an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,

-CH ₂ CH ₂ N (R ¹ ) SO ₂ - group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) or

-CH ₂ CH (OZ ¹ ) CH ₂ - group (provided that Z ¹ is a hydrogen atom or an acetyl group) or

- (CH ₂ ) _m --SO ₂ - (CH ₂ ) _n - group or - (CH ₂ ) _m -S- (CH ₂ ) _n- group wherein m is 1 to 10 and n is 0 to 10, . The aliphatic group is preferably an alkylene group (especially 1 to 4 carbon atoms, for example 1 or 2). The aromatic group or the cyclic aliphatic group may be substituted or unsubstituted. The S group or SO ₂ group may be bonded directly to the R f group.

Specific examples of the fluorine-containing monomer (a) include, but are not limited to, the following.

[Wherein Rf is a fluoroalkyl group having 1 to 6 carbon atoms]

(b) Halogenated olefin monomers

The halogenated olefin monomer (b) is preferably an olefin having 2 to 20 carbon atoms which is substituted by 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin monomer (b) is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred examples of the halogenated olefin monomer (b) are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide and vinylidene iodide. Vinyl chloride is preferable because the water resistance (durability particularly in water resistance) becomes high.

The non-fluorine monomer (c) may be a non-fluorine-free monomer (c1) and / or a non-fluorine-crosslinkable monomer (c2).

( c1 ) Non-fluorine Incompatible  Monomer

The non-fluorine-free non-crosslinking monomer (c1) is a monomer not containing a fluorine atom. The non-fluorine-free crosslinkable monomer (c1) has no crosslinkable functional group. Unlike the crosslinkable monomer (c2), the non-fluorine-free crosslinkable monomer (c1) is incompatible. The non-fluorine-incompatible monomer (c1) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine-incompatible monomer (c1) is preferably a vinyl monomer containing no fluorine. The non-fluorine-incompatible monomer (c1) is generally a compound having one carbon-carbon double bond.

The preferred non-fluorine-free crosslinkable monomer (c1)

[Wherein A is a hydrogen atom, a methyl group, or a halogen atom (e.g., a chlorine atom, a bromine atom and an iodine atom) other than a fluorine atom,

T represents a hydrogen atom, a straight or cyclic hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms), or a linear or cyclic hydrocarbon group having 1 to 31 carbon atoms (for example, 1 to 20 carbon atoms) Device]

May be used.

Examples of the straight chain or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, the cyclic aliphatic group having 4 to 30 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, the carbon chain having 7 to 30 carbon atoms Lt; / RTI > aliphatic hydrocarbon group.

Examples of the chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond include -C (= O) -OQ and -OC (= O) -Q wherein Q is a straight or branched An aliphatic hydrocarbon group, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms). A linear or branched aliphatic hydrocarbon group having 12 to 30 carbon atoms, particularly 18 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms, A straight chain or branched aliphatic hydrocarbon group having 12 to 30 (particularly 18 to 30) carbon atoms, and a cyclic aliphatic group having 4 to 30 carbon atoms are particularly preferable.

Preferable examples of the non-fluorine-incompatible monomer (c1) include ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol ) Acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl alkyl ether. The non-fluorine-incompatible monomer (c1) is not limited to these examples.

The non-fluorine-free crosslinkable monomer (c1) may be a (meth) acrylate ester having an alkyl group. The number of carbon atoms of the alkyl group may be 1 to 30, and may be, for example, 6 to 30 (for example, 10 to 30). For example, the non-fluorine-free cross-linking monomer (c1)

Wherein A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom)

A ² is an alkyl group represented by C _n H _{2n + 1} (n = 1 to 30)

May be used.

It is preferable that the fluorine-containing polymer has a repeating unit derived from an acrylate (CH ₂ = CA ¹ COOA ² ) in which A ² is an alkyl group having 12 to 30 carbon atoms, particularly 18 to 30 carbon atoms desirable.

The non-fluorine-incompatible monomer (c1) may be a (meth) acrylate monomer having a cyclic hydrocarbon group. The (meth) acrylate monomer (B) having a cyclic hydrocarbon group is a compound having a cyclic hydrocarbon group (preferably monovalent) and a monovalent (meth) acrylate group. A monovalent cyclic hydrocarbon group and a monovalent (meth) acrylate group are directly bonded. Examples of the cyclic hydrocarbon group include saturated or unsaturated, monocyclic, polycyclic, and bridged groups. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group preferably has 4 to 20 carbon atoms. The cyclic hydrocarbon group includes a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. The carbon number of the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 10 or less. It is preferable that the carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to the ester group in the (meth) acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group. The (meth) acrylate group is an acrylate group or a methacrylate group, but a methacrylate group is preferred. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentyl methacrylate, dicyclopentyl methacrylate, Cyclopentanyl acrylate, dicyclopentenyl acrylate, and the like.

( c2 )  Non-fluorine Crosslinkability  Monomer

The fluorine-containing polymer of the present invention may have a repeating unit derived from a non-fluorine-crosslinkable monomer (c2). The non-fluorine-crosslinkable monomer (c2) is a monomer not containing a fluorine atom. The non-fluorine-crosslinkable monomer (c2) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The non-fluorine-crosslinkable monomer (c2) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a block isocyanate group, an amino group, and a carboxyl group. The non-fluorine-crosslinkable monomer (c2) may be a mono (meth) acrylate, (meth) diacrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine-crosslinkable monomer (c2) may be di (meth) acrylate.

Examples of the nonfluorine-crosslinkable monomer (c2) include diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, (Meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 1,6-cyclohexanedimethylacrylate -Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like, but are not limited thereto.

In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.

By copolymerizing the non-fluorine-free crosslinkable monomer (c1) and / or the non-fluorine crosslinkable monomer (c2), water repellency and antifouling property and their performance can be improved by the properties of cleaning, washing resistance, solubility in solvents, hardness, Various properties can be improved as needed.

In the fluorine-containing polymer, the amount of the halogenated olefin (b) is 2 to 500 parts by weight, for example, 5 to 200 parts by weight, particularly 10 to 150 parts by weight, particularly 20 To 50 parts by weight, and the amount of the non-fluorine monomer (c) may be 1200 parts by weight or less, for example, 0.1 to 400 parts by weight, particularly 0.5 to 250 parts by weight, particularly 1 to 50 parts by weight.

The amount of the fluorine-free monomer (c1) in the fluorine-containing polymer is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight, relative to 100 parts by weight of the fluorine-containing monomer (a) The amount of the non-fluorine-crosslinkable monomer (c2) may be 50 parts by weight or less, for example, 30 parts by weight or less, particularly 0.1-20 parts by weight.

When the same type of monomers (for example, a halogenated olefin monomer and a fluorine-containing monomer) are contained in both the first monomer and the second monomer, the same kind of monomers (in particular, halogenated olefin monomers) The weight ratio of the homopolymer (particularly, the halogenated olefin monomer) in the two monomers may be 3 to 97:97 to 3, for example 5 to 90:95 to 10, in particular 10 to 70:90 to 30.

The fluorine-containing polymer in the present invention can be produced by any of ordinary polymerization methods, and the conditions of the polymerization reaction can be arbitrarily selected. Such polymerization methods include solution polymerization, suspension polymerization and emulsion polymerization.

In the solution polymerization, a method of dissolving the monomer in an organic solvent and substituting with nitrogen in the presence of a polymerization initiator, followed by heating and stirring at 30 to 120 ° C for 1 to 10 hours is employed. As the polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicar And the like. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.

The organic solvent is one that dissolves the monomer in an inert state and includes, for example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone Ketone, specifically, methyl ethyl ketone, diisobutyl ketone), an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, , Methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, tetrachlorodi Fluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in an amount of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total amount of the monomers.

In the emulsion polymerization, a method in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and the resulting mixture is subjected to nitrogen substitution and then stirred at 50 to 80 ° C for 1 to 10 hours to effect copolymerization. The polymerization initiator may be at least one selected from the group consisting of benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine- Examples of the organic peroxides include water-soluble ones such as isobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate, and azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t -Butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator is used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

In order to obtain a copolymer aqueous dispersion having excellent stability to stand, it is preferable to use an emulsifying apparatus capable of imparting strong crushing energy such as a high pressure homogenizer or an ultrasonic homogenizer to atomize the monomer into water, Is preferably used. As the emulsifier, various emulsifiers such as anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. It is preferred to use anionic and / or nonionic and / or cationic emulsifiers. When the monomers are completely incompatible, it is preferable to add a compatibilizing agent sufficiently compatible with these monomers, for example, a water-soluble organic solvent or a low molecular weight monomer. By the addition of the compatibilizing agent, it is possible to improve emulsification and copolymerization.

Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight , For example, 10 to 40 parts by weight. Examples of the monomer having a low molecular weight include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate and the like. The amount of the monomer is preferably 1 to 50 For example, 10 to 40 parts by weight.

In the polymerization, a chain transfer agent may be used. Depending on the amount of chain transfer agent used, the molecular weight of the copolymer can be varied. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol and the like (particularly, alkyl mercaptans such as (for example, 1 to 30 carbon atoms)), sodium hypophosphite, sodium hydrogen sulfite Salt. The chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.

The copolymerization of the fluorine-containing polymer can be carried out by batch addition (one-step polymerization) or by batch addition (multi-stage polymerization, particularly two-step polymerization). However, when a crosslinkable monomer is used, it may be added in a batch.

In the two-step polymerization, a polymerization reaction is generally carried out with a liquid containing the first monomer to prepare a first polymer, and subsequently, a polymer reaction is carried out with a liquid containing the first polymer and the second monomer to form a second polymer To obtain a fluorine-containing polymer composed of the first polymer and the second polymer. The polymerization of the second polymer may be initiated during the polymerization of the first polymer, or the polymerization of the second polymer may be initiated after completion of polymerization of the first polymer. (I. E., 40 to 100%), especially 70% or more (i. E., 10 to 100%) of the polymerization of the first polymer (i. E., Polymerization of the first monomer) , 70 to 100%), the polymerization of the second polymer may be initiated. The termination percentage of the polymerization reaction (that is,% of the polymerization reaction progress ratio) means the mole% of the reacted monomers (polymerized monomers). For example, when the polymerization reaction is completed at 10%, the polymerized monomer is 10 mol% and the unreacted (un polymerized) monomer is 90 mol%. When the first monomer is a combination of at least two kinds of monomers, the molar percentage of the first monomer is based on the total moles of at least two kinds of monomers in the first monomer.

During the polymerization of the first polymer means that the polymerization reaction of the first polymer (i.e., the polymerization reaction of the first monomer) is not completely terminated. For example, the polymerization of the first polymer may be terminated by at least 10% to less than 40%, at least 40% to less than 70%, or at least 70% to less than 100% (particularly 80% to 99%, in particular 85% to 98% Thereafter, the polymerization of the second polymer may be initiated.

After the completion of the polymerization of the first polymer, it means that about 100% of the polymerization reaction of the first polymer (i.e., the polymerization of the first monomer) is terminated.

When the polymerization of the second polymer is initiated during the polymerization of the first polymer, the second polymer has the repeating units derived from the first monomer and the second monomer. When the polymerization of the second polymer is initiated after completion of the polymerization of the first polymer, the second polymer has a repeating unit derived from only the second monomer.

In the fluorine-containing polymer of the present invention, the first polymer is not chemically bonded or chemically bonded to the second polymer.

It is preferable that the unreacted non-fluorine ratio in the polymerization system does not substantially exist in the cross-linking monomer at the time when the polymerization of the second monomer is initiated. Means that the amount of the unreacted non-fluorine-containing cross-linking monomer is 10 mol% or less, preferably 8 mol or less, relative to the amount of the cross-linking monomers to be added, at the time of initiating the polymerization of the second monomer % Or less, more preferably 5 mol% or less, particularly 3 mol% or less, particularly 1 mol% or less. Since the unreacted non-fluorine-free cross-linking monomer is substantially absent, the fluorine-containing polymer is excellent in the ability to prevent roll contamination due to adhesion of the polymer to the roll during the processing of the treatment agent containing the fluorine-containing polymer.

The fluorine-containing polymer of the present invention is preferably produced by emulsion polymerization. In the particles of the aqueous dispersion formed by the first polymer and the second polymer, the second polymer may encapsulate the first polymer, and the fluorine-containing polymer may be such that the core of the first polymer Or may have a surrounding core / shell structure.

The fluorine-containing polymer can be applied to the substrate cloth by any of the methods known for forming a film of a polymer on a substrate cloth. Generally, a fluorine-containing polymer film can be formed on a polymer by applying a liquid containing a fluorine-containing polymer and a liquid medium onto a substrate cloth, and then removing the liquid medium by drying or the like. In the liquid containing the fluorine-containing polymer and the liquid medium, the concentration of the fluorine-containing polymer may be, for example, 0.01 to 20% by weight, particularly 0.05 to 10% by weight. The substrate cloth may be immersed in the solution, or the solution may be applied or sprayed onto the substrate cloth. The substrate cloth to which the liquid has been applied is dried, for example, to 100 占 폚 to 200 占 폚, for example, to exhibit lyophobicity.

The textile product to be treated is typically a fabric, which includes fabrics, knits and nonwovens, garments in the form of garments, and carpets, while fibers or yarns or intermediate fiber products (e.g., slivers, . The fiber product material may be selected from natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or leucel), or synthetic fibers (such as polyester, polyamide or acrylic fibers , Or a mixture of fibers (e.g., a mixture of natural fibers and synthetic fibers, etc.). The production polymer of the present invention is particularly effective in making cellulose-based fibers (for example, cotton or rayon, etc.) oily and oil-repellent. In addition, the process of the present invention generally makes the textile product hydrophobic and water repellent.

Alternatively, the fibrous substrate may be a leather. The preparation polymer may also be applied to the leather from aqueous solutions or aqueous emulsions at various stages of leather processing, for example during the wet processing period of the leather, or during the finishing period of the leather, in order to make the leather hydrophobic and oleophobic.

Alternatively, the fibrous substrate may be paper. The preparation polymer may be applied to preformed paper or may be applied at various stages of paper making, for example during the drying of paper.

The surface treatment agent (fluorine-containing treatment agent) of the present invention is preferably in the form of solution, emulsion or aerosol. The surface treatment agent comprises a fluorine-containing polymer (active component of the surface treatment agent) and a medium (particularly, a liquid medium such as an organic solvent and / or water). In the surface treatment agent, the concentration of the fluorine-containing polymer may be, for example, 0.01 to 50% by weight.

The surface treatment agent (fluorine-containing treatment agent) of the present invention preferably comprises a fluorine-containing polymer and an aqueous medium. In the present specification, the term " aqueous medium " means an organic solvent (the amount of organic solvent is 80 parts by weight or less, for example, 0.1 to 50 parts by weight, particularly 5 to 100 parts by weight, To 30 parts by weight). The fluorine-containing polymer is preferably prepared by emulsion polymerization to prepare a dispersion of the fluorine-containing polymer. The surface treatment agent is preferably an aqueous dispersion in which particles of the fluorine-containing polymer are dispersed in an aqueous medium. In the dispersion, the average particle diameter of the fluorine-containing polymer is preferably 0.01 to 200 micrometers, for example, 0.1 to 5 micrometers, particularly 0.05 to 0.2 micrometer. The average particle diameter can be measured by a dynamic light scattering apparatus, an electron microscope or the like.

The surface treatment agent of the present invention can be applied to a subject to be treated by a conventional method. Usually, a method of dispersing and diluting the surface treatment agent with an organic solvent or water, and adhering the surface treatment agent to the surface of the material to be treated by a known method such as dip coating, spray coating, or air bubble coating and drying is adopted. If necessary, curing may be carried out with appropriate crosslinking agent. It is also possible to add an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, etc. to the surface treatment agent of the present invention. The concentration of the fluorine-containing polymer in the treatment liquid to be brought into contact with the substrate may be 0.01 to 20% by weight, particularly 0.05 to 10% by weight (particularly in the case of immersion coating).

Example

EXAMPLES Next, the present invention will be described in detail with reference to Examples, Comparative Examples and Test Examples. However, these descriptions do not limit the present invention.

In the following, parts or percentages are by weight unless otherwise specified.

The characteristics were measured in the following manner.

The monomer composition in the polymer

The polymer was subjected to elemental analysis (F atom, Cl atom and C atom), IR spectroscopy, 1 H NMR spectroscopy and 19 F NMR spectroscopy to determine the monomer composition (% by weight) in the polymer.

dynamic Viscoelastic  Measure

10 g of the aqueous dispersion of the polymer was dispersed in 20 g of methanol, and the mixture was suspended in a centrifuge at 10000 rpm for 60 minutes to separate the acrylic polymer and the emulsifier to obtain a sample polymer for measurement. The complex viscosity ratio (? *) Of the polymer was measured by a dynamic viscoelasticity measuring device RHEOSOL-G3000 (manufactured by UBM Co., Ltd.). One gram of the sample polymer was heated at a frequency of 0.5 Hz and a measurement temperature of 40 DEG C to 180 DEG C at 5 DEG C / min to measure dynamic viscoelasticity.

Volatile solvent

The aqueous dispersion of the polymer was diluted with water to a solid concentration of 1% by weight to adjust the treatment solution. The nylon cloth was immersed in the treating liquid, squeezed at 4 kg / cm 2 and 4 m / min, and heat treated at 170 ° C for 1 minute, and then the solvent resistance of the treated cloth was evaluated. Solvent solubility was measured by dropping a drop of DMF, MEK, toluene, and ethyl acetate on the test cloth, and measuring the time taken for the solvent to absorb into the cloth to a maximum of 120 seconds. The higher the value, the better the solubility in solvent.

Backside of coating resin

The aqueous dispersion of the polymer was diluted with water to a solid concentration of 1% by weight to adjust the treatment solution. After the nylon cloth was immersed in the treating solution and squeezed at 4 kg / cm 2 and 4 m / min in a mangling manner and heat-treated at 170 ° C. for 1 minute, a polyurethane resin having a concentration of 30% in MEK / toluene / DMF as a solvent Rezamin ME-3612LP manufactured by Sekka Kogyo Co., Ltd.) was uniformly applied to one side of a nylon cloth, dried at 100 ° C for 1 minute, and then heat-treated at 150 ° C for 1 minute. The uncoated surface was observed with naked eyes and the back side of the resin was exposed.

◎: If it is not at all, it does not come out.

○: If it is very slight,

X: If the amount is large, there is a leak.

Peel strength of synthetic film

The aqueous dispersion of the polymer was diluted with water to a solid concentration of 1% by weight to adjust the treatment solution. A nylon cloth was immersed in the treatment liquid and squeezed at 4 kg / cm 2 at 4 m / min and heat-treated at 170 ° C. for 1 minute. Thereafter, a urethane resin adhesive having a concentration of 50% using MEK and ethyl acetate as a solvent (DIC Co., Ltd.) was applied to one surface of a nylon cloth in the form of dots, and a synthetic film of polyurethane was pressed and heat-treated at 120 ° C for 2 minutes. The obtained nylon cloth was repeatedly washed 20 times with AATCC 88B (1) (III), and the peeled state of the synthetic film was visually observed, and the state was evaluated as follows.

◎: No peeling at all

○: Very slight peeling.

X: The peeling can be clearly seen

Example 1

Two-step polymerization:

A 1 L autoclave was charged with 179 g of C ₆ F ₁₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (abbreviated as "C6SFMA"), 25 g of stearyl acrylate (StA), 75.8 g of tripropylene glycol, 12.7 g of ethylene lauryl ether, 2.47 g of polyoxyethylene oleyl ether, 5.05 g of polyoxyethylene isotridecyl ether and 2.66 g of dialkyl (Uji) dimethyl ammonium chloride were placed, heated at 60 DEG C, Emulsified and dispersed. After emulsification and dispersion, 1.92 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 1 hour (polymerization reaction C6SFMA 99% end, StA 97% end). Subsequently, 60 g of vinyl chloride was press-filled and reacted for 2 hours to obtain an aqueous dispersion of the polymer. And the characteristics of the aqueous dispersion having the concentration adjusted to pure water so that the solid content concentration became 30% by weight were measured. The results are shown in Table 2.

Example 2

A dispersion of the polymer was obtained in the same manner as in Example 1 except that 0.025 g of lauryl mercaptan was added after emulsification.

At the time of charging the vinyl chloride (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFMA and 96% of StA.

Example 3

A polymer dispersion was obtained in the same manner as in Example 1 except that 0.12 g of lauryl mercaptan was added after emulsification.

At the time of vinyl chloride charging (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFMA and 95% of StA.

Example 4

A polymer dispersion was obtained in the same manner as in Example 1 except that 0.19 g of lauryl mercaptan was added after emulsification.

At the time of charging the vinyl chloride (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFMA and 96% of StA.

Example 5

C ₆ F ₁₃ CH a dispersion of polymer in _{2 CH 2 OCOC (CH 3)} = CH 2 179g instead of _{C 6 F 13 CH 2 CH 2} OCOCH = CH 2 (C6SFA) same manner as in Example 2 was used in 179g except .

At the time of charging vinyl chloride (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFA and 95% of StA.

Example 6

A polymer dispersion was obtained in the same manner as in Example 2 except that 25 g of cyclohexyl methacrylate (CHMA) was used instead of 25 g of stearyl acrylate (StA).

At the time of charging the vinyl chloride (at the end of the first stage polymerization), the polymerization reaction was completed by 99% end of C6SFMA and 98% end of CHMA.

Example 7

A dispersion of the polymer was obtained in the same manner as in Example 2 except that 25 g of isobornyl acrylate (IBMA) was used instead of 25 g of stearyl acrylate (StA).

At the time of charging the vinyl chloride (at the end of the first stage polymerization), the polymerization reaction was 99% end of C6SFMA and 99% end of IBMA.

Example 8

A dispersion of the polymer was obtained in the same manner as in Example 2 except that 0.25 g of neopentyl glycol diacrylate (NP-A) was added to Example 2.

At the time of charging the vinyl chloride (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFMA and 96% of StA.

Example 9

A dispersion of the polymer was obtained in the same manner as in Example 2 except that 2.25 g of diacetone acrylamide (DAAM) was added to Example 2.

At the time of charging the vinyl chloride (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFMA and 96% of StA.

Example 10

A polymer dispersion was obtained in the same manner as in Example 2 except that 2.25 g of glycidyl methacrylate (GLA) was added to Example 2.

At the time of charging the vinyl chloride (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFMA and 96% of StA.

Example 11

A polymer dispersion was obtained in the same manner as in Example 2 except that 2.25 g of isopropyl acrylamide (NIPAM) was added to Example 2.

At the time of charging the vinyl chloride (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFMA and 96% of StA.

Example 12

1 step polymerization:

A 1 L autoclave was charged with 179 g of C ₆ F ₁₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , 25 g of stearyl acrylate, 0.25 g of neopentyl glycol diacrylate, 75.8 g of tripropylene glycol, 446 g of pure water, 12.7 g of ether, 2.47 g of polyoxyethylene oleyl ether, 5.05 g of polyoxyethylene isotridecyl ether and 2.66 g of dialkyl (Uji) dimethylammonium chloride were placed and heated at 60 DEG C, and then emulsified and dispersed with a high pressure homogenizer . After emulsification, 0.025 g of lauryl mercaptan was added, and 60 g of vinyl chloride was press-filled. Further, 1.92 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. And the characteristics of the aqueous dispersion having the concentration adjusted to pure water so that the solid content concentration became 30% by weight were measured. The results are shown in Table 2.

Comparative Example 1

A dispersion of the polymer was obtained in the same manner as in Example 1 except that 0.25 g of lauryl mercaptan was added after emulsification.

At the time of vinyl chloride charging (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFMA and 95% of StA.

Comparative Example 2

A polymer dispersion was obtained in the same manner as in Example 1 except that 0.38 g of lauryl mercaptan was added after emulsification.

At the time of charging the vinyl chloride (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFMA and 96% of StA.

Comparative Example 3

A dispersion of the polymer was obtained in the same manner as in Example 2 except that 0.38 g of neopentyl glycol diacrylate was added to Example 2.

At the time of charging the vinyl chloride (at the end of the first stage polymerization), the polymerization reaction terminated with 99% of C6SFMA and 96% of StA.

Comparative Example 4

A dispersion of the polymer was obtained in the same manner as in Example 12 except that neopentyl glycol diacrylate was not added.

Comparative Example 5

A dispersion of the polymer was obtained in the same manner as in Comparative Example 4 except that the amount of laurylmercaptan added after emulsification was changed to 1.25 g.

The properties of each example are shown in Table 2.

The breathable waterproof cloth of the present invention is excellent in moisture permeability, water resistance and washability.

The breathable waterproof cloth of the present invention can be used for clothing materials such as sports clothing materials, winter clothing materials, waterproof sheets, for example, tents, sleeping bags and antifouling waterproof sheets, shoes and gloves.

Claims (19)

A breathable waterproof fabric comprising an intermediate layer containing a fluorine-containing polymer and a breathable waterproof layer comprising a synthetic resin,
When the fluorine-
(a) Formula:

Wherein X is a hydrogen atom or a methyl group,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
And Rf is a fluoroalkyl group having 1 to 6 carbon atoms]
A fluorine-containing monomer represented by the formula
(b) a halogenated olefin monomer, and
(c) a non-fluorine monomer having no fluorine atom and having at least one carbon-carbon double bond,
Wherein the fluorine-containing polymer is a fluorine-containing polymer having a dynamic viscoelasticity at 160 DEG C of 400 Pa.s or more. The method according to claim 1,
The fluorine-containing monomer (a)

Wherein X is a hydrogen atom or a methyl group;
Y is -O- or -NH-;
Z represents an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,
-CH ₂ CH ₂ N (R ¹ ) SO ₂ - group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) or
-CH ₂ CH (OZ ¹ ) CH ₂ - group (provided that Z ¹ is a hydrogen atom or an acetyl group) or
- (CH ₂ ) _m --SO ₂ - (CH ₂ ) _n - group or - (CH ₂ ) _m -S- (CH ₂ ) _n- group wherein m is 1 to 10 and n is 0 to 10, ,
And Rf is a straight or branched fluoroalkyl group having 1 to 6 carbon atoms]
Waterproof cloth. 3. The method according to claim 1 or 2,
The halogenated olefin monomer (b) is an olefin having 2 to 20 carbon atoms which is substituted with a chlorine atom, a bromine atom or an iodine atom. 4. The method according to any one of claims 1 to 3,
The halogenated olefin monomer (b) is at least one member selected from the group consisting of vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, vinylidene bromide, and vinylidene iodide. 5. The method according to any one of claims 1 to 4,
The non-fluorine monomer (c) is a non-crosslinkable monomer or a crosslinkable monomer. 6. The method according to any one of claims 1 to 5,
The non-fluorine monomer (c)

Wherein A is a hydrogen atom, a methyl group or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom and an iodine atom), T is a hydrogen atom, a straight or cyclic hydrocarbon group having 1 to 30 carbon atoms , Or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond]
The breathable waterproof fabric is shown as. 7. The method according to any one of claims 1 to 6,
The non-fluorine monomer (c), which is a crosslinking monomer, is a mono (meth) acrylate having a reactive group, (meth) diacrylate or mono (meth) acrylamide. 8. The method according to any one of claims 1 to 7,
Wherein the synthetic resin is at least one selected from the group consisting of a polyurethane resin, an acrylic resin and a polyester resin. 9. The method according to any one of claims 1 to 8,
Wherein the moisture permeable waterproof layer is formed by applying a synthetic resin or by attaching a film of a synthetic resin. 10. The method of claim 9,
The synthetic resin film is attached to the intermediate layer of the fluorine-containing polymer by an adhesive. 11. The method according to any one of claims 1 to 10,
And the dynamic viscoelasticity of the fluorine-containing polymer at 150 캜 and 170 캜 is not less than 500 Pa · s and not less than 300 Pa · s, respectively. (I) a step of applying a fluorine-containing treating agent comprising a fluorine-containing polymer to a fiber fabric to form an intermediate layer containing a fluorine-containing polymer, and
(Ii) a step of forming a moisture-permeable waterproof layer by applying a synthetic resin to the intermediate layer of the fluorine-containing polymer
The method of manufacturing a moisture permeable waterproof fabric according to claim 1, 13. The method of claim 12,
Wherein the application of the synthetic resin is performed by applying a synthetic resin or by adhering a film of a synthetic resin. The method according to claim 12 or 13,
Wherein the synthetic resin is at least one selected from the group consisting of a polyurethane resin, an acrylic resin and a polyester resin. The method according to claim 13 or 14,
And a film of a synthetic resin is adhered to an intermediate layer of the fluorine-containing polymer by an adhesive. Wherein the fluorine-containing treating agent comprising a fluorine-containing polymer is applied to a fiber fabric to form an intermediate layer of the fluorine-containing polymer. (a) Formula:

Wherein X is a hydrogen atom or a methyl group,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
And Rf is a fluoroalkyl group having 1 to 6 carbon atoms]
A fluorine-containing monomer represented by the formula
(b) a halogenated olefin monomer, and
(c) a non-fluorine monomer having no fluorine atom and having at least one carbon-carbon double bond,
Containing fluorine-containing polymer having a dynamic viscoelasticity at 160 DEG C of 400 Pa-s or more. A process for producing a fluorine-containing polymer in the moisture-permeable, waterproof fabric of claim 1,
In the manufacturing method,
(I) a step of polymerizing the fluorine-containing monomer (a) and, if necessary, the non-fluorine monomer (c) to obtain a first polymer, and
(II) a step of producing a fluorine-containing polymer by preparing a second polymer formed by the halogenated olefin monomer (b) by polymerizing the halogenated olefin monomer (b) in the presence of the first polymer
≪ / RTI > 19. The method of claim 18,
Wherein the unreacted non-fluorine non-crossing monomer is substantially absent from the polymerization system at the time when the polymerization of the second monomer is initiated.