TWI605939B - Moisture permeable waterproof fabric - Google Patents

Description

Moisture permeable waterproof cloth

The present invention relates to a moisture-permeable waterproof fabric that can be used as a clothing, a waterproof sheet, a shoe, a glove, and the like.

In the past, various techniques have been proposed for the moisture-permeable waterproof fabric (for example, Japanese Patent Publication No. Sho 60-47955 or Japanese Patent Publication No. Hei 4-18066).

The fluoropolymer can impart water repellency and water repellency to the fabric, and can be used as a barrier resin for preventing bleed out of the synthetic resin on the opposite side of the cloth substrate when the synthetic resin forming the moisture permeable waterproof layer is applied. .

However, a polymer containing a fluoroalkyl group having a fluoroalkyl group having 6 or less in response to environmental problems has a low anti-seepage effect when coated with a synthetic resin, and has a problem of easily infiltrating a synthetic resin on the opposite side of the cloth substrate. .

Further, when a film of a synthetic resin is attached, since the adhesive penetrates the fabric, the subsequent effect is weakened, and the peeling strength of the synthetic resin film is lowered.

Patent Document 1: Japanese Patent Publication No. 60-47955

Patent Document 2: Japanese Special Fair 4-18066

The object of the present invention is to provide a moisture permeability, water resistance and washable A moisture-permeable waterproof fabric with excellent polyester properties.

Another object of the present invention is to provide a moisture-permeable waterproof fabric which does not bleed out to the surface on the opposite side of the cloth substrate when the synthetic resin forming the moisture-permeable waterproof layer is applied to the cloth substrate.

The present inventors have found that the above object can be attained when an intermediate layer containing a specific fluoropolymer is disposed between a cloth substrate and a moisture permeable waterproof layer, and the present invention has been completed.

The present invention provides a moisture-permeable waterproof fabric which has an intermediate layer containing a fluoropolymer and a moisture-permeable waterproof fabric containing a moisture-permeable waterproof layer of a synthetic resin, wherein the fluoropolymer has the following Repeating units derived from (a) to (c), and the dynamic viscoelasticity at 160 ° C is 400 Pa. Above s, formula (a): CH ₂ = C(-X)-C(=O)-YZ-Rf fluorinated monomer [wherein, X is a hydrogen atom or a methyl group, and Y is -O - or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 6 carbon atoms; (b) a halogenated olefin monomer, and (c) a fluorine-free metal if necessary A non-fluorine monomer having at least one carbon-carbon double bond of an atom.

In the present invention, there are the following aspects.

A. A method for producing a moisture-permeable waterproof fabric, comprising the steps of: (i) using a fluorine-containing treatment agent containing a fluorine-containing polymer for a fiber cloth to form an intermediate layer containing a fluorine-containing polymer, and (ii) a step of forming a moisture-permeable waterproof layer by using a synthetic resin (for example, by coating a synthetic resin or a film to which a synthetic resin is applied) on the intermediate layer of the fluoropolymer.

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

C. A fluorine-containing treatment agent for moisture-permeable waterproof cloth, comprising a repeating unit derived from the following (a) to (c), and having a dynamic viscoelasticity of 400 Pa at 160 ° C. Above s fluoropolymer.

Formula (a): a fluorine-containing monomer represented by CH ₂ =C(-X)-C(=O)-YZ-Rf [wherein X is a hydrogen atom or a methyl group, and Y is -O- or -NH -, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 6 carbon atoms; (b) a halogenated olefin monomer, and (c) optionally a fluorine-free atom and having at least one Non-fluorinated monomer of carbon-carbon double bond.

D. A method for producing a fluoropolymer in a moisture permeable waterproofing fabric, comprising the steps of: (I) polymerizing a fluorine-containing monomer (a) and optionally a non-fluorine monomer (c) to obtain a first a step of polymer, and (II) polymerizing and halogenating the olefin monomer (b) in the presence of the first polymer, thereby producing a second polymer formed of the halogenated olefin monomer (b), thereby producing a fluorine-containing compound The step of the polymer.

The moisture-permeable waterproof fabric of the present invention is excellent in moisture permeability, water resistance, and washing resistance.

According to the present invention, when the synthetic resin forming the moisture-permeable waterproof layer is applied to the cloth substrate, the synthetic resin does not bleed out to the surface on the opposite side of the cloth substrate.

The moisture permeable waterproof fabric has a cloth substrate, an intermediate layer containing a fluoropolymer on the surface of the cloth substrate 1, and a moisture permeable waterproof layer on the intermediate layer. The intermediate layer can be formed inside the cloth substrate. A graphic layer or a decorative graphic layer may be disposed on the moisture permeable waterproof layer. No layer may be provided on the other surface of the cloth substrate.

The cloth substrate is generally formed of natural fibers and/or synthetic fibers. The fiber of the cloth substrate may be natural fiber (for example, cotton or wool, etc.), chemical fiber (for example, mucus or lyocell, etc.), or synthetic fiber (for example, polyester, polyamide or Acrylic fiber, etc.), or a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.). The form of the cloth base material may, for example, be a woven fabric, a knitted fabric, a non-woven fabric, a raised fabric or the like. The thickness of the cloth substrate is generally from 0.05 to 10 mm, for example from 0.1 to 1 mm.

The moisture permeable waterproof layer contains a synthetic resin. The moisture permeable waterproof layer is generally a microporous film. Specific examples of the synthetic resin are a polyurethane resin, a polyurethane 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 contain an additive such as an isocyanate. The thickness of the moisture permeable waterproof layer is generally from 10 to 100 μm, for example from 20 to 50 μm.

The intermediate layer contains a fluoropolymer. The intermediate layer may be formed only of a fluoropolymer or may also contain an additive such as a melamine resin or a blocked isocyanide. Acid esters, etc. The thickness of the intermediate layer is generally from 0.1 to 1 μm, for example from 0.2 to 0.3 μm. The intermediate layer is excellent in solvent property, and is separated from an organic solvent such as dimethylformamide, toluene or methyl ethyl ketone.

The dynamic viscoelasticity of the fluoropolymer at 160 ° C is 400 Pa. s above.

The dynamic viscoelasticity of the fluoropolymer at 150 ° C is 500 Pa. Above s, especially at 900Pa. Above s is better. The dynamic viscoelasticity of the fluoropolymer at 160 ° C is 400 Pa. Above s, especially at 600Pa. For example, above 800Pa. Above s is better. The dynamic viscoelasticity of the fluoropolymer at 170 ° C is 300 Pa. Above s, especially at 700Pa. Above s is better.

The dynamic viscoelasticity of the fluoropolymer at 150 ° C is 2500Pa. Below s, for example, it can be 2200Pa. s below. The dynamic viscoelasticity of the fluoropolymer at 160 ° C is 2500 Pa. s below, especially 2300Pa. Below s, for example, it can be 2100Pa. s below. The dynamic viscoelasticity of the fluoropolymer at 170 ° C is 2300 Pa. Below s, for example, it can be 2000Pa. s below.

When the dynamic viscoelasticity is too low (for example, the dynamic viscoelasticity at 160 ° C is less than 400 Pa.s), offset is generated, and peeling of the moisture-permeable waterproof layer is liable to occur. When the dynamic viscoelasticity is lower than a certain value, the moisture-permeable waterproof layer will sufficiently adhere to the intermediate layer.

The manufacture of the moisture permeable waterproofing fabric is carried out by the following steps: (i) a step of using a fluorine-containing treatment agent containing a fluorine-containing polymer to form an intermediate layer of a fluorine-containing polymer, and (ii) a step of forming a moisture-permeable waterproof layer over the intermediate layer of the fluoropolymer. The formation of the moisture-permeable waterproof layer can be carried out, for example, by applying a synthetic resin or a film to which a synthetic resin is attached.

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

The fluoropolymer having a repeating unit derived from a fluorine-containing monomer and a non-fluorine monomer can be produced by one-time filling (one-stage polymerization) or fractional packing (multistage polymerization, particularly two-stage polymerization). Since the effect of preventing the bleeding of the synthetic resin can be improved, it is preferable to use a divided filling. The divided filling (multistage polymerization, particularly the two-stage polymerization) means that the loading of one or more monomers is delayed (starting polymerization), and charging of one or more types of monomers (starting polymerization) is carried out. The term "second-stage polymerization" refers to a polymerization of a second monomer containing one or more other monomers in the presence of a first polymer obtained by polymerizing a first monomer containing one or more kinds of monomers.

Multi-stage polymerization is a polymerization of two or more stages, such as two-stage polymerization, three-stage polymerization, and four-stage polymerization. In the three-stage polymerization, a third polymer which delays the loading of the second polymer is used in addition to the first polymer and the second polymer. For the polymerization of four or more stages, the monomer of the fourth or more is further used.

Hereinafter, a two-stage polymerization representative of a multi-stage polymerization will be described.

In a fractional charge (particularly a two-stage polymerization), generally, the fluoropolymer contains fluorine contained in the first polymer formed from the first monomer and the second polymer formed from the second monomer. In the polymer, the fluoropolymer comprises: polymerizing the second monomer in the presence of the first polymer, and at least one of the first monomer and the second monomer contains the fluorine-containing monomer (a). The first monomer does not contain a halogenated olefin monomer (b), and the second monomer contains a halogenated olefin monomer (b).

Fractional filling (especially two-stage filling) method, A method for producing a fluoropolymer comprising a first polymer formed of a first monomer and a second polymer formed of a second monomer, wherein the method has the following steps: (I) 1 step of polymerizing the monomer to obtain a first polymer, and (II) polymerizing the second monomer in the presence of the first polymer to obtain a second polymer, the first monomer and the second single At least one of the bodies contains a fluorine-containing monomer, the first single system contains a non-fluorine non-crosslinkable monomer, and the halogenated olefin monomer is not contained, and the second monomer is a method for producing a halogenated olefin monomer.

In the present invention, the first monomer may contain a halogenated olefin monomer or may not contain a halogenated olefin monomer. The first monomer is preferably a halogen-free olefin monomer.

The fluoropolymer 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 are chemically bonded. Alternatively, the first polymer and the second polymer may be physically bonded without forming a chemical bond. In the case of physical bonding, the first polymer forms a core and the second polymer forms a core/shell structure of the shell. In the core/shell structure, the first polymer and the second polymer are not chemically bonded, but may be chemically bonded.

In the present invention, the monomer is a fluorine-containing monomer (a) and a halogenated olefin monomer (b). The non-fluorine monomer (c) may be used as needed, and may be a non-fluorine non-crosslinkable monomer and/or a non-fluorine crosslinkable monomer. The non-fluorine monomer (c) is preferably a non-fluorine non-crosslinkable monomer (c1), and may be a non-fluorine crosslinkable monomer (c2).

At least one of the first monomer and the second monomer contains a fluorine-containing monomer. Preferably, the first monomer contains a fluorine-containing monomer, and the second monomer does not contain a fluorine-containing monomer.

Preferably, the first monomer does not contain a halogenated olefin monomer, and the second monomer contains a halogenated olefin monomer. The second monomer may also contain only halogenated olefin monomers.

The first monomer may also contain a non-fluorine non-crosslinkable monomer. The second monomer is preferably one which does not contain a non-fluorine non-crosslinkable monomer. When the second monomer does not contain a non-fluorine non-crosslinkable monomer, the effect of preventing the contamination of the roll due to adhesion of the polymer to the roll is excellent in the processing of the treatment agent containing the fluoropolymer.

At least one of the first monomer and the second monomer may further contain a non-fluorine crosslinkable monomer. When the fluoropolymer contains a non-fluorine crosslinkable monomer, the first monomer may contain no non-fluorine crosslinkable monomer, and the second monomer may contain a non-fluorine crosslinkable monomer, or 1 The monomer contains a non-fluorine crosslinkable monomer, and the second monomer does not contain a non-fluorine crosslinkable monomer.

The preferred types of the monomers in the first monomer and the second monomer are as follows.

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

It is also preferred that the fluorine-containing monomer and the non-fluorine-crosslinkable monomer are present in the first monomer and the second monomer, respectively. That is, the fluorine-containing monomer is present in the first monomer and the second monomer. It is also preferable that the non-fluorine-crosslinkable monomer other than the first state and the second monomer are the same as those of the first and second monomers. .

(a) fluoromonomer

Fluorine-containing single system: a fluorine-containing monomer represented by CH ₂ =C(-X)-C(=O)-YZ-Rf, wherein X is a hydrogen atom or a methyl group, and 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. ]. Z is, for example, a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group, for example, a group represented by the formula -(CH ₂ ) _x - (wherein, x is 1 to 10), or -SO ₂ 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 carbon number of 1 to 10 a linear alkyl group or a branched alkyl group), or a formula -CH ₂ CH(OR ³ )CH ₂ - (wherein R ³ represents a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms (for example, A a group represented by a fluorenyl group or an ethyl hydrazide group or the like, or a group represented by the formula -Ar-CH ₂ - (wherein, Ar is an optionally extended aryl group having a substituent), -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n -yl or -(CH ₂ ) _m -S-(CH ₂ ) _n -yl (where m is from 1 to 10 and n is from 0 to 10).

The fluorine-containing monomer (a) is preferably an acrylate or acrylamide represented by the following formula (I), CH ₂ =C(-X)-C(=O)-YZ-Rf (I)

[wherein, X is a hydrogen atom or a methyl group; Y is -O- or -NH-; Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms), -CH ₂ CH(OZ ¹ )CH ₂ - group (wherein Z ¹ is a hydrogen atom) Or ethoxylated), -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n -yl or -(CH ₂ ) _m -S-(CH ₂ ) _n -yl (where m is 1 to 10, n It is 0 to 10), and Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms. ].

The α-position of the fluorine-containing monomer (a) (acrylic acid ester or methacrylic acid ester) may be substituted with a halogen atom or the like. Therefore, in the formula (1), X may also be a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (wherein 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 linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, and a substitution. Or unsubstituted phenyl.

In the above formula (1), the Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is from 1 to 6, especially from 4 to 6. Examples of the Rf group are -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 , -C ₈ F ₁₇ and the like.

Z preferably is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, or a -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (wherein R ¹ Is an alkyl group having 1 to 4 carbon atoms, -CH ₂ CH(OZ ¹ )CH ₂ - group (wherein Z ¹ is a hydrogen atom or an ethylene group), -(CH ₂ ) _m -SO ₂ -(CH _{2 n} - group or -(CH ₂ ) _m -S-(CH ₂ ) _n - group (where m is 1 to 10 and n is 0 to 10)). The aliphatic group is preferably an alkylene group (particularly a carbon number of 1 to 4, such as 1 or 2). The aromatic group or the cyclic aliphatic group may be substituted or unsubstituted. The S group or the SO ₂ group may be directly bonded to the Rf group.

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

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -Rf

CH ₂ =C(-H)-C(=O)-OC ₆ H ₄ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ N(-CH ₃ )SO ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ N(-C ₂ H ₅ )SO ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-CH ₂ CH(-OH)CH ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-CH ₂ CH(-OCOCH ₃ )CH ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-H)-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-NH-(CH ₂ ) ₂ -Rf

[In the above formula, Rf is a fluoroalkyl group having 1 to 6 carbon atoms. ]

(b) Halogenated olefin monomer

The halogenated olefin monomer (b) is preferably an olefin having 2 to 20 carbon atoms which is substituted with a chlorine atom, a bromine atom or an iodine atom of 1 to 10. 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 having 1 to 5 carbon atoms. Preferred examples of the halogenated olefin monomer (b) are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as dichloroethylene, dibromoethylene and diiodoethylene. Vinyl chloride is preferred because it can improve water resistance (especially durability against water resistance).

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

(c1) non-fluorine non-crosslinkable monomer

The non-fluorine non-crosslinkable monomer (c1) is a monomer having no fluorine atom. The non-fluorine non-crosslinkable monomer (c1) does not have a crosslinkable functional group. The non-fluorine non-crosslinkable monomer (c1) is different from the crosslinkable monomer (c2) and is non-crosslinkable. The non-fluorine non-crosslinkable monomer (c1) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (c1) is preferably a fluorine-free ethylene monomer. The non-fluorine non-crosslinkable monomer (c1), in general, is a compound having one carbon-carbon double bond.

A preferred non-fluorine non-crosslinkable monomer (c1) can be of the formula: CH ₂ =CA-T

[In the formula, A 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); and T is a hydrogen atom and a chain having a carbon number of 1 to 30 (for example, 1 to 20). A hydrocarbon compound having a cyclic or cyclic hydrocarbon group or a chain or cyclic carbon group having an ester bond of 1 to 31 (for example, 1 to 20).

Examples of the chain or cyclic hydrocarbon group having 1 to 30 carbon atoms are a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, and a carbon number of 6 to 30. An aromatic hydrocarbon group or an aromatic hydrocarbon group having 7 to 30 carbon atoms.

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

Preferred examples of the non-fluorine non-crosslinkable monomer (c1) include, for example, ethylene, vinyl acetate, propionitrile, styrene, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. , methoxypolyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, and vinyl alkyl ether. The non-fluorine non-crosslinkable monomer (c1) is not limited to these examples.

The non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate having an alkyl group. The number of carbon atoms of the alkyl group may be from 1 to 30, for example from 6 to 30 (for example, from 10 to 30). For example, the non-fluorine non-crosslinkable monomer (c1) may be of the formula: CH ₂ =CA ¹ COOA ²

[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); and A ² is a C _n H _2n+1 (n=1 to 30) Indicates the alkyl group. The acrylate represented.

Since the polymer can be highly prevented from adhering to the rollers, and therefore, the fluorine-containing polymer, preferably having a carbon number of A ² is from 12 to 30, especially 18 to 30 of the alkyl acrylate (CH ₂ = CA ¹ COOA ² ) Derived repeating units.

The non-fluorine non-crosslinkable 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 (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth) acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth) acrylate group are directly bonded. The cyclic hydrocarbon group may, for example, be a saturated or unsaturated monocyclic group, a polycyclic group or a crosslinked cyclic group. A cyclic hydrocarbon group is preferred as a saturated one. The cyclic hydrocarbon group preferably has a carbon number of 4 to 20. Cyclic hydrocarbon The base may, for example, be 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, or an aromatic aliphatic group having 7 to 20 carbon atoms. The number of carbon atoms of the cyclic hydrocarbon group is 15 or less, and particularly preferably 10 or less. The carbon atom in the ring of the cyclic hydrocarbon group is preferably an ester group directly bonded to the (meth) acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a tertiary butylcyclohexyl group, an isodecyl group, a dicyclopentanyl group, and a dicyclopentenyl group. The (meth) acrylate group is an acrylate group or a methacrylate group, and a methacrylate group is preferred. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl methacrylate, butyl cyclohexyl methacrylate, benzyl methacrylate, isodecyl methacrylate, isodecyl acrylate, and the like. Dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, and the like.

(c2) non-fluorine crosslinkable monomer

The fluoropolymer of the present invention may also have a repeating unit derived from a non-fluorine crosslinkable monomer (c2). The non-fluorine crosslinkable monomer (c2) is a monomer having no 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 containing no 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 blocked isocyanate group, an amine group, a carboxyl group and the like. The non-fluorine-crosslinkable monomer (c2) may be a mono(meth)acrylate, a (meth)diacrylate or a mono(methyl)methyleneamine having a reactive group. Alternatively, the non-fluorine crosslinkable monomer (c2) may be a di(meth)acrylate.

The non-fluorine-crosslinkable monomer (c2) may, for example, be diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (A) Acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) propylene Acid ester, 2-acetamethylene ethoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 1,6-hexane The alcohol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. are not limited to these.

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

By polymerizing the non-fluorine non-crosslinkable monomer (c1) and/or the non-fluorine crosslinkable monomer (c2), it is possible to improve the water repellency or the antifouling property as well as the cleaning resistance and resistance of the properties. Various properties such as detergency, solubility in a solvent, hardness, and touch.

In the fluoropolymer, the halogenated olefin (b) is used in an amount of 2 to 500 parts by weight, for example 5 to 200 parts by weight, particularly 10 to 150 parts by weight, based on 100 parts by weight of the fluoromonomer (a). It is 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.

In the fluoropolymer, the amount of the non-fluorine non-crosslinkable monomer (c1) is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 to 1 part by weight based on 100 parts by weight of the fluorinated monomer (a). The amount of the non-fluorine-crosslinkable monomer (c2) is 50 parts by weight or less, for example, 30 parts by weight or less, particularly preferably 0.1 to 20 parts by weight, per 100 parts by weight.

When the same type of monomer (for example, a halogenated olefin monomer and a fluorine-containing monomer) is contained in both the first monomer and the second monomer, the same monomer (especially a halogenated olefin monomer) in the first monomer The weight ratio of the same monomer (especially the halogenated olefin monomer) in the second monomer is from 3 to 97:97 to 3, for example from 5 to 90:95 to 10, particularly from 10 to 70:90 to 30.

The fluoropolymer in the present invention can be produced by any usual polymerization method, and the conditions of the polymerization reaction can also be arbitrarily selected. Examples of the polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization.

The solution polymerization is carried out by dissolving a monomer in an organic solvent in the presence of a polymerization initiator, and heating and stirring at a temperature of from 30 to 120 ° C for 1 to 10 hours. The polymerization initiator may, for example, be azobisisobutyronitrile, benzammonium peroxide, di-tertiary butyl peroxide, lauryl peroxide, cumene hydroperoxide or triisobutyl peroxyisobutyrate. Ester, diisopropyl peroxydicarbonate, 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 such that the monomer can be dissolved under inactivity, for example, it can be an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate), or a ketone (for example). A ketone having 2 to 30 carbon atoms, specifically, methyl ethyl ketone or diisobutyl ketone, an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropanol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, and 1,4. - Dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane Alkane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, 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 of the monomers.

The emulsion polymerization is carried out by emulsifying a monomer in water in the presence of a polymerization initiator and an emulsifier, and after substituting nitrogen, stirring is carried out at 50 to 80 ° C for 1 to 10 hours to copolymerize. As a polymerization initiator, benzene peroxide can be used. Hyperthyroidism, ruthenium peroxide, butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropenyl peroxide, acetonitrile peroxide, azobisisobutyl hydrazine- Water-soluble ones of dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, etc., or azobisisobutyronitrile, benzammonium peroxide, di- and tri-butyl peroxide An oil-soluble one of a base, a lauryl peroxide, cumene hydroperoxide, a tertiary butyl peroxyisobutyrate, or a diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

In order to obtain an aqueous dispersion of the copolymer which is excellent in stability, it is preferred to use an emulsification device such as a high-pressure homogenizer or an ultrasonic homogenizer which can impart a strong breaking energy to make the monomer granulated in water and use oil-soluble. The polymerization initiator is subjected to polymerization. Further, the emulsifier may be an anionic, cationic or nonionic emulsifier, and is used in an amount of from 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. It is preferred to use an anionic and/or nonionic and/or cationic emulsifier. When the monomers are not completely compatible, it is preferred to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer which enables the monomers to be sufficiently compatible. Emulsifying properties and copolymerization properties can be improved by adding a compatibilizing agent.

The water-soluble organic solvent may, for example, be acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol or the like, and is 1 to 50 parts by weight, for example, 10 parts by weight based on 100 parts by weight of water. It is used in the range of 40 parts by weight. Further, examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like, and 100 parts by weight based on the total amount of the monomers. It can be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.

In the polymerization, a chain transfer agent can also be used. According to the use of chain transfer agent The amount can change the molecular weight of the copolymer. Examples of the chain transfer agent include a thiol group-containing compound such as lauryl mercaptan, thioglycol, or thioglycerol (particularly (for example, an alkylthiol having 1 to 30 carbon atoms), sodium phosphite, and sodium hydrogen sulfite. Such as inorganic salts. The amount of the chain transfer agent used may be 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 fluoropolymer can be carried out by one-time filling (one-stage polymerization) or fractional packing (multi-stage polymerization, especially two-stage polymerization). Partial loading is preferred, but when cross-linking monomers are used, they can be filled at once.

In the second-stage polymerization, generally, a first polymer is polymerized by a liquid containing a first monomer to produce a first polymer, and then a first polymer and a liquid containing a second monomer are subjected to a polymerization reaction to produce a first polymer. 2, a polymer, and a fluoropolymer composed of a first polymer and a second polymer. The polymerization of the second polymer may be started in the polymerization of the first polymer, or the polymerization of the second polymer may be started after the polymerization of the first polymer is completed. The polymerization reaction of the first polymer (that is, the polymerization reaction of the first monomer) ends 10% or more (that is, 10 to 100%), for example, 40% or more (that is, 40 to 100%), particularly After 70% or more (i.e., 70 to 100%), the polymerization of the second polymer is started. The percentage of completion of the polymerization reaction (that is, the ratio of the polymerization reaction to %) means the molar % of the monomer (polymerized monomer) which completes the reaction. For example, when the polymerization reaction is 10%, the monomer which is polymerized is 10 mol%, and the unreacted (unpolymerized) monomer is 90 mol%. When the first monomer is a combination of at least two monomers, the mole % of the first monomer is based on the total of at least two monomers of the first monomer.

The polymerization of the first polymer means that the polymerization reaction of the first polymer (that is, the polymerization reaction of the first monomer) is not completely completed. For example, it may be 10% or more to less than 40%, 40% or more to less than the end of the polymerization of the first polymer. The polymerization of the second polymer is started after 70%, or 70% or more to less than 100% (particularly 80 to 99%, particularly 85% to 98%).

When the polymerization of the first polymer is completed, it means that the reaction of the first polymer (that is, the polymerization reaction of the first monomer) is about 100%.

When the polymerization of the second polymer is started in the polymerization of the first polymer, the second polymer has a repeating unit derived from the first monomer and the second monomer. When the polymerization of the second polymer is started after the polymerization of the first polymer is completed, the second polymer has only the repeating unit derived from the second monomer.

In the fluoropolymer of the present invention, the first polymer may or may not be chemically bonded to the second polymer.

At the time of starting the polymerization of the second monomer, it is preferred that substantially no unreacted non-fluorine non-crosslinkable monomer is present in the polymerization system. The term "substantially absent" means that the amount of unreacted non-fluorine non-crosslinkable monomer at the time of starting the polymerization of the second monomer is relative to the amount of the non-fluorine non-crosslinkable monomer charged. 10 mol% or less, preferably 8 mol% or less, more preferably 5 mol% or less, particularly preferably 3 mol% or less, particularly preferably 1 mol% or less. When the non-fluorine non-crosslinkable monomer is substantially absent, the effect of preventing the contamination of the roll due to adhesion of the polymer to the roll is excellent in the processing of the treatment agent containing the fluoropolymer.

The fluoropolymer of the present invention is preferably produced by emulsion polymerization. In the particles of the aqueous dispersion formed of the first polymer and the second polymer, the second polymer may surround the first polymer, and the fluoropolymer may have a first polymer surrounded by the shell of the second polymer. The core/shell structure of the core.

The fluoropolymer may be used for the substrate cloth by any known method in order to form a film of the polymer on the substrate cloth. In general, fluoropolymerization After the substance and the liquid containing the liquid medium are used on the cloth substrate, the film of the fluoropolymer can be formed on the polymer by removing the liquid medium by drying or the like. The concentration of the fluoropolymer in the fluoropolymer and the liquid containing the liquid medium may be, for example, 0.01 to 20% by weight, particularly 0.05 to 10% by weight. The substrate cloth may be immersed in a solution, or the liquid may be attached or sprayed to the substrate cloth. The substrate cloth using the liquid can be dried, for example, in order to exhibit liquid repellency, and is preferably heated, for example, at 100 ° C to 200 ° C.

The treated fibrous product, typically a cloth, also comprises a fabric, a knitted fabric and a non-woven fabric, a cloth in the form of a garment, and a carpet, and may also be a fiber or a yarn or an intermediate fiber product (for example, a sliver or a thick Yarn, etc.). The fibrous product material may be natural fibers (for example, cotton or wool, etc.), chemical fibers (for example, mucus or soluble fibers, etc.), or synthetic fibers (for example, polyester, polyamide or acrylic fibers, etc.). Alternatively, a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.). The polymer produced by the present invention is particularly effective in oleophobicity and oil repellency of cellulose-based fibers (for example, cotton or enamel). Further, the method of the present invention generally makes the fibrous product hydrophobic and water repellency.

Alternatively, the fibrous substrate may also be leather. In order to produce a polymer and to make the leather hydrophobic and oleophobic, it can be used for leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, for example, during the wet processing of leather or during the processing of leather.

Alternatively, the fibrous substrate can also be paper. The manufactured polymer can be used in previously formed paper or in various stages of papermaking, such as during the drying of paper.

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

The surface treatment agent (fluorine-containing treatment agent) of the present invention preferably contains a fluorine-containing polymer and an aqueous medium. In the present specification, the term "aqueous medium" means a medium containing only water and an organic solvent in addition to water (the amount of the organic solvent is 80 parts by weight or less, for example, 0.1 to 50 parts by weight based on 100 parts by weight of water. Parts, especially 5 to 30 parts by weight of the medium. The fluoropolymer is preferably produced by emulsion polymerization to produce a dispersion of a fluoropolymer. The surface treatment agent is preferably an aqueous dispersion in which particles of the fluoropolymer are dispersed in an aqueous medium. The average particle diameter of the fluoropolymer in the dispersion is preferably from 0.01 to 200 μm, for example from 0.1 to 5 μm, particularly from 0.05 to 0.2 μm. The average particle diameter can be measured by a dynamic light scattering device, an electron microscope, or the like.

The surface treatment agent of the present invention can be used in the object to be treated by a conventional method. Usually, the surface treatment agent is dispersed in an organic solvent or water, diluted, and adhered to the surface of the object to be dried by a known method such as dip coating, spray coating, or bubble coating. Further, if necessary, it may be used together with a suitable crosslinking agent to carry out curing. Further, the surface treatment agent of the present invention may be added with an insecticide, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixative, an anti-wrinkle agent, or the like. The concentration of the fluoropolymer in the treatment liquid in contact with the substrate may be (particularly, during dip coating) of 0.01 to 20% by weight, particularly 0.05 to 10% by weight.

[Examples]

Next, the present invention will be specifically described by way of examples, comparative examples and test examples. However, the invention is not limited to the description.

Hereinafter, parts or %, unless otherwise specified, means parts by weight or % by weight.

The characteristics were measured by the following methods.

Monomer composition in the polymer:

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

Dynamic viscoelasticity measurement:

10 g of the aqueous dispersion of the polymer was dispersed in 20 g of methanol, and the acrylic polymer was separated from the emulsifier at 10,000 rpm for 60 minutes in a centrifuge to obtain a sample polymer for measurement. The complex viscosity (η*) of the polymer was measured by a dynamic viscoelasticity measuring apparatus RHEOSOL-G3000 (manufactured by UBM). The dynamic viscoelasticity was measured by raising the temperature of the sample polymer by 1 g, the frequency of 0.5 Hz, and the measurement temperature from 40 ° C to 5 ° C / min to 180 ° C.

Dial solvent:

The aqueous dispersion of the polymer was diluted with water so that the solid content concentration became 1% by weight, and the mixture was adjusted to a treatment liquid. The nylon fabric was immersed in the treatment liquid, wrung at 4 kg/cm ² and 4 m/min in a roll, and heat-treated at 170 ° C for 1 minute, and the solvent property of the treated cloth was evaluated.

For the solvent property, DMF, MEK, toluene, and ethyl acetate were respectively dropped on the test cloth, and the time during which the solvent was absorbed by the cloth was measured (up to 120 seconds), and the solvent property was shown by time. The higher the value, the better the solvent property.

Exudation of coating resin:

The aqueous dispersion of the polymer was diluted with water so that the solid content concentration became 1% by weight, and the mixture was adjusted to a treatment liquid. The nylon cloth was immersed in the treatment liquid, wrung at 4 kg/cm ² and 4 m/min with a roll, and after heat treatment at 170 ° C for 1 minute, a polyaminocarboxylic acid having a concentration of 30% in MEK/toluene/DMF as a solvent was used. The ester resin (RESAMINE ME-3612LP manufactured by Daisei Seiki Co., Ltd.) was uniformly applied to one side of the nylon fabric, dried at 100 ° C for 1 minute, and then heat-treated at 150 ° C for 1 minute. The non-coated surface was visually observed, and the bleed out of the resin was evaluated as follows.

◎: no leakage at all

○: very little exudation

×: a large amount of oozing

Peel strength of synthetic film:

The aqueous dispersion of the polymer was diluted with water so that the solid content concentration became 1% by weight, and the mixture was adjusted to a treatment liquid. The nylon cloth was immersed in the treatment liquid, wrung at 4 kg/cm ² , 4 m/min with a roll, and heat treated at 170 ° C for 1 minute, and then a urethane having a concentration of 50% in MEK/ethyl acetate as a solvent. A resin-based adhesive (CRISVON 4010FT) was applied to one side of the nylon fabric, and the synthetic film of the polyurethane was pressure-bonded, followed by heat treatment at 120 ° C for 2 minutes. The obtained nylon fabric was repeatedly washed 20 times with AATCC 88B (1) (III), and the peeled state of the synthetic film was visually observed, and the state thereof was evaluated as follows.

◎: no peeling at all

○: There is very little peeling

×: Clearly known to be stripped

Example 1

Two-stage aggregation:

In a 1 L autoclave, 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, and 446 g of pure water were placed. 12.7 g of oxyethylene lauryl ether, 2.47 g of polyoxyethylene oleyl ether, 5.05 g of polyoxyethylene isotridecyl ether, 2.66 g of dialkyl (bovine ester) dimethyl ammonium chloride, after heating at 60 ° C It is emulsified and dispersed by a high pressure homogenizer. After emulsifying and dispersing, 1.92 g of 2,2-azobis(2-formamidinylpropane) hydrochloride was added, and the reaction was carried out at 60 ° C for 1 hour (polymerization C6SFMA completed 99%, StA completed 97%). Next, 60 g of vinyl chloride was charged and further reacted for 2 hours to obtain an aqueous dispersion of the polymer. The concentration of the aqueous dispersion was measured by adjusting the concentration with pure water so that the solid content concentration thereof was 30% by weight. The results are shown in Table A.

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 the emulsification.

The polymerization reaction in the vinyl chloride filling time point (the end of a polymerization period) was 99% for C6SFMA and 96% for StA.

Example 3

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

The polymerization reaction at the time of filling of the vinyl chloride (the end of a polymerization period) was 99% for C6SFMA and 95% for StA.

Example 4

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

The polymerization reaction at the time of filling of vinyl chloride (the end of a polymerization period) was 99% for C6SFMA and 96% for StA.

Example 5

Except that _{C 6 F 13 CH 2 CH 2} OCOCH = CH 2 (C6SFA) 179g substituted _{C 6 F 13 CH 2 CH 2} OCOC (CH 3) = CH 2 179g addition, in the same manner as described in Example 2 to obtain a polymer of Dispersion.

The polymerization reaction at the time of filling of the vinyl chloride (the end of a polymerization period) was 99% for C6SFA and 95% for StA.

Example 6

A dispersion of the polymer 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).

The polymerization reaction at the time of filling of the vinyl chloride (the end of a polymerization period) was 99% for C6SFMA and 98% for CHMA.

Example 7

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

The polymerization reaction at the time of filling of vinyl chloride (the end of polymerization) was 99% for C6SFMA and 99% for 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 in Example 2.

The polymerization reaction at the time of filling of vinyl chloride (the end of a polymerization period) was 99% for C6SFMA and 96% for 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 in Example 2.

The polymerization reaction at the time of filling of vinyl chloride (the end of a polymerization period) was 99% for C6SFMA and 96% for StA.

Example 10

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

The polymerization reaction at the time of filling of vinyl chloride (the end of a polymerization period) was 99% for C6SFMA and 96% for StA.

Example 11

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

The polymerization reaction at the time of filling of vinyl chloride (the end of a polymerization period) was 99% for C6SFMA and 96% for StA.

Example 12

In a 1 L autoclave, 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, and 446 g of pure water were placed. 12.7g of polyoxyethylene lauryl ether, 2.47g of polyoxyethylene oleyl ether, 5.05g of polyoxyethylene isotridecyl ether, 2.66g of dialkyl (bovine ester) dimethyl ammonium chloride, heated at 60 ° C Thereafter, it was emulsified and dispersed by a high pressure homogenizer. After emulsification, 0.025 g of lauryl mercaptan was added, and 60 g of vinyl chloride was pressed into the filling. Further, 1.92 g of 2,2-azobis(2-methylamidinopropane) 2 hydrochloride was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. The concentration of the aqueous dispersion was measured by adjusting the concentration with pure water so that the solid content concentration thereof was 30% by weight. The results are shown in Table A.

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 the emulsification.

Polymerization reaction at the point of filling of vinyl chloride (the end of polymerization) C6SFMA completed 99% and StA completed 95%.

Comparative example 2

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

The polymerization reaction at the time of filling of vinyl chloride (the end of a polymerization period) was 99% for C6SFMA and 96% for 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 in Example 2.

The polymerization reaction at the time of filling of vinyl chloride (the end of a polymerization period) was 99% for C6SFMA and 96% for 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 lauryl mercaptan added after the emulsification was changed to 1.25 g.

The characteristics of each example are shown in Table A.

The moisture-permeable waterproof fabric of the present invention is excellent in moisture permeability, water resistance and washing resistance.

The moisture-permeable waterproof fabric of the present invention can be used for clothing materials such as sportswear or cold-resistant fabrics, waterproof sheets, such as tents, sleeping bags and anti-fouling waterproof sheets, shoes and gloves, and the like.

Claims (19)

A moisture-permeable waterproof fabric having an intermediate layer containing a fluoropolymer and a moisture-permeable waterproof layer containing a synthetic resin, wherein the fluoropolymer has the following (a) and (b) Repeat unit, and the dynamic viscoelasticity at 160 °C is 400Pa. Above s and is 2300Pa. s or less; (a) Formula: CH ₂ =C(-X)-C(=O)-YZ-Rf fluorinated monomer [wherein, X is a hydrogen atom or a methyl group, and Y is -O- Or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 6 carbon atoms; and (b) a halogenated olefin monomer; the fluoropolymer is contained in the first The first polymer formed by the body and the second polymer formed of the second monomer, and the second polymer of the fluoropolymer is polymerized in the presence of the first polymer; the first monomer At least one of the second monomers contains a fluorine-containing monomer (a), the first monomer does not contain a halogenated olefin monomer (b), and the second single system contains a halogenated olefin monomer (b). The moisture-permeable waterproof fabric according to claim 1, wherein the fluorine-containing monomer (a) is represented by the following formula (I): CH ₂ =C(-X)-C(=O)- YZ-Rf (I) [wherein, X is a hydrogen atom or a methyl group; Y is -O- or -NH-; Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, a -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms), a -CH ₂ CH(OZ ¹ )CH ₂ - group (wherein , Z ¹ is a hydrogen atom or an ethylene group), or a -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n - group or a -(CH ₂ ) _m -S-(CH ₂ ) _n - group (where m is 1 to 10, n is 0 to 10); Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms. The moisture-permeable tarpaulin shown in claim 1 or 2, wherein 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. The moisture-permeable tarpaulin according to claim 1 or 2, wherein the halogenated olefin monomer (b) is selected from the group consisting of vinyl chloride, vinyl bromide, iodoethylene, dichloroethylene, dibromoethylene and diiodide. At least one of the group consisting of vinylidene. The moisture-permeable waterproof fabric according to claim 1 or 2, wherein the fluoropolymer is further derived from (c) a non-fluorine monomer having no fluorine atom and having at least one carbon-carbon double bond. The repeating unit, the non-fluorinated monomer (c) is a non-crosslinkable monomer or a crosslinkable monomer. The moisture-permeable waterproof fabric according to claim 5, wherein the non-fluorinated monomer (c) is represented by the following formula: CH ₂ = CA-T [wherein, A is a hydrogen atom, a methyl group, Or a halogen atom other than a fluorine atom; T is a hydrogen atom, a chain 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 moisture-permeable waterproof fabric according to claim 5, wherein the non-fluorinated monomer (c) which is a crosslinkable monomer is a mono(meth)acrylate or a (meth)acrylate having a reactive group. Acrylate or mono(meth)acrylamide. The moisture-permeable waterproof fabric according to claim 1 or 2, 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 moisture-permeable waterproof fabric according to claim 1 or 2, wherein the moisture-permeable waterproof layer is formed by coating a synthetic resin or a film to which a synthetic resin is attached. The moisture-permeable waterproof fabric according to claim 9, wherein the synthetic resin film is adhered to the intermediate layer of the fluoropolymer by an adhesive. The moisture-permeable waterproof fabric according to claim 1 or 2, wherein the dynamic viscoelasticity of the fluoropolymer at 150 ° C and 170 ° C is 500 Pa. s above, 300pa. s above. A method for producing a moisture-permeable waterproof fabric according to claim 1, which comprises the steps of: (i) using a fluorine-containing treatment agent containing a fluorine-containing polymer for the fiber cloth to form a fluorine-containing polymerization product; And the step of (ii) using a synthetic resin on the intermediate layer of the fluoropolymer, thereby forming a moisture-permeable waterproof layer. The production method according to claim 12, wherein the use of the synthetic resin is carried out by applying a synthetic resin or a film to which a synthetic resin is attached. The production method according to claim 12, 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 manufacturing method according to claim 13, wherein the film of the synthetic resin is adhered to the intermediate layer of the fluoropolymer by an adhesive. The invention relates to a fluorine-containing treatment agent for moisture-permeable waterproof cloth, which comprises: a repeating unit derived from the following (a) and (b), and a dynamic viscoelasticity of 160 Pa at 160 ° C. Above s and is 2300Pa. For fluoropolymers below s, formula (a): fluoromonomer represented by 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, Rf is a fluoroalkyl group having 1 to 6 carbon atoms; and (b) a halogenated olefin monomer; the fluoropolymer The first polymer formed of the first monomer and the second polymer formed of the second monomer, and the second polymer is polymerized in the presence of the first polymer; the first monomer At least one of the second monomers contains a fluorine-containing monomer (a), the first monomer does not contain a halogenated olefin monomer (b), and the second single system contains a halogenated olefin monomer (b). A method for producing a fluoropolymer in a moisture-permeable waterproof fabric according to claim 1, wherein the method comprises the steps of: (I) polymerizing a first monomer containing a fluorine-containing monomer (a) to obtain a first a step of polymerizing (1), and polymerizing a second monomer containing a halogenated olefin monomer (b) in the presence of a first polymer, thereby producing a second single containing a halogenated olefin monomer (b) A step of preparing a fluoropolymer by forming a second polymer. The process according to claim 17, wherein at the time of starting the polymerization of the second monomer, substantially no unreacted non-fluorine non-crosslinkable monomer is present in the polymerization system. A method for treating a fiber cloth, which is characterized in that a fluorine-containing treatment agent for a moisture-permeable waterproof cloth according to claim 16 of the patent application is used for the fiber cloth to form an intermediate layer of the fluorine-containing polymer.