CN104411880B - Moisture-permeable water-proof fabric - Google Patents

Moisture-permeable water-proof fabric Download PDF

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Publication number
CN104411880B
CN104411880B CN201380035883.3A CN201380035883A CN104411880B CN 104411880 B CN104411880 B CN 104411880B CN 201380035883 A CN201380035883 A CN 201380035883A CN 104411880 B CN104411880 B CN 104411880B
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monomer
fluoropolymer
moisture
fluorine
polymer
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CN104411880A (en
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原良辅
川部留美
宫原正弘
福森正树
奥村胜也
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Daikin Industries Ltd
Nicca Chemical Co Ltd
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Daikin Industries Ltd
Nicca Chemical Co Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing

Abstract

The present invention provides a kind of penetrability, water resistance and the excellent moisture-permeable water-proof fabric of washing fastness.The moisture-permeable water-proof fabric has the intermediate layer containing fluoropolymer and the moisture-permeability waterproof layer containing synthetic resin, fluoropolymer has the repetitive unit from following monomers (a), (b) and (c), and the dynamic viscoelastic at 160 DEG C is more than 400Pas, (a) fluorochemical monomer shown in following formula, CH2=C (- X)-C (=O)-Y-Z-Rf [in formula, X is hydrogen atom or methyl, and Y is-O- or-NH-, and Z is the organic group of Direct Bonding or divalence, and Rf is the fluoroalkyl of carbon number 1~6]；(b) halogenated olefins monomer；(c) non-fluorine monomer using as needed, without fluorine atom and at least with a carbon-to-carbon double bond.

Description

Moisture-permeable water-proof fabric
Technical field
The present invention relates to a kind of moisture-permeable water-proof fabric that can be used as dress material, waterproof sheet, footwear and gloves etc..
Background technology
At present, on moisture-permeable water-proof fabric, motion have various technologies (for example, Japanese Patent Publication 60-47955 publications, Japanese Patent Publication 4-18066 publications).
Fluoropolymer not only assigns cloth and silk water-repellent oil-repellent and Water Pressure Resistance, is also used as and forms moisture-permeability waterproof layer in coating Synthetic resin when, prevent the exudation preventing agent of synthetic resin to the exudation of cloth base material opposite side to be utilized.
However, as the polymer containing fluoroalkyl that the fluoroalkyl carbon number corresponding to environmental problem is less than 6, deposit Exudation in painting synthetic resin prevent effect is low, easy generation synthetic resin to the opposite side of cloth base material penetrate into the problem of.
In addition, when attaching synthetic resin film, exist since bonding agent penetrates into cloth and silk, adhesive effect dies down, synthesis tree The problem of peel strength of adipose membrane reduces.
Prior art literature
Patent document
Patent document 1：Japanese Patent Publication 60-47955 publications
Patent document 2：Japanese Patent Publication 4-18066 publications
The content of the invention
Problems to be solved by the invention
It is an object of the present invention to provide a kind of penetrability, water resistance and the excellent moisture-permeable water-proof fabric of washing fastness.
Another object of the present invention is, there is provided a kind of to be coated with by the synthetic resin for forming moisture-permeability waterproof layer in cloth base material When, synthetic resin not to the opposite side of cloth base material surface ooze out moisture-permeable water-proof fabric.
A technical solution to solve project
The inventors discovered that the intermediate layer containing specific fluoropolymer is being arranged on cloth base material and moisture-permeability waterproof layer Between when, can realize above-mentioned purpose so that complete the present invention.
The present invention provides a kind of moisture-permeable water-proof fabric, it has the intermediate layer containing fluoropolymer and contains synthetic resin Moisture-permeability waterproof layer, fluoropolymer has the repetitive unit from following monomers (a), (b) and (c), and dynamic at 160 DEG C State viscoplasticity is more than 400Pas,
(a) fluorochemical monomer shown in following formula,
CH2=C (- X)-C (=O)-Y-Z-Rf
[in formula, X is hydrogen atom or methyl,
Y is-O- or-NH-,
Z is the organic group of Direct Bonding or divalence,
Rf is the fluoroalkyl of carbon number 1~6.]
(b) halogenated olefins monomer；
(c) non-fluorine monomer using as needed, without fluorine atom and at least with a carbon-to-carbon double bond.
There is such a way in the present invention.
A. a kind of manufacture method of moisture-permeable water-proof fabric, it is characterised in that including：
(i) the fluorine-containing inorganic agent containing fluoropolymer is suitable for fiber fabric, is formed containing in fluoropolymer The process of interbed and
(ii) by be applicable on the intermediate layer of fluoropolymer synthetic resin (for example, by painting synthetic resin or Person attaches synthetic resin film), the process for forming moisture-permeability waterproof layer.
B. a kind of processing method of fiber fabric, it is characterised in that：By by the fluorine-containing inorganic agent containing fluoropolymer Suitable for fiber fabric, the intermediate layer of fluoropolymer is formed.
C. the fluorine-containing inorganic agent of a kind of moisture-permeable water-proof fabric, it is characterised in that：It contains fluoropolymer, the fluoropolymer Thing has a repetitive unit from following monomers (a), (b) and (c), and the dynamic viscoelastic at 160 DEG C for 400Pas with On,
(a) fluorochemical monomer shown in following formula,
CH2=C (- X)-C (=O)-Y-Z-Rf
[in formula, X is hydrogen atom or methyl,
Y is-O- or-NH-,
Z is the organic group of Direct Bonding or divalence,
Rf is the fluoroalkyl of carbon number 1~6.]
(b) halogenated olefins monomer；
(c) non-fluorine monomer using as needed, without fluorine atom and at least with a carbon-to-carbon double bond.
D. the preparation method of the fluoropolymer in a kind of moisture-permeable water-proof fabric, it is characterised in that including：
(I) fluorochemical monomer (a) and non-fluorine monomer (c) as needed are polymerize, obtain first polymer process and
(II) halogenated olefins monomer (b) is polymerize in the presence of first polymer, thus manufactured by halogenated olefins monomer (b) second polymer formed, the process for obtaining fluoropolymer.
The effect of invention
Penetrability, water resistance, the washing fastness of the moisture-permeable water-proof fabric of the present invention are excellent.
According to the present invention, by formed moisture-permeability waterproof layer synthetic resin be coated with cloth base material when, synthetic resin not to The surface exudation of the opposite side of cloth base material.
Embodiment
Moisture-permeable water-proof fabric has cloth base material, the intermediate layer containing fluoropolymer on a surface of cloth base material With the moisture-permeability waterproof layer on intermediate layer.Intermediate layer can also be formed at the inside of cloth base material.On moisture-permeability waterproof layer Performance pattern or motif layer can be set.Layer can be not provided with the other surfaces of cloth base material.
In general, cloth base material is formed by natural fiber and/or synthetic fibers.The fiber of cloth base material can be natural fiber (for example, cotton or wool etc.), chemical fibre (for example, viscose or lyocell (Lyocell) etc.) or synthetic fibers (for example, Polyester, polyamide or acrylic fiber etc.), or can be the mixture of fiber (for example, natural fiber and synthetic fibers is mixed Compound etc.).As the form of cloth base material, such as woven fabric, knitted fabric, non-woven fabrics, nylon loop etc. can be enumerated.The thickness of cloth base material Degree is generally 0.05~10mm, is, for example, 0.1~1mm.
Moisture-permeability waterproof layer contains synthetic resin.In general, moisture-permeability waterproof layer is micro-porous film.The concrete example of synthetic resin It is polyurethane based resin, polyaminoacid polyurethane based resin, acrylic resin, polyester resin, polytetrafluoroethyl-ne vinyl resin Deng.Moisture-permeability waterproof layer can be formed only by synthetic resin, or can also contain additive such as isocyanates.Moisture-permeability waterproof layer Thickness be generally 10~100 μm, be, for example, 20~50 μm.
Contain fluoropolymer in intermediate layer.Intermediate layer can only be formed by fluoropolymer, or can also contain addition Agent, for example, melmac, blocked isocyanate etc..In general, the thickness in intermediate layer is 0.1~1 μm, is, for example, 0.2 ~0.3 μm.Group solvent borne in intermediate layer is excellent, can dial the organic solvents such as dimethylformamide, toluene and methyl ethyl ketone.
Dynamic viscoelastic of the fluoropolymer at 160 DEG C is more than 400Pas.
Dynamic viscoelastic of the fluoropolymer at 150 DEG C is more than 500Pas, particularly preferably more than 900Pas. Dynamic viscoelastic of the fluoropolymer at 160 DEG C is more than 400Pas, particularly preferably more than 600Pas, such as preferably For more than 800Pas.Dynamic viscoelastic of the fluoropolymer at 170 DEG C is more than 300Pas, particularly preferably More than 700Pas.
Dynamic viscoelastic of the fluoropolymer at 150 DEG C can be below 2500Pas, be, for example, 2200Pas with Under.Dynamic viscoelastic of the fluoropolymer at 160 DEG C can be below 2500Pas, specifically for below 2300Pas, example Such as it is below 2100Pas.Dynamic viscoelastic of the fluoropolymer at 170 DEG C can be below 2300Pas, be, for example, Below 2000Pas.
During dynamic viscoelastic too low (for example, the dynamic viscoelastic at 160 DEG C is less than 400Pas), easily permeate To the back side, the stripping of moisture-permeability waterproof layer easily occurs.When dynamic viscoelastic is less than certain value, moisture-permeability waterproof layer is filled with intermediate layer Divide closely sealed.
The manufacture of moisture-permeable water-proof fabric can be carried out by the following method, and this method includes：
(i) the fluorine-containing inorganic agent containing fluoropolymer is suitable for fiber fabric, forms the intermediate layer of fluoropolymer Process and
(ii) process that the moisture-permeability waterproof layer of synthetic resin is formed on the intermediate layer of fluoropolymer.
The formation of moisture-permeability waterproof layer can for example be carried out by painting synthetic resin or by attaching synthetic resin film.
Fluoropolymer has the repetitive unit from fluorochemical monomer as essential component.Fluoropolymer can also have Repetitive unit from non-fluorine monomer.
Can be (single by disposably feeding intake with the fluoropolymer from fluorochemical monomer and the repetitive unit of non-fluorine monomer Step polymerization) or fed batch (multistep polymerization, particularly two-stage polymerization) manufacture.Due to the effect for preventing exudation of synthetic resin Height, is preferably fed in batches.(multistep polymerization, particularly two-stage polymerization) is fed in batches it is meant that being later than more than one monomer Feed intake (polymerization starts), carries out feeding intake (polymerization starts) for another above monomer.Two-stage polymerization will be it is meant that will contain In the presence of the first polymer that first monomer polymerization of more than one monomer obtains, carry out containing others more than one The polymerization of the second comonomer of monomer.
Multistep polymerization is polymerization more than two steps, such as two-stage polymerization, three steps polymerize and the polymerization of four steps.The polymerization of three steps is to remove Outside first polymer and second polymer, the third polymer for being later than second polymer and feeding intake is used.Polymerizations more than four steps Be reuse more than the 4th monomer.
Hereinafter, the two-stage polymerization of the representative as multistep polymerization is illustrated.
It is fed in batches in (particularly two-stage polymerization), in general, fluoropolymer by the first monomer comprising being formed The fluoropolymer of first polymer and the second polymer formed by second comonomer,
Second comonomer polymerize in the presence of first polymer,
At least one party of first monomer and second comonomer contains fluorochemical monomer (a),
First monomer is free of halogenated olefins monomer (b),
Second comonomer contains halogenated olefins monomer (b).
It is containing the first polymer formed by the first monomer and by second to be fed in batches (particularly two-stage polymerization) method The preparation method of the fluoropolymer for the second polymer that monomer is formed, the preparation method include：
(I) by the first monomer polymerization, obtain first polymer process,
(II) second comonomer is polymerize in the presence of first polymer, the process for being derived from second polymer,
At least one party of first monomer and second comonomer contains fluorochemical monomer,
First monomer contains the non-crosslinked property monomer of non-fluorine, without halogenated olefins monomer,
Second comonomer contains halogenated olefins monomer.
In the present invention, the first monomer can contain halogenated olefins monomer, can not also contain halogenated olefins monomer.First is single Body is preferably free of halogenated olefins monomer.
The fluoropolymer of the present invention has the repetitive unit from the first monomer and the repetitive unit from second comonomer. First polymer and second polymer can also be copolymerized.That is, first polymer and second polymer can be with chemical bonds.Alternatively, First polymer and second polymer do not form chemical bond, can be with physical bond.The example of physical bond is first polymer shape Nucleation, second polymer form the core/shell structure of shell.In core/shell structure, although first polymer and second polymer have does not change Situation about combining is learned, but can also chemical bond.
In the present invention, as monomer, fluorochemical monomer (a) and halogenated olefins monomer (b) are used.Non-fluorine monomer (c) can root Can be the non-crosslinked property monomer of non-fluorine and/or non-fluorine cross-linkable monomer according to needing to use.Non-fluorine monomer (c) is preferably that non-fluorine is non- Cross-linkable monomer (c1), and/or can be non-fluorine cross-linkable monomer (c2).
At least one party of first monomer and second comonomer contains fluorochemical monomer.It is preferred that the first monomer contains fluorochemical monomer, the Two monomers are free of fluorochemical monomer.
It is preferred that the first monomer is free of halogenated olefins monomer, second comonomer contains halogenated olefins monomer.Second comonomer can also Only it is made of halogenated olefins monomer.
First monomer can contain the non-crosslinked property monomer of non-fluorine.It is preferred that second comonomer is free of the non-crosslinked property monomer of non-fluorine.It is logical Crossing makes second comonomer be free of the non-crosslinked property monomer of non-fluorine, in the working process of the inorganic agent containing fluoropolymer, prevents from gathering Compound is attached to the excellent performance for causing roller to pollute on roller.
At least one party of first monomer and second comonomer can contain non-fluorine cross-linkable monomer.Fluoropolymer contains non-fluorine Can be the first monomer without non-fluorine cross-linkable monomer and second comonomer contains non-fluorine cross-linkable monomer during cross-linkable monomer, or Person can be that the first monomer contains non-fluorine cross-linkable monomer and second comonomer is free of non-fluorine cross-linkable monomer.
The preferred kind of monomer in first monomer and second comonomer has in the following manner.
[table 1]
In the present invention, (the first monomer is fluorochemical monomer and the non-crosslinked property monomer of non-fluorine, second comonomer for particularly preferred mode 2 It is halogenated olefins monomer).
Further preferably fluorochemical monomer and non-fluorine cross-linkable monomer are respectively present in the side of the both sides of the first monomer and second comonomer Formula.That is, side same with mode 1~7 further preferably in addition to the both sides that fluorochemical monomer is present in the first monomer and second comonomer Formula, mode identical with mode 1~7 in addition to the both sides that non-fluorine cross-linkable monomer is present in the first monomer and second comonomer.
(a) fluorochemical monomer
Fluorochemical monomer is fluorochemical monomer shown in following formula,
CH2=C (- X)-C (=O)-Y-Z-Rf
[in formula, X is hydrogen atom or methyl,
Y is-O- or-NH-,
Z is the organic group of Direct Bonding or divalence,
Rf is the fluoroalkyl of carbon number 1~6.]
Z for example can be the straight-chain alkyl-sub or branched alkylidene, such as formula-(CH of carbon number 1~202)x- (formula In, x is 1~10.) shown in group or formula-SO2N(R1)R2- or formula-CON (R1)R2Shown group (in formula, R1For The alkyl of carbon number 1~10, R2For the straight-chain alkyl-sub or branched alkylidene of carbon number 1~10.) or formula- CH2CH(OR3)CH2- (in formula, R3Represent the acyl group (such as formoxyl or acetyl group etc.) of hydrogen atom or carbon number 1~10.) Shown group or formula-Ar-CH2- (in formula, Ar is according to the arlydene for needing to have substituent.) shown in base Group ,-(CH2)m- SO2- (CH2)n- base or-(CH2)m- S- (CH2)n- base (wherein, m is that 1~10, n is 0~10).
Fluorochemical monomer (a) is preferably acrylate or acrylamide shown in the following general formula (I),
CH2=C (- X)-C (=O)-Y-Z-Rf (I)
[in formula, X is hydrogen atom or methyl,
Y is-O- or-NH-,
Z is the aliphatic group of carbon number 1~10, the aromatic group of carbon number 6~18 or annular aliphatic base Group ,-CH2CH2N(R1)SO2- base (wherein, R1For the alkyl of carbon number 1~4.) ,-CH2CH(OZ1)CH2- base is (wherein, Z1For hydrogen atom or acetyl group) ,-(CH2)m- SO2- (CH2)n- base or-(CH2)m- S- (CH2)n- base (wherein, m It is 0~10 for 1~10, n),
Rf is the straight-chain of carbon number 1~6 or the fluoroalkyl of branched.].
(acrylate or methacrylate) α for having fluorochemical monomer (a) substitutes the situation for having halogen atom etc..Cause This, in formula (1), X can be the straight-chain of carbon number 2~21 or alkyl, fluorine atom, chlorine atom, bromine atoms, the iodine of branched Atom, CFX1X2Base (wherein, X1And X2It is hydrogen atom, fluorine atom, chlorine atom, bromine atoms or iodine atom.), cyano group, carbon number 1~21 straight-chain or the fluoroalkyl of branched, substituted or non-substituted benzyl, substituted or non-substituted phenyl.
In above-mentioned formula (1), Rf bases are preferably perfluoroalkyl.The carbon number of Rf bases is 1~6, is more particularly 4~6.Rf bases Example be-CF3,-CF2CF3,-CF2CF2CF3,-CF (CF3)2,-CF2CF2CF2CF3,-CF2CF(CF3)2,-C (CF3)3,-(CF2)4CF3,-(CF2)2CF(CF3)2,-CF2C(CF3)3,-CF (CF3)CF2CF2CF3,-(CF2)5CF3,- (CF2)3CF(CF3)2,-(CF2)4CF(CF3)2,-C8F17Deng.
Z is preferably the aromatic group or ring-shaped fat of the aliphatic group of carbon number 1~10, carbon number 6~18 Race's group ,-CH2CH2N(R1)SO2- base (wherein, R1It is the alkyl of carbon number 1~4.) ,-CH2CH(OZ1)CH2- base (its In, Z1It is hydrogen atom or acetyl group.) ,-(CH2)m- SO2- (CH2)n- base or-(CH2)m- S- (CH2)n- base (its In, m is that 1~10, n is 0~10).Aliphatic group be preferably alkylidene (particularly carbon number be 1~4, be, for example, 1 or 2.).Aromatic group or cyclic aliphatic group can be substituted or non-substituted.S bases or SO2Base can be with Rf base direct keys Close.
As the concrete example of fluorochemical monomer (a), such as following monomer can be illustrated, but not limited by these.
CH2=C (- H)-C (=O)-O- (CH2)2- Rf
CH2=C (- H)-C (=O)-O-C6H4- Rf
CH2=C (- H)-C (=O)-O- (CH2)2N (- CH3)SO2- Rf
CH2=C (- H)-C (=O)-O- (CH2)2N (- C2H5)SO2- Rf
CH2=C (- H)-C (=O)-O-CH2CH (- OH) CH2- Rf
CH2=C (- H)-C (=O)-O-CH2CH (- OCOCH3)CH2- Rf
CH2=C (- H)-C (=O)-O- (CH2)2- S-Rf
CH2=C (- H)-C (=O)-O- (CH2)2- S- (CH2)2- Rf
CH2=C (- H)-C (=O)-O- (CH2)3- SO2- Rf
CH2=C (- H)-C (=O)-O- (CH2)2- SO2- (CH2)2- Rf
CH2=C (- H)-C (=O)-NH- (CH2)2- Rf
CH2=C (- CH3)-C (=O)-O- (CH2)2- S-Rf
CH2=C (- CH3)-C (=O)-O- (CH2)2- S- (CH2)2- Rf
CH2=C (- CH3)-C (=O)-O- (CH2)3- SO2- Rf
CH2=C (- CH3)-C (=O)-O- (CH2)2- SO2- (CH2)2- Rf
CH2=C (- CH3)-C (=O)-NH- (CH2)2- Rf
[in above-mentioned formula, Rf is the fluoroalkyl of carbon number 1~6.]
(b) halogenated olefins monomer
Halogenated olefins monomer (b) be preferably substitute the chlorine atom for having 1~10, bromine atoms or iodine atom carbon number 2~ 20 alkene.Halogenated olefins monomer (b) is preferably the chlorinated alkenes of carbon number 2~20, particularly with 1~5 chlorine atom Carbon number 2~5 alkene.The preferred concrete example of halogenated olefins monomer (b) is ethylene halide, for example, vinyl chloride, vinyl bromide, Iodoethylene；Vinylidene halide, such as vinylidene chloride, inclined vinyl bromide, inclined iodoethylene.Due to water resistance, (particularly water resistance is durable Property) high, it is advantageous to vinyl chloride.
Non-fluorine monomer (c) can be the non-crosslinked property monomer (c1) of non-fluorine and/or non-fluorine cross-linkable monomer (c2).
(c1) the non-crosslinked property monomer of non-fluorine
The non-crosslinked property monomer (c1) of non-fluorine is free from the monomer of fluorine atom.The non-crosslinked property monomer (c1) of non-fluorine is without crosslinking Property functional group.The non-crosslinked property monomer (c1) of non-fluorine is different from cross-linkable monomer (c2), is non-crosslinked property.The non-crosslinked property monomer of non-fluorine (c1) it is preferably the non-fluorine monomer with carbon-to-carbon double bond.The non-crosslinked property monomer (c1) of non-fluorine is preferably not fluorine-containing vinyl list Body.In general the non-crosslinked property monomer (c1) of non-fluorine is the compound with a carbon-to-carbon double bond.
The preferable non-crosslinked property monomer (c1) of non-fluorine can be compound shown in following formula,
CH2=CA-T
[in formula, A is the halogen atom (such as chlorine atom, bromine atoms and iodine atom) beyond hydrogen atom, methyl or fluorine atom,
T is hydrogen atom, the chain of carbon number 1~30 (such as 1~20) or cricoid alkyl or the chain with ester bond The organic group of shape or cricoid carbon number 1~31 (such as 1~20).]
The example of the chain of carbon number 1~30 or cricoid alkyl is the fat of the straight or branched of carbon number 1~30 Fat race alkyl, the cyclic aliphatic group of carbon number 4~30, the aromatic hydrocarbyl of carbon number 6~30, carbon number 7~ 30 aromatic-aliphatic alkyl.
The example of the organic group of chain or cricoid carbon number 1~31 with ester bond is-C (=O)-O-Q (wherein, Q is the aliphatic alkyl of the straight or branched of carbon number 1~30, carbon number 4~30 with-O-C (=O)-Q Cyclic aliphatic group, aromatic hydrocarbyl, the aromatic-aliphatic alkyl of carbon number 7~30 of carbon number 6~30).It is excellent Select aliphatic alkyl, the ring-type fat of carbon number 4~30 of the straight or branched of carbon number 12~30 (particularly 18~30) Fat race group, the aromatic hydrocarbyl of carbon number 6~30, the aromatic-aliphatic alkyl of carbon number 7~30, particularly preferred carbon are former Aliphatic alkyl, the annular aliphatic base of carbon number 4~30 of the straight or branched of subnumber 12~30 (particularly 18~30) Group.
The preference of the non-crosslinked property monomer (c1) of non-fluorine includes such as ethene, vinyl acetate, acrylonitrile, styrene, poly- Ethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxy Base polypropylene glycol (methyl) acrylate and vinyl alkyl ethers.The non-crosslinked property monomer (c1) of non-fluorine limits from these examples.
The non-crosslinked property monomer (c1) of non-fluorine can be with alkyl (methyl) acrylate.The carbon number of alkyl can be with It is 1~30, such as can is 6~30 (for example, 10~30).For example, the non-crosslinked property monomer (c1) of non-fluorine can be below general formula Shown acrylate,
CH2=CA1COOA2
[in formula, A1It is the halogen atom beyond hydrogen atom, methyl or fluorine atom (for example, chlorine atom, bromine atoms and iodine are former Son),
A2It is CnH2n+1Alkyl shown in (n=1~30).]
Due to preventing polymer from being improved to the performance that roller adheres to, so fluoropolymer, which preferably has, is derived from A2For carbon atom Acrylate (the CH of number 12~30, particularly 18~30 alkyl2=CA1COOA2) repetitive unit.
The non-crosslinked property monomer (c1) of non-fluorine can be with cyclic hydrocarbon group (methyl) acrylate monomer.With cyclic hydrocarbon (methyl) acrylate monomer (B) of base is that (methyl) with (preferably monovalence) cyclic hydrocarbon group and monovalence is acrylate-based Compound.(methyl) acrylate-based Direct Bonding of the cyclic hydrocarbon group and monovalence of monovalence.It can be enumerated as cyclic hydrocarbon group full And/or undersaturated monocyclic base, polycyclic group, crosslinking ring group etc..The preferred saturated group of cyclic hydrocarbon group.The carbon number of cyclic hydrocarbon group Preferably 4~20.Carbon number 4~20 can be enumerated as cyclic hydrocarbon group, is particularly 5~12 cyclic aliphatic group, carbon The aromatic group of atomicity 6~20, the aromatic-aliphatic group of carbon number 7~20.The carbon number of cyclic hydrocarbon group is 15 Hereinafter, such as particularly preferably less than 10.Ester of the nuclear carbon atom of cyclic hydrocarbon group preferably with (methyl) in acrylate-based Base Direct Bonding.The cyclic aliphatic group of the preferred saturation of cyclic hydrocarbon group.The concrete example of cyclic hydrocarbon group is cyclohexyl, tert-butyl group ring Hexyl, isobornyl, Bicvclopentyl, double cyclopentenyl.It is acrylate-based or methacrylate that (methyl) is acrylate-based Base, preferred methacrylate base.As the concrete example of the monomer with cyclic hydrocarbon group, methacrylic acid hexamethylene can be enumerated Ester, t-butyl cyclohexyl ester, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, first The bicyclic pentyl ester of base acrylic acid, the bicyclic pentyl ester of acrylic acid, acrylic acid dicyclopentenyloxyethyl methacrylate etc..
(c2) non-fluorine cross-linkable monomer
The fluoropolymer of the present invention can have the repetitive unit from non-fluorine cross-linkable monomer (c2).Non-fluorine bridging property Monomer (c2) is free from the monomer of fluorine atom.Non-fluorine cross-linkable monomer (c2) at least has 2 reactive groups and/or carbon-to-carbon Double bond, can be free from the compound of fluorine.Non-fluorine cross-linkable monomer (c2) be have at least two carbon-to-carbon double bond compound, Or the compound with least one carbon-to-carbon double bond and at least one reactive group.The example of reactive group for hydroxyl, Epoxy group, chloromethyl, blocked isocyanate base, amino, carboxyl etc..Non-fluorine cross-linkable monomer (c2) can have reactive base List (methyl) acrylate, (methyl) diacrylate or single (methyl) acrylamide of group.Alternatively, non-fluorine cross-linkable monomer (c2) it can be two (methyl) acrylate.
Two acetone (methyl) acrylamide, (methyl) acryloyl are for example may be exemplified as non-fluorine cross-linkable monomer (c2) Amine, N- methylols (methyl) acrylamide, (methyl) dihydroxypropyl methyl esters, (methyl) Hydroxyethyl Acrylate, 3- are chloro- 2- hydroxypropyls (methyl) acrylate, 2- acetoacetoxyethyls (methyl) acrylate, butadiene, isoprene, Chlorobutadiene, (methyl) glycidyl acrylate, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl) Acrylate etc., but do not limited by these.
In this specification, " (methyl) acrylate " means acrylate or methacrylate, " (methyl) acryloyl Amine " means acrylamide or Methacrylamide.
By the way that the non-crosslinked property monomer (c1) of non-fluorine and/or non-fluorine cross-linkable monomer (c2) are copolymerized, can change as needed Kind water-repellent oil-repellent, the resistance to cleaning of soil resistance and these performances, washing fastness, dissolubility, hardness, sense of touch for solvent Etc. various properties.
In fluoropolymer, relative to 100 parts by weight of fluorochemical monomer (a), the amount of halogenated olefins (b) can be 2~500 weights Part is measured, is, for example, 5~200 parts by weight, specifically for 10~150 parts by weight, more particularly 20~50 parts by weight, non-fluorine monomer (c) Amount can be, for example, 0.1~400 parts by weight below 1200 parts by weight, specifically for 0.5~250 parts by weight, more particularly 1 ~50 parts by weight.
In fluoropolymer, relative to 100 parts by weight of fluorochemical monomer (a), the amount of the non-crosslinked property monomer (c1) of non-fluorine can be with It is, for example, 0.1~300 parts by weight below 1000 parts by weight, specifically for 1~200 parts by weight, non-fluorine cross-linkable monomer (c2) Amount can be below 50 parts by weight, be, for example, below 30 parts by weight, specifically for 0.1~20 parts by weight.
Same kind of monomer (for example, halogenated olefins monomer and fluorochemical monomer) is in the both sides of the first monomer and second comonomer In contain in the case of, the list of the same race in same monomers in the first monomer (particularly, halogenated olefins monomer) and second comonomer The weight ratio of body (particularly, halogenated olefins monomer) can be 3~97: 97~3, be, for example, 5~90: 95~10, specifically for 10 ~70: 90~30.
Fluoropolymer in the present invention can use any manufacture of common polymerization, and the bar of polymerisation Part also can be selected arbitrarily.As such polymerization, polymerisation in solution, suspension polymerisation, emulsion polymerization can be enumerated.
In polymerisation in solution, it can use in the presence of polymerization initiator, monomer is dissolved in organic solvent, carry out nitrogen and take Dai Hou, the method when heating stirring 1~10 is small in the range of 30~120 DEG C.As polymerization initiator, such as idol can be enumerated Nitrogen bis-isobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl group mistake Aoxidize pivalate, diisopropyl peroxydicarbonate etc..Relative to 100 parts by weight of monomer, with 0.01~20 parts by weight, example Such as polymerization initiator is used for the scope of 0.01~10 parts by weight.
Organic solvent is solvent inert to monomer and dissolving these materials, and for example, esters are (for example, carbon number 2 ~30 ester, specifically, ethyl acetate, butyl acetate), ketone (for example, the ketone of carbon number 2~30, specifically, first Base ethyl ketone, diisobutyl ketone), alcohol (for example, the alcohol of carbon number 1~30, specifically, isopropanol).As organic solvent Specific example, acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, hexamethylene, benzene, first can be enumerated Benzene, dimethylbenzene, petroleum ether, tetrahydrofuran, 1,4- dioxanes, methyl ethyl ketone, methylisobutylketone, diisobutyl ketone, acetic acid second Ester, butyl acetate, 1,1,2,2- tetrachloroethanes, 1,1,1- trichloroethanes, trichloro ethylene, perchloroethylene, tetrachlorodifluoroethane, Trichorotrifluoroethane etc..Relative to 100 parts by weight of total of monomer, with 10~2000 parts by weight, such as 50~1000 parts by weight Scope use organic solvent.
In emulsion polymerization, using in the presence of polymerization initiator and emulsifying agent, monomer is emulsified in water, carry out nitrogen and take Dai Hou, when 50~80 DEG C of scope stirring 1~10 is small, makes the method for its copolymerization.Polymerization initiator can use benzoyl peroxide Formyl, lauroyl peroxide, TBPB tertiary butyl perbenzoate, 1- hydroxy-cyclohexyls hydroperoxides, 3- carboxypropanoyl peroxides Compound, acetyl peroxide, two NSC 18620s of azo-dihydrochloride, azodiisobutyronitrile, sodium peroxide, potassium peroxydisulfate, persulfuric acid The water miscible material such as ammonium or azodiisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxidating The oil-soluble material such as thing, cumene hydroperoxide, t-butylperoxy pivarate, diisopropyl peroxydicarbonate.Phase For 100 parts by weight of monomer, polymerization initiator is used with the scope of 0.01~10 parts by weight.
In order to obtain the excellent copolymer aqueous dispersions of shelf-stability, it is desirable to use high pressure homogenisers, ultrasonic wave homogeneous The emulsifier unit that can assign strength crushing energy of device etc, monomer corpusculed in water is drawn using oil-soluble polymerization Hair agent is polymerize.In addition, the various emulsifying agents of anionic property, cationic or nonionic can be used as emulsifying agent, Relative to 100 parts by weight of monomer, used with the scope of 0.5~20 parts by weight.Preferably using anionic property and/or nonionic And/or the emulsifying agent of cationic.In the case where monomer is completely incompatible, preferably addition makes the phase that these monomers are fully compatible Hold agent, for example, addition water-miscible organic solvent, the monomer of low molecular weight.By adding compatilizer, it is possible to increase emulsibility and altogether Poly- property.
As water-miscible organic solvent, acetone, methyl ethyl ketone, ethyl acetate, propane diols, a contracting dipropyl two can be enumerated Alcohol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol etc., can be with 1~50 weight relative to 100 parts by weight of water Part, the scope of such as 10~40 parts by weight use.In addition, the monomer as low molecular weight, can enumerate methyl methacrylate, Glycidyl methacrylate, 2,2,2- trifluoroethyl methacrylates etc., relative to 100 parts by weight of total amount of monomer, It can be used with 1~50 parts by weight, the scope of such as 10~40 parts by weight.
Chain-transferring agent can be used in polymerization.Corresponding to the usage amount of chain-transferring agent, the molecular weight of copolymer can be changed. Compound that the example of chain-transferring agent is lauryl mercaptan, thioglycol, thioglycerol etc. containing sulfydryl (particularly, (such as carbon Atomicity 1~30) alkyl hydrosulfide), sodium hypophosphite, inorganic salts such as sodium hydrogensulfite etc..The usage amount of chain-transferring agent relative to 100 parts by weight of total amount of monomer, can be used with 0.01~10 parts by weight, the scope of such as 0.1~5 parts by weight.
The copolymerization of fluoropolymer can be by disposably feeding intake (single step polymerization) or being fed in batches (multistep polymerization, spy It is not two-stage polymerization) manufacture.It is preferred that being fed in batches, but when using cross-linkable monomer, can also disposably be fed intake.
In two-stage polymerization, in general, polymerisation manufacture first polymer is carried out in the liquid containing the first monomer, Then, polymerisation manufacture second polymer is carried out in the liquid containing first polymer and second comonomer, is obtained by first The fluoropolymer that polymer and second polymer are formed.It can start the poly- of second polymer in the polymerization of first polymer Close, or start the polymerization of second polymer after the completion of the polymerization of first polymer.Can first polymer polymerization it is anti- Answer (that is, the polymerisation of the first monomer) finish more than 10% (that is, 10~100%), for example more than 40% (that is, 40~ 100%), the polymerization of second polymer is started after (that is, 70~100%) particularly more than 70%.Polymerisation terminates to compare Example % (that is, polymerisation carries out ratio %) means mole % of the monomer (monomer of polymerization) reacted.For example, polymerization is anti- When should terminate 10%, the monomer having polymerize is 10 moles of %, and the monomer of unreacted (unpolymerized) is 90 moles of %.First monomer is During the combination of at least two kinds of monomers, total molal quantitys of mole % of the first monomer based at least two kinds of monomers in the first monomer.
Mean that the polymerisation (that is, the polymerisation of the first monomer) of first polymer does not have in the polymerization of first polymer It is fully completed.For example, being aggregated in for first polymer finish more than 10%~less than 40%, more than 40%~deficiency 70% or more than 70%~after (particularly 80%~99%, more particularly 85%~98%), can start less than 100% The polymerization of second polymer.
Meaning the polymerisation of first polymer after the completion of the polymerization of first polymer, (that is, the polymerization of the first monomer is anti- Should) about finish 100%.
When starting the polymerization of second polymer in the polymerization of first polymer, second polymer, which has, is derived from the first monomer With the repetitive unit of second comonomer.When starting the polymerization of second polymer after the completion of the polymerization of first polymer, the second polymerization Thing has the repetitive unit for being only derived from second comonomer.
In the fluoropolymer of the present invention, first polymer carries out chemical bond or without chemistry knot with second polymer Close.
At the time of the polymerization of second comonomer is started, it is non-that unreacted non-fluorine is preferably created substantially absent in polymerization system Cross-linkable monomer.Be created substantially absent it is meant that start second comonomer polymerization at the time of, the unreacted non-crosslinked property of non-fluorine The amount of monomer is 10 moles of below %, is preferably 8 moles of below %, further relative to the non-crosslinked property monomer of non-fluorine of input Preferably 5 moles of below %, specifically for 3 moles of below %, more particularly 1 mole of below %.By making unreacted non-fluorine non- Cross-linkable monomer is created substantially absent, and in the working process of the inorganic agent containing fluoropolymer, prevents polymer to be attached to The excellent performance for causing roller to pollute on roller.
The fluoropolymer of the present invention is preferably manufactured by emulsion polymerization.By first polymer and second polymer shape Into water-borne dispersions particle in, second polymer can surround first polymer, and fluoropolymer can have by the The shell of dimerization compound surrounds the core/shell structure of the core of first polymer.
Fluoropolymer can by order on base material cloth formed polymer film known to method it is any Suitable for base material cloth.In general, after the liquid containing fluoropolymer and liquid medium is suitable on cloth base material, utilize It is dry etc. to remove liquid medium, the film of fluoropolymer can be formed on polymer.Containing fluoropolymer and liquid In the liquid of medium, the concentration of fluoropolymer can be such as 0.01~20 weight %, specifically for 0.05~10 weight %.Can Base material cloth to be soaked in the solution, alternatively, liquid can be adhered to or be sprayed on base material cloth.It has been applicable in the base material of liquid Cloth, such as in order to show liquid repellency, be dried, preferably for example heated with 100 DEG C~200 DEG C.
It is typically cloth, including woven fabric, knitted fabric and non-woven fabrics, dress material product as processed fibre The cloth and carpet of form are but it is also possible to be fiber or yarn or median fiber product (for example, sliver or rove etc.).Fibre material Material can be natural fiber (for example, cotton or wool etc.), chemical fibre (for example, viscose or lyocell (Lyocell) etc.) or Synthetic fibers (for example, polyester, polyamide or acrylic fiber etc.), or can be the mixture of fiber (for example, natural fiber With the mixture of synthetic fibers etc.).The manufacture polymer of the present invention is made by cellulosic fibre (for example, cotton or artificial silk etc.) It is especially effective when into oleophobic property and dialling oiliness.In addition, in general fibre is made hydrophobicity and dialled by the method for the present invention It is water-based.
Alternatively, fibrous substrate can be leather.In order to which leather is made hydrophobicity and oleophobic property, manufacture can be polymerize Thing in the various stages of leather processing, such as can during the moistening processing of leather in or finishing in leather during It is middle that manufacture polymer is suitable for leather by aqueous solution or aqueous emulsifying thing.
Alternatively, fibrous substrate can be paper.Manufacture polymer can be suitable for preshaped paper, or in paper processed Each stage for example suitable for during the drying of paper.
The form of the surface conditioning agent (fluorine-containing inorganic agent) of the present invention preferably solution, lotion or aerosol.Surface conditioning agent Containing fluoropolymer (active ingredient of surface conditioning agent) and medium (particularly liquid medium, for example, organic solvent and/or Water).In surface conditioning agent, the concentration of fluoropolymer for example can be 0.01~50 weight %.
The surface conditioning agent (fluorine-containing inorganic agent) of the present invention preferably comprises fluoropolymer and aqueous medium.This specification In, " aqueous medium " means the medium being only made of water and also containing organic solvent, (amount of organic solvent is phase except water It is below 80 parts by weight for 100 parts by weight of water, is, for example, 0.1~50 parts by weight, specifically for 5~30 parts by weight.) medium. Fluoropolymer preferably manufactures the dispersion liquid of fluoropolymer by emulsion polymerization.Of surface conditioning agent preferred fluoropolymer The scattered aqueous liquid dispersion in an aqueous medium of grain.In dispersion liquid, the average grain diameter of fluoropolymer is preferably 0.01~200 micro- Rice, is, for example, 0.1~5 micron, specifically for 0.05~0.2 micron.Average grain diameter can pass through dynamic light scattering device, electronic display Micro mirror etc. measures.
The surface conditioning agent of the present invention can be suitable for treated object by existing known method.Generally use is by the table Surface treatment agent is dispersed in organic solvent or water and is diluted, and by known methods such as dip-coating, spraying, foam coatings, makes its attached In the surface of treated object and the method that is dried.In addition, if needing, can be applicable at the same time simultaneously with appropriate crosslinking agent Cured.Moreover, insect-proof agent, softening agent, antiseptic, fire retardant, anti-quiet can be added into the surface conditioning agent of the present invention Electric agent, coating fixative, anti-creasing agent etc. are used in combination.The concentration of fluoropolymer in the treatment fluid contacted with base material is (especially It is in case of dipping) can be 0.01~20 weight %, specifically for 0.05~10 weight %.
Embodiment
Then, embodiment, comparative example and test example is enumerated the present invention is specifically described.But these explanations are not right The present invention, which is formed, to be limited.
In illustrating below, part or % in case of no particular description, represent parts by weight or weight %.
Characteristic is carried out as follows measure.
Monomer composition in polymer
For polymer, carry out elemental analysis (F atom, Cl atoms and C atoms), IR optical spectroscopies, 1H NMR optical spectroscopies and 19F NMR optical spectroscopies, try to achieve the monomer composition (weight %) in polymer.
Measurement of Dynamic Viscoelasticity
The aqueous liquid dispersion 10g of polymer is dispersed in methanol 20g, by obtained matter utilization whizzer with 60 Minute 10000rpm separation acrylate copolymer and emulsifying agent, obtain test sample polymer.Pass through Measurement of Dynamic Viscoelasticity Device RHEOSOL-G3000 ((strain) UBM systems) measures the complex viscosity (η *) of the polymer.For sample polymer 1g, in frequency Under rate 0.5Hz, measuring temperature is warming up to 180 DEG C with 5 DEG C/min by 40 DEG C, measures dynamic viscoelastic.
Dial solvent borne
It is 1 weight % that the aqueous liquid dispersion of polymer is diluted with water into solid component concentration, so as to adjust treatment fluid.Will Nylon cloth is immersed in treatment fluid, using roller in 4kg/cm2, wring out under conditions of 4m/ minutes, be heat-treated 1 point at 170 DEG C Zhong Hou, evaluates the solvent borne of dialling for the treatment of cloth.
On dialling solvent borne, DMF, MEK, toluene, ethyl acetate are dripped one respectively and dropped on experiment cloth, measure solvent is by cloth The time of absorption, until 120 seconds maximum, is represented as solvent borne is dialled with the time.The high expression of numerical value dials solvent with good Property.
The back side infiltration of coating resin
It is 1 weight % that the aqueous liquid dispersion of polymer is diluted with water into solid component concentration, so as to adjust treatment fluid.Will Nylon cloth is immersed in treatment fluid, using roller in 4kg/cm2, wring out under conditions of 4m/ minutes, be heat-treated 1 point at 170 DEG C Zhong Hou, by be 30% using MEK/ toluene/concentration of the DMF as solvent polyurethane resin (refine big day industry RESAMINE ME-3612LP) it is uniformly coated on the single side of nylon cloth, after 100 DEG C 1 minute dry, is heat-treated 1 minute at 150 DEG C.It is logical Cross and visually uncoated surface is observed, evaluated according to the back side infiltration below to resin.
◎：Permeated completely without the back side
○：More only the back side is permeated
×：There is the substantial amounts of back side to permeate
Synthesize the peel strength of film
It is 1 weight % that the aqueous liquid dispersion of polymer is diluted with water into solid component concentration, so as to adjust treatment fluid.Will Nylon cloth is immersed in treatment fluid, using roller in 4kg/cm2, wring out under conditions of 4m/ minutes, be heat-treated 1 point at 170 DEG C Zhong Hou, polyurethane type resin bonding agent (Dainippon Ink Chemicals's system for being 50% by the concentration using MEK and ethyl acetate as solvent CRISVON 4010FT) point-like is coated on the single side of nylon cloth, after the synthesis membrane pressure of polyurethane is connect, 2 points are heat-treated at 120 DEG C Clock.By the nylon cloth of acquisition by AATCC88B (1) (III) repeated washing 20 times after, by visual observation pairing film forming stripped shape State is observed, according to evaluating below its state.
◎：Completely without stripping
○：More only peel off
×：Peeled off with obvious
Embodiment 1
Two-stage polymerization：
C is added into the autoclave of 1L6F13CH2CH2OCOC(CH3)=CH2(referred to as " C6SFMA ".) 179g, acrylic acid Stearyl ester (StA) 25g, tripropylene glycol 75.8g, pure water 446g, polyoxyethylene lauryl ether 12.7g, polyethylene glycol oxide Oily ether 2.47g, polyethylene glycol oxide isotridecyl ether 5.05g, dialkyl group (tallow) dimethyl ammonium chloride 2.66g, at 60 DEG C After heating, make its emulsion dispersion using high pressure homogenisers.After emulsion dispersion, 2,2- of addition azos, two (2- amidine propanes) disalt Hydrochlorate 1.92g, when 60 DEG C of reactions 1 are small, (C6SFMA has terminated 99%, StA and has terminated 97%) in polymerisation.Then, pressurize Fill vinyl chloride 60g, then react 2 it is small when, obtain the aqueous liquid dispersion of polymer.Concentration, which is carried out, using pure water is adjusted to its solid-state Component is 30 weight %, and the characteristic of the aqueous liquid dispersion to obtaining is measured.The results are shown in Table A.
Embodiment 2
In addition to lauryl mercaptan 0.025g is added after emulsification, point of polymer is obtained using method similarly to Example 1 Dispersion liquid.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFMA has terminated 99%, StA and tied in polymerisation Beam 96%.
Embodiment 3
In addition to lauryl mercaptan 0.12g is added after emulsification, the scattered of polymer is obtained using method similarly to Example 1 Liquid.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFMA has terminated 99%, StA and tied in polymerisation Beam 95%.
Embodiment 4
In addition to lauryl mercaptan 0.19g is added after emulsification, the scattered of polymer is obtained using method similarly to Example 1 Liquid.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFMA has terminated 99%, StA and tied in polymerisation Beam 96%.
Embodiment 5
Except using C6F13CH2CH2OCOCH=CH2(C6SFA) 179g replaces C6F13CH2CH2OCOC(CH3)=CH2179g with Outside, the dispersion liquid of polymer is obtained using method similarly to Example 2.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFA has terminated 99%, StA and tied in polymerisation Beam 95%.
Embodiment 6
Except using cyclohexyl methacrylate (CHMA) 25g replace stearyl acrylate (StA) 25g in addition to, using with reality Apply the dispersion liquid that the same method of example 2 obtains polymer.
(single step polymerize finish time) is filled the moment in vinyl chloride, C6SFMA has terminated 99%, CHMA in polymerisation Terminate 98%.
Embodiment 7
Except using isobornyl acrylate (IBMA) 25g replace stearyl acrylate (StA) 25g in addition to, using with implementation The same method of example 2 obtains the dispersion liquid of polymer.
(single step polymerize finish time) is filled the moment in vinyl chloride, C6SFMA has terminated 99%, IBMA in polymerisation Terminate 99%.
Embodiment 8
In addition to neopentylglycol diacrylate (NP-A) 0.25g is added into embodiment 2, using similarly to Example 2 Method obtain polymer dispersion liquid.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFMA has terminated 99%, StA and tied in polymerisation Beam 96%.
Embodiment 9
In addition to diacetone acrylamide (DAAM) 2.25g is added into embodiment 2, side similarly to Example 2 is utilized Method obtains the dispersion liquid of polymer.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFMA has terminated 99%, StA and tied in polymerisation Beam 96%.
Embodiment 10
In addition to glycidyl methacrylate (GLA) 2.25g is added into embodiment 2, using similarly to Example 2 Method obtain polymer dispersion liquid.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFMA has terminated 99%, StA and tied in polymerisation Beam 96%.
Embodiment 11
In addition to N-isopropylacrylamide (NIPAM) 2.25g is added into embodiment 2, side similarly to Example 2 is utilized Method obtains the dispersion liquid of polymer.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFMA has terminated 99%, StA and tied in polymerisation Beam 96%.
Embodiment 12
Single step polymerize：
C is added into 1L autoclaves6F13CH2CH2OCOC(CH3)=CH2179g, lauryl acrylate 25g, neopentyl glycol Diacrylate 0.25g, tripropylene glycol 75.8g, pure water 446g, polyoxyethylene lauryl ether 12.7g, polyethylene glycol oxide Oily ether 2.47g, polyethylene oxide base isotridecyl ether 5.05g, dialkyl group (tallow) dimethyl ammonium chloride 2.66g, 60 DEG C heating after, make its emulsion dispersion using high pressure homogenisers.After emulsion dispersion, lauryl mercaptan 0.025g, pressurization filling chlorine are added Ethene 60g.2,2- azos, two (2- amidine propanes) dihydrochloride 1.92g is further added, when 60 DEG C of reactions 3 are small, is obtained The aqueous liquid dispersion of polymer.It is 30 weight % to carry out concentration to be adjusted to its solid component concentration using pure water, to obtained water The characteristic of property dispersion liquid is measured.The results are shown in Table A.
Comparative example 1
In addition to lauryl mercaptan 0.25g is added after emulsification, the scattered of polymer is obtained using method similarly to Example 1 Liquid.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFMA has terminated 99%, StA and tied in polymerisation Beam 95%.
Comparative example 2
In addition to lauryl mercaptan 0.38g is added after emulsification, the scattered of polymer is obtained using method similarly to Example 1 Liquid.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFMA has terminated 99%, StA and tied in polymerisation Beam 96%.
Comparative example 3
In addition to neopentylglycol diacrylate 0.38g is added into embodiment 2, method similarly to Example 2 is utilized Obtain the dispersion liquid of polymer.
Filled the moment (single step polymerize finish time) in vinyl chloride, C6SFMA has terminated 99%, StA and tied in polymerisation Beam 96%.
Comparative example 4
In addition to neopentylglycol diacrylate is not added, point of polymer is obtained using method similarly to Example 12 Dispersion liquid.
Comparative example 5
In addition to the lauryl mercaptan quantitative change added after by emulsification is 1.25g, gathered using the method same with comparative example 4 The dispersion liquid of compound.
The characteristic of each example is shown in Table A.
Industrial applicability
The penetrability of moisture-permeable water-proof fabric of the present invention, water resistance and washing fastness are excellent.
The moisture-permeable water-proof fabric of the present invention can be used in dress material, for example move dress material, cold-proof dress material, waterproof sheet, such as Tent, sleeping bag and antifouling waterproof sheet, footwear and gloves etc..

Claims (19)

  1. A kind of 1. moisture-permeable water-proof fabric, it is characterised in that：
    It has the intermediate layer containing fluoropolymer and the moisture-permeability waterproof layer containing synthetic resin,
    Fluoropolymer has the repetitive unit from following monomers (a), (b) and (c), and the dynamic viscoelastic at 160 DEG C For more than 400Pas and below 2300Pas,
    (a) fluorochemical monomer shown in following formula,
    CH2=C (- X)-C (=O)-Y-Z-Rf
    In formula, X is hydrogen atom or methyl, and Y is-O- or-NH-, and Z is the organic group of Direct Bonding or divalence, and Rf is carbon The fluoroalkyl of atomicity 1~6；
    (b) halogenated olefins monomer；
    (c) non-fluorine monomer using as needed, without fluorine atom and at least with a carbon-to-carbon double bond,
    Fluoropolymer is to include the first polymer formed by the first monomer and the second polymer formed by second comonomer Fluoropolymer,
    Second comonomer polymerize in the presence of first polymer,
    At least one party of first monomer and second comonomer contains fluorochemical monomer (a),
    First monomer is free of halogenated olefins monomer (b),
    Second comonomer contains halogenated olefins monomer (b).
  2. 2. moisture-permeable water-proof fabric as claimed in claim 1, it is characterised in that：
    Fluorochemical monomer (a) is monomer shown in following formula,
    CH2=C (- X)-C (=O)-Y-Z-Rf (I)
    In formula, X is hydrogen atom or methyl, and Y is-O- or-NH-,
    Z be the aliphatic group of carbon number 1~10, the aromatic group of carbon number 6~18 or cyclic aliphatic group ,- CH2CH2N(R1)SO2- base ,-CH2CH(OZ1)CH2- base ,-(CH2)m- SO2- (CH2)n- base or-(CH2)m- S- (CH2)n- base, wherein, R1It is the alkyl of carbon number 1~4, Z1It is hydrogen atom or acetyl group, m is that 1~10, n is 0~10,
    Rf is the straight-chain of carbon number 1~6 or the fluoroalkyl of branched.
  3. 3. moisture-permeable water-proof fabric as claimed in claim 1 or 2, it is characterised in that：
    Halogenated olefins monomer (b) is the alkene for the carbon number 2~20 that substitution has chlorine atom, bromine atoms or iodine atom.
  4. 4. moisture-permeable water-proof fabric as claimed in claim 1 or 2, it is characterised in that：
    Halogenated olefins monomer (b) is in vinyl chloride, vinyl bromide, iodoethylene, vinylidene chloride, inclined vinyl bromide and inclined iodoethylene It is at least one.
  5. 5. moisture-permeable water-proof fabric as claimed in claim 1 or 2, it is characterised in that：
    Non-fluorine monomer (c) is non-cross-linkable monomer or cross-linkable monomer,
    Non-crosslinked property monomer is included in the first monomer, and is not included in second comonomer.
  6. 6. moisture-permeable water-proof fabric as claimed in claim 1 or 2, it is characterised in that：
    Non-fluorine monomer (c) is monomer shown in following formula,
    CH2=CA-T
    In formula, A is the halogen atom beyond hydrogen atom, methyl or fluorine atom,
    T is hydrogen atom, the chain of carbon number 1~30 or cricoid alkyl or chain or cricoid carbon original with ester bond The organic group of subnumber 1~31.
  7. 7. moisture-permeable water-proof fabric as claimed in claim 1 or 2, it is characterised in that：
    Non-fluorine monomer (c) as cross-linkable monomer is list (methyl) acrylate, two (methyl) third for having reactive group Olefin(e) acid ester or single (methyl) acrylamide.
  8. 8. moisture-permeable water-proof fabric as claimed in claim 1 or 2, it is characterised in that：
    Synthetic resin is selected from least one of polyurethane resin, acrylic resin and polyester resin.
  9. 9. moisture-permeable water-proof fabric as claimed in claim 1 or 2, it is characterised in that：
    Moisture-permeability waterproof layer is formed by painting synthetic resin or by attaching synthetic resin film.
  10. 10. moisture-permeable water-proof fabric as claimed in claim 9, it is characterised in that：
    Synthetic resin film is attached to the intermediate layer of fluoropolymer by bonding agent.
  11. 11. moisture-permeable water-proof fabric as claimed in claim 1 or 2, it is characterised in that：
    Dynamic viscoelastic of the fluoropolymer at 150 DEG C and at 170 DEG C be respectively more than 500Pas, 300Pas with On.
  12. A kind of 12. manufacture method of moisture-permeable water-proof fabric, for the moisture-permeable water-proof fabric described in manufacturing claims 1, the manufacture Method is characterized in that, including：
    (i) the fluorine-containing inorganic agent containing fluoropolymer is suitable for fiber fabric, forms the intermediate layer containing fluoropolymer Process and
    (ii) by being applicable in synthetic resin on the intermediate layer of fluoropolymer, the process for forming moisture-permeability waterproof layer.
  13. 13. manufacture method as claimed in claim 12, it is characterised in that：
    Synthetic resin is applicable in by painting synthetic resin or attaching synthetic resin film to carry out.
  14. 14. the manufacture method as described in claim 12 or 13, it is characterised in that：
    Synthetic resin is selected from least one of polyurethane resin, acrylic resin and polyester resin.
  15. 15. manufacture method as claimed in claim 13, it is characterised in that：
    Synthetic resin film is attached to the intermediate layer of fluoropolymer by bonding agent.
  16. A kind of 16. fluorine-containing inorganic agent of moisture-permeable water-proof fabric, it is characterised in that：
    It contains fluoropolymer, which, which has, is derived from following monomers (a), the repetitive unit of (b) and (c), and Dynamic viscoelastic at 160 DEG C is more than 400Pas and below 2300Pas,
    (a) fluorochemical monomer shown in following formula,
    CH2=C (- X)-C (=O)-Y-Z-Rf
    In formula, X is hydrogen atom or methyl, and Y is-O- or-NH-, and Z is the organic group of Direct Bonding or divalence, and Rf is carbon The fluoroalkyl of atomicity 1~6；
    (b) halogenated olefins monomer；
    (c) non-fluorine monomer using as needed, without fluorine atom and at least with a carbon-to-carbon double bond,
    Fluoropolymer is to include the first polymer formed by the first monomer and the second polymer formed by second comonomer Fluoropolymer,
    Second comonomer polymerize in the presence of first polymer,
    At least one party of first monomer and second comonomer contains fluorochemical monomer (a),
    First monomer is free of halogenated olefins monomer (b),
    Second comonomer contains halogenated olefins monomer (b).
  17. A kind of 17. preparation method of fluoropolymer, for the fluoropolymer in the moisture-permeable water-proof fabric described in manufacturing claims 1 Thing, the preparation method be characterized in that, including：
    (I) fluorochemical monomer (a) and non-fluorine monomer (c) as needed are polymerize, obtain first polymer process and
    (II) halogenated olefins monomer (b) is polymerize in the presence of first polymer, thus manufactured by halogenated olefins monomer (b) shape Into second polymer, the process for obtaining fluoropolymer.
  18. 18. the preparation method of fluoropolymer as claimed in claim 17, it is characterised in that：
    At the time of the polymerization of second comonomer is started, the non-crosslinked property of unreacted non-fluorine is created substantially absent in polymerization system Monomer.
  19. A kind of 19. processing method of fiber fabric, it is characterised in that：
    By the way that the fluorine-containing inorganic agent of the moisture-permeable water-proof fabric described in claim 16 is suitable for fiber fabric, fluoropolymer is formed The intermediate layer of thing.
CN201380035883.3A 2012-07-06 2013-07-04 Moisture-permeable water-proof fabric Active CN104411880B (en)

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