CN104411880A - Moisture-permeable waterproof fabric - Google Patents
Moisture-permeable waterproof fabric Download PDFInfo
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- CN104411880A CN104411880A CN201380035883.3A CN201380035883A CN104411880A CN 104411880 A CN104411880 A CN 104411880A CN 201380035883 A CN201380035883 A CN 201380035883A CN 104411880 A CN104411880 A CN 104411880A
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- monomer
- moisture
- fluorine
- fluoropolymer
- polymer
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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
-
- 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
- D06M15/263—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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a moisture-permeable waterproof fabric having excellent moisture permeability, water resistance and launderability, and comprising an intermediate layer containing a fluorine-containing polymer, and a moisture-permeable waterproof layer containing a synthetic resin. The fluorine-containing polymer has repeating units derived from: (a) a fluorine-containing monomer represented by the formula, CH2=C(-X)-C(=O)-Y-Z-Rf [wherein, X is a hydrogen atom or a methyl group, Y is -O- or -NH-, Z is a directly-bonded or divalent organic group, and Rf is a fluoroalkyl group with 1 to 6 carbons]; (b) a halogenated olefin monomer; and (c) a fluorine-free monomer that is used as necessary, does not have a fluorine atom, and has at least one carbon-carbon double bond. The fluorine-containing polymer has a dynamic viscoelasticity of at least 400 Pa.s at 160 DEG C.
Description
Technical field
The present invention relates to a kind of moisture-permeable water-proof fabric that can use as dress material, waterproof sheet, footwear and gloves etc.
Background technology
At present, about moisture-permeable water-proof fabric, motion has various technology (such as, Japanese Patent Publication 60-47955 publication, Japanese Patent Publication 4-18066 publication).
Fluoropolymer not only gives cloth and silk water-repellent oil-repellent and Water Pressure Resistance, also as when being coated with the synthetic resin of formation moisture-permeability waterproof layer, prevent the preventing agent of oozing out that synthetic resin oozes out to cloth base material opposition side to be utilized.
But, as corresponding to the polymer containing fluoroalkyl that the fluoroalkyl carbon number of environmental problem is less than 6, when there is painting synthetic resin, ooze out the problem that low, the easy generation synthetic resin of preventing effectiveness infiltrates to cloth base material opposition side.
In addition, when attaching synthetic resin film, exist because bonding agent penetrates into cloth and silk, adhesive effect dies down, the problem of the peel strength reduction of synthetic resin film.
Prior art document
Patent document
Patent document 1: Japanese Patent Publication 60-47955 publication
Patent document 2: Japanese Patent Publication 4-18066 publication
Summary of the invention
Invent problem to be solved
The object of the invention is to, the moisture-permeable water-proof fabric of a kind of poisture-penetrability, resistance to water and washing resistance excellence is provided.
Other object of the present invention is, provide a kind of when being coated with the synthetic resin forming moisture-permeability waterproof layer at cloth base material, synthetic resin is not to the moisture-permeable water-proof fabric that the surface of cloth base material opposition side is oozed out.
For solving the technical scheme of problem
The present inventor finds when being arranged between cloth base material and moisture-permeability waterproof layer in the intermediate layer containing specific fluoropolymer, can realize above-mentioned purpose, so that complete the present invention.
The invention provides a kind of moisture-permeable water-proof fabric, it has the intermediate layer containing fluoropolymer and the moisture-permeability waterproof layer containing synthetic resin, fluoropolymer has the repetitive being derived from following monomer (a), (b) and (c), and the dynamic viscoelastic 160 DEG C time is more than 400Pas
Fluorochemical monomer shown in (a) following formula,
CH
2＝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) use as required, not contain fluorine atoms and at least there is the non-fluorine monomer of a carbon-to-carbon double bond.
Following mode is had in the present invention.
A. a manufacture method for moisture-permeable water-proof fabric, is characterized in that, comprising:
I fluorine-containing finishing agent containing fluoropolymer is applicable to fiber fabric by (), formed containing fluoropolymer intermediate layer operation and
(ii) by being suitable for synthetic resin (such as, by painting synthetic resin or attaching synthetic resin film) on the intermediate layer of fluoropolymer, the operation of moisture-permeability waterproof layer is formed.
B. a processing method for fiber fabric, is characterized in that: by the fluorine-containing finishing agent containing fluoropolymer is applicable to fiber fabric, forms the intermediate layer of fluoropolymer.
C. the fluorine-containing finishing agent of moisture-permeable water-proof fabric, it is characterized in that: it contains fluoropolymer, this fluoropolymer has the repetitive being derived from following monomer (a), (b) and (c), and the dynamic viscoelastic 160 DEG C time is more than 400Pas
Fluorochemical monomer shown in (a) following formula,
CH
2＝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) use as required, not contain fluorine atoms and at least there is the non-fluorine monomer of a carbon-to-carbon double bond.
D. a method for making for the fluoropolymer in moisture-permeable water-proof fabric, is characterized in that, comprising:
(I) by fluorochemical monomer (a) and the polymerization of non-fluorine monomer (c) as required, obtain the first polymer operation and
(II) under the existence of the first polymer, halogenated olefins monomer (b) is polymerized, manufactures the second polymer formed by halogenated olefins monomer (b) thus, obtain the operation of fluoropolymer.
The effect of invention
The poisture-penetrability of moisture-permeable water-proof fabric of the present invention, resistance to water, washing resistance are excellent.
According to the present invention, when being coated with the synthetic resin forming moisture-permeability waterproof layer at cloth base material, synthetic resin does not ooze out to the surface of the opposition side of cloth base material.
Detailed description of the invention
Moisture-permeable water-proof fabric have cloth base material, on a surface of cloth base material containing the intermediate layer of fluoropolymer and the moisture-permeability waterproof layer on intermediate layer.Intermediate layer also can be formed at the inside of cloth base material.Performance pattern or motif layer also can be set on moisture-permeability waterproof layer.On other surfaces of cloth base material, can not layer be set.
In general, cloth base material is formed by natural fabric and/or synthetic fiber.The fiber of cloth base material can be natural fabric (such as, cotton or wool etc.), chemical fibre (such as, viscose or Lyocell (Lyocell) etc.) or synthetic fiber are (such as, polyester, polyamide or acrylic fiber etc.), or can be the mixture (such as, the mixture etc. of natural fabric and synthetic fiber) of fiber.As the form of cloth base material, such as, can enumerate woven fabric, knitted fabric, nonwoven fabric, nylon loop etc.The thickness of cloth base material is generally 0.05 ~ 10mm, such as, be 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 is polyurethane based resin, polyamino acid polyurethane based resin, acrylic resin, polyester resin, polytetrafluoroethyl-ne vinyl resin etc.Moisture-permeability waterproof layer can only be formed by synthetic resin, or also can contain additive such as isocyanates.The thickness of moisture-permeability waterproof layer is generally 10 ~ 100 μm, such as, be 20 ~ 50 μm.
Fluoropolymer is contained in intermediate layer.Intermediate layer can only be formed by fluoropolymer, or also can contain additive, such as, and melmac, blocked isocyanate etc.In general, the thickness in intermediate layer is 0.1 ~ 1 μm, such as, be 0.2 ~ 0.3 μm.Group solvent borne in intermediate layer is excellent, can dial the organic solvents such as dimethyl formamide, toluene and methyl ethyl ketone.
The dynamic viscoelastic of fluoropolymer 160 DEG C time is more than 400Pas.
The dynamic viscoelastic of fluoropolymer 150 DEG C time is more than 500Pas, is particularly preferably more than 900Pas.The dynamic viscoelastic of fluoropolymer 160 DEG C time is more than 400Pas, is particularly preferably more than 600Pas, such as, be preferably more than 800Pas.The dynamic viscoelastic of fluoropolymer 170 DEG C time is more than 300Pas, is particularly preferably more than 700Pas.
The dynamic viscoelastic of fluoropolymer 150 DEG C time can be below 2500Pas, such as, be below 2200Pas.The dynamic viscoelastic of fluoropolymer 160 DEG C time can be below 2500Pas, and being in particular below 2300Pas, such as, is below 2100Pas.The dynamic viscoelastic of fluoropolymer 170 DEG C time can be below 2300Pas, such as, be below 2000Pas.
During dynamic viscoelastic too low (such as, the dynamic viscoelastic 160 DEG C time is less than 400Pas), easily penetrate into the back side, the stripping of moisture-permeability waterproof layer easily occurs.When dynamic viscoelastic is lower than certain value, moisture-permeability waterproof layer and intermediate layer are fully closely sealed.
The manufacture of moisture-permeable water-proof fabric can be undertaken by following method, and the method comprises:
I fluorine-containing finishing agent containing fluoropolymer is applicable to fiber fabric by (), formed fluoropolymer intermediate layer operation and
(ii) on the intermediate layer of fluoropolymer, form the operation of the moisture-permeability waterproof layer of synthetic resin.
The formation of moisture-permeability waterproof layer such as can be carried out by painting synthetic resin or by attaching synthetic resin film.
Fluoropolymer have be derived from fluorochemical monomer repetitive as essential component.Fluoropolymer also can have the repetitive being derived from non-fluorine monomer.
The fluoropolymer with the repetitive being derived from fluorochemical monomer and non-fluorine monomer can be fed intake (single step polymerization) or fed batch (multistep polymerization, particularly two-stage polymerization) manufacture by disposable.Because the effect preventing oozing out of synthetic resin is high, preferred fed batch.Fed batch (multistep polymerization, particularly two-stage polymerization) means, is later than feed intake (polymerization starts) of more than one monomer, carries out feed intake (polymerization starts) of more than one other monomers.Two-stage polymerization means, under the existence of the first polymer obtained by the first monomer polymerization containing more than one monomer, carries out the polymerization of the second comonomer of more than one the monomer containing other.
Multistep polymerization is the polymerization of more than two steps, such as two-stage polymerization, three step polymerizations and the polymerization of four steps.Three step polymerizations are except the first polymer and the second polymer, use the terpolymer being later than the second polymer and feeding intake.Polymerizations more than four steps be re-use more than the 4th monomer.
Below, the two-stage polymerization of the representative as multistep polymerization is described.
In fed batch (particularly two-stage polymerization), in general, fluoropolymer is the fluoropolymer comprising the first polymer formed by the first monomer and the second polymer formed by second comonomer,
Second comonomer is polymerized under the existence of the first polymer,
At least one party of the first monomer and second comonomer contains fluorochemical monomer (a),
First monomer does not contain halogenation olefinic monomer (b),
Second comonomer contains halogenated olefins monomer (b).
Fed batch (particularly two-stage polymerization) method is the method for making of the fluoropolymer containing the first polymer formed by the first monomer and the second polymer formed by second comonomer, and this method for making comprises:
(I) by the first monomer polymerization, obtain the operation of the first polymer,
(II) under the existence of the first polymer, second comonomer is polymerized, obtains the operation of the second polymer thus,
At least one party of the first monomer and second comonomer contains fluorochemical monomer,
First monomer contains non-fluorine non-crosslinked monomer, not containing halogenation olefinic monomer,
Second comonomer contains halogenated olefins monomer.
In the present invention, the first monomer can contain halogenated olefins monomer, also can not contain halogenated olefins monomer.First monomer is not preferably containing halogenation olefinic monomer.
Fluoropolymer of the present invention has the repetitive being derived from the first monomer and the repetitive being derived from second comonomer.First polymer and the second polymer also can copolymerization.That is, the first polymer and the second polymer can chemical bond.Or the first polymer and the second polymer do not form chemical bond, can physical bond.The example of physical bond is the core/shell structure that the first polymer forms core, the second polymer forms shell.In core/shell structure, although the first polymer and the second polymer have not chemically combined situation, also can chemical bond.
In the present invention, as monomer, use fluorochemical monomer (a) and halogenated olefins monomer (b).Non-fluorine monomer (c) can use as required, can be non-fluorine non-crosslinked monomer and/or non-fluorine cross-linkable monomer.Non-fluorine monomer (c) is preferably non-fluorine non-crosslinked monomer (c1), and/or can be non-fluorine cross-linkable monomer (c2).
At least one party of the first monomer and second comonomer contains fluorochemical monomer.Preferably the first monomer contains fluorochemical monomer, and second comonomer is not containing fluorochemical monomer.
Preferably the first monomer is not containing halogenation olefinic monomer, and second comonomer contains halogenated olefins monomer.Second comonomer also can be only made up of halogenated olefins monomer.
First monomer can contain non-fluorine non-crosslinked monomer.Preferred second comonomer is not containing non-fluorine non-crosslinked monomer.By making second comonomer not containing non-fluorine non-crosslinked monomer, in the processing process of the finishing agent containing fluoropolymer, polymer is prevented to be attached to the excellent performance that roller causes roller to pollute.
At least one party of the first monomer and second comonomer can contain non-fluorine cross-linkable monomer.When fluoropolymer contains non-fluorine cross-linkable monomer, can be the first monomer not containing non-fluorine cross-linkable monomer and second comonomer contains non-fluorine cross-linkable monomer, or can be that the first monomer contains non-fluorine cross-linkable monomer and second comonomer not containing non-fluorine cross-linkable monomer.
The preferred kind of the monomer in the first monomer and second comonomer has with under type.
[table 1]
In the present invention, particularly preferably mode 2 (the first monomer is fluorochemical monomer and non-fluorine non-crosslinked monomer, and second comonomer is halogenated olefins monomer).
Also preferably fluorochemical monomer and non-fluorine cross-linkable monomer are present in the mode of the both sides of the first monomer and second comonomer respectively.That is, be also preferably present in the first monomer mode same with mode 1 ~ 7 except the both sides of second comonomer, be present in the first monomer mode identical with mode 1 ~ 7 except the both sides of second comonomer except non-fluorine cross-linkable monomer except fluorochemical monomer.
(a) fluorochemical monomer
Fluorochemical monomer is the fluorochemical monomer shown in following formula,
CH
2＝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 can be such as straight-chain alkyl-sub-or branched alkylidene, the such as formula-(CH of carbon number 1 ~ 20
2)
x-(in formula, x is 1 ~ 10.) shown in group or formula-SO
2n (R
1) R
2-or formula-CON (R
1) R
2shown group (in formula, R
1for the alkyl of carbon number 1 ~ 10, R
2for straight-chain alkyl-sub-or the branched alkylidene of carbon number 1 ~ 10.) or formula-CH
2cH (OR
3) CH
2-(in formula, R
3represent the acyl group (such as formoxyl or acetyl group etc.) of hydrogen atom or carbon number 1 ~ 10.) shown in group or formula-Ar-CH
2-(in formula, Ar is for have substituent arlydene as required.) shown in group ,-(CH
2)
m-SO
2-(CH
2)
n-Ji or-(CH
2)
m-S-(CH
2)
n-Ji (wherein, m is 1 ~ 10, n is 0 ~ 10).
Fluorochemical monomer (a) is the acrylate shown in following general formula (I) or acrylamide preferably,
CH
2＝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 cyclic aliphatic group ,-CH
2cH
2n (R
1) SO
2-Ji (wherein, R
1for the alkyl of carbon number 1 ~ 4.) ,-CH
2cH (OZ
1) CH
2-Ji (wherein, Z
1for hydrogen atom or acetyl group) ,-(CH
2)
m-SO
2-(CH
2)
n-Ji or-(CH
2)
m-S-(CH
2)
n-Ji (wherein, m is 1 ~ 10, n is 0 ~ 10),
Rf is the straight-chain of carbon number 1 ~ 6 or the fluoroalkyl of branched.]。
(acrylate or methacrylate) α position of fluorochemical monomer (a) is had to replace the situation having halogen atom etc.Therefore, in formula (1), X can be the straight-chain of carbon number 2 ~ 21 or alkyl, fluorine atom, chlorine atom, bromine atoms, atomic iodine, the CFX of branched
1x
2base (wherein, X
1and X
2hydrogen atom, fluorine atom, chlorine atom, bromine atoms or atomic iodine.), the straight-chain of cyano group, carbon number 1 ~ 21 or the fluoroalkyl of branched, substituted or non-substituted benzyl, substituted or non-substituted phenyl.
In above-mentioned formula (1), Rf base is preferably perfluoroalkyl.The carbon number of Rf base is 1 ~ 6, is more particularly 4 ~ 6.The example of Rf base is-CF
3,-CF
2cF
3,-CF
2cF
2cF
3,-CF (CF
3)
2,-CF
2cF
2cF
2cF
3,-CF
2cF (CF
3)
2,-C (CF
3)
3,-(CF
2)
4cF
3,-(CF
2)
2cF (CF
3)
2,-CF
2c (CF
3)
3,-CF (CF
3) CF
2cF
2cF
3,-(CF
2)
5cF
3,-(CF
2)
3cF (CF
3)
2,-(CF
2)
4cF (CF
3)
2,-C
8f
17deng.
Z is preferably the aliphatic group of carbon number 1 ~ 10, the aromatic group of carbon number 6 ~ 18 or cyclic aliphatic group ,-CH
2cH
2n (R
1) SO
2-Ji (wherein, R
1it is the alkyl of carbon number 1 ~ 4.) ,-CH
2cH (OZ
1) CH
2-Ji (wherein, Z
1hydrogen atom or acetyl group.) ,-(CH
2)
m-SO
2-(CH
2)
n-Ji or-(CH
2)
m-S-(CH
2)
n-Ji (wherein, m is 1 ~ 10, n is 0 ~ 10).Aliphatic group is preferably alkylidene, and (particularly carbon number is 1 ~ 4, such as, be 1 or 2.)。Aromatic group or cyclic aliphatic group can be substituted or non-substituted.S base or SO
2base can with Rf base Direct Bonding.
As the concrete example of fluorochemical monomer (a), such as, can illustrate following monomer, but do not limited by these.
CH
2＝C(－H)－C(＝O)－O－(CH
2)
2－Rf
CH
2＝C(－H)－C(＝O)－O－C
6H
4－Rf
CH
2＝C(－H)－C(＝O)－O－(CH
2)
2N(－CH
3)SO
2－Rf
CH
2＝C(－H)－C(＝O)－O－(CH
2)
2N(－C
2H
5)SO
2－Rf
CH
2＝C(－H)－C(＝O)－O－CH
2CH(－OH)CH
2－Rf
CH
2＝C(－H)－C(＝O)－O－CH
2CH(－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 above-mentioned formula, Rf is the fluoroalkyl of carbon number 1 ~ 6.]
(b) halogenated olefins monomer
Halogenated olefins monomer (b) is preferably the alkene replacing and have the chlorine atom of 1 ~ 10, the carbon number 2 ~ 20 of bromine atoms or atomic iodine.Halogenated olefins monomer (b) is preferably the chlorinated alkenes of carbon number 2 ~ 20, particularly has the alkene of the carbon number 2 ~ 5 of the chlorine atom of 1 ~ 5.The preferred concrete example of halogenated olefins monomer (b) is ethylene halide, such as vinyl chloride, bromine ethene, iodoethylene; Vinylidene halide, such as vinylidene chloride, partially bromine ethene, partially iodoethylene.Because resistance to water (particularly the durability of resistance to water) is high, so preferred vinyl chloride.
Non-fluorine monomer (c) can be non-fluorine non-crosslinked monomer (c1) and/or non-fluorine cross-linkable monomer (c2).
(c1) non-fluorine non-crosslinked monomer
Non-fluorine non-crosslinked monomer (c1) is the monomer of not contain fluorine atoms.Non-fluorine non-crosslinked monomer (c1) does not have cross-linking functional group.Non-fluorine non-crosslinked monomer (c1) is different from cross-linkable monomer (c2), is non-crosslinked.Non-fluorine non-crosslinked monomer (c1) preferably has the non-fluorine monomer of carbon-to-carbon double bond.Non-fluorine non-crosslinked monomer (c1) is preferably not fluorine-containing vinyl monomer.Non-fluorine non-crosslinked monomer (c1) is in general the compound with a carbon-to-carbon double bond.
Preferred non-fluorine non-crosslinked monomer (c1) can be the compound shown in following formula,
CH
2＝CA－T
[in formula, A is the halogen atom (such as chlorine atom, bromine atoms and atomic iodine) beyond hydrogen atom, methyl or fluorine atom,
T is hydrogen atom, the chain of carbon number 1 ~ 30 (such as 1 ~ 20) or the alkyl of ring-type or have the organic group of the chain of ester bond or the carbon number 1 ~ 31 (such as 1 ~ 20) of ring-type.]
The example of the chain of carbon number 1 ~ 30 or the alkyl of ring-type is aliphatic alkyl, the cyclic aliphatic group of carbon number 4 ~ 30, the aromatic hydrocarbyl of carbon number 6 ~ 30, the aromatic-aliphatic alkyl of carbon number 7 ~ 30 of the straight or branched of carbon number 1 ~ 30.
The example with the organic group of the chain of ester bond or the carbon number 1 ~ 31 of ring-type is-C (=O)-O-Q and-O-C (=O)-Q (wherein, Q is aliphatic alkyl, the cyclic aliphatic group of carbon number 4 ~ 30, the aromatic hydrocarbyl of carbon number 6 ~ 30, the aromatic-aliphatic alkyl of carbon number 7 ~ 30 of the straight or branched of carbon number 1 ~ 30).The aliphatic alkyl of the straight or branched of preferred carbon number 12 ~ 30 (particularly 18 ~ 30), the cyclic aliphatic group of carbon number 4 ~ 30, the aromatic hydrocarbyl of carbon number 6 ~ 30, the aromatic-aliphatic alkyl of carbon number 7 ~ 30, the particularly preferably aliphatic alkyl of the straight or branched of carbon number 12 ~ 30 (particularly 18 ~ 30), the cyclic aliphatic group of carbon number 4 ~ 30.
The preference of non-fluorine non-crosslinked monomer (c1) comprises such as ethene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate and vinyl alkyl ethers.Non-fluorine non-crosslinked monomer (c1) does not limit by these examples.
Non-fluorine non-crosslinked monomer (c1) can be have alkyl (methyl) acrylate.The carbon number of alkyl can be 1 ~ 30, such as, can be 6 ~ 30 (such as, 10 ~ 30).Such as, non-fluorine non-crosslinked monomer (c1) can be the acrylate shown in following general formula,
CH
2＝CA
1COOA
2
[in formula, A
1the halogen atom (such as, chlorine atom, bromine atoms and atomic iodine) beyond hydrogen atom, methyl or fluorine atom,
A
2c
nh
2n+1alkyl shown in (n=1 ~ 30).]
Because the performance preventing polymer from adhering to roller improves, so fluoropolymer preferably has be derived from A
2for the acrylate (CH of the alkyl of carbon number 12 ~ 30, particularly 18 ~ 30
2=CA
1cOOA
2) repetitive.
Non-fluorine non-crosslinked monomer (c1) can be have cyclic hydrocarbon group (methyl) acrylate monomer.(methyl) acrylate monomer (B) with cyclic hydrocarbon group has the acrylate-based compound of (methyl) of (preferred monovalence) cyclic hydrocarbon group and monovalence.The cyclic hydrocarbon group of monovalence and (methyl) acrylate-based Direct Bonding of monovalence.Saturated or undersaturated monocycle base, many cyclic groups, crosslinked cyclic group etc. can be enumerated as cyclic hydrocarbon group.The preferred saturated group of cyclic hydrocarbon group.The carbon number of cyclic hydrocarbon group is preferably 4 ~ 20.Carbon number 4 ~ 20 can be enumerated, particularly cyclic aliphatic group, the aromatic group of carbon number 6 ~ 20, the aromatic-aliphatic group of carbon number 7 ~ 20 of 5 ~ 12 as cyclic hydrocarbon group.The carbon number of cyclic hydrocarbon group is less than 15, such as, be particularly preferably less than 10.Ester group Direct Bonding during the nuclear carbon atom of cyclic hydrocarbon group is preferably acrylate-based with (methyl).The cyclic aliphatic group that cyclic hydrocarbon group is preferably saturated.The concrete example of cyclic hydrocarbon group is cyclohexyl, tert-butylcyclohexyl, isobornyl, Bicvclopentyl, double cyclopentenyl.(methyl) is acrylate-based is acrylate-based or methacrylate based, preferred methacrylate base.As the concrete example of monomer with cyclic hydrocarbon group, cyclohexyl methacrylate, t-butyl cyclohexyl ester, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, methacrylic acid dicyclo pentyl ester, acrylic acid dicyclo pentyl ester, acrylic acid dicyclopentenyloxyethyl methacrylate etc. can be enumerated.
(c2) non-fluorine cross-linkable monomer
Fluoropolymer of the present invention can have the repetitive being derived from non-fluorine cross-linkable monomer (c2).Non-fluorine cross-linkable monomer (c2) is the monomer of not contain fluorine atoms.Non-fluorine cross-linkable monomer (c2) at least has 2 reactive groups and/or carbon-to-carbon double bond, can be not fluorine-containing compound.Non-fluorine cross-linkable monomer (c2) has the compound of at least 2 carbon-to-carbon double bonds or has the compound of at least 1 carbon-to-carbon double bond and at least 1 reactive group.The example of reactive group is hydroxyl, epoxy radicals, chloromethyl, blocked isocyanate base, amino, carboxyl etc.Non-fluorine cross-linkable monomer (c2) can be have list (methyl) acrylate of reactive group, (methyl) diacrylate or single (methyl) acrylamide.Or non-fluorine cross-linkable monomer (c2) can be two (methyl) acrylate.
Two acetone (methyl) acrylamide such as can be illustrated as non-fluorine cross-linkable monomer (c2), (methyl) acrylamide, N-methylol (methyl) acrylamide, (methyl) dihydroxypropyl methyl esters, (methyl) Hydroxyethyl Acrylate, 3-chlorine-2-hydroxyl propyl group (methyl) acrylate, 2-acetoacetoxyethyl (methyl) acrylate, butadiene, isoprene, chlorobutadiene, (methyl) glycidyl acrylate, 1, 6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate etc., but do not limited by these.
In this description, " (methyl) acrylate " means acrylate or methacrylate, and " (methyl) acrylamide " means acrylamide or Methacrylamide.
By by non-fluorine non-crosslinked monomer (c1) and/or non-fluorine cross-linkable monomer (c2) copolymerization, the resistance to cleaning of water-repellent oil-repellent, soil resistance and these performances, washing resistance, the various character such as dissolubility, hardness, sense of touch for solvent can be improved as required.
In fluoropolymer, relative to fluorochemical monomer (a) 100 weight portion, the amount of halogenated olefins (b) can be 2 ~ 500 weight portions, be such as 5 ~ 200 weight portions, be in particular 10 ~ 150 weight portions, be more particularly 20 ~ 50 weight portions, the amount of non-fluorine monomer (c) can be below 1200 weight portions, be such as 0.1 ~ 400 weight portion, be in particular 0.5 ~ 250 weight portion, be more particularly 1 ~ 50 weight portion.
In fluoropolymer, relative to fluorochemical monomer (a) 100 weight portion, the amount of non-fluorine non-crosslinked monomer (c1) can be below 1000 weight portions, it is such as 0.1 ~ 300 weight portion, be in particular 1 ~ 200 weight portion, the amount of non-fluorine cross-linkable monomer (c2) can be below 50 weight portions, such as, be below 30 weight portions, be in particular 0.1 ~ 20 weight portion.
The monomer of same kind (such as, halogenated olefins monomer and fluorochemical monomer) when containing in the both sides of the first monomer and second comonomer, same monomers in first monomer (particularly, halogenated olefins monomer) and second comonomer in same monomers (particularly, halogenated olefins monomer) weight ratio can be 3 ~ 97: 97 ~ 3, be such as 5 ~ 90: 95 ~ 10, be in particular 10 ~ 70: 90 ~ 30.
Fluoropolymer in the present invention can manufacture by any one of common polymerization, and the condition of polymerisation also can be selected arbitrarily.As such polymerization, polymerisation in solution, suspension polymerization, emulsion polymerisation can be enumerated.
In polymerisation in solution, can adopt under the existence of polymerization initiator, make monomer be dissolved in organic solvent, after carrying out nitrogen replacement, in the scope of 30 ~ 120 DEG C, add the thermal agitation method of 1 ~ 10 hour.As polymerization initiator, such as, can enumerate azodiisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butylperoxy pivarate, diisopropyl peroxydicarbonate etc.Relative to monomer 100 weight portion, with 0.01 ~ 20 weight portion, be such as 0.01 ~ 10 weight portion scope use polymerization initiator.
Organic solvent is the solvent being inertia to monomer and dissolving these materials, be such as ester class (such as, the ester of carbon number 2 ~ 30, specifically, ethyl acetate, butyl acetate), ketone (such as, the ketone of carbon number 2 ~ 30, specifically, methyl ethyl ketone, diisobutyl ketone), alcohol (such as, the alcohol of carbon number 1 ~ 30, specifically, isopropyl alcohol).As the object lesson of organic solvent, acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene,toluene,xylene, benzinum, oxolane, 1 can be enumerated, 4-diox, methyl ethyl ketone, methylisobutylketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethanes, 1,1,1-trichloroethanes, trichloro-ethylene, perchloroethylene, tetrachlorodifluoroethane, trichorotrifluoroethane etc.Relative to total 100 weight portion of monomer, with the scope of 10 ~ 2000 weight portions, such as 50 ~ 1000 weight portions with an organic solvent.
In emulsion polymerisation, adopt under the existence of polymerization initiator and emulsifying agent, make monomer emulsification in water, after carrying out nitrogen replacement, stir 1 ~ 10 hour the scopes of 50 ~ 80 DEG C, make the method for its copolymerization.Polymerization initiator can use benzoyl peroxide, lauroyl peroxide, TBPB tertiary butyl perbenzoate, 1-hydroxy-cyclohexyl hydroperoxides, 3-carboxypropanoyl peroxide, acetyl peroxide, azo two NSC 18620s-dihydrochloride, azodiisobutyronitrile, sodium peroxide, potassium peroxydisulfate, the water miscible material such as ammonium persulfate or azodiisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butylperoxy pivarate, the oil-soluble material such as diisopropyl peroxydicarbonate.Relative to monomer 100 weight portion, use polymerization initiator with the scope of 0.01 ~ 10 weight portion.
In order to obtain the copolymer aqueous dispersions of shelf-stability excellence, wishing the emulsifier unit can giving powerful crushing energy using high pressure homogenisers, ultrasonic homogenizer and so on, by monomer corpusculed in water, using oil-soluble polymerization initiator to be polymerized.In addition, the various emulsifying agents of anionic property, cationic or nonionic can be used as emulsifying agent, relative to monomer 100 weight portion, use with the scope of 0.5 ~ 20 weight portion.The emulsifying agent of preferred use anionic property and/or nonionic and/or cationic.In the complete inconsistent situation of monomer, preferably add the compatilizer making these monomers fully compatible, such as, add water-miscible organic solvent, low-molecular-weight monomer.By adding compatilizer, emulsibility and copolymerizable can be improved.
As water-miscible organic solvent, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol etc. can be enumerated, relative to water 100 weight portion, can use with the scope of 1 ~ 50 weight portion, such as 10 ~ 40 weight portions.In addition, as low-molecular-weight monomer, methyl methacrylate, glycidyl methacrylate, 2 can be enumerated, 2,2-trifluoroethyl methacrylate etc., relative to total amount 100 weight portion of monomer, can use with the scope of 1 ~ 50 weight portion, such as 10 ~ 40 weight portions.
Can usage chain transfer agent in polymerization.Corresponding to the use amount of chain-transferring agent, the molecular weight of copolymer can be changed.The example of chain-transferring agent is the inorganic salts etc. such as compound (particularly, (such as carbon number 1 ~ 30) alkyl hydrosulfide), sodium hypophosphite, sodium hydrogensulfite containing sulfydryl such as lauryl mercaptan, THIOGLYCOL, thioglycerol.The use amount of chain-transferring agent, relative to total amount 100 weight portion of monomer, can use with the scope of 0.01 ~ 10 weight portion, such as 0.1 ~ 5 weight portion.
The copolymerization of fluoropolymer can be fed intake (single step polymerization) or fed batch (multistep polymerization, particularly two-stage polymerization) manufacture by disposable.Preferred fed batch, but when using cross-linkable monomer, also can disposable feeding intake be carried out.
In two-stage polymerization, in general, in the liquid containing the first monomer, carry out polymerisation manufacture the first polymer, then, in the liquid containing the first polymer and second comonomer, carry out polymerisation manufacture the second polymer, obtain the fluoropolymer be made up of the first polymer and the second polymer.The polymerization of the second polymer can be started in the polymerization of the first polymer, or after the polymerization of the first polymer completes, start the polymerization of the second polymer.Can in the polymerisation of the first polymer (namely, the polymerisation of the first monomer) finish more than 10% (namely, 10 ~ 100%), such as more than 40% (namely, 40 ~ 100%), particularly more than 70% (namely, 70 ~ 100%), after, the polymerization of the second polymer is started.Polymerisation terminate ratio % (that is, polymerisation carries out ratio %) mean the monomer (monomer of polymerization) reacted % by mole.Such as, when polymerisation terminates 10%, the monomer be polymerized is 10 % by mole, and the monomer of unreacted (polymerization) is 90 % by mole.When first monomer is the combination of at least 2 kinds of monomers, the first monomer % by mole based on the total molal quantity of at least 2 kinds of monomers in the first monomer.
Mean in the polymerization of the first polymer that the polymerisation (that is, the polymerisation of the first monomer) of the first polymer does not terminate completely.Such as, being aggregated in of first polymer finish more than 10% ~ less than 40%, more than 40% ~ less than 70% or more than 70% ~ and less than 100% (particularly 80% ~ 99%, more especially 85% ~ 98%), after, the polymerization of the second polymer can be started.
Mean that the polymerisation (that is, the polymerisation of the first monomer) of the first polymer approximately finishes 100% after the polymerization of the first polymer completes.
When starting the polymerization of the second polymer in the polymerization of the first polymer, the second polymer has the repetitive being derived from the first monomer and second comonomer.When starting the polymerization of the second polymer after the polymerization of the first polymer completes, the second polymer has the repetitive being only derived from second comonomer.
In fluoropolymer of the present invention, the first polymer and the second polymer carry out chemical bond or do not have chemical bond.
When starting the polymerization of second comonomer, preferably in polymerization system, there is not in fact unreacted non-fluorine non-crosslinked monomer.Do not exist in fact and mean, when starting the polymerization of second comonomer, the amount of unreacted non-fluorine non-crosslinked monomer is relative to the non-fluorine non-crosslinked monomer dropped into, it is less than 10 % by mole, be preferably less than 8 % by mole, more preferably less than 5 % by mole, be in particular less than 3 % by mole, be more particularly less than 1 % by mole.By making unreacted non-fluorine non-crosslinked monomer not exist in fact, in the processing process of the finishing agent containing fluoropolymer, polymer is prevented to be attached to the excellent performance that roller causes roller to pollute.
Fluoropolymer of the present invention manufactures preferably by emulsion polymerisation.In the particle of the water-borne dispersions formed by the first polymer and the second polymer, the first polymer can surround by the second polymer, and fluoropolymer can have the core/shell structure of the core being surrounded the first polymer by the shell of the second polymer.
Fluoropolymer can by being applicable to base material cloth in order to any one of the known method of the film that forms polymer on base material cloth.In general, after the liquid containing fluoropolymer and liquid medium is applicable on cloth base material, utilizes dry grade to be removed by liquid medium, the film of fluoropolymer can be formed on polymer.In the liquid containing fluoropolymer and liquid medium, the concentration of fluoropolymer can be such as 0.01 ~ 20 % by weight, is in particular 0.05 ~ 10 % by weight.Base material cloth can be soaked in the solution, or, by liquid attachment or can be sprayed on base material cloth.Being suitable for the base material cloth of liquid, such as, in order to show liquid repellency, having carried out drying, preference is as heated with 100 DEG C ~ 200 DEG C.
As processed fibre, cloth typically comprising cloth and the carpet of woven fabric, knitted fabric and nonwoven fabric, dress material product form, but also can be fiber or yarn or median fiber goods (such as, sliver or rove etc.).Fabric material can be natural fabric (such as, cotton or wool etc.), chemical fibre (such as, viscose or Lyocell (Lyocell) etc.) or synthetic fiber are (such as, polyester, polyamide or acrylic fiber etc.), or can be the mixture (such as, the mixture etc. of natural fabric and synthetic fiber) of fiber.Manufacture polymer of the present invention is effective especially when cellulosic fibre (such as, cotton or artificial silk etc.) is made oleophobic property and dialled oiliness.In addition, in general fibre is made hydrophobicity and water-repellancy by method of the present invention.
Or fibrous substrate can be leather.In order to leather is made hydrophobicity and oleophobic property, polymer can be manufactured in the various stages of leather processing, such as can during the fine finishining during the moistening processing of leather or at leather in manufacture polymer is applicable to leather by the aqueous solution or aqueous emulsifying thing.
Or fibrous substrate can be paper.Manufacture polymer can be applicable to preshaped paper, or between the dry period being such as applicable to paper in each stage of paper processed in.
Surface conditioning agent of the present invention (fluorine-containing finishing agent) preferred solution, emulsion or aerocolloidal form.Surface conditioning agent contains fluoropolymer (active component of surface conditioning agent) and medium (particularly liquid medium, such as organic solvent and/or water).In surface conditioning agent, the concentration of fluoropolymer can be such as 0.01 ~ 50 % by weight.
Surface conditioning agent of the present invention (fluorine-containing finishing agent) is preferably containing fluoropolymer and aqueous medium.In this description, " aqueous medium " means the medium that is only made up of water and also containing organic solvent, (amount of organic solvent is below 80 weight portions relative to water 100 weight portion except water, be such as 0.1 ~ 50 weight portion, be in particular 5 ~ 30 weight portions.) medium.Fluoropolymer manufactures the dispersion liquid of fluoropolymer preferably by emulsion polymerisation.The Granular composite aqueous liquid dispersion in an aqueous medium of surface conditioning agent preferred fluoropolymer.In dispersion liquid, the average grain diameter of fluoropolymer is preferably 0.01 ~ 200 micron, such as, be 0.1 ~ 5 micron, be in particular 0.05 ~ 0.2 micron.Average grain diameter can by mensuration such as dynamic light scattering device, electron microscopes.
Surface conditioning agent of the present invention can be applicable to treated object by existing known method.This surface conditioning agent is dispersed in organic solvent or water by usual employing to be diluted, and by known methods such as dip-coating, spraying, foam coatings, makes its surface being attached to treated object and carries out dry method.In addition, if needed, can be suitable for suitable crosslinking agent simultaneously and be cured.And, insect-proof agent, softener, antiseptic, fire retardant, antistatic additive, coating fixative, anti-creasing agent etc. can be added in surface conditioning agent of the present invention and carry out and use.Can be 0.01 ~ 20 % by weight with the concentration (particularly in case of dipping) of the fluoropolymer in the treatment fluid of substrate contact, be in particular 0.05 ~ 10 % by weight.
Embodiment
Then, enumerate embodiment, comparative example and test example to be specifically described the present invention.But these explanations do not form restriction to the present invention.
In below illustrating, part or % in case of no particular description, represent weight portion or % by weight.
Characteristic measures as follows.
monomer composition in polymer
For polymer, carry out elementary analysis (F atom, Cl atom and C atom), IR optical spectroscopy, 1H NMR optical spectroscopy and 19F NMR optical spectroscopy, try to achieve monomer composition (% by weight) in polymer.
measurement of Dynamic Viscoelasticity
The aqueous liquid dispersion 10g of polymer is dispersed in methyl alcohol 20g, by the matter utilization whizzer that obtains with 60 minutes 10000rpm separation of propylene acid polymers and emulsifying agent, obtains test sample polymer.The complex viscosity (η *) of this polymer is measured by Measurement of Dynamic Viscoelasticity device RHEOSOL-G3000 ((strain) UBM system).For sample polymer 1g, under frequency 0.5Hz, measure temperature and be warmed up to 180 DEG C with 5 DEG C/min by 40 DEG C, measure dynamic viscoelastic.
dial solvent borne
Solid component concentration is become to be 1 % by weight the aqueous liquid dispersion thin up of polymer, thus adjustment treatment fluid.Nylon cloth is immersed in treatment fluid, uses mangle at 4kg/cm
2, 4m/ minute condition under wring out, 170 DEG C of heat treatments after 1 minute, the solvent borne of dialling for the treatment of cloth is evaluated.
About dialling solvent borne, DMF, MEK, toluene, ethyl acetate being dripped respectively one and dropping on test cloth, measuring the time that solvent is absorbed by cloth, until maximum 120 seconds, as dialling solvent borne time representation.The expression that numerical value is high has good group solvent borne.
the back side infiltration of coating resin
Solid component concentration is become to be 1 % by weight the aqueous liquid dispersion thin up of polymer, thus adjustment treatment fluid.Nylon cloth is immersed in treatment fluid, uses mangle at 4kg/cm
2, 4m/ minute condition under wring out, 170 DEG C of heat treatments after 1 minute, by the concentration that is solvent with MEK/ toluene/DMF be 30% polyurethane resin (refine large day industry RESAMINE ME-3612LP processed) be uniformly coated on the one side of nylon cloth, 100 DEG C of dryings after 1 minute, 150 DEG C of heat treatments 1 minute.By visual, uncoated surface is observed, evaluate according to the infiltration of the following back side to resin.
◎: permeate completely without the back side
Zero: only have some back side to permeate
×: there is a large amount of back side infiltrations
the peel strength of synthesis film
Solid component concentration is become to be 1 % by weight the aqueous liquid dispersion thin up of polymer, thus adjustment treatment fluid.Nylon cloth is immersed in treatment fluid, uses mangle at 4kg/cm
2, 4m/ minute condition under wring out, 170 DEG C of heat treatments after 1 minute, by the concentration that is solvent with MEK and ethyl acetate be 50% polyurethane type resin bonding agent (Dainippon Ink Chemicals CRISVON 4010FT) point-like be coated on the one side of nylon cloth, after the synthesis mould of polyurethane is connect, 120 DEG C of heat treatments 2 minutes.By the nylon cloth of acquisition by after AATCC88B (1) (III) repeated washing 20 times, observed by the stripping state of visual involutory film forming, according to following, its state is evaluated.
◎: completely without stripping
Zero: only have and a bit peel off
×: there is obvious stripping
Embodiment 1
Two-stage polymerization:
C is added in the autoclave of 1L
6f
13cH
2cH
2oCOC (CH
3)=CH
2(referred to as " C6SFMA ".) 179g, stearyl acrylate ester (StA) 25g, tripropylene glycol 75.8g, pure water 446g, polyoxyethylene lauryl ether 12.7g, polyethylene glycol oxide oil ether 2.47g, polyethylene glycol oxide isotridecyl ether 5.05g, dialkyl group (tallow) dimethyl ammonium chloride 2.66g, after heating at 60 DEG C, high pressure homogenisers is used to make its emulsion dispersion.After emulsion dispersion, add 2,2-azo two (2-amidine propane) dihydrochloride 1.92g, 60 DEG C of reactions, 1 hour (C6SFMA has terminated 99%, StA and terminated 97% in polymerisation).Then, vinyl chloride 60g is filled in pressurization, then reacts 2 hours, obtains the aqueous liquid dispersion of polymer.Utilizing pure water to carry out concentration, to be adjusted to its solid state component be 30 % by weight, measures the characteristic of the aqueous liquid dispersion obtained.Result is shown in Table A.
Embodiment 2
Except adding lauryl mercaptan 0.025g after emulsification, method is similarly to Example 1 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, StA and has terminated 96%.
Embodiment 3
Except adding lauryl mercaptan 0.12g after emulsification, method is similarly to Example 1 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, StA and has terminated 95%.
Embodiment 4
Except adding lauryl mercaptan 0.19g after emulsification, method is similarly to Example 1 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, StA and has terminated 96%.
Embodiment 5
Except using C
6f
13cH
2cH
2oCOCH=CH
2(C6SFA) 179g replaces C
6f
13cH
2cH
2oCOC (CH
3)=CH
2beyond 179g, method is similarly to Example 2 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFA has terminated 99%, StA and has terminated 95%.
Embodiment 6
Except use cyclohexyl methacrylate (CHMA) 25g replaces except stearyl acrylate ester (StA) 25g, method is similarly to Example 2 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, CHMA and has terminated 98%.
Embodiment 7
Except use isobornyl acrylate (IBMA) 25g replaces except stearyl acrylate ester (StA) 25g, method is similarly to Example 2 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, IBMA and has terminated 99%.
Embodiment 8
Except adding except neopentylglycol diacrylate (NP-A) 0.25g in embodiment 2, method is similarly to Example 2 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, StA and has terminated 96%.
Embodiment 9
Except adding except diacetone acrylamide (DAAM) 2.25g in embodiment 2, method is similarly to Example 2 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, StA and has terminated 96%.
Embodiment 10
Except adding except glycidyl methacrylate (GLA) 2.25g in embodiment 2, method is similarly to Example 2 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, StA and has terminated 96%.
Embodiment 11
Except adding except N-isopropylacrylamide (NIPAM) 2.25g in embodiment 2, method is similarly to Example 2 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, StA and has terminated 96%.
Embodiment 12
Single step is polymerized:
C is added in 1L autoclave
6f
13cH
2cH
2oCOC (CH
3)=CH
2179g, lauryl acrylate 25g, neopentylglycol diacrylate 0.25g, tripropylene glycol 75.8g, pure water 446g, polyoxyethylene lauryl ether 12.7g, polyethylene glycol oxide oil ether 2.47g, polyethylene oxide base isotridecyl ether 5.05g, dialkyl group (tallow) dimethyl ammonium chloride 2.66g, after heating at 60 DEG C, high pressure homogenisers is used to make its emulsion dispersion.After emulsion dispersion, add lauryl mercaptan 0.025g, vinyl chloride 60g is filled in pressurization.Add 2,2-azo two (2-amidine propane) dihydrochloride 1.92g further, 60 DEG C of reactions 3 hours, obtain the aqueous liquid dispersion of polymer.Utilizing pure water to carry out concentration, to be adjusted to its solid component concentration be 30 % by weight, measures the characteristic of the aqueous liquid dispersion obtained.Result is shown in Table A.
Comparative example 1
Except adding lauryl mercaptan 0.25g after emulsification, method is similarly to Example 1 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, StA and has terminated 95%.
Comparative example 2
Except adding lauryl mercaptan 0.38g after emulsification, method is similarly to Example 1 utilized to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, StA and has terminated 96%.
Comparative example 3
Add except neopentylglycol diacrylate 0.38g except in embodiment 2, utilize method similarly to Example 2 to obtain the dispersion liquid of polymer.
Fill the moment (single step polymerization finish time) at vinyl chloride, in polymerisation, C6SFMA has terminated 99%, StA and has terminated 96%.
Comparative example 4
Except not adding except neopentylglycol diacrylate, method is similarly to Example 12 utilized to obtain the dispersion liquid of polymer.
Comparative example 5
Except the lauryl mercaptan quantitative change will added after emulsification is except 1.25g, the method same with comparative example 4 is utilized to obtain the dispersion liquid of polymer.
The characteristic of each example is shown in Table A.
Utilizability in industry
The poisture-penetrability of moisture-permeable water-proof fabric of the present invention, resistance to water and washing resistance are excellent.
Moisture-permeable water-proof fabric of the present invention can be used in dress material, such as motion 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 moisture-permeable water-proof fabric, is characterized in that:
It has the intermediate layer containing fluoropolymer and the moisture-permeability waterproof layer containing synthetic resin,
Fluoropolymer has the repetitive being derived from following monomer (a), (b) and (c), and the dynamic viscoelastic 160 DEG C time is more than 400Pas,
Fluorochemical monomer shown in (a) following formula,
CH
2＝C(－X)－C(＝O)－Y－Z－Rf
In formula, X is hydrogen atom or methyl, the organic group of Y to be-O-or-NH-, Z be Direct Bonding or divalence, and Rf is the fluoroalkyl of carbon number 1 ~ 6;
(b) halogenated olefins monomer;
(c) use as required, not contain fluorine atoms and at least there is the non-fluorine monomer of a carbon-to-carbon double bond.
2. moisture-permeable water-proof fabric as claimed in claim 1, is characterized in that:
Fluorochemical monomer (a) is the monomer shown in following formula,
CH
2＝C(－X)－C(＝O)－Y－Z－Rf (Ⅰ)
In formula, X is hydrogen atom or methyl, and Y is-O-or-NH-,
Z is the aliphatic group of carbon number 1 ~ 10, the aromatic group of carbon number 6 ~ 18 or cyclic aliphatic group ,-CH
2cH
2n (R
1) SO
2-Ji ,-CH
2cH (OZ
1) CH
2-Ji ,-(CH
2)
m-SO
2-(CH
2)
n-Ji or-(CH
2)
m-S-(CH
2)
n-Ji, wherein, R
1the alkyl of carbon number 1 ~ 4, Z
1be hydrogen atom or acetyl group, m is 1 ~ 10, n is 0 ~ 10,
Rf is the straight-chain of carbon number 1 ~ 6 or the fluoroalkyl of branched.
3. moisture-permeable water-proof fabric as claimed in claim 1 or 2, is characterized in that:
Halogenated olefins monomer (b) replaces the alkene having the carbon number 2 ~ 20 of chlorine atom, bromine atoms or atomic iodine.
4. the moisture-permeable water-proof fabric according to any one of claims 1 to 3, is characterized in that:
Halogenated olefins monomer (b) is for being selected from least one in vinyl chloride, bromine ethene, iodoethylene, vinylidene chloride, partially bromine ethene and inclined iodoethylene.
5. the moisture-permeable water-proof fabric according to any one of Claims 1 to 4, is characterized in that:
Non-fluorine monomer (c) is non-cross-linkable monomer or cross-linkable monomer.
6. the moisture-permeable water-proof fabric according to any one of Claims 1 to 5, is characterized in that:
Non-fluorine monomer (c) is the monomer shown in following formula,
CH
2＝CA－T
In formula, A is the halogen atom (such as chlorine atom, bromine atoms and atomic iodine) beyond hydrogen atom, methyl or fluorine atom,
T is hydrogen atom, the chain of carbon number 1 ~ 30 or the alkyl of ring-type or have the organic group of the chain of ester bond or the carbon number 1 ~ 31 of ring-type.
7. the moisture-permeable water-proof fabric according to any one of claim 1 ~ 6, is characterized in that:
Non-fluorine monomer (c) being as cross-linkable monomer has list (methyl) acrylate of reactive group, two (methyl) acrylate or single (methyl) acrylamide.
8. the moisture-permeable water-proof fabric according to any one of claim 1 ~ 7, is characterized in that:
Synthetic resin is be selected from least one in polyurethane resin, acrylic resin and mylar.
9. the moisture-permeable water-proof fabric according to any one of claim 1 ~ 8, is characterized in that:
Moisture-permeability waterproof layer is formed by painting synthetic resin or by attaching synthetic resin film.
10. moisture-permeable water-proof fabric as claimed in claim 9, is characterized in that:
Synthetic resin film is attached to the intermediate layer of fluoropolymer by bonding agent.
11. moisture-permeable water-proof fabrics according to any one of claim 1 ~ 10, is characterized in that:
The dynamic viscoelastic of fluoropolymer 150 DEG C time and 170 DEG C time is respectively more than 500Pas, more than 300Pas.
The manufacture method of 12. 1 kinds of moisture-permeable water-proof fabrics, for the manufacture of moisture-permeable water-proof fabric according to claim 1, the feature of this manufacture method is, comprising:
I fluorine-containing finishing agent containing fluoropolymer is applicable to fiber fabric by (), formed containing fluoropolymer intermediate layer operation and
(ii) by being suitable for synthetic resin on the intermediate layer of fluoropolymer, the operation of moisture-permeability waterproof layer is formed.
13. manufacture methods as claimed in claim 12, is characterized in that:
The applicable of synthetic resin is undertaken by painting synthetic resin or attaching synthetic resin film.
14. manufacture methods as described in claim 12 or 13, is characterized in that:
Synthetic resin is be selected from least one in polyurethane resin, acrylic resin and mylar.
15. manufacture methods as described in claim 13 or 14, is characterized in that:
Synthetic resin film is attached to the intermediate layer of fluoropolymer by bonding agent.
The processing method of 16. 1 kinds of fiber fabrics, is characterized in that:
By the fluorine-containing finishing agent containing fluoropolymer is applicable to fiber fabric, form the intermediate layer of fluoropolymer.
17. 1 kinds of fluorine-containing finishing agents of moisture-permeable water-proof fabric, is characterized in that:
It contains fluoropolymer, and this fluoropolymer has the repetitive being derived from following monomer (a), (b) and (c), and the dynamic viscoelastic 160 DEG C time is more than 400Pas,
Fluorochemical monomer shown in (a) following formula,
CH
2＝C(－X)－C(＝O)－Y－Z－Rf
In formula, X is hydrogen atom or methyl, the organic group of Y to be-O-or-NH-, Z be Direct Bonding or divalence, and Rf is the fluoroalkyl of carbon number 1 ~ 6;
(b) halogenated olefins monomer;
(c) use as required, not contain fluorine atoms and at least there is the non-fluorine monomer of a carbon-to-carbon double bond.
The method for making of 18. 1 kinds of fluoropolymers, for the manufacture of the fluoropolymer in moisture-permeable water-proof fabric according to claim 1, the feature of this method for making is, comprising:
(I) by fluorochemical monomer (a) and the polymerization of non-fluorine monomer (c) as required, obtain the first polymer operation and
(II) under the existence of the first polymer, halogenated olefins monomer (b) is polymerized, manufactures the second polymer formed by halogenated olefins monomer (b) thus, obtain the operation of fluoropolymer.
The method for making of 19. fluoropolymers as claimed in claim 18, is characterized in that:
When making the polymerization of second comonomer start, in polymerization system, there is not in fact unreacted non-fluorine non-crosslinked monomer.
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| JP2012-152745 | 2012-07-06 | ||
| JP2012152745 | 2012-07-06 | ||
| PCT/JP2013/068415 WO2014007345A1 (en) | 2012-07-06 | 2013-07-04 | Moisture-permeable waterproof fabric |
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| JP (1) | JP5922774B2 (en) |
| KR (1) | KR101665226B1 (en) |
| CN (1) | CN104411880B (en) |
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| WO2015194049A1 (en) * | 2014-06-20 | 2015-12-23 | 日華化学株式会社 | Water-oil repellent composition and production method for water- and oil-repellent textile product |
| US10842902B2 (en) * | 2017-09-01 | 2020-11-24 | Ppg Industries Ohio, Inc. | Treated membrane for fragrance delivery |
| JP7157307B2 (en) * | 2018-05-11 | 2022-10-20 | ダイキン工業株式会社 | Water and oil repellents and textile products |
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| KR101665226B1 (en) | 2016-10-11 |
| CN104411880B (en) | 2018-05-11 |
| WO2014007345A1 (en) | 2014-01-09 |
| TW201410456A (en) | 2014-03-16 |
| JP5922774B2 (en) | 2016-05-24 |
| TWI605939B (en) | 2017-11-21 |
| JPWO2014007345A1 (en) | 2016-06-02 |
| KR20150015535A (en) | 2015-02-10 |
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