CN107675504A - Non-woven fabrics - Google Patents

Non-woven fabrics Download PDF

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Publication number
CN107675504A
CN107675504A CN201610626325.XA CN201610626325A CN107675504A CN 107675504 A CN107675504 A CN 107675504A CN 201610626325 A CN201610626325 A CN 201610626325A CN 107675504 A CN107675504 A CN 107675504A
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China
Prior art keywords
monomer
woven fabrics
weight
alkyl
methyl
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CN201610626325.XA
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Chinese (zh)
Inventor
南晋
南晋一
福森正树
榎本孝司
山本育男
朱敏
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to CN201610626325.XA priority Critical patent/CN107675504A/en
Priority to CN202410220458.1A priority patent/CN118087269A/en
Priority to US15/662,437 priority patent/US20180038044A1/en
Publication of CN107675504A publication Critical patent/CN107675504A/en
Pending legal-status Critical Current

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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
    • D06M15/263—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent
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    • 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
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    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
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    • 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
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    • 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
    • D06M15/267—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 amino or quaternary ammonium groups
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    • 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
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
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    • D06M2101/16—Synthetic fibres, other than mineral fibres
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    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A kind of non-woven fabrics, it is attached with fluoropolymer on base material, wherein, fluoropolymer has：(a) repeat unit of fluorochemical monomer is derived from, the fluorochemical monomer is α chloropropenes acid esters or α chloroacrylamides with fluoro-alkyl；It is derived from the repeat unit of halo alkene monomer, fluoropolymer do not have is derived from repeat unit with carbon number more than 18 (methyl) acrylate of the alkyl of the straight-chain of (such as more than 16, particularly more than 14) or branched (b).Non-woven fabrics has excellent water-repellent oil-repellent, such as with excellent strong water-repellancy and high water pressure resistance.

Description

Non-woven fabrics
Technical field
The present invention relates to non-woven fabrics, and in particular to is attached with the non-woven fabrics of fluoropolymer.
Background technology
The scheme handled with fluorine-containing inorganic agent fibre is proposed in the prior art.
International Publication No. 2010/030044 discloses a kind of agent composition containing fluoropolymer, and this is fluorine-containing Repeat unit of the polymer with (methyl) acrylate monomer from fluorochemical monomer and with cyclic hydrocarbon group.International Publication No. No. 2011/122442 discloses a kind of agent composition containing fluoropolymer, and the fluoropolymer, which has, is derived from α-chlorine Acrylate and with alkyl (methyl) acrylate monomer repeat unit.In these publications, not to non-woven fabrics Using being studied.
International Publication 2013/99611 describes the scheme handled with fluorine-containing inorganic agent non-woven fabrics.But nothing Gratifying water-repellent oil-repellent can not be obtained by spinning cloth.
Patent document 1：International Publication No. 2010/030044
Patent document 2：International Publication No. 2011/122442
Patent document 3：International Publication 2013/99611
The content of the invention
An object of the present invention is to provide a kind of water-repellent oil-repellent and the non-woven fabrics of high mechanical strength.
The present invention relates to the non-woven fabrics for being attached with fluoropolymer.
The present invention provides a kind of non-woven fabrics, and it is attached with fluoropolymer on base material, and fluoropolymer has：
(a) be derived from fluorochemical monomer repeat unit, the fluorochemical monomer for fluoro-alkyl α-chloroacrylic acid ester or α-chloroacrylamide；With
(b) repeat unit of halo alkene monomer is derived from,
Fluoropolymer, which does not have, to be derived from carbon number more than 18 (such as more than 16, particularly more than 14) Straight-chain or branched alkyl (methyl) acrylate repeat unit.
Fluoropolymer assigns water-repellancy to base material, dials oiliness and/or soil resistance.
Invention effect
The non-woven fabrics of the present invention has excellent water-repellent oil-repellent, such as excellent strong water-repellancy and high water pressure resistance, also With excellent mechanical strength, for example high tensile strength.
Embodiment
In the present invention, fluoropolymer is attached with non-woven fabrics.The non-woven fabrics for being attached with fluoropolymer for example may be used With by the way that fluorine-containing inorganic agent is applied into non-woven fabrics (untreated non-woven fabrics base material) to manufacture.
Fluorine-containing inorganic agent contains fluoropolymer and liquid medium.
[fluoropolymer]
Fluoropolymer has：
(a) be derived from fluorochemical monomer repeat unit, the fluorochemical monomer for fluoro-alkyl α-chloroacrylic acid ester or α-chloroacrylamide；With
(b) repeat unit of halo alkene monomer is derived from,
Fluoropolymer does not have the (first for being derived from the alkyl with straight-chain or branched of the carbon number more than 18 Base) acrylate repeat unit.
(a) fluorochemical monomer
Fluorochemical monomer (a) can be formula：CH2Compound shown in=C (- Cl)-C (=O)-Y-Z-Rf.
[in formula, Y is-O- or-NH-, and Z is the organic group of Direct Bonding or divalence, and Rf is the fluorine of carbon number 1~20 Substituted alkyl.]
Fluorochemical monomer is preferably the compound shown in below general formula：
CH2=C (- Cl)-C (=O)-Y-Z-Rf (I)
[in formula, Y is-O- or-NH-；
Z be Direct Bonding,
Straight-chain or branched aliphatic group (particularly alkylidene) such as formula-(CH of carbon number 1~202)x- (formula In, x be 1~10) shown in group,
The aromatic group or cyclic aliphatic group of carbon number 6~30,
Formula-R2(R1)N-SO2- or formula-R2(R1) shown in N-CO- group (in formula, R1For the alkyl of carbon number 1~10, R2Straight-chain alkyl-sub or branched alkylidene for carbon number 1~10),
Formula-CH2CH(OR3)CH2-(Ar-O)p- (in formula, R3For the acyl group of hydrogen atom or carbon number 1~10 (such as formyl Base or acetyl group etc.), Ar represent as needed have substituent arlydene, p represent 0 or 1) shown in group,
Formula-CH2-Ar-(O)q- (in formula, Ar be according to the arlydene for needing that there is substituent, q be 0 or 1) shown in base Group or
-(CH2)m-SO2-(CH2)n- base or-(CH2)m-S-(CH2)n- base (wherein, m is that 1~10, n is 0~10)；
Rf is the straight-chain of carbon number 1~20 or the fluoro-alkyl of branched].
In fluorochemical monomer, Rf bases are preferably perfluoroalkyl.The carbon number of Rf bases is preferably 1~12, and for example, 1~6, Particularly 4~6, more preferably 6.The example of Rf bases has-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.
The preferred Y bases of fluorochemical monomer are-O- acrylate.
Z bases are specifically as follows carbon number 1~20 (such as carbon number 1~10, particularly 1~4, particularly 1 or 2) Straight-chain or branched aliphatic group (such as alkylidene), such as formula-(CH2)xGroup shown in-(in formula, x be 1~10),
The aromatic group or cyclic aliphatic group of carbon number 6~18,
Formula-R2(R1)N-SO2- or formula-R2(R1) shown in N-CO- group (in formula, R1For the alkyl of carbon number 1~10, R2Straight-chain alkyl-sub or branched alkylidene for carbon number 1~10), such as-CH2CH2N(R1)SO2- base (wherein, R1For carbon The alkyl of atomicity 1~4),
Formula-CH2CH(OR3)CH2-[Ar-(O)q]p- (in formula, R3For the acyl group of hydrogen atom or carbon number 1~10 (such as Formoxyl or acetyl group etc.), Ar be according to the arlydene (such as phenylene) for needing that there is substituent, p is 0 or 1, q are 0 or 1) Shown group,
Formula-(CH2)n-Ar-(O)q- (in formula, Ar is to be according to the arlydene (such as phenylene) for needing to have substituent, n 0~10, q be 0 or 1) shown in group or
-(CH2)m-SO2-(CH2)n- base or-(CH2)m-S-(CH2)n- base (wherein, m be 1~10, n be 0~10).
Aromatic group or cyclic aliphatic group can be substituted or non-substituted.S bases or SO2Base can be direct with Rf bases Bonding.
As the concrete example of fluorochemical monomer (a), such as following compound can be illustrated, but be not limited to these.
CH2=C (- Cl)-C (=O)-O- (CH2)2-Rf
CH2=C (- Cl)-C (=O)-O- (CH2)4-Rf
CH2=C (- Cl)-C (=O)-O- (CH2)2-S-Rf
CH2=C (- Cl)-C (=O)-O- (CH2)2-S-(CH2)2-Rf
CH2=C (- Cl)-C (=O)-O- (CH2)2-SO2-Rf
CH2=C (- Cl)-C (=O)-O- (CH2)2-SO2-(CH2)2-Rf
CH2=C (- Cl)-C (=O)-NH- (CH2)2-Rf
CH2=C (- Cl)-C (=O)-O- (CH2)3-S-Rf
CH2=C (- Cl)-C (=O)-O- (CH2)3-S-(CH2)2-Rf
CH2=C (- Cl)-C (=O)-O- (CH2)3-SO2-Rf
CH2=C (- Cl)-C (=O)-O- (CH2)3-SO2-(CH2)2-Rf
CH2=C (- Cl)-C (=O)-O-CH2CH2N(CH3)SO2-Rf
CH2=C (- Cl)-C (=O)-O-CH2CH(OCOCH3)CH2-Rf
CH2=C (- Cl)-C (=O)-O-CH2- Ph-O-Rf (here, Ph is Isosorbide-5-Nitrae-phenylene)
CH2=C (- Cl)-C (=O)-O-CH2CH(OH)CH2-Ph-O-Rf
CH2=C (- Cl)-C (=O)-O-CH2-Ph-Rf
CH2=C (- Cl)-C (=O)-O-CH2CH(OCOCH3)CH2-Ph-Rf
[in above-mentioned formula, Rf is the fluoro-alkyl of carbon number 1~20.]
(b) halo alkene monomer
Halo alkene monomer (haloalkene) does not preferably have fluorine atom.
Haloalkene is preferably by the alkene of the carbon number 2~20 of 1~10 chlorine atom, bromine atoms or iodine atom substitution. Haloalkene is preferably the alkene of the chloro alkene of carbon number 2~20, the particularly carbon number 2~5 with 1~5 chlorine atom. The preferable concrete example of haloalkene is：Halogen ethene, such as vinyl chloride, bromine ethene, iodoethylene；Vinylidene halide, such as vinylidene chloride, Inclined bromine ethene, inclined iodoethylene.It is preferred that vinyl chloride and vinylidene chloride, particularly preferred vinyl chloride.
(c) other monomers
Demonomerization (a) and other monomers (c) beyond (b) are not preferably fluorine-containing.As other monomers (c), can enumerate non- The non-crosslinked property monomer (c1) of fluorine and non-fluorine cross-linkable monomer (c2).
Other monomers (c) be free of with carbon number more than 18 (such as more than 16, particularly more than 14) it is straight (methyl) acrylate of chain or the alkyl of branched.I.e., in the present invention, without using with carbon number more than 18 (methyl) acrylate of the straight-chain of (such as more than 16, particularly more than 14) or the alkyl of branched, such as (first Base) stearyl acrylate ester or (methyl) acrylic acid behenyl ester.
(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-bridging property.The non-crosslinked property list of non-fluorine Body (c1) 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 Monomer.The non-crosslinked property monomer (c1) of non-fluorine is usually the compound with 1 carbon-to-carbon double bond.
The preferable non-crosslinked property monomer (c1) of non-fluorine is formula：CH2Compound shown in=CA-T.
[in formula, A is that (such as chlorine atom, bromine atoms and iodine are former for hydrogen atom, methyl or halogen atom in addition to fluorine atom Son),
T is hydrogen atom, the chain (straight chain of carbon number 1~17 (such as 2~15, particularly 3~14, particularly 4~13) Shape or branched) alkyl, carbon number 4~30 ring-type alkyl or with ester bond chain or ring-type carbon number 1~31 organic group.]
The example of the alkyl of the ring-type of carbon number 4~30 has the cyclic aliphatic group of carbon number 4~30, carbon atom The aromatic hydrocarbyl of number 6~30, the aromatic-aliphatic alkyl of carbon number 7~30.
The example of the organic group of the carbon number 1~31 of chain or ring-type with ester bond has-C (=O)-O-Q and-O- C (=O)-Q is (here, Q is the chain (straight chain of carbon number 1~17 (such as 2~15, particularly 3~14, particularly 4~13) Shape or branched) aliphatic alkyl, cyclic aliphatic group, the aromatic hydrocarbon of carbon number 6~30 of carbon number 4~30 The aromatic-aliphatic alkyl of base, carbon number 7~30).
The preferred exemplary of the non-crosslinked property monomer (c1) of non-fluorine for example including ethene, vinyl acetate, acrylonitrile, styrene, Polyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, first Epoxide polypropylene glycol (methyl) acrylate and vinyl alkyl ethers.The non-crosslinked property monomer (c1) of non-fluorine is not limited to these and shown Example.
The non-crosslinked property monomer (c1) of non-fluorine can be (methyl) acrylate with alkyl.The carbon number of alkyl can be with For 1~17, such as can be 2~15 (particularly 3~14, particularly 4~13).Such as the non-crosslinked property monomer (c1) of non-fluorine can be with For formula：CH2=CA1COOA2Shown acrylate.
[in formula, A1For hydrogen atom, methyl or halogen atom in addition to fluorine atom, (such as chlorine atom, bromine atoms and iodine are former Son),
A2For CnH2n+1Alkyl shown in (n=1~17).]
A2Preferable concrete example for butyl, lauryl.
The non-crosslinked property monomer (c1) of non-fluorine can be (methyl) acrylate monomer with cyclic hydrocarbon group.
Acrylate monomer containing cyclic hydrocarbon group is preferably formula：CH2=CA21- C (=O)-O-A22Shown compound.
[in formula, A21For hydrogen atom or methyl, A22For the group containing cyclic hydrocarbon of carbon number 4~30.]
Acrylate monomer containing cyclic hydrocarbon group is the glass transition temperature of its homopolymer high (such as more than 50 DEG C, spy Be not more than 80 DEG C) monomer.
Acrylate monomer containing cyclic hydrocarbon group does not have fluoro-alkyl.Acrylate monomer containing cyclic hydrocarbon group can contain There is fluorine atom, but be preferably free of fluorine atom.
A21It can be hydrogen atom.
A22For that can have the cyclic hydrocarbon group of chain-like groups (such as alkyl of straight-chain or branched).As cyclic hydrocarbon Base, saturation or undersaturated, monocyclic base, more ring groups, bridged ring base etc. can be enumerated.Cyclic hydrocarbon group is preferably saturated cyclic alkyl. The carbon number of cyclic hydrocarbon group is 4~30, preferably 6~20.As cyclic hydrocarbon group, can enumerate：Carbon number 4~20, spy It is not 5~12 cyclic aliphatic group, aromatic group, the aromatic-aliphatic of carbon number 7~20 of carbon number 6~20 Group.The carbon number of cyclic hydrocarbon group is particularly preferably below 15, for example below 12.Cyclic hydrocarbon group is preferably the ring-type of saturation Aliphatic group.The concrete example of cyclic hydrocarbon group has cyclohexyl, tert-butylcyclohexyl, isobornyl, bicyclopentane base, dicyclopentenyl Base, adamantyl.
As the concrete example of the acrylate monomer containing cyclic hydrocarbon group, can enumerate：(methyl) cyclohexyl acrylate, (first Base) t-butylcyclohexyl ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, the ring of (methyl) acrylic acid two Pentyl ester, (methyl) acrylic acid dicyclopentenyl ester, the 2-ethoxyethyl acetate of two ring of (methyl) acrylic acid penta, the ring pentyl ester of (methyl) acrylic acid three, (first Base) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid -2- methyl -2- Buddha's warrior attendants alkyl ester, (methyl) acrylic acid-2-ethyl -2- adamantane Ester etc..
By the acrylate monomer containing cyclic hydrocarbon group be present, water-repellancy and dial oiliness raising that copolymer is assigned.
(c2) non-fluorine cross-linkable monomer
Fluoropolymer can have the repeat unit from non-fluorine cross-linkable monomer (c2).Non-fluorine cross-linkable monomer (c2) It is free from the monomer of fluorine atom.Non-fluorine cross-linkable monomer (c2) can be double with least two reactive group and/or carbon-to-carbon Key and not fluorine-containing compound.Non-fluorine cross-linkable monomer (c2) can be compound with least two carbon-to-carbon double bond or Compound with least one carbon-to-carbon double bond and at least one reactive group.The example of reactive group has hydroxyl, epoxy Base, chloromethyl, blocked isocyanate base, amino, carboxyl etc..Non-fluorine cross-linkable monomer (c2) can be with reactive group Single (methyl) acrylate, two (methyl) acrylate or single (methyl) acrylamide.Or non-fluorine cross-linkable monomer (c2) can Think two (methyl) acrylate.
As non-fluorine cross-linkable monomer (c2), such as two acetone (methyl) acrylamide, (methyl) acryloyl can be illustrated Amine, N- methylols (methyl) acrylamide, methylol (methyl) acrylate, ethoxy (methyl) acrylate, the chloro- 2- hydroxyls of 3- Propyl group (methyl) acrylate, 2- acetoacetoxyethyls (methyl) acrylate, butadiene, isoprene, chlorobutadiene, Glycidyl (methyl) acrylate, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl) acrylate Deng.
By being copolymerized the non-crosslinked property monomer (c1) of non-fluorine and/or non-fluorine cross-linkable monomer (c2), can change as needed Kind water-repellent oil-repellent and the resistance to spatter property of soil resistance and these performances, washing fastness, dissolubility, hardness, thoughts and feelings to solvent Deng various properties.
In this manual, it is not only that hydrogen is former including α positions in the case of referred to as " acrylate " or " acrylamide " The compound of son, also substituted including α positions by other groups (organic group or halogen atom of the monovalence e.g., including including methyl) Compound.In this manual, " (methyl) acrylate " refers to acrylate or methacrylate, " (methyl) propylene Acid amides " refers to acrylamide or Methacrylamide.
Monomer (a), monomer (b), monomer (c) (such as monomer (c1) and (c2) respective) can each be individually for a kind, or It can also be combination of more than two kinds.
In fluoropolymer, the amount of fluorochemical monomer (a) can be the weight of 20 weight %~90 relative to fluoropolymer Measure %, the weight % of preferably 30 weight %~80.
In fluoropolymer, relative to the parts by weight of fluorochemical monomer (a) 100,
The amount of halo alkene monomer (b) is 5~300 parts by weight, such as can be 10~200 parts by weight, particularly 20~100 Parts by weight, specifically for 30~80 parts by weight,
The amount of other monomers (c) is 0~800 parts by weight, such as can be 1~300 parts by weight, particularly 2~200 weight Part, specifically for 3~100 parts by weight.
In fluoropolymer, relative to the parts by weight of fluorochemical monomer (a) 100,
The amount of the non-crosslinked property monomer (c1) of non-fluorine can be 0~500 parts by weight, for example, 1~300 parts by weight, particularly 2 ~200 parts by weight, specifically for 3~100 parts by weight,
The amount of non-fluorine cross-linkable monomer (c2) can be 0~80 parts by weight, for example, 0~50 parts by weight, particularly 0.1~ 30 parts by weight, specifically for 1~20 parts by weight.
The number-average molecular weight (Mn) typically 1000~1000000, for example, 5000~500000 of fluoropolymer, Particularly 3000~200000.The number-average molecular weight (Mn) of fluoropolymer is generally carried out using GPC (gel permeation chromatography) Measure.
In the present invention, it is copolymerized monomer (a)~(c), is dispersed or dissolved containing for fluoropolymer in media as well Fluorine inorganic agent (surface treatment composition).
Monomer can be made at least one kind of chemical combination in blocked isocyanate compounds and organopolysiloxane compound It is polymerize in the presence of thing.Relative to the parts by weight of monomer 100, blocked isocyanate compounds (or organopolysiloxane chemical combination Thing) amount can be 0~100 parts by weight, for example, 1~50 parts by weight.
It is polymerize by making monomer in the presence of blocked isocyanate compounds, can obtains that there is end-blocking isocyanic acid The fluoropolymer of ester group.Blocked isocyanate compounds are isocyanic acids obtained from being blocked using at least one end-capping reagent Ester.As the example of end-capping reagent, oximes, phenols, alcohols, thio-alcohol, amide-type, acid imide, imidazoles, urea can be enumerated Class, amine, imines, pyrazoles and activity methene compound class.The other examples of end-capping reagent can enumerate pyridine phenols, sulphur Phenols, diones and esters.Blocked isocyanate compounds can utilize compound modified with hydrophilic radical.
By making monomer in organopolysiloxane compound (such as Mercaptofunctional organopolysiloxane, vinyl functional Property organopolysiloxane) in the presence of polymerize, the fluoropolymer with siloxy group can be obtained.In 1 embodiment party In formula, Mercaptofunctional organopolysiloxane includes the siloxane unit with following average formulas：
(R2SiO)a(RRNSiO)b(RRSSiO)c
[in formula, a is 0~4000,0~1000 or 0~400,
B is 1~1000,1~100 or 1~50,
C is 1~1000,1~100 or 1~50；
The monovalence alkane that R independently is the organic group of monovalence, R is the hydrocarbon of carbon number 1~30, R is carbon number 1~12 Base or R are methyl；
RNFor the organic group of the amino functional of monovalence defined above,
RSFor the organic group of the Mercaptofunctional of monovalence defined above.]
Relative to fluorine-containing inorganic agent or surface treatment composition, the amount of fluoropolymer (solid constituent) can be about 0.01~60 weight %, preferably from about 0.1~40 weight %, particularly preferably about 5~35 weight % amount.
Fluoropolymer can exist in the form of dissolving solution in organic solvent, but preferably with water system dispersion Form is present.
[liquid medium]
Liquid medium can be aqueous medium.Aqueous medium can be individually for water or water and (water miscibility) organic solvent Mixture.Relative to liquid medium, the amount of organic solvent can be below 30 weight %, for example below 10 weight % (preferably More than 0.1%).Liquid medium is preferably individually for water.Liquid medium can be only organic solvent.
Relative to fluorine-containing inorganic agent (or surface treatment composition), the amount of liquid medium can be 30~99.1 weights Measure %, particularly 50~99 weight %.
[surfactant]
Fluorine-containing inorganic agent can contain surfactant.In the case where fluorine-containing inorganic agent contains aqueous medium, preferably contain Fluorine inorganic agent contains surfactant.Fluorine-containing inorganic agent preferably comprises fluoropolymer, liquid medium (being preferably aqueous medium) And surfactant.
In the present invention, surfactant can be selected from nonionic surface active agent, cationic surface active agent, It is at least one kind of in anion surfactant and amphoteric surfactant.
As the example of nonionic surface active agent, ether, ester, ester ether, alkanolamide, polynary alkohol and amine oxygen can be enumerated Compound.
The example of ether has the compound with oxyalkylene (preferably polyoxyethylene).
The example of ester has the ester of alcohol and aliphatic acid.The example of alcohol have the carbon number 1 of 1~6 yuan (particularly 2~5 yuan)~ The alcohol (such as aliphatic alcohol) of 50 (particularly carbon numbers 3~30).The example of aliphatic acid has carbon number 2~50, is particularly The saturated or undersaturated aliphatic acid of carbon number 5~30.
The example of ester ether has the compound that the ester addition of alcohol and aliphatic acid has oxyalkylene (particularly oxygen ethylidene).Alcohol Example has alcohol (such as the aliphatic of the carbon number 1~50 (particularly carbon number 3~30) of 1~6 yuan (particularly 2~5 yuan) Alcohol).The example of aliphatic acid has the saturated or undersaturated aliphatic acid of carbon number 2~50, particularly carbon number 5~30.
The example of alkanolamide is formed by aliphatic acid and alkanolamine.Alkanolamide can be monoalkylol amide or dialkanol ammonia Base.The example of aliphatic acid has the saturated or undersaturated aliphatic acid of carbon number 2~50, particularly carbon number 5~30.Alkanol Amine can be the carbon number 2~50 with 1~3 amino and 1~5 hydroxyl, particularly 5~30 alkanol.
Polyalcohol can be the alcohol of 2~5 yuan of carbon number 3~30.
Amine oxide can be the oxide (such as carbon number 5~50) of amine (secondary amine or preferred tertiary amine).
Nonionic surface active agent is preferably that the non-ionic surface with oxyalkylene (preferably polyoxyethylene) is lived Property agent.The carbon number of alkylidene in oxyalkylene is preferably 2~10.Oxygen in the molecule of nonionic surface active agent is sub- The number of alkyl is preferably generally 2~100.
Nonionic surface active agent is selected from ether, ester, ester ether, alkanolamide, polyalcohol and amine oxide, it is however preferred to have The nonionic surface active agent of oxyalkylene.
Nonionic surface active agent can be aliphatic (saturation and/or unsaturation) base of straight-chain and/or branched Alkylene oxide adduct, the PAG of straight-chain and/or branched aliphatic acid (saturation and/or unsaturation) Ester, polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), the alkylidene of acetylenediol Oxide addition product etc..Wherein, the structure of alkylene oxide addition part and polyalkylene glycol moiety is preferably polyoxy second Alkene (POE), polyoxypropylene (POP) or POE/POP copolymers (can be random copolymer, or block copolymer).
In addition, (Biodegradable, environmental hormone etc.) considers from terms of environment the problem of, preferred non-ionic surfactant Agent is the structure without aromatic group.
Nonionic surface active agent can be formula：R1O-(CH2CH2O)p-(R2O)q-R3Shown compound.
[in formula, R1The alkenyl or acyl group of alkyl or carbon number 2~22 for carbon number 1~22,
R2It is identical or different independently of one another, it is the alkylidene of carbon number more than 3 (such as 3~10),
R3For the alkenyl of hydrogen atom, the alkyl of carbon number 1~22 or carbon number 2~22,
P is more than 2 number,
Q is 0 or more than 1 number.]
R1It is preferred that carbon number is 8~20, particularly preferably 10~18.As R1Preferable concrete example, the moon can be enumerated Gui Ji, tridecyl, oil base.
R2Example have propylidene, butylidene.
In nonionic surface active agent, p can be more than 3 number (such as 5~200).Q can be more than 2 number (such as 5~200).That is ,-(R2O)q- polyoxy alkylidene chain can be formed.
Nonionic surface active agent can be that center has hydrophilic polyoxyethylene chain and hydrophobic oxygen alkylene The polyoxyethylene alkylidene alkyl ether of base chain (particularly polyoxy alkylidene chain)., can be with as hydrophobic oxyalkylene chain Oxygen propylene chain, oxygen butylidene chain, styrene chain etc. are enumerated, wherein, preferred oxygen propylene chain.
Preferable nonionic surface active agent is formula：R1O-(CH2CH2O)pSurfactant shown in-H.
[in formula, R1It is same as above with p implication.]
The concrete example of nonionic surface active agent has：
C10H21O-(CH2CH2O)p-(C3H6O)q-H
C12H25O-(CH2CH2O)p-(C3H6O)q-H
C16H31O-(CH2CH2O)p-(C3H6O)q-H
C16H33O-(CH2CH2O)p-(C3H6O)q-H
C18H35O-(CH2CH2O)p-(C3H6O)q-H
C18H37O-(CH2CH2O)p-(C3H6O)q-H
C12H25O-(CH2CH2O)p-(C3H6O)q-C12H25
C16H31O-(CH2CH2O)p-(C3H6O)q-C16H31
C16H33O-(CH2CH2O)p-(C3H6O)q-C12H25
iso-C13H27O-(CH2CH2O)p-(C3H6O)q-H
C10H21COO-(CH2CH2O)p-(C3H6O)q-H
C16H33COO-(CH2CH2O)p-(C3H6O)q-C12H25Deng.
[in formula, p and q implication are same as above.]
The concrete example of nonionic surface active agent includes ethylidene oxide and hexylphenol, isooctyl phenol, 16 Alkanol, oleic acid, alkane (C12-C16) mercaptan, sorbitan mono fatty acid (C7-C19) or alkyl (C12-C18) amine etc. condensation life Into thing.
For the ratio of polyoxyethylene block, relative to the molecular weight of nonionic surface active agent (copolymer), Can be 5~80 weight %, such as 30~75 weight %, particularly 40~70 weight %.
The mean molecule quantity of nonionic surface active agent is usually 300~5,000, for example, 500~3, and 000.
Nonionic surface active agent can be used alone or two or more kinds may be used.
Nonionic surface active agent is preferably combination of more than two kinds.In combination of more than two kinds, at least one kind of nonionic Type surfactant can be R1Base (and/or R3Base) be branched alkyl (such as isotridecyl) R1O-(CH2CH2O)p- (R2O)q-R3[particularly R1O-(CH2CH2O)p- H] shown in compound.Relative to total the 100 of nonionic surface active agent Parts by weight, R1Base is that the amount of the nonionic surface active agent of branched alkyl can be 5~100 parts by weight, for example, 8~50 weights Measure part, particularly 10~40 parts by weight.In combination of more than two kinds, remaining nonionic surface active agent can be R1Base (and/or R3Base) for the R of (saturation and/or undersaturated) straight chained alkyl (such as lauryl (positive lauryl))1O-(CH2CH2O)p- (R2O)q-R3[particularly R1O-(CH2CH2O)p- H] shown in compound.
As nonionic surface active agent, such as can enumerate：Polyoxyethylene ether, polyoxyethylene benzene Base ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxy ethylene sorbitol alcohol acid anhydride fatty acid ester, polyoxy Ethylidene sorbitan fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid glyceride, polyglyceryl fatty acid ester, sugarcane Sugar fatty acid ester, polyoxyethylene amine, polyoxyethylene fatty acid amide, fatty acid alkyl alcohol amide, alkylalkanol acyl Amine, acetylenediol, the oxygen ethylidene addition product of acetylenediol, polyethylene glycol polyethylene glycol block copolymer etc..It is preferred that polyoxy is sub- Ethyl alkyl ether and polyoxy ethylene sorbitol alcohol acid anhydride fatty acid ester.More preferably polyoxyethylene ethers.
Cationic surface active agent can be amine salt, quaternary ammonium salt, ethyleneoxide addition type ammonium salt.As cationic table The concrete example of face activating agent, is not particularly limited, and can enumerate：Alkylamine salt, amino alcohol fatty acid derivatives, polyamine aliphatic acid The amine salt cationic surfactants such as derivative, imidazoline, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl Quaternary ammonium salt cationic surfactants such as base ammonium salt, pyridiniujm, alkyl isoquinolinium salt, zephiran chloride ammonium etc..
The preferable example of cationic surface active agent has compound R21-N+(-R22)(-R23)(-R24)X-。
[in formula, R21、R22、R23And R24For the alkyl of carbon number 1~30,
X is anionic group.]
R21、R22、R23And R24Concrete example have alkyl (such as methyl, butyl, stearyl, palmityl).X concrete example has Halogen (such as chlorine), sour (such as hydrochloric acid, acetic acid).
Cationic surface active agent is particularly preferably monoalkyltrimethyl ammonium salts (carbon number 4~30 of alkyl).
Cationic surface active agent is preferably ammonium salt.Cationic surface active agent can be formula：R1 p-N+R2 qX-It is shown Ammonium salt.
[in formula, R1For C12More than (such as C12~C50) straight-chain and/or branched aliphatic (saturation and/or not Saturation) group,
R2For H or C1~C4Alkyl, benzyl, polyoxyethylene (oxygen ethylidene number be, for example, 1 (particularly 2, specifically for 3) ~50) (particularly preferred CH3、C2H5),
X is halogen atom, C1~C4Aliphatic acid alkali,
P is 1 or 2, q are 2 or 3, and p+q=4.]
R1Carbon number can be 12~50, such as 12~30.
As the concrete example of cationic surface active agent, can enumerate：Trimethyl ammonium acetate, trimethyl ten Tetra-alkyl ammonium chloride, cetyl trimethylammonium bromide, trimethyloctadecyl ammonium chloride, (dodecyl methyl benzyl) front three Ammonium chloride, benzododecinium ammonium chloride, methyl dodecyl two (hydrogen polyoxyethylene) ammonium chloride, benzyl 12 Alkyl two (hydrogen polyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleoyl amine hydrochlorate, dialkyl group (also aurochs Fat) alkyl dimethyl ammonium chloride etc..It is preferred that the cationic emulsifier with ammonium chloride structure.Further preferably there is octadecyl Or the ammonium chloride knot of the alkyl (particularly alkyl) of the long-chain such as cetyl (such as carbon number 10~30, particularly 14~24) The cationic emulsifier of structure.
As the concrete example of anionic surfactant, can enumerate：NaLS, the ethanol of lauryl sulfate three Amine, polyoxyethylenelauryl ether sodium sulphate, polyoxyethylene nonylphenyl ether sulfate, polyoxyethylenelauryl ether sulfuric acid Triethanolamine, cocoyl sarcosine sodium, N- cocounut oil acyl methyl taurines sodium, polyoxyethylene coconut palm sodium alkylether sulphate, diether oneself Base sodium sulfosuccinate, alpha-olefin sodium sulfonate, lauryl sodium phosphate, polyoxyethylenelauryl ether sodium phosphate, perfluoroalkyl carboxylic Hydrochlorate (trade name Unidyne DS-101,102 (Daikin Ind Ltd's systems)) etc..Anionic surfactant is preferably The salt (such as organic acid and inorganic base or salt of amine) of organic acid.More preferably alkyl sulfate salt (such as ROSO3 -M+) (alkyl (R Base) carbon number be, for example, 8~30.M is alkali metal (such as sodium or potassium)).
As the concrete example of amphoteric surfactant, amine oxide class, phenyl amines, imidazolinium betaine can be enumerated Class, amide betaine class, acetic acid glycine betaine etc., it can specifically enumerate lauryl betaine, stearyl betaine, lauryl carboxylic first Base hydroxyethyl imidazole quinoline glycine betaine, lauryl dimethyl aminoacetic acid glycine betaine, fatty acid amide propyl dimethylamino vinegar Sour glycine betaine etc..Oxide-based (such as the R of preferred amines3(each R bases are, for example, that the alkyl of carbon number 1~30 (is particularly to N=O Alkyl)).
Nonionic surface active agent, cationic surface active agent, anionic surfactant and amphoteric surface live Property agent respectively can be one kind or two or more combination.
Fluorine-containing inorganic agent can also contain addition in addition to containing fluoropolymer, liquid medium and surfactant Agent.The example of additive has silicon-containing compound, wax, acryl emulsion etc..The other examples of additive have other fluoropolymers It is thing, rate of drying conditioning agent, crosslinking agent, film auxiliary agent, phase solvent, surfactant, antifreezing agent, viscosity modifier, ultraviolet Light absorbers, antioxidant, pH adjusting agent, defoamer, hand modifier, sliding conditioning agent, antistatic agent, hydrophilic agent, Antiseptic, preservative, insect-proof agent, aromatic, fire retardant etc..
Fluoropolymer and non-fluorinated polymer in the present invention can by any manufacture of common polymerization, and And the condition of polymerisation can also be selected arbitrarily.As such polymerization, can enumerate polymerisation in solution, suspension polymerisation, Emulsion polymerization.
In polymerisation in solution, can use makes monomer dissolving in organic solvent in the presence of polymerization initiator, in nitrogen After displacement, the heating stirring method of 1~10 hour in the range of 30~120 DEG C.As polymerization initiator, can enumerate for example Azodiisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, isopropyl benzene hydroperoxide, peroxide Change the neopentanoic acid tert-butyl ester, di-isopropyl peroxydicarbonate etc..Relative to the parts by weight of monomer 100, polymerization initiator with 0.01~ The scope of 20 parts by weight, such as 0.01~10 parts by weight uses.
Organic solvent in nonactive, and can dissolve monomer to monomer, for example, can be ester (such as carbon number 2~ 30 ester, specifically there is ethyl acetate, butyl acetate), (such as the ketone of carbon number 2~30 specifically has MEK, two isobutyls to ketone Base ketone), alcohol (such as alcohol of carbon number 1~30, specifically there is isopropanol).As the concrete example of organic solvent, third can be enumerated Ketone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, hexamethylene, benzene,toluene,xylene, petroleum ether, tetrahydrochysene Furans, 1,4- dioxanes, MEK, methyl iso-butyl ketone (MIBK), diisobutyl ketone, ethyl acetate, butyl acetate, the chloroethenes of 1,1,2,2- tetra- Alkane, 1,1,1- trichloroethanes, trichloro ethylene, perchloroethylene, tetrachlorodifluoroethane, trichorotrifluoroethane etc..Relative to monomer Total 100 parts by weight, organic solvent are used with 10~2000 parts by weight, the scope of such as 50~1000 parts by weight.
In emulsion polymerization, it can use in the presence of polymerization initiator and emulsifying agent, monomer is emulsified in water, enter After the displacement of row nitrogen, the method for polymerizeing 1~10 hour it is stirred in 50~80 DEG C of scopes.Polymerization initiator can use peroxide Change benzoyl, lauroyl peroxide, peroxidized t-butyl perbenzoate, 1- hydroxycyclohexyl hydroperoxides, 3- carboxypropanoyl mistakes Oxide, acetyl peroxide, the NSC 18620 dihydrochloride of azo two, azodiisobutyronitrile, sodium peroxide, potassium peroxydisulfate, persulfuric acid The water miscible polymerization initiator such as ammonium or azodiisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide The oil-soluble polymerization such as compound, isopropyl benzene hydroperoxide, tert-Butyl peroxypivalate, di-isopropyl peroxydicarbonate triggers Agent.Relative to the parts by weight of monomer 100, polymerization initiator is used with the scope of 0.01~10 parts by weight.
In order to obtain the excellent aqueous polymer dispersion of shelf-stability, preferably using high pressure homogenizer or ultrasonic wave homogeneous The emulsifier unit that can assign strong size reduction energy of machine etc, monomer is set micronized and to be polymerize in water.In addition, , can be using the various emulsifying agents of anionic, cationic or nonionic, relative to the weight of monomer 100 as emulsifying agent Part, used with the scope of 0.5~20 parts by weight.It is preferred that the emulsification using anionic and/or nonionic and/or cationic Agent.In the case where monomer not exclusively mixes, preferably addition makes the phase solvent that these monomers fully mix, such as addition water solubility The monomer of organic solvent or low molecule amount.It by adding phase solvent, can improve emulsibility and copolymerizable.
As water-miscible organic solvent, acetone, MEK, ethyl acetate, propane diols, DPG list first can be enumerated Ether, DPG, tripropylene glycol, ethanol etc., can be with 1~50 parts by weight, such as 10~40 weights relative to the parts by weight of water 100 The scope for measuring part uses.In addition, the monomer as low molecule amount, can enumerate methyl methacrylate, Glycidyl methacrylate Glyceride, 2,2,2- trifluoroethyl methacrylates etc., can be with 1~50 weight relative to the parts by weight of total amount 100 of monomer Part, the scope of such as 10~40 parts by weight use.
Chain-transferring agent can be used in polymerization.The usage amount of chain-transferring agent be can correspond to change the molecule of polymer Amount.The example of chain-transferring agent has compound (particularly (such as the carbon containing mercapto of lauryl mercaptan, thioglycol, thioglycerin etc. Atomicity 1~30) alkyl hydrosulfide), sodium hypophosphite, inorganic salts such as sodium hydrogensulfite etc..Relative to the weight of total amount 100 of monomer Part, the usage amount of chain-transferring agent can be used with 0.01~10 parts by weight, the scope of such as 0.1~5 parts by weight.
The fluorine-containing inorganic agent of the present invention can be the form of solution, emulsion (particularly aqueous liquid dispersion) or aerosol, excellent Elect aqueous liquid dispersion as.Fluorine-containing inorganic agent contains polymer (active component of surface conditioning agent) and medium (particularly liquid Jie Matter, such as organic solvent and/or water).For example, relative to fluorine-containing inorganic agent, the amount of medium can be 5~99.9 weight %, special It is not 10~80 weight %.
In fluorine-containing inorganic agent, the concentration of polymer can be 0.01~95 weight %, for example, 5~50 weight %.
The fluorine-containing inorganic agent of the present invention can be applied to non-woven fabrics base material by existing known method.Generally, can adopt It is diluted with the fluorine-containing inorganic agent is scattered in organic solvent or water, utilizes side known to dip-coating, spraying, foam coating etc. Method makes it be attached to the surface of treated object and the method being dried.Alternatively, it is also possible to as needed and appropriate crosslinking agent Apply, and solidified together.Insect-proof agent, softening agent, antiseptic, fire-retardant can also be added in the fluorine-containing inorganic agent of the present invention Agent, antistatic additive, coating fixative, anti-creasing agent etc. and be used in combination.The concentration of polymer in the treatment fluid contacted with base material can be with For 0.01~10 weight % (the particularly situation of dip coated), for example, 0.05~10 weight %.
[non-woven fabrics base material]
The non-woven fabrics of the present invention can be by being applied to non-woven fabrics base material to manufacture by fluorine-containing inorganic agent.Non-woven fabrics base material leads to It is often untreated non-woven fabrics, the non-woven fabrics of particularly non-application medicaments.
The example for forming the fiber of non-woven fabrics base material has natural fiber, synthetic fibers, semisynthetic fibre, regenerated fiber and nothing Machine fiber.Fiber can be used alone or two or more kinds may be used.
The example of natural fiber has the cellulose fibres such as cotton, flax, wood pulp, chitin, chitosan, wool, silk.Wood pulp Concrete example have ground wood pulp (GP), the groundwood pulp of pressure is levigate ground wood pulp (PGW), thermomechanical pulp (TMP) etc., the needle height of tree The non-bleached kraft pulp of yield (HNKP, N material), coniferous tree bleached kraft pulp (NBKP, N material, NB materials), broad leaf tree do not bleach ox Chemical pulp, Deinking Pulp (DIP), the secondary stocks (WP) such as mulberry paper slurry (LUKP, L material), bleached hardwood kraft pulp (LBKP, L material) Etc. old paper pulp or semi-chemical pulp (CP) etc..
The example of synthetic fibers has polyethylene terephthalate, polybutylene terephthalate (PBT), polytrimethylene The polyester of terephthalate, copolyester etc.；LLDPE, low density polyethylene (LDPE), high density polyethylene (HDPE), poly- third The polyolefin such as alkene；The polyamide such as nylon 6, nylon66 fiber, NYLON610, nylon 46；The acryloyl fiber of polyacrylonitrile etc.；Polyethylene Alcohol, polyurethane, polyvinyl chloride.
The example of semisynthetic fibre has acetate fiber, triacetate fiber.
The example of regenerated fiber has artificial silk, CUP, polynosic fiber (Polynosic rayon), lyocell fine Tie up (Lyocell), tencel (Tencel).
The example of inorfil has glass fibre, carbon fiber.
The combination of the preferred natural fiber of fiber and synthetic fibers of non-woven fabrics base material, such as cellulose fibre are formed with gathering The combination of ester fiber, particularly wood pulp cellulose and the combination of polyester fiber (such as pet fiber). In the combination of natural fiber and synthetic fibers, the weight ratio of natural fiber and synthetic fibers can be 5：95~95：5, be, for example, 30：70~70：30.Or in the case where non-woven fabrics needs intensity or durability etc., the weight of natural fiber and synthetic fibers Than that can be 5：95~70：30, for example, 10：90~50：50, particularly 15：85~45：55.
Fluoropolymer can be applied to by the known any means for being handled with liquid fibre Non-woven fabrics base material.Non-woven fabrics base material can be immersed in liquid (liquid, such as solution or dispersion liquid containing fluoropolymer), Or liquid can also be adhered to or sparged non-woven fabrics base material.Non-woven fabrics base material through processing in order to show water-repellent oil-repellent and It is dried, is preferably heated with such as 100 DEG C~200 DEG C.
Or polymer can be applied to non-woven fabrics base material by ablution, such as can be in washing application or dry cleaning process It is applied to non-woven fabrics base material in.
Relative to the parts by weight of non-woven fabrics base material 100, the amount of fluoropolymer of non-woven fabrics base material is attached to typically 0.001~20 parts by weight, for example, 0.01~5 parts by weight, particularly 0.05~1 parts by weight.
" processing " refers to by impregnating, spraying, being coated with etc. inorganic agent being applied to treated object.By processing, as place The polymer of reason agent active ingredient is impregnated with the inside of treated object and/or is attached to the surface of treated object.
Embodiment
Hereinafter, embodiment is enumerated, the present invention is described in detail, but the present invention is not limited to these embodiments.
Hereinafter, as long as no specified otherwise, part, % or than representing parts by weight, weight % or weight ratio.
The step of experiment, is as described below.
Spray water-repellancy experiment (Spray)
Carry out spraying water-repellancy experiment according to JIS-L-1092.Water-repellancy experiment is sprayed (as shown in the table 1 of following records) Represented by water-repellancy No..
It is at least 250ml glass funnel using volume and 20 seconds~30 seconds nozzles for spraying 250ml water can be used.Experiment Piece frame is a diameter of 15cm metal frame.Prepare 3 test sheets that size is about 20cm × 20cm, sheet material is fixed on experiment Piece fixed frame, makes sheet material not have gauffer.The center of spraying is placed in the center of sheet material.The water of room temperature is added in glass funnel (250mL), to test sheet (time for passing through 25 seconds~30 seconds) spraying.Holding frame is removed from platform, catches holding frame One end, it is downside to make forward surface, with the end of the hard thing gently opposite side of percussion.Holding frame is further rotated 180 °, repeat Identical step, fall excessive water droplet.It is 0,50,70,80,90 and according to sequence evaluating of the water-repellancy from bad to excellent 100 scoring, by wet test film compared with percentage of wetted soil is compared with reference material.Result is asked for according to the average value of 3 measure.
【Table 1】
Water-repellancy tests (IPA)
By treated experiment cloth 21 DEG C of temperature, humidity 65% constant temperature and humidity machine in preserve more than 4 hours.Experimental liquid Also used (shown in isopropanol (IPA), water and its mixed liquor, table 2) with the experimental liquid of 21 DEG C of preservations of temperature.Experiment is in temperature 21 DEG C, carry out in the thermostatic constant wet chamber of humidity 65%.50 microlitres of experimental liquid is smoothly added dropwise on experiment cloth, after placing 30 seconds, If drop is remained on experiment cloth, the experimental liquid is qualified.For water-repellancy, by the isopropanol of qualified experimental liquid (IPA) maximum of content (volume %) is counted as it, according to bad to the good degree of water-repellancy, with FAIL, 0,1,2, 3rd, 4,5,6,7,8,9 and 10 12 grades evaluation.
【Table 2】
IPR (Water Impact Penetration Resistance) is tested
IPR experiments are carried out according to AATCC Test Method 42-2000.
Water pressure resistance tests (Hydro Head)
According to AATCC 127-2003 water pressure resistance test method(s)s, water pressure resistance measure device measure water pressure resistance is used.
Tensile strength test
Treated experiment cloth is cut into 15cm × 5cm, utilizes the tensile strength and transverse direction of stretching test machine determination longitudinal direction Tensile strength.
Production Example 1
CF is added in 1000ml autoclaves3CF2-(CF2CF2)n-CH2CH2OCOC (Cl)=CH2(n=2.0) 97.2g, third Olefin(e) acid lauryl 73.66g, pure water 405g, water-based two alcohol series solvents 34.8g, alkyl amine oxide 11.75g, polyoxyethylene alkane Base ether 6.17g, disperseed 15 minutes with ultrasonic emulsification with 60 DEG C under agitation.After carrying out nitrogen displacement in autoclave, chlorine is added Ethene 43g, the solution of water soluble starter 0.86g and water 9g containing azo group are added, reacted 5 hours, polymerize with 60 DEG C The aqueous liquid dispersion of thing.The composition of polymer and the composition of charged monomer are basically identical.
Production Example 2
CF is added in 1000ml autoclaves3CF2-(CF2CF2)n-CH2CH2OCOC (Cl)=CH2(n=2.0) 97.2g, third Olefin(e) acid butyl ester 73.66g, pure water 405g, water-based two alcohol series solvents 34.8g, alkyl amine oxide 11.75g, polyoxyethylene Ether 6.17g, disperseed 15 minutes with ultrasonic emulsification with 60 DEG C under agitation.After carrying out nitrogen displacement in autoclave, chloroethene is added Alkene 43g, the solution of water soluble starter 0.86g and water 9g containing azo group are added, reacted 5 hours with 60 DEG C, obtain polymer Aqueous liquid dispersion.The composition of polymer and the composition of charged monomer are basically identical.
Production Example 3
CF is added in 1000ml autoclaves3CF2-(CF2CF2)n-CH2CH2OCOC (Cl)=CH2(n=2.0) 97.2g, third Olefin(e) acid lauryl 49.1g, isobornyl methacrylate 24.5g, pure water 405g, water-based two alcohol series solvents 34.8g, alkylamine oxygen Compound 11.75g, polyoxyethylene ether 6.17g, are disperseed 15 minutes with 60 DEG C with ultrasonic emulsification under agitation.To high pressure After carrying out nitrogen displacement in kettle, vinyl chloride 43g is added, adds the solution of water soluble starter 0.86g and water 9g containing azo group, with 60 DEG C are reacted 5 hours, obtain the aqueous liquid dispersion of polymer.The composition of polymer and the composition of charged monomer are basically identical.
Compare Production Example 1
CF is added in 1000ml autoclaves3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2(n=2.0) 133g, third Olefin(e) acid lauryl 37.6g, pure water 405g, water-based two alcohol series solvents 34.8g, alkyl amine oxide 11.75g, polyoxyethylene alkane Base ether 6.17g, disperseed 15 minutes with ultrasonic emulsification with 60 DEG C under agitation.After carrying out nitrogen displacement in autoclave, chlorine is added Ethene 43g, the solution of water soluble starter 0.86g and water 9g containing azo group are added, reacted 5 hours, polymerize with 60 DEG C The aqueous liquid dispersion of thing.The composition of polymer and the composition of charged monomer are basically identical.
Compare Production Example 2
CF is added in 1000ml autoclaves3CF2-(CF2CF2)n-CH2CH2OCOC (Cl)=CH2(n=2.0) 97.2g, third Olefin(e) acid stearyl ester 73.66g, pure water 405g, water-based two alcohol series solvents 34.8g, alkyl amine oxide 11.75g, polyoxyethylene alkane Base ether 6.17g, disperseed 15 minutes with ultrasonic emulsification with 60 DEG C under agitation.After carrying out nitrogen displacement in autoclave, chlorine is added Ethene 43g, the solution of water soluble starter 0.86g and water 9g containing azo group are added, reacted 5 hours, polymerize with 60 DEG C The aqueous liquid dispersion of thing.The composition of polymer and the composition of charged monomer are basically identical.
Embodiment 1
Obtained waterborne liquid in Production Example 1 is diluted using pure water so that fluoropolymer concentration is 30% solid Body composition, afterwards, 30% dilution 1.8g, crosslinking agent (blocked isocyanate) 0.20g are diluted with pure water, prepared 100g experimental liquid.By 4 wood pulp/polyester non-woven fabrics (510mm × 205mm, wood pulp/polyester weight than 30/70) be immersed in In the testing liquid, ironer is passed through, after being dried 30 seconds with 100 DEG C, is handled 2 minutes with pin stenter with 170 DEG C.Afterwards, Experiment cloth is carried out to spray drying experiment, water-repellancy experiment, water pressure resistance experiment, IPA experiments, tensile strength test.Result is shown In table 3.
Embodiment 2~4 and comparative example 1
By Production Example 2~4 and compare obtained polymer in Production Example 1 and handled similarly to Example 1, sprayed Drench water-repellancy experiment, water-repellancy experiment, water pressure resistance experiment, IPA experiments, tensile strength test.Show the result in table 3.
In table, the implication of abbreviation is as follows.
Referred to as Chemical combination name chemical formula
C6SFClA C6F13CH2CH2OCOC (Cl)=CH2
C6SFMA C6F13CH2CH2OCOC(CH3)=CH2
LA Lauryl acrylate
BA Butyl acrylate
StA Stearyl acrylate ester
VCM Vinyl chloride
IBMA Isobornyl methacrylate
【Table 3】
Industrial utilizability
The non-woven fabrics of the present invention can be in medical application, industrial materials purposes, civil construction purposes, agricultural and gardening purposes etc. Middle use.Specific purposes has operating coat, packing sheet, sheet, pillowcase, paper nappy and sanitary napkin etc..

Claims (9)

  1. A kind of 1. non-woven fabrics, it is characterised in that：
    Fluoropolymer is attached with base material,
    Fluoropolymer has：
    (a) repeat unit of fluorochemical monomer is derived from, the fluorochemical monomer is α-chloroacrylic acid ester or α-chlorine with fluoro-alkyl Acrylamide；With
    (b) repeat unit of halo alkene monomer is derived from,
    Fluoropolymer does not have (methyl) third for being derived from the alkyl with straight-chain or branched of the carbon number more than 18 The repeat unit of olefin(e) acid ester.
  2. 2. non-woven fabrics according to claim 1, it is characterised in that：
    Fluorochemical monomer (a) is the compound shown in following formula,
    CH2=C (- Cl)-C (=O)-Y-Z-Rf
    In formula, Y is-O- or-NH-,
    Z is the organic group of Direct Bonding or divalence,
    Rf is the fluoro-alkyl of carbon number 1~20.
  3. 3. non-woven fabrics according to claim 1 or 2, it is characterised in that：
    Halo alkene monomer (b) is by the alkene of the carbon number 2~20 of 1~10 chlorine atom, bromine atoms or iodine atom substitution.
  4. 4. non-woven fabrics according to claim 1 or 2, it is characterised in that：
    Fluorochemical monomer also has：
    (c) it is derived from (methyl) of the alkyl without fluoro-alkyl and with straight-chain or branched of the carbon number below 17 The repeat unit of acrylate or (methyl) acrylamide monomer.
  5. 5. non-woven fabrics according to claim 1 or 2, it is characterised in that：
    Fluoropolymer also has selected from least one of following repeat unit：
    (d) with cyclic hydrocarbon group (methyl) acrylate or (methyl) acrylamide monomer and
    (e) it is derived from the repeat unit of non-fluorine bridging property (methyl) acrylate or (methyl) acrylamide monomer.
  6. 6. non-woven fabrics according to claim 1 or 2, it is characterised in that：
    Base material is the combination of cellulose fibre and polyester fiber.
  7. 7. non-woven fabrics according to claim 1 or 2, it is characterised in that：
    The amount of fluorochemical monomer (a) is the weight % of 20 weight %~90 relative to fluoropolymer, and the amount of halo alkene monomer (b) is relative In the parts by weight of fluorochemical monomer (a) 100 be 5~300 parts by weight.
  8. 8. non-woven fabrics according to claim 1 or 2, it is characterised in that：
    It is 0.01~5 parts by weight that the amount of the fluoropolymer of non-woven fabrics base material, which is attached to, relative to the parts by weight of non-woven fabrics base material 100.
  9. A kind of 9. manufacture method of non-woven fabrics according to any one of claims 1 to 8, it is characterised in that：
    By applications of fluoropolymers in base material.
CN201610626325.XA 2016-08-02 2016-08-02 Non-woven fabrics Pending CN107675504A (en)

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