CN103119097A - Acryl-fluorine composite polymer particles - Google Patents
Acryl-fluorine composite polymer particles Download PDFInfo
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- CN103119097A CN103119097A CN201180046089XA CN201180046089A CN103119097A CN 103119097 A CN103119097 A CN 103119097A CN 201180046089X A CN201180046089X A CN 201180046089XA CN 201180046089 A CN201180046089 A CN 201180046089A CN 103119097 A CN103119097 A CN 103119097A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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Abstract
Provided are acryl-fluorine composite polymer particles which are capable of acquiring water resistance even by a forced drying method and which are capable of reducing the amount of fluororesin while still maintaining weather resistance and chemical resistance, and an aqueous coating composition using the particles. That is, there are provided acryl-fluorine composite polymer particles comprising: (A) a vinylidene fluoride polymer containing, as structural units, at least one type of a fluoroolefin unit selected from a group consisting of a tetrafluoroethylene unit, a hexafluoropropylene unit and a chlorotrifluoroethylene unit, and a vinylidene fluoride unit; and (B) a crosslinkable acrylic polymer (B) containing a (meth)acrylic acid ester unit (b1) which is compatible with the vinylidene fluoride polymer (A), a (meth)acrylic acid ester unit (b2) which is incompatible with the vinylidene fluoride polymer (A), and a (meth)acrylic monomer unit (b3) having a crosslinkable group capable of cross-linking by heating. The mass ratio of vinylidene fluoride polymer (A)/crosslinkable acrylic polymer (B) is 10/90 to 90/10.
Description
Technical field
The present invention relates to be suitable for various base material paint applications with the new fluorinated copolymer particle of the binding agent of composition, the aqueous paint composition that contains the aqueous dispersion of this fluorinated copolymer particle and contain this aqueous dispersion.
Background technology
As the paint application composition, except organic solvent is coating, consider the known water-borne coatings that has take water as dispersion medium from the aspect to the improvement of the concern of physical environment and painting operation environment.In addition, this considers on the one hand from the application of building materials, the particularly building materials such as roof material, outer wall, require it to have excellent weather resistance, carried out especially the exploitation take the fluoro-resin of the excellences such as weathering resistance, water tolerance, chemical proofing, film-forming properties as the water-based paint compositions of binding agent.
But fluoro-resin is poor with the adaptation of other material in fact, thereby is carrying out various improvement aspect the adaptation of base material.For example, put down in writing in patent documentation 1, to make vinylidene fluoride (VDF) be fluoro-resin when carrying out seeding polymerization with the monomer mixture that contains (methyl) acrylate and ethylenically unsaturated monomers under seed grain exists, be below 50 quality % by making the monomer with cyclohexyl that contains 0.5 quality %～45 quality % in monomer mixture, making monomer mixture simultaneously with respect to fluoro-resin, resulting fluorine-containing based polymer aqueous liquid dispersion can provide filming of adaptation excellence.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 08-259773 communique
Summary of the invention
Invent problem to be solved
For water-based paint compositions, be coating composition than solvent, need spended time in its drying, thereby usually carry out mandatory drying.Forced drying was carried out 3 seconds～10 minutes 60 ℃～200 ℃ (temperature of base material) usually, its result, and according to the composition of resin, film forming can be insufficient, thereby coating strength can reduce, and water tolerance also can reduce in addition, sometimes can be impaired with the bonding interface of base material.
In addition, aspect from the expensive fluoro-resin of other viewpoint, particularly reduction, also carried out reducing the research of fluoro-resin ratio, but in order to have given play to the characteristic of fluoro-resin, this reduces is limited, need to make more than the ratio of fluoro-resin is at least 50 quality %, to need in practical be 60 quality %～70 quality %.
From the viewpoint of these, also have room for improvement aspect the adaptation reduction of fluorine-containing based polymer aqueous liquid dispersion due to forced drying of patent documentation 1 record, and need to increase the ratio of acrylic resin.
The inventor conducts in-depth research in order to solve this problem, found that, in the vinylformic acid of fluoropolymer and acrylic monomer-fluorine composite polymer particle, by trying every possible means aspect the composition of the crosslinkable acrylic based polymer that consists of particle, also can guarantee water tolerance even utilize the forced drying method, and can keep weathering resistance and chemical proofing, can reduce the fluoro-resin amount simultaneously, thereby complete the present invention.
Solve the means of problem
Namely, the present invention relates to a kind of vinylformic acid-fluorine composite polymer particle, it is by vinylidene fluoride based polymer (A) and (B) vinylformic acid that consists of of crosslinkable acrylic based polymer (B)-fluorine composite polymer particle, and described vinylidene fluoride based polymer (A) contains and selects at least a fluoroolefins unit in the group that free tetrafluoroethylene units, R 1216 unit and trifluorochloroethylene unit form and contain vinylidene fluoride units as structural unit; Described crosslinkable acrylic based polymer (B) contain with this vinylidene fluoride based polymer (A) for (methyl) acrylic ester unit (b1) of consistency, with this vinylidene fluoride based polymer (A) for (methyl) acrylic ester unit (b2) of non-compatibility and have by heating (methyl) acrylic monomer unit (b3) of crosslinkable groups that can be crosslinked; Wherein, vinylidene fluoride based polymer (A)/crosslinkable acrylic based polymer (B) is 10/90～90/10 by quality ratio.
The invention still further relates to the aqueous dispersion that contains vinylformic acid of the present invention-fluorine composite polymer particle, further relate to the aqueous paint composition that contains this aqueous dispersion.
The invention effect
According to the present invention, a kind of vinylformic acid-fluorine composite polymer particle can be provided, even this composite polymer particle utilizes the forced drying method also can guarantee water tolerance, and can be in the situation that keep weathering resistance and chemical proofing reduction fluoro-resin amount.
Embodiment
Vinylformic acid of the present invention-fluorine composite polymer particle be by VDF based polymer (A) and (B) crosslinkable acrylic based polymer (B) consist of, described VDF based polymer (A) contains and selects at least a fluoroolefins unit in the group that free tetrafluoroethylene (TFE) unit, R 1216 (HFP) unit and trifluorochloroethylene (CTFE) unit form and contain vinylidene fluoride (VDF) unit as structural unit;
Described crosslinkable acrylic based polymer (B) contain with this VDF based polymer (A) for (methyl) acrylic ester unit (b1) of consistency, with this VDF based polymer (A) for (methyl) acrylic ester unit (b2) of non-compatibility and have by heating (methyl) acrylic monomer unit (b3) of crosslinkable groups that can be crosslinked, wherein, VDF based polymer (A)/crosslinkable acrylic based polymer (B) is 10/90～90/10 by quality ratio.
VDF based polymer (A) and crosslinkable acrylic based polymer (B) exist in single particle.VDF based polymer (A) and crosslinkable acrylic based polymer (B) can chemical bondings, also bonding not.The mass ratio of VDF based polymer (A) and crosslinkable acrylic based polymer (B) is for consisting of VDF based polymer (A) and the mass ratio of crosslinkable acrylic based polymer (B) in single particle of single particle.
The below describes each composition.
As the VDF based polymer (A) in the present invention, except VDF, also contain select group that free tetrafluoroethylene (TFE) unit, R 1216 (HFP) unit and trifluorochloroethylene (CTFE) unit form at least a fluoroolefins unit as structural unit.As the VDF based polymer (A) in the present invention, preferably contain tetrafluoroethylene units and trifluorochloroethylene unit.
For as the particularly preferred VDF based polymer of VDF based polymer (A), can enumerate VDF/TFE multipolymer, VDF/TFE/CTFE multipolymer, VDF/HFP multipolymer, VDF/TFE/HFP multipolymer, VDF/CTFE multipolymer etc.
As required, also can contain derive from other fluoroolefins, can be the structural unit of monomer with the non-fluorine of fluoroolefins copolymerization.
As other fluoroolefins, for example can enumerate: perfluor (alkyl vinyl ether),
[changing 1]
Deng perfluoroolefine; Vinyl fluoride, trifluoro-ethylene, trifluoro propene, five fluorine propylene, tetrafluoeopropene, hexafluoro-isobutene, 2,3,3,3-tetrafluoeopropene, 1,3,3,3-tetrafluoeopropene, 1,1,3,3, the non-perfluoroolefines such as 3-five fluorine propylene.As perfluor (alkyl vinyl ether), can enumerate perfluor (methylvinylether) (PMVE), perfluor (ethyl vinyl ether) (PEVE), perfluor (propyl vinyl ether) (PPVE) etc.
In addition, also can use the fluoroolefins that contains functional group.As the fluoroolefins that contains functional group, can enumerate for example represented compound of formula (1):
CX
1 2=CX
2-(Rf)
m-Y
1 (1)
(in formula, Y
1For-OH ,-COOH ,-SO
2F ,-SO
3M
2(M
2Be hydrogen atom, NH
4Base or basic metal), carboxylate salt, carboxylic ester group, epoxy group(ing) or cyano group; X
1And X
2Identical or different, be hydrogen atom or fluorine atom; Rf is that carbonatoms is that 1～40 the fluorine-containing alkylidene group of divalent, carbonatoms are that 1～40 fluorine-containing alkylidene oxide or carbonatoms are 2～40 and contain the fluorine-containing alkylidene group of divalent of ehter bond; M is 0 or 1).
As concrete example, can enumerate such as following compound etc.:
[changing 2]
[changing 3]
Polymkeric substance (A) can contain based on the repeating unit that contains the iodine monomer.As containing the iodine monomer, also can use the iodide of the perfluoroalkyl vinyl ethers such as the perfluor (6,6-dihydro-6-iodo-3-oxa--1-hexene) put down in writing in Japanese JP 5-63482 communique for example or Japanese kokai publication sho 62-12734 communique, perfluor (5-iodo-3-oxa--1-amylene).
Polymkeric substance (A) can contain based on can be the repeating unit of monomer with the non-fluorine of fluoroolefins copolymerization.
The fluorine element content of VDF based polymer is preferably 50 quality %～76 quality %, 60 quality %～70 quality % more preferably.
The manufacture method of VDF based polymer (A) is not particularly limited, and can utilize existing known emulsion polymerization to carry out.
Crosslinkable acrylic based polymer (B) in the present invention contain with VDF based polymer (A) for (methyl) acrylic ester unit (b1) of consistency, with VDF based polymer (A) for (methyl) acrylic ester unit (b2) of non-compatibility and have by heating (methyl) acrylic monomer unit (b3) of crosslinkable groups that can be crosslinked.
(b1) be (methyl) acrylate (hereinafter also referred to as " consistency (methyl) acrylate ") of consistency with VDF based polymer (A)
Consistency (methyl) acrylate (b1) has been given play to and has been improved VDF based polymer (A) and the consistency of crosslinkable acrylic based polymer (B), the effect that improves the integraty of vinylformic acid-fluorine composition polymer, and the film-forming properties when making Air drying simultaneously is good.
As the concrete example of consistency (methyl) acrylate (b1), but example goes out carbonatoms is 1～4 chain-like alkyl ester, one kind or two or more such as in methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, n propyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, isopropyl methacrylate etc.Wherein, consider aspect the favorable solubility the VDF based polymer, be preferably one kind or two or more in methyl methacrylate (MMA), β-dimethyl-aminoethylmethacrylate (EMA), n-BMA (n-MBA), n-butyl acrylate (n-BA), ethyl propenoate (EA), methyl acrylate etc.
Consider from the transparency good aspect of filming, the content of consistency (methyl) acrylate (b1) is preferably 10 quality % of crosslinkable acrylic based polymer (B)～90 quality %, 20 quality %～75 quality % more preferably.
(b2) be (methyl) acrylate (hereinafter also referred to as " non-compatibility (methyl) acrylate ") of non-compatibility with VDF based polymer (A)
Non-compatibility (methyl) acrylate (b2) has been given play to the effect of adaptation of film-forming properties, raising and the base material of vinylformic acid when improving forced drying-fluorine composition polymer, makes simultaneously the water tolerance of filming good.
Need to prove, for " with VDF based polymer (A) be consistency " and " with VDF based polymer (A) be non-compatibility ", with VDF based polymer (A) when mixing with monomer, for transparent situation is called " being consistency with VDF based polymer (A) ", in addition, when mixing for muddy situation be called " with VDF based polymer (A) be non-compatibility ".
As the concrete example of non-compatibility (methyl) acrylate (b2), can enumerate carbonatoms and be 6～20 chain-like alkyl ester, carbonatoms and be 6～20 the alkyl ester with alicyclic structure or carbonatoms and be 6～20 aryl ester.but example goes out one kind or two or more in following substances for example: Ethyl acrylate, ethyl acrylate, the 2-hydroxy acrylate, 2-hydroxypropyl acrylate, the vinylformic acid n-propyl, isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate base ester, 2-ethoxyethyl group acrylate, 2-methoxy ethyl acrylate, N-Hexyl methacrylate, methacrylic acid-2-ethylhexyl, the 2-hydroxyl-metacrylate, methacrylic acid-2-hydroxypropyl acrylate, n propyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, lauryl methacrylate(LMA), methacrylic acid tridecyl ester, the methacrylic acid stearyl ester, 2-ethoxyethyl group methacrylic ester, the chain-like alkyl esters such as 2-methoxy ethyl methacrylic ester, the ester ring type alkyl esters such as cyclohexyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, the aryl ester such as benzyl acrylate, benzyl methacrylate.Wherein, consider from the aspect that the weathering resistance of filming is good, preferred carbonatoms is that 6～20 chain-like alkyl ester and/or carbonatoms are 6～20 the alkyl ester with alicyclic structure, particularly preferably ethyl acrylate (2-EHA) and/or cyclohexyl methacrylate (CHMA).
Consider from the aspect that film-forming properties, adaptation are good, the content of non-compatibility (methyl) acrylate (b2) is preferably 5 quality % of crosslinkable acrylic based polymer (B)～85 quality %, 15 quality %～70 quality % more preferably.
(b3) has (methyl) acrylic monomer (following also referred to as " (methyl) acrylic monomer that contains crosslinkable groups ") of crosslinkable groups that can be crosslinked by heating
(methyl) acrylic monomer (b3) that contains crosslinkable groups suppresses the effects such as muddiness that separate, suppress film of non-compatibility (methyl) acrylic ester unit (b2) and VDF based polymer (A) in acrylic acid polymer (B) when having given play to the film forming of vinylformic acid when forced drying-fluorine composition polymer, make simultaneously with the adaptation of base material good.
Contain crosslinkable groups that (methyl) acrylic monomer (b3) of crosslinkable groups has for by heat can be crosslinked functional group.Thereby the crosslinkable groups such as the non-blocked isocyanate base of cold cross-linking are not the crosslinkable groups for (methyl) acrylic monomer (b3) that contains crosslinkable groups in the present invention.
As crosslinkable groups that can be crosslinked by heating, can enumerate such as epoxy group(ing), carboxyl, hydroxyl, amino, methylol amide base, silyl, carbodiimide, oxazolinyl, blocked isocyanate base, aziridinyl etc., consider preferred epoxy group(ing), carboxyl from the aspect that has good stability of emulsion.
As (methyl) acrylic monomer that contains crosslinkable groups with epoxy group(ing), can enumerate glycidyl compounds such as glycidyl acrylate, glycidyl methacrylate (GMA), the aspect that has good stability during from polymerization considers, one kind or two or more in preferred glycidyl acrylate, glycidyl methacrylate.(methyl) acrylic monomer that contains crosslinkable groups contains in the situation of epoxy group(ing), intergranular film-forming properties, more good with the adaptation of base material during application.
As (methyl) acrylic monomer that contains crosslinkable groups with carboxyl, can enumerate one kind or two or more such as in vinylformic acid, phthalic acid 2-acryloxy ethyl ester, hexahydro-phthalic acid 2-acryloxy ethyl ester, methacrylic acid, phthalic acid 2-methacryloxy ethyl ester, hexahydro-phthalic acid 2-methacryloxy ethyl ester etc., consider one kind or two or more in preferred vinylformic acid (AA), methacrylic acid (MAA) from stability of emulsion good aspect.(methyl) acrylic monomer that contains crosslinkable groups contains in the situation of carboxyl, intergranular film-forming properties, more good with the adaptation of base material during application.
As (methyl) acrylic monomer that contains crosslinkable groups with hydroxyl, can enumerate one kind or two or more such as in vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, methacrylic acid-2-hydroxypropyl acrylate etc.
As having amino (methyl) acrylic monomer that contains crosslinkable groups, can enumerate one kind or two or more such as in amino-ethyl acrylate, dimethylamino acrylate, diethyllaminoethyl acrylate, amino-ethyl methacrylic ester, dimethylamino methyl acrylate, diethyllaminoethyl methacrylic ester, 2-(O-(1 '-methyl propylidene is amino) carboxyamino) ethyl-methyl acrylate etc.
As (methyl) acrylic monomer that contains crosslinkable groups with methylol amide base, can enumerate one kind or two or more such as in methylolation acrylamide, alkoxymethyl acrylamide etc.
As (methyl) acrylic monomer that contains crosslinkable groups with silyl, can enumerate one kind or two or more in following monomer for example:
CH
2=CHCOO(CH
2)
3Si(OCH
3)
3、
CH
2=CHCOO(CH
2)
3Si(CH
3)(OCH
3)
2、
CH
2=CHCOO(CH
2)
3Si(OC
2H
5)
3、
CH
2=CHCOO(CH
2)
3Si(CH
3)(OC
2H
5)
2、
CH
2=C(CH
3)COO(CH
2)
3Si(OCH
3)
3、
CH
2=C(CH
3)COO(CH
2)
3Si(CH
3)(OCH
3)
2、
CH
2=C(CH
3)COO(CH
2)
3Si(OC
2H
5)
3、
CH
2=C(CH
3)COO(CH
2)
3Si(CH
3)(OC
2H
5)
2、
CH
2=C(CH
3)COO(CH
2)
2O(CH
2)
3Si(OCH
3)
3、
CH
2=C(CH
3)COO(CH
2)
2(CH
2)
3Si(CH
3)(OCH
3)
2、
CH
2=C(CH
3)COO(CH
2)
11Si(OCH
3)
3、
CH
2=C (CH
3) COO (CH
2)
11Si (CH
3) (OCH
3)
2Deng.
For these (methyl) acrylic monomers (b3) that contains crosslinkable groups, can be not limited to the kind of crosslinkable groups and share two or more.can enumerate described as follows the share of example: the acrylic monomer and the acrylic monomer that contains carboxyl that contain epoxy group(ing), the acrylic monomer and the acrylic monomer that contains hydroxyl that contain epoxy group(ing), the acrylic monomer and the acrylic monomer that contains amino that contain epoxy group(ing), the acrylic monomer and the acrylic monomer that contains the methylol amide base that contain epoxy group(ing), the acrylic monomer and the acrylic monomer that contains carbodiimide that contain carboxyl, contain the acrylic monomer of carboxyl and the acrylic monomer of Han You oxazolinyl, the acrylic monomer and the acrylic monomer that contains the blocked isocyanate base that contain hydroxyl, the acrylic monomer and the acrylic monomer that contains aziridinyl that contain hydroxyl, the acrylic monomer and the acrylic monomer that contains carboxyl that contain hydroxyl, the acrylic monomer and the acrylic monomer that contains the methylol amide base that contain hydroxyl, the acrylic monomer and the acrylic monomer that contains aziridinyl that contain the methylol amide base, the acrylic monomer and the acrylic monomer that contains carboxyl that contain the methylol amide base, contain amino acrylic monomer and the acrylic monomer that contains aziridinyl, etc., wherein, when the acrylic monomer that will contain epoxy group(ing) share with the acrylic monomer that contains carboxyl, the stability of emulsion is excellent especially.
Consider from stability of emulsion good aspect, the content that contains (methyl) acrylic monomer (b3) of crosslinkable groups is preferably 1 quality % of crosslinkable acrylic based polymer (B)～20 quality %, 1 quality %～5 quality % more preferably.In addition, in the situation that contain (methyl) acrylic monomer unit (b3) that contains crosslinkable groups more than 2 kinds, carry out suitably selecting to get final product in the mode of above-mentioned scope with total amount.For example, in the situation that share the acrylic monomer that contains epoxy group(ing) and the acrylic monomer that contains carboxyl, be preferably 70/30～30/70 scope by quality ratio.
In crosslinkable acrylic based polymer (B), except above-mentioned (b1)～(b3), also can contain above-mentioned (b1)～(b3) other structural unit in addition in the scope of not damaging effect of the present invention.As other structural unit, can enumerate such as aromatic vinyl monomer unit, above-mentioned (b3) contain epoxy group(ing) monomeric unit, above-mentioned (b3) unsaturated carboxylic acid in addition in addition is that monomeric unit, vinyl ether are that monomer, ethylene series monomer, water-disintegrable ethene base system monomer, the vinyl ester that contains silyl are monomer etc.
As aromatic vinyl monomer, but example goes out the styrenics such as vinylbenzene, alpha-methyl styrene.As containing the epoxy group(ing) monomer, but example goes out allyl glycidyl ether etc.
Be monomer as unsaturated carboxylic acid, can enumerate such as vinylacetic acid, butenoic acid, styracin, 3-allyloxy propionic acid, 3-(2-allyloxy ethoxy carbonyl) propionic acid, methylene-succinic acid, methylene-succinic acid monoesters, toxilic acid, toxilic acid monoesters, maleic anhydride, fumaric acid, fumaric monoalkylester, O-phthalic vinyl acetate, pyromellitic acid vinyl acetate, undecylenic acid etc.
Be monomer as vinyl ether, can enumerate the alkyl vinyl ethers, contain the vinyl ethers of hydroxyl etc.; As the vinyl ether that contains hydroxyl, can enumerate such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methyl propyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methyl butyl vinyl ether, 5-hydroxyl amyl group vinyl ether, 6-hydroxyl hexyl vinyl ether, 2-hydroxyethyl allyl ethers, 4-hydroxybutyl allyl ethers, allylin etc.
As the ethylene series monomer, can enumerate such as ethene, propylene, n-butene, iso-butylene, vinylbenzene etc.
As the water-disintegrable ethene base system monomer that contains silyl, can enumerate for example following monomer:
CH
2=CHSi(OCH
3)
3、
CH
2=CHSi(CH
3)(OCH
3)
2、
CH
2=C(CH
3)Si(OCH
3)
3、
CH
2=C(CH
3)Si(CH
3)(OCH
3)
2、
CH
2=CHSi(OC
2H
5)
3、
CH
2=CHSi(OC
3H
7)
3、
CH
2=CHSi(OC
4H
9)
3、
CH
2=CHSi(OC
6H
13)
3、
CH
2=CHSi(OC
8H
17)
3、
CH
2=CHSi(OC
10H
21)
3、
CH
2=CHSi(OC
12H
25)
3、
CH
2=CHCH
2OCO(o-C
6H
4)COO(CH
2)
3Si(OCH
3)
3、
CH
2=CHCH
2OCO(o-C
6H
4)COO(CH
2)
3Si(CH
3)(OCH
3)
2、
CH
2=CH(CH
2)
4Si(OCH
3)
3、
CH
2=CH(CH
2)
8Si(OCH
3)
3、
CH
2=CHO(CH
2)
3Si(OCH
3)
3、
CH
2=CHCH
2O(CH
2)
3Si(OCH
3)
3、
CH
2=CHCH
2OCO (CH
2)
10Si (OCH
3)
3Deng.
Be monomer as vinyl ester, can enumerate the class such as the vinyl carboxylates ester such as vinyl-acetic ester, propionate, vinyl butyrate, isopropylformic acid vinyl acetate, trimethylacetic acid vinyl acetate, vinyl caproate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, hexahydrobenzoic acid vinyl acetate, vinyl benzoate, p-tert-butyl benzoic acid vinyl acetate etc.
Above-mentioned (b1)～(b3) other monomer in addition at crosslinkable acrylic based polymer (B) although in content also according to the difference of monomeric species and difference is preferably below 10 quality %.
In the present invention, as preferred concrete composition of crosslinkable acrylic based polymer (B), can enumerate such as MMA/2-EHA/MAA/GMA (60～80/10～30/0.5～5/0.5～10 mass ratio), n-BA/CHMA/MAA/GMA (10～30/55～80/0.5～10/0.5～5 mass ratio), MMA/n-BA/CHMA/MAA/GMA (1～50/5～40/1～70/0.5～5/0.5～10 mass ratio) etc., but not only be defined in this.
For the ratio of the VDF based polymer (A) in vinylformic acid of the present invention-fluorine composition polymer with crosslinkable acrylic based polymer (B), VDF based polymer (A)/crosslinkable acrylic based polymer (B) is 10/90～90/10 by quality ratio, is preferably 10/90～70/30.If (A)/(B) greater than for example 70/30, be that VDF based polymer (A) surpasses 70 quality %, the film-forming properties during application, with the advantage of adaptation of base material and so on can be impaired.More preferably (A)/(B) is 20/80～50/50.Further preferred (A)/(B) is 30/70～40/60.
In the manufacturing of vinylformic acid of the present invention-fluorine composite polymer particle, polymerization used can adopt existing known polymerization, particularly emulsion polymerization, particularly preferably can adopt for example seeding polymerization method.The seeding polymerization method is not particularly limited, and can carry out under existing known method and condition.
For example, the seeding polymerization of acrylic monomer mixture can be undertaken by following method: VDF based polymer particle have the downhill reaction system in the disposable method that adds whole amounts of acrylic monomer mixture; After the part of input acrylic monomer mixture was reacted, continuous or gradation dropped into the method for residual content; Drop into continuously the method for whole amounts of acrylic monomer mixture; Etc..
In addition, the polymerizing condition of this seeding polymerization is identical with common letex polymerization.For example, add emulsifying agent, polymerization starter, chain-transfer agent, the sequestrant that uses in case of necessity, pH adjusting agent etc. in the aqueous medium that contains VDF based polymer particle, can carry out polymerization by carry out reaction in 0.5 hour～6 hours the temperature of 10 ℃～90 ℃.
As emulsifying agent, can be for reactive emulsifier, also can be non-reacted emulsifying agent, perhaps they can be share.As non-reacted emulsifying agent, can enumerate existing known anionic emulsifier, non-ionic emulsifier, they can be used separately or share.According to circumstances, also can use amphoteric emulsifier.
Polymerization starter used during as seeding polymerization just be not particularly limited as long as can be used for free radical reaction in aqueous medium, according to circumstances, also can be used in combination with reductive agent.As spendable water-soluble polymerization initiator, can enumerate for example persulphate, hydrogen peroxide; As reductive agent, can enumerate pyrosulphite hydrogen sodium, sodium bisulfite, L-AA sodium, rongalite etc.As oil-soluble polymerization initiator, can enumerate such as di-isopropyl peroxydicarbonate (IPP), benzoyl peroxide, DBP, Diisopropyl azodicarboxylate (AIBN) etc.For the consumption of polymerization starter, with respect to every 100 mass parts acrylic monomer mixtures, be generally 0.05 mass parts～2.0 mass parts.
As the chain-transfer agent that can use when the seeding polymerization, can enumerate such as halohydrocarbon such as chloroform, tetracol phenixin; The thio-alcohols such as n-dodecyl mercaptan, uncle's lauryl mercaptan, n-octyl mercaptan; Etc..For the consumption of chain-transfer agent, with respect to every 100 mass parts acrylic monomer mixtures, be generally 0～5.0 mass parts.
In the manufacturing of vinylformic acid of the present invention-fluorine composite polymer particle, for VDF based polymer particle and the ratio that contains the acrylic monomer mixture of above-mentioned (b1)～(b3), with respect to VDF based polymer particle 100 mass parts, the acrylic monomer mixture is more than 100 mass parts.Further, the aspect consideration that the film-forming properties during from application is good, with respect to VDF based polymer particle 100 mass parts, the acrylic monomer mixture is more than 110 mass parts, in particular for more than 150 mass parts.
The invention still further relates to the aqueous dispersion that contains aforesaid propylene acid-fluorine composite polymer particle.In the present invention, the particle diameter of the vinylformic acid in aqueous dispersion-fluorine composite polymer particle is preferably 50nm～300nm.50nm～250nm more preferably.If particle diameter is less than 50nm, the concentration of the vinylformic acid of aqueous dispersion-fluorine composite polymer particle usage range namely 30 quality % when above the viscosity of aqueous dispersion enlarge markedly, can hinder the coating equalization.On the other hand, if surpass 300nm, the sedimentation stability of resulting aqueous dispersion has the tendency of reduction, and causes sometimes the rising of the minimum film-forming temperature of vinylformic acid-fluorine composite polymer particle.
From the aspect of coating purposes, the solid component concentration of the aqueous dispersion of vinylformic acid of the present invention-fluorine composite polymer particle is preferably 30 quality %～65 quality %, 35 quality %～50 quality % more preferably.
The aqueous dispersion of vinylformic acid of the present invention-fluorine composite polymer particle can be used for various uses with various forms.
For example, but example goes out the formed material of the forming component of filming, film or the sheet material of various coating compositions, and binder compositions, printing ink be with composition etc., but is not limited to these.In situation about using as aqueous paint composition, even in the situation that utilize forced drying to carry out film forming, also can improve the cementability with base material.
The aqueous dispersion of vinylformic acid of the present invention-fluorine composite polymer particle can be made by above-mentioned seeding polymerization method.
the aqueous dispersion of vinylformic acid of the present invention-fluorine composite polymer particle can suitably be made by the manufacture method that contains following operation: interpolation is (methyl) acrylate (b1) of consistency with VDF based polymer (A) in the aqueous liquid dispersion that comprises the particle that is made of VDF based polymer (A), with VDF based polymer (A) be (methyl) acrylate (b2) of non-compatibility, (methyl) acrylic monomer (b3) with crosslinkable groups that can be crosslinked by heating, and the operation of polymerization starter, and the operation that (methyl) acrylate (b1), (methyl) acrylate (b2) and (methyl) acrylic monomer (b3) are reacted.
The invention still further relates to the aqueous paint composition that contains above-mentioned aqueous dispersion.Aqueous paint composition of the present invention uses above-mentioned vinylformic acid-fluorine composite polymer particle as film forming material (film formation material), can adopt in addition existing known additive and blending ratio.For example, as the concentration of vinylformic acid-fluorine composite polymer particle, select to get final product in the scope about for example 10 quality %～60 quality %.
In addition, in the situation that preparation adds the aqueous paint composition that pigment is arranged, mix the pigment dispersion (this pigment dispersion utilizes the colo(u)rant dispersion machine such as sand mill that the pigment such as water, titanium dioxide, defoamer, pigment dispersing agent, pH adjusting agent etc. are disperseed to form in advance) of predetermined amount and the film forming auxiliary of predetermined amount in the aqueous liquid dispersion of vinylformic acid-fluorine composite polymer particle, add afterwards the thickening material of predetermined amount to mix, suitably add other necessary additive to get final product.In the situation that the aqueous paint composition of pigment is not added in preparation, add as required entry, film forming auxiliary, defoamer, thickening material, pH adjusting agent, other needed additive in the aqueous liquid dispersion of vinylformic acid-fluorine composite polymer particle, mix by known method and get final product.
As the additive of coating purposes, can add as required film forming auxiliary, frostproofer, pigment, weighting agent, pigment dispersing agent, defoamer, flow agent, rheology adjusting agent, sanitas, UV light absorber, antioxidant, matting agent, lubricant, vulcanizing agent etc.
Be not particularly limited as the base material of using aqueous paint composition of the present invention, applicable to following base material: the metals such as melting coated steel sheet, stainless steel plate, aluminium steel plate are base material; Slate, ceramic industry are that the potteries such as sizing (サ イ ジ Application グ) material, foamed concrete, glass are base material; The plastic basis materials such as polychlorovinyl sheet material, PET film, polycarbonate, acrylic film.As the melting coated steel sheet, can enumerate such as hot-dip galvanized steel sheet, molten zinc plating-aluminium-magnesium alloy steel plate, melting and aluminize-zinc steel plate, melting Aludip etc.
As aqueous paint composition of the present invention being coated on the method for various base materials, can adopt existing known method and condition.For example, can adopt spraying, roller coat, flow coat on base material; The coating processs such as application based on roller, bristle.
Drying means after application is not particularly limited, seasoning at ambient temperature, also can spend time of drying and carry out the drying under low temperature (5 ℃～60 ℃), and for coating composition of the present invention, even carry out the forced drying under normal temperature～200 ℃, particularly 60 ℃～200 ℃ (base material temperature), also can form filming of weathering resistance, water tolerance, intensity, base material adaptation, film-forming properties excellence.The needed time of forced drying is generally 3 seconds～and 10 minutes.
As coating composition, but example go out weatherability coating that weatherability coating uses with composition, particularly building materials with the interior exterior inside and outside coatings with coating composition, electric product of composition, automobile with the coating composition of composition, office machine or kitchen appliance class etc., consider from weathering resistance weather resistance good aspect, can particularly advantageously be applied to building materials with the weatherability coating composition.
Embodiment
Next the present invention will be described based on embodiment, but the present invention is not limited in these embodiment.
Embodiment 1
(manufacturing of the aqueous liquid dispersion of VDF based polymer (A))
Will be as the VdF/TFE/CTFE multipolymer of VDF based polymer particle (=72.1/14.9/13 (% by mole)) (VTC) aqueous liquid dispersion of particle (solid component concentration 45.5 quality %) 659.3g be added in the removable flask of glass system of 2.0L volume, add wherein Newcol707SF as emulsifying agent (Japanese emulsifying agent Co., Ltd. make) 37.1g and water 56.8g, fully mix the preparation aqueous liquid dispersion.
Next, add methyl methacrylate (MMA) 185.2g (71.2 quality %), ethyl acrylate (2EHA) 49.9g (19.2 quality %), glycidyl methacrylate (GMA) 14.3g (5.5 quality %), methacrylic acid (MAA) 10.7g (4.1 quality %) in the glass of 1.0L volume flask processed, the preparation monomer solution.
The interior temperature of removable flask is warming up to 80 ℃, utilizes 3 hours the monomer solution of all measuring is added in the aqueous liquid dispersion of above-mentioned VDF/TFE/CTFE copolymer pellet.And, added ammonium persulphate (APS) (the 1 quality % aqueous solution) 41.1g every 30 minutes 7 times in the same time-division that drips monomer solution, carry out simultaneously polymerization.After polymerization begins 5 hours, reaction soln is cooled to room temperature and comes termination reaction, obtain the aqueous dispersion (solid component concentration 52.0 quality %) of vinylformic acid-fluorine composite polymer particle.Acrylic acid polymer in resulting vinylformic acid-fluorine composition polymer part consist of MMA/2EHA/MAA/GMA=71.2/19.2/4.1/5.5 (quality % ratio).In addition, the part of the VDF based polymer in resulting vinylformic acid-fluorine composite polymer particle is 50/50 with the mass ratio (VDF/ vinylformic acid) of acrylic acid polymer part.
(preparation of water-borne coatings)
Use the aqueous liquid dispersion of resulting vinylformic acid-fluorine composition polymer, utilize triethylamine to be neutralized to pH7.5.Film coalescence aid (diethylene adipate) is added in aqueous liquid dispersion with 5 quality %/solids components, utilizes Three-OneMotor to carry out stirring in 30 minutes, preparation Clear paint use coating composition.
(making of one coat application and test film)
Utilize scraping strip coating machine that resulting aqueous paint composition is coated with and be filled to Al-Zn coated steel (Japanese Testpanel Co., Ltd. make), carry out drying under 140 ℃ of lower conditions of 7 seconds, produced the test film of the transparent coating with thickness 4 μ m.
Use resulting test film to carry out the evaluation of following characteristic.The results are shown in table 1.
(film-forming properties)
(metewand)
The aqueous sodium hydroxide solution 20 μ L of 10 quality % are dropped to test film.After dropping, with following 5 grades to estimating to the time that produces till bubble.1: rear 2 minutes of dropping with interior generation bubble; 2: produce bubble between 2～5 minutes after dripping; 3: produce bubble between 5～10 minutes after dripping; 4: produce bubble between 10～15 minutes after dripping; 5: produce or do not produce bubble more than after dripping rear 15 minutes.
(outward appearance)
(metewand)
By whether agglutinator being arranged on the visual test film that judges made, playing drum (ふ く れ), crackle (cutting れ) etc.Zero has represented that drum, crackle etc. do not occur entirely; △ has represented that drum, crackle etc. are more than 1 and are in 5; * represented that drum, crackle etc. are more than 5.
(initial stage adaptation)
Place after 24 hours after dried coating film, take JIS D0202-1988 as benchmark, test film is carried out the checker belt stripping test.Use cellulose film band (" CT24 ", Mi Qibang Co., Ltd. make), utilize finger belly with its driving fit on film, peel off afterwards.Judgement represents with the number without the grid (マ ス order) of peeling off in 25 lattice (マ ス).
(weathering resistance)
(test method)
The test film of made is inserted in the accelerated weathering test machine, use the infrared spectroscopy spectrum of ATR method (Attenuated Total Reflectance) mensuration after 322 hours.Be used to from the C-H of acrylate stretching vibration (1700cm
-1Near) rate of fall-off that absorbs estimates weather resisteant.
Accelerated weathering test machine (SUV): Super UV Tester, Iwasaki Electric Co., Ltd. make
Testing campaign: 11 hours (63 ℃ of blackboard temperatures, relative humidity 70%) → dewfall 11 hours (30 ℃ of blackboard temperatures, relative humidity 100%) of 1 hour → exposure of pure water spraying (every 10 seconds).Should circulate as 1 circulation (23 hours).
Test period: 322 hours (14 circulations)
(metewand)
Test film surface element after using ATR method (Attenuated Total Reflectance) to test carries out the infrared spectroscopy spectrometry.The test film of test film before accelerated weathering test with test rear (after 322 hours) compared.To 1150cm
-1Near C-F stretching vibration absorbs carries out stdn, confirms 1700cm
-1Whether near the C-H stretching vibration from acrylate has decay before and after being absorbed in test.Zero the expression with the test before compare 1700cm
-1What near the C-H stretching vibration from acrylate absorbed decays in 10%; △ represents decay greater than 10% and is in 25%; * expression decay is greater than 25%.
ATR measures: the FT-IR Spectrometer Spectorum100 that uses Perkin Elmer society to make
(making of clear finish (ト ッ プ Network リ ア) application and test film)
In the upper primer coating of Al-Zn coated steel (Japanese Testpanel society make): Da Jin society makes (Zeffle hides hot base coat), intermediate coat: Da Jin society's manufacturing (Zeffle hides hot base coat), obtain coated plate, use scraping strip coating machine resulting aqueous paint composition of application on this coated plate, carry out 1 day drying, produce the test film of the transparent coating with thickness 10 μ m.
(initial stage driving fit test)
Take JIS D0202-1988 as benchmark, test film is carried out the checker belt stripping test.Use cellulose film band (" CT24 ", Mi Qibang Co., Ltd. make), utilize finger belly with its driving fit on film, peel off afterwards.Judgement is to represent without the grid number of peeling off in 25 lattice.
(initial stage water resistant test)
Under 23 ℃, the immersion of resulting test film was processed 1 day, rise immediately after taking-up bulging (swollen れ) (JISK5600-8-2), crackle (JIS K5600-8-4), peel off the evaluation of (JIS K5600-8-5) grade.
(secondary fitness test)
In addition, take out after immersion is processed, after carrying out 1 day drying under 23 ℃, carry out the checker belt stripping test take JIS D0202-1988 as benchmark.Use cellulose film band (" CT24 ", Mi Qibang Co., Ltd. make), utilize finger belly with its driving fit on film, peel off afterwards.Judgement represents with the number without the grid of peeling off in 25 lattice.
(playing drum)
Play the metewand of drum grade (JIS K5600-8-2)
Density is divided into grade 0～5 (density little be 0), and size is divided into grade S1～S5 (size of S1 is little), for example is recited as 2 (S1).
(crackle)
The metewand of crackle grade (JIS K5600-8-4)
Density is divided into grade 0～5 (density little be 0), and size is divided into grade S0～S5 (size of S0 is little), and the degree of depth is divided into grade a～c (depth as shallow of a), for example is recited as 2 (S1) b.
(peeling off)
Peel off the metewand of grade (JIS K5600-8-5)
Density is divided into grade 0～5 (density little be 0), and size is divided into grade S1～S5 (size of S1 is little), and the degree of depth is divided into grade a～b (depth as shallow of a), for example is recited as 2 (S1) a.
(general water resistant test)
Under 23 ℃, test film is carried out immersion in 6 days and process, work immediately the evaluation of rousing (JIS K5600-8-2), crackle (JIS K5600-8-4), peeling off (JIS K5600-8-5) grade after taking-up.
(secondary fitness test)
In addition, take out after immersion is processed, after carrying out 1 all dryings under 23 ℃, carry out the checker belt stripping test take JIS D0202-1988 as benchmark.Use cellulose film band (" CT24 ", Mi Qibang Co., Ltd. make), utilize finger belly with its driving fit on film, peel off afterwards.Judgement represents with the number without the grid of peeling off in 25 lattice.
(weathering resistance)
The test film of made is inserted in the accelerated weathering test machine, every the mensuration that necessarily loops gloss number, L value, a value, b value.Calculate gloss retention by its result, the weather resisteant of filming is estimated.
Accelerated weathering test machine (SUV): Super UV Tester, Iwasaki Electric Co., Ltd. make
Testing campaign: 11 hours (63 ℃ of blackboard temperatures, relative humidity 70%) → dewfall 11 hours (30 ℃ of blackboard temperatures, relative humidity 100%) of 1 hour → exposure of pure water spraying (every 10 seconds).Should circulate as 1 circulation (23 hours).
Test period: 966 hours (42 circulations)～1610 hours (70 circulations)
Embodiment 2～4
As acrylic acid polymer acrylic monomer mixture, use the monomer mixture shown in table 1, in addition, carry out similarly to Example 1 seeding polymerization, obtain respectively vinylformic acid-fluorine composition polymer.
Use the aqueous liquid dispersion of resulting vinylformic acid-fluorine composite polymer particle, prepare similarly to Example 1 Clear paint use coating composition, form similarly to Example 1 and film, make test film, various characteristics is studied.The results are shown in table 1.
Comparative example 1
As acrylic acid polymer acrylic monomer mixture, that uses MMA/n-BA/AA=98.0/1.0/1.0 (quality % ratio) relatively uses monomer mixture, in addition, carry out similarly to Example 1 seeding polymerization, obtain relatively using vinylformic acid-fluorine composition polymer.Acrylic acid polymer part consist of MMA/n-BA/AA=98.0/1.0/1.0 (quality % ratio).In addition, in resulting vinylformic acid-fluorine composite polymer particle, VDF based polymer part is 70/30 with the mass ratio (VDF/ vinylformic acid) of acrylic acid polymer part.
Use the aqueous liquid dispersion of resulting vinylformic acid-fluorine composite polymer particle, prepare similarly to Example 1 Clear paint use coating composition, form similarly to Example 1 and film, make test film, various characteristics is studied.The results are shown in table 1.
In table 1, the shorthand notation of monomer represents following compound.
MMA: methyl methacrylate
N-BA: n-butyl acrylate
CHMA: cyclohexyl methacrylate
2-EHA: ethyl acrylate
GMA: glycidyl methacrylate
MAA: methacrylic acid
AA: vinylformic acid
MPTES:3-methacryloxypropyl triethoxyl silane
Table 1
As shown in Table 1, containing the vinylformic acid of composition (b1), composition (b2), composition (b3)-fluorine composition polymer is improved the adaptation with base material.
Embodiment 5
As VDF based polymer particle, use VdF/TFE multipolymer (=80/20 (% by mole)) (VT) aqueous liquid dispersion of particle (solid component concentration 10.0 quality %), in addition, carry out similarly to Example 3 seeding polymerization, obtain vinylformic acid-fluorine composition polymer.
Use the aqueous liquid dispersion of resulting vinylformic acid-fluorine composite polymer particle, prepare similarly to Example 1 Clear paint use coating composition, form similarly to Example 1 and film, make test film, various characteristics is studied.The results are shown in table 2.
Embodiment 6
As VDF based polymer particle, use VdF/HFP multipolymer (=91/9 (% by mole)) aqueous liquid dispersion (solid component concentration 10.0 quality %) of (VH) particle, in addition, carry out similarly to Example 3 seeding polymerization, obtain vinylformic acid-fluorine composition polymer.
Use the aqueous liquid dispersion of resulting vinylformic acid-fluorine composite polymer particle, prepare similarly to Example 1 Clear paint use coating composition, form similarly to Example 1 and film, make test film, various characteristics is studied.The results are shown in table 2.
Table 2
As shown in Table 2, the vinylformic acid-VDF that contains composition (b1), composition (b2), composition (b3) is that the fluorine composition polymer is improved the adaptation with base material.
Claims (9)
1. vinylformic acid-fluorine composite polymer particle, it is the vinylformic acid that is made of vinylidene fluoride based polymer (A) and crosslinkable acrylic based polymer (B)-fluorine composite polymer particle,
Described vinylidene fluoride based polymer (A) contains and selects at least a fluoroolefins unit in the group that free tetrafluoroethylene units, R 1216 unit and trifluorochloroethylene unit form and contain vinylidene fluoride units as structural unit;
Described crosslinkable acrylic based polymer (B) contains with this vinylidene fluoride based polymer (A) for (methyl) acrylic ester unit (b1) of consistency, be (methyl) acrylic ester unit (b2) of non-compatibility and (methyl) acrylic monomer unit (b3) with this vinylidene fluoride based polymer (A), described (methyl) acrylic monomer unit (b3) have by heat can be crosslinked crosslinkable groups;
Wherein, vinylidene fluoride based polymer (A)/crosslinkable acrylic based polymer (B) is 10/90～90/10 by quality ratio.
2. vinylformic acid as claimed in claim 1-fluorine composite polymer particle, wherein, vinylidene fluoride based polymer (A) contains tetrafluoroethylene units and trifluorochloroethylene unit.
3. vinylformic acid as claimed in claim 1-fluorine composite polymer particle, wherein, vinylidene fluoride based polymer (A) is vinylidene fluoride/tetrafluoroethylene copolymer.
4. vinylformic acid as claimed in claim 1-fluorine composite polymer particle, wherein, vinylidene fluoride based polymer (A) is vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer.
5. vinylformic acid as claimed in claim 1-fluorine composite polymer particle, wherein, vinylidene fluoride based polymer (A) is vinylidene fluoride/hexafluoropropylene copolymer.
6. vinylformic acid as described in any one of claim 1～5-fluorine composite polymer particle, wherein, consistency (methyl) acrylic ester unit (b1) is that (methyl) acrylic acid carbonatoms is 1～4 chain-like alkyl ester units.
7. vinylformic acid as described in any one of claim 1～6-fluorine composite polymer particle, wherein, non-compatibility (methyl) acrylic ester unit (b2) is that (methyl) acrylic acid carbonatoms that has or do not have alicyclic structure is 6～20 alkyl ester unit.
8. aqueous dispersion, wherein, this aqueous dispersion contains the described vinylformic acid of any one of claim 1～7-fluorine composite polymer particle.
9. aqueous paint composition, wherein, this aqueous paint composition contains aqueous dispersion claimed in claim 8.
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| CN111433240A (en) * | 2017-12-20 | 2020-07-17 | 大金工业株式会社 | Core-shell type particles, dispersions and powders |
| CN111989355A (en) * | 2018-03-30 | 2020-11-24 | 大金工业株式会社 | Aqueous dispersion, coating film, coated article, and method for producing aqueous dispersion |
| CN112839970A (en) * | 2018-11-22 | 2021-05-25 | 东丽株式会社 | Fluoropolymer particles |
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| US20140235783A1 (en) * | 2011-09-30 | 2014-08-21 | Daikin Industries, Ltd. | Composition and coated article |
| JP2014152186A (en) * | 2013-02-05 | 2014-08-25 | Jsr Corp | Aqueous fluororesin composition |
| JP6222458B2 (en) * | 2013-10-01 | 2017-11-01 | Jsr株式会社 | Paint composition, paint and painted body |
| JP6359953B2 (en) * | 2013-11-07 | 2018-07-18 | 株式会社日本触媒 | Film forming aid |
| WO2016171217A1 (en) | 2015-04-21 | 2016-10-27 | ダイキン工業株式会社 | Aqueous dispersion, coating film, and coated article |
| WO2019170694A1 (en) | 2018-03-08 | 2019-09-12 | Solvay Sa | A process for the preparation of a solid polymer electrolyte useful in batteries |
| JP2022013956A (en) * | 2018-10-29 | 2022-01-19 | Ａｇｃ株式会社 | Aqueous coating composition and coated article |
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| US5646201A (en) * | 1993-09-22 | 1997-07-08 | Daikin Industries, Ltd. | Aqueous dispersion of fluorine-containing copolymer |
| JPH07268163A (en) * | 1994-03-30 | 1995-10-17 | Japan Synthetic Rubber Co Ltd | Water-based fluororesin composition |
| CN1117979A (en) * | 1994-06-01 | 1996-03-06 | 埃勒夫阿托化学有限公司 | Stable aqueous dispersive body of hydroxyleste fluoridated copolymer and acrylic copolymer and preparation and application as aqueous pait of same |
| JPH08170045A (en) * | 1994-12-20 | 1996-07-02 | Japan Synthetic Rubber Co Ltd | Aqueous coating material for inorganic building material |
| JP2003171520A (en) * | 2001-12-04 | 2003-06-20 | Daikin Ind Ltd | Crosslinkable fluorine-containing resin aqueous composition |
| JP2003286440A (en) * | 2002-03-28 | 2003-10-10 | Jsr Corp | Aqueous dispersion and coated article |
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| CN106188385A (en) * | 2016-08-16 | 2016-12-07 | 衡水新光化工有限责任公司 | A kind of fluorine carbon emulsion for multicolor finish and preparation technology thereof |
| CN106188385B (en) * | 2016-08-16 | 2018-06-01 | 衡水新光新材料科技有限公司 | A kind of fluorine carbon emulsion and its preparation process for multicolor finish |
| CN111433240A (en) * | 2017-12-20 | 2020-07-17 | 大金工业株式会社 | Core-shell type particles, dispersions and powders |
| CN111989355A (en) * | 2018-03-30 | 2020-11-24 | 大金工业株式会社 | Aqueous dispersion, coating film, coated article, and method for producing aqueous dispersion |
| CN112839970A (en) * | 2018-11-22 | 2021-05-25 | 东丽株式会社 | Fluoropolymer particles |
| CN112839970B (en) * | 2018-11-22 | 2022-08-30 | 东丽株式会社 | Fluoropolymer particles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103119097B (en) | 2016-03-16 |
| JP5229367B2 (en) | 2013-07-03 |
| KR20130072254A (en) | 2013-07-01 |
| WO2012043580A1 (en) | 2012-04-05 |
| KR101502710B1 (en) | 2015-03-13 |
| JP2012092316A (en) | 2012-05-17 |
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