CN103119097B - Vinylformic acid-fluorine composite polymer particle - Google Patents
Vinylformic acid-fluorine composite polymer particle Download PDFInfo
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- CN103119097B CN103119097B CN201180046089.XA CN201180046089A CN103119097B CN 103119097 B CN103119097 B CN 103119097B CN 201180046089 A CN201180046089 A CN 201180046089A CN 103119097 B CN103119097 B CN 103119097B
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- 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
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- 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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- 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
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- 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
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- 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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- C08L2312/00—Crosslinking
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Abstract
The invention provides a kind of vinylformic acid-fluorine composite polymer particle and the water-based paint compositions employing this particle, even if this composite polymer particle utilizes forced drying method also can guarantee water tolerance, and when maintaining weathering resistance, chemical proofing, fluoro-resin amount can be reduced.A kind of vinylformic acid-fluorine composite polymer particle, it is vinylformic acid-fluorine composite polymer particle of being made up of vinylidene fluoride polymer (A) and (B) crosslinkable acrylic based polymer (B), and described vinylidene fluoride polymer (A) is containing at least one fluoroolefin unit be selected from the group that be made up of tetrafluoroethylene units, R 1216 unit and trifluorochloroethylene unit and contain vinylidene fluoride units as structural unit; Described crosslinkable acrylic based polymer (B) containing with this vinylidene fluoride polymer (A) (methyl) acrylic ester unit (b1) that is consistency, with this vinylidene fluoride polymer (A) (methyl) acrylic ester unit (b2) that is non-compatibility and (methyl) acrylic monomer unit (b3) of having by heating the crosslinkable groups carrying out being cross-linked; Wherein, vinylidene fluoride polymer (A)/crosslinkable acrylic based polymer (B) is 10/90 ~ 90/10 by quality ratio.
Description
Technical field
The present invention relates to new fluorinated copolymer particle, the aqueous dispersion containing this fluorinated copolymer particle and the aqueous paint composition containing this aqueous dispersion of the binding agent that can be suitable for various base material paint application composition.
Background technology
As paint application composition, except organic solvent system coating, from the viewpoint of to the concern of physical environment and the improvement of painting operation environment, there will be a known with water is the water-borne coatings of dispersion medium.In addition, from this consideration on the one hand of application of the building materials such as building materials, particularly roof material, outer wall, require that it has excellent weather resistance, carried out especially with the exploitation of the fluoro-resin that weathering resistance, water tolerance, chemical proofing, film-forming properties etc. the are excellent water-based paint compositions that is binding agent.
But fluoro-resin is poor with the adaptation of other material in fact, thus with the adaptation of base material in carried out various improvement.Such as, describe in patent documentation 1, vinylidene fluoride (VDF) is made to be that fluoro-resin is under seed grain exists and when the monomer mixture containing (methyl) acrylate and ethylenically unsaturated monomers carries out seeding polymerization, by making the monomer with cyclohexyl containing 0.5 quality % ~ 45 quality % in monomer mixture, make monomer mixture be below 50 quality % relative to fluoro-resin simultaneously, the fluorine-containing based polymer aqueous liquid dispersion obtained can provide the film of excellent adhesion.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 08-259773 publication
Summary of the invention
Invent problem to be solved
For water-based paint compositions, compared to solvent system coating composition, in its drying, need spended time, thus usually carry out mandatory drying.Forced drying carries out 3 seconds ~ 10 minutes, its result, according to the composition of resin 60 DEG C ~ 200 DEG C (temperature of base material) usually, film forming can be insufficient, thus 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, from other viewpoint, the aspect particularly reducing expensive fluoro-resin, also carry out the research reducing fluoro-resin ratio, but in order to give play to the characteristic of fluoro-resin, this reduction is limited, need the ratio making fluoro-resin to be at least more than 50 quality %, needing in practical is 60 quality % ~ 70 quality %.
From the viewpoint of these, the fluorine-containing based polymer aqueous liquid dispersion that patent documentation 1 is recorded also has room for improvement in the adaptation reduction caused by forced drying, and needs the ratio increasing acrylic resin.
The present inventor conducts in-depth research to solve this problem, found that, in the vinylformic acid-fluorine composite polymer particle of fluoropolymer and acrylic monomer, by trying every possible means in the composition of crosslinkable acrylic based polymer forming particle, even if utilize forced drying method also can guarantee water tolerance, and weathering resistance and chemical proofing can be maintained, fluoro-resin amount can be reduced simultaneously, thus 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 vinylformic acid-fluorine composite polymer particle of being made up of vinylidene fluoride polymer (A) and (B) crosslinkable acrylic based polymer (B), and described vinylidene fluoride polymer (A) is containing at least one fluoroolefin unit be selected from the group that be made up of tetrafluoroethylene units, R 1216 unit and trifluorochloroethylene unit and contain vinylidene fluoride units as structural unit; Described crosslinkable acrylic based polymer (B) containing with this vinylidene fluoride polymer (A) (methyl) acrylic ester unit (b1) that is consistency, with this vinylidene fluoride polymer (A) (methyl) acrylic ester unit (b2) that is non-compatibility and (methyl) acrylic monomer unit (b3) of having by heating the crosslinkable groups that can be cross-linked; Wherein, vinylidene fluoride polymer (A)/crosslinkable acrylic based polymer (B) is 10/90 ~ 90/10 by quality ratio.
The invention still further relates to the aqueous dispersion containing vinylformic acid of the present invention-fluorine composite polymer particle, relate to aqueous paint composition containing this aqueous dispersion further.
Invention effect
According to the present invention, a kind of vinylformic acid-fluorine composite polymer particle can being provided, even if this composite polymer particle utilizes forced drying method also can guarantee water tolerance, and fluoro-resin amount can be reduced when maintaining weathering resistance and chemical proofing.
Embodiment
Vinylformic acid of the present invention-fluorine composite polymer particle is for being made up of VDF based polymer (A) and (B) crosslinkable acrylic based polymer (B), and described VDF based polymer (A) is containing at least one fluoroolefin unit be selected from the group that be made up of tetrafluoroethylene (TFE) unit, R 1216 (HFP) unit and trifluorochloroethylene (CTFE) unit and contain vinylidene fluoride (VDF) unit as structural unit;
Described crosslinkable acrylic based polymer (B) containing with this VDF based polymer (A) (methyl) acrylic ester unit (b1) that is consistency, with this VDF based polymer (A) (methyl) acrylic ester unit (b2) that is non-compatibility and (methyl) acrylic monomer unit (b3) of having by heating the crosslinkable groups that can be cross-linked, 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 bonding, also can not bonding.The mass ratio of VDF based polymer (A) and crosslinkable acrylic based polymer (B) is the VDF based polymer (A) and crosslinkable acrylic based polymer (B) mass ratio in single particle that form single particle.
Below each composition is described.
As the VDF based polymer (A) in the present invention, except VDF, also containing being selected from least one fluoroolefin unit of the group be made up of tetrafluoroethylene (TFE) unit, R 1216 (HFP) unit and trifluorochloroethylene (CTFE) unit as structural unit.As the VDF based polymer (A) in the present invention, preferably containing tetrafluoroethylene units and trifluorochloroethylene unit.
For as the particularly preferred VDF based polymer of VDF based polymer (A), VDF/TFE multipolymer, VDF/TFE/CTFE multipolymer, VDF/HFP multipolymer, VDF/TFE/HFP multipolymer, VDF/CTFE multipolymer etc. can be enumerated.
As required, also can containing derive from other fluoroolefins, can with the structural unit of the non-fluorine system monomer of fluoroolefins copolymerization.
As other fluoroolefins, can enumerate such as: perfluor (alkyl vinyl ether),
[changing 1]
Deng perfluoroolefine; The non-perfluorinated alkene such as vinyl fluoride, trifluoro-ethylene, trifluoro propene, five fluorine propylene, tetrafluoeopropene, hexafluoro-isobutene, 2,3,3,3-tetrafluoeopropenes, 1,3,3,3-tetrafluoeopropene, 1,1,3,3,3-five fluorine propylene.As perfluor (alkyl vinyl ether), perfluor (methylvinylether) (PMVE), perfluor (ethyl vinyl ether) (PEVE), perfluor (propyl vinyl ether) (PPVE) etc. can be enumerated.
In addition, the fluoroolefins containing functional group can also be used.As the fluoroolefins containing functional group, the compound such as represented by formula (1) can be enumerated:
CX
1 2=CX
2-(Rf)
m-Y
1(1)
(in formula, Y
1for-OH ,-COOH ,-SO
2f ,-SO
3m
2(M
2for 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 to be carbonatoms be 1 ~ 40 the fluorine-containing alkylidene group of divalent, carbonatoms be 1 ~ 40 fluorine-containing alkylidene oxide or carbonatoms be 2 ~ 40 and the fluorine-containing alkylidene group of divalent containing ehter bond; M is 0 or 1).
As concrete example, such as following compound etc. can be enumerated:
[changing 2]
[changing 3]
Polymkeric substance (A) can contain based on the repeating unit containing iodine monomer.As containing iodine monomer, also can use the iodide of the perfluoroalkyl vinyl ether such as perfluor (6,6-dihydro-6-iodo-3-oxa--1-hexene), perfluor (the iodo-3-oxa-of 5--1-amylene) recorded in such as Japanese Patent Publication 5-63482 publication or Japanese Laid-Open Patent Publication 62-12734 publication.
Polymkeric substance (A) can containing based on can with the repeating unit of the non-fluorine system monomer of fluoroolefins copolymerization.
The fluorine element content of VDF based polymer is preferably 50 quality % ~ 76 quality %, more preferably 60 quality % ~ 70 quality %.
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 containing with VDF based polymer (A) (methyl) acrylic ester unit (b1) that is consistency, with VDF based polymer (A) (methyl) acrylic ester unit (b2) that is non-compatibility and (methyl) acrylic monomer unit (b3) of having by heating the crosslinkable groups that can be cross-linked.
(b1) (methyl) acrylate (hereafter also referred to as " consistency (methyl) acrylate ") being consistency with VDF based polymer (A)
Consistency (methyl) acrylate (b1) has given play to the consistency improving VDF based polymer (A) and crosslinkable acrylic based polymer (B), the effect improving the integraty of vinylformic acid-fluorine composition polymer, makes film-forming properties during Air drying good simultaneously.
As the concrete example of consistency (methyl) acrylate (b1), can exemplify carbonatoms is one kind or two or more in chain-like alkyl ester, the such as methyl acrylate, ethyl propenoate, n-propyl, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, n propyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, isopropyl methacrylate etc. of 1 ~ 4.Wherein, consider in the favorable solubility VDF based polymer, what be preferably in methyl methacrylate (MMA), β-dimethyl-aminoethylmethacrylate (EMA), n-BMA (n-MBA), n-butyl acrylate (n-BA), ethyl propenoate (EA), methyl acrylate etc. is one kind or two or more.
Good from the viewpoint of the film transparency, the content of consistency (methyl) acrylate (b1) is preferably 10 quality % ~ 90 quality % of crosslinkable acrylic based polymer (B), more preferably 20 quality % ~ 75 quality %.
(b2) (methyl) acrylate (hereafter also referred to as " non-compatibility (methyl) acrylate ") being non-compatibility with VDF based polymer (A)
Non-compatibility (methyl) acrylate (b2) given play to vinylformic acid when improving forced drying-fluorine composition polymer film-forming properties, improve and the effect of adaptation of base material, make the water tolerance of film good simultaneously.
It should be noted that, for " be consistency with VDF based polymer (A) " and " be non-compatibility with VDF based polymer (A) ", when VDF based polymer (A) is mixed with monomer, for transparent situation is called " be consistency with VDF based polymer (A) ", in addition, be that muddy situation is called " be non-compatibility with VDF based polymer (A) " when mixing.
As the concrete example of non-compatibility (methyl) acrylate (b2), can enumerate carbonatoms be 6 ~ 20 chain-like alkyl ester, carbonatoms be 6 ~ 20 the alkyl ester with alicyclic structure or carbonatoms be the aryl ester of 6 ~ 20.What can exemplify in such as following substances is one kind or two or more: Ethyl acrylate, ethyl acrylate, 2-hydroxy acrylate, 2-hydroxypropyl acrylate, n-propyl, isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate base ester, 2-ethoxyethyl acrylate, 2-methoxyethyl acrylate, N-Hexyl methacrylate, methacrylic acid-2-ethylhexyl, 2-hydroxyl-metacrylate, Hydroxypropyl methacrylate, n propyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, lauryl methacrylate(LMA), Tridecyl methacrylate base ester, stearyl methacrylate, 2-ethoxyethyl methacrylates, the chain-like alkyl esters such as 2-ihethoxyethyl methacrylate, 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, good from the viewpoint of the weathering resistance of film, preferred carbonatoms be 6 ~ 20 chain-like alkyl ester and/or carbonatoms be 6 ~ 20 the alkyl ester with alicyclic structure, particularly preferably ethyl acrylate (2-EHA) and/or cyclohexyl methacrylate (CHMA).
Good from the viewpoint of film-forming properties, adaptation, the content of non-compatibility (methyl) acrylate (b2) is preferably 5 quality % ~ 85 quality % of crosslinkable acrylic based polymer (B), is more preferably 15 quality % ~ 70 quality %.
(b3) there is (methyl) acrylic monomer (hereinafter also referred to " (methyl) acrylic monomer containing crosslinkable groups ") by heating the crosslinkable groups that can be cross-linked
Suppress the effects such as the muddiness being separated, suppressing film of non-compatibility (methyl) acrylic ester unit (b2) in acrylic acid polymer (B) and VDF based polymer (A) when (methyl) acrylic monomer (b3) containing crosslinkable groups has given play to the film forming of the vinylformic acid-fluorine composition polymer when forced drying, make with the adaptation of base material good simultaneously.
The crosslinkable groups that (methyl) acrylic monomer (b3) containing crosslinkable groups has is by heating the functional group that can be cross-linked.Thus, the crosslinkable groups such as non-blocked isocyanate base of cold cross-linking is not the crosslinkable groups of (methyl) acrylic monomer (b3) containing crosslinkable groups in the present invention.
As the crosslinkable groups that can be cross-linked by heating, such as epoxy group(ing), carboxyl, hydroxyl, amino, methylol amide base, silyl, carbodiimide, oxazolinyl, blocked isocyanate base, aziridinyl etc. can be enumerated, good from the viewpoint of emulsion intercalation method, preferred epoxy group(ing), carboxyl.
As (methyl) acrylic monomer containing crosslinkable groups with epoxy group(ing), the such as glycidyl compound such as glycidyl acrylate, glycidyl methacrylate (GMA) can be enumerated, from the viewpoint of having good stability during polymerization, one kind or two or more in preferred glycidyl acrylate, glycidyl methacrylate.When (methyl) acrylic monomer containing crosslinkable groups contains epoxy group(ing), intergranular film-forming properties during application, more good with the adaptation of base material.
As (methyl) acrylic monomer containing crosslinkable groups with carboxyl, that can enumerate in such as vinylformic acid, phthalic acid 2-acryloyloxyethyl ester, hexahydro-phthalic acid 2-acryloyloxyethyl ester, methacrylic acid, phthalic acid 2-methacryloyloxyethyl, hexahydro-phthalic acid 2-methacryloyloxyethyl etc. is one kind or two or more, good from the viewpoint of stability of emulsion, one kind or two or more in preferred vinylformic acid (AA), methacrylic acid (MAA).When (methyl) acrylic monomer containing crosslinkable groups contains carboxyl, intergranular film-forming properties during application, more good with the adaptation of base material.
As have hydroxyl containing (methyl) acrylic monomer of crosslinkable groups, that can enumerate in such as vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, Hydroxypropyl methacrylate etc. is one kind or two or more.
As having amino (methyl) acrylic monomer containing crosslinkable groups, that can enumerate in such as aminoethylacrylate, dimethylamino acrylate, diethyllaminoethyl acrylate, amidoethyl methacrylate, dimethylamino methyl acrylate, diethyllaminoethyl methacrylic ester, 2-(O-(1 '-methyl propylene is amino) carboxyamino) ethylmethyl acrylate etc. is one kind or two or more.
As have methylol amide base containing (methyl) acrylic monomer of crosslinkable groups, that can enumerate in such as methylolation acrylamide, alkoxymethyl acrylamide etc. is one kind or two or more.
As have silyl containing (methyl) acrylic monomer of crosslinkable groups, that can enumerate in such as following monomer is one kind or two or more:
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.
These are contained to (methyl) acrylic monomer (b3) of crosslinkable groups, the kind of crosslinkable groups can be not limited to and share two or more.Example can be enumerated share described as follows: the acrylic monomer containing epoxy group(ing) and the acrylic monomer containing carboxyl, acrylic monomer containing epoxy group(ing) and the acrylic monomer containing hydroxyl, acrylic monomer containing epoxy group(ing) and the acrylic monomer containing amino, acrylic monomer containing epoxy group(ing) and the acrylic monomer containing methylol amide base, acrylic monomer containing carboxyl and the acrylic monomer containing carbodiimide, the acrylic monomer of the acrylic monomer containing carboxyl and Han You oxazolinyl, acrylic monomer containing hydroxyl and the acrylic monomer containing blocked isocyanate base, acrylic monomer containing hydroxyl and the acrylic monomer containing aziridinyl, acrylic monomer containing hydroxyl and the acrylic monomer containing carboxyl, acrylic monomer containing hydroxyl and the acrylic monomer containing methylol amide base, acrylic monomer containing methylol amide base and the acrylic monomer containing aziridinyl, acrylic monomer containing methylol amide base and the acrylic monomer containing carboxyl, containing amino acrylic monomer and the acrylic monomer containing aziridinyl, etc., wherein, when acrylic monomer containing epoxy group(ing) is share with the acrylic monomer containing carboxyl, emulsion intercalation method is excellent especially.
Good from the viewpoint of stability of emulsion, the content of (methyl) acrylic monomer (b3) containing crosslinkable groups is preferably 1 quality % ~ 20 quality % of crosslinkable acrylic based polymer (B), more preferably 1 quality % ~ 5 quality %.In addition, when containing (methyl) acrylic monomer unit (b3) of crosslinkable groups containing two or more, suitably select in the mode of total amount in above-mentioned scope.Such as, when share the acrylic monomer containing epoxy group(ing) and the acrylic monomer containing carboxyl, be preferably the scope of 70/30 ~ 30/70 by quality ratio.
In crosslinkable acrylic based polymer (B), except above-mentioned (b1) ~ (b3), also can containing other structural unit beyond above-mentioned (b1) ~ (b3) in the scope not damaging effect of the present invention.As other structural unit, the unsaturated carboxylic acid system monomeric unit, vinyl ether system monomer, olefinic monomers, the water-disintegrable ethene base system monomer, vinyl ester system monomer etc. containing silyl that contain beyond epoxy based monomers unit, above-mentioned (b3) beyond such as aromatic vinyl monomer unit, above-mentioned (b3) can be enumerated.
As aromatic vinyl monomer, the styrenic such as vinylbenzene, alpha-methyl styrene can be exemplified.As containing epoxy based monomers, allyl glycidyl ether etc. can be exemplified.
As unsaturated carboxylic acid system monomer, 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, maleic mono-ester, maleic anhydride, fumaric acid, fumaric monoalkylester, phthalate, pyromellitic acid vinyl acetate, undecylenic acid etc. can be enumerated.
As vinyl ether system monomer, alkyl vinyl ethers, vinyl ethers etc. containing hydroxyl can be enumerated; As the vinyl ether containing hydroxyl, 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-Hydroxy pentyl vinyl ether, 6-hydroxyl hexyl vinyl ether, 2-hydroxyethyl allyl ethers, 4-hydroxybutyl allyl ethers, allylin etc. can be enumerated.
As olefinic monomers, such as ethene, propylene, n-butene, iso-butylene, vinylbenzene etc. can be enumerated.
As the water-disintegrable ethene base system monomer containing silyl, such as following monomer can be enumerated:
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.
As vinyl ester system monomer, the vinyl carboxylates ester classes etc. such as such as vinyl-acetic ester, propionate, vinyl butyrate, vinyl isobutyrate ester, 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 can be enumerated.
Other monomer beyond above-mentioned (b1) ~ (b3) at crosslinkable acrylic based polymer (B) although in content also different according to the difference of monomeric species, be preferably below 10 quality %.
In the present invention, as the preferably concrete composition of crosslinkable acrylic based polymer (B), 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. can be enumerated, but be not limited to 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) is greater than such as 70/30, namely VDF based polymer (A) is more than 70 quality %, then film-forming properties during application, can be impaired with the advantage of the adaptation of base material and so on.More preferably (A)/(B) is 20/80 ~ 50/50.Preferably (A)/(B) is 30/70 ~ 40/60 further.
Polymerization used in the manufacture of vinylformic acid of the present invention-fluorine composite polymer particle can adopt existing known polymerization, particularly emulsion polymerization, particularly preferably can adopt such as seeded polymerization.Seeded polymerization is not particularly limited, and can carry out under existing known method and condition.
Such as, the seeding polymerization of acrylic monomer mixture is undertaken by following method: there is the disposable method adding the whole amount of acrylic monomer mixture in downhill reaction system at VDF based polymer particle; After the part dropping into acrylic monomer mixture is reacted, continuously or gradation drop into the method for residual content; The method of the whole amount of continuous input acrylic monomer mixture; Etc..
In addition, the polymerizing condition of this seeding polymerization is identical with common letex polymerization.Such as, in the aqueous medium containing VDF based polymer particle, add emulsifying agent, polymerization starter, chain-transfer agent, the sequestrant used if desired, pH adjusting agent etc., be polymerized by carrying out reaction in 0.5 hour ~ 6 hours the temperature of 10 DEG C ~ 90 DEG C.
As emulsifying agent, can be reactive emulsifier, also for non-reacted emulsifying agent, or they can be share.As non-reacted emulsifying agent, existing known anionic emulsifier, non-ionic emulsifier can be enumerated, they can be used alone or share.According to circumstances, also amphoteric emulsifier can be used.
As polymerization starter used during seeding polymerization, as long as can just be not particularly limited for free radical reaction in an aqueous medium, according to circumstances, also can combinationally use with reductive agent.As spendable water-soluble polymerization initiator, such as persulphate, hydrogen peroxide can be enumerated; As reductive agent, pyrosulphite hydrogen sodium, sodium bisulfite, L-AA sodium, rongalite etc. can be enumerated.As oil-soluble polymerization initiator, such as di-isopropyl peroxydicarbonate (IPP), benzoyl peroxide, DBP, Diisopropyl azodicarboxylate (AIBN) etc. can be enumerated.For the consumption of polymerization starter, relative 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 seeding polymerization, can enumerate such as: the halohydrocarbon such as chloroform, tetracol phenixin; The thio-alcohols such as n-dodecyl mercaptan, tertiary lauryl mercaptan, n octylmercaptan; Etc..For the consumption of chain-transfer agent, relative to every 100 mass parts acrylic monomer mixtures, be generally 0 ~ 5.0 mass parts.
In the manufacture of vinylformic acid of the present invention-fluorine composite polymer particle, for the ratio of VDF based polymer particle with the acrylic monomer mixture containing above-mentioned (b1) ~ (b3), relative to VDF based polymer particle 100 mass parts, acrylic monomer mixture is more than 100 mass parts.Further, good from the viewpoint of film-forming properties during application, relative to VDF based polymer particle 100 mass parts, acrylic monomer mixture is more than more than 110 mass parts, especially 150 mass parts.
The invention still further relates to the aqueous dispersion containing 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.Be more preferably 50nm ~ 250nm.If particle diameter is less than 50nm, then vinylformic acid-fluorine the composite polymer particle of aqueous dispersion concentration usage range that is more than 30 quality % time aqueous dispersion viscosity enlarge markedly, coating equalization can be hindered.On the other hand, if more than 300nm, then the sedimentation stability of obtained aqueous dispersion has the tendency of reduction, and causes the rising of the minimum film-forming temperature of vinylformic acid-fluorine composite polymer particle sometimes.
From the aspect of coating applications, 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 %, is more preferably 35 quality % ~ 50 quality %.
The aqueous dispersion of vinylformic acid of the present invention-fluorine composite polymer particle can be used in various uses with various form.
Such as, the formed material of the film forming component of various coating composition, film or sheet material can be exemplified, and binder compositions, ink composition etc., but be not limited to these.When using as aqueous paint composition, even if when utilizing forced drying to carry out film forming, the cementability with base material also can be improved.
The aqueous dispersion of vinylformic acid of the present invention-fluorine composite polymer particle manufactures by above-mentioned seeded polymerization.
The aqueous dispersion of vinylformic acid of the present invention-fluorine composite polymer particle suitably manufactures by the manufacture method containing following operation: (methyl) acrylate (b1) that interpolation and VDF based polymer (A) are consistency in the aqueous liquid dispersion comprising the particle be made up of VDF based polymer (A), (methyl) acrylate (b2) being non-compatibility with VDF based polymer (A), there is (methyl) acrylic monomer (b3) by heating the crosslinkable groups that can be cross-linked, 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 containing 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 existing known additive and blending ratio in addition.Such as, as the concentration of vinylformic acid-fluorine composite polymer particle, carry out selecting in the scope of such as 10 quality % ~ 60 about quality %.
In addition, when preparation adds the aqueous paint composition having pigment, the pigment dispersion (this pigment dispersion utilizes the colo(u)rant dispersion machines such as sand mill to disperse to form to the pigment such as water, titanium dioxide, defoamer, pigment dispersing agent, pH adjusting agent etc. in advance) of predetermined amount and the film adjuvants of predetermined amount is uniformly mixed in the aqueous liquid dispersion of vinylformic acid-fluorine composite polymer particle, the thickening material adding predetermined amount afterwards mixes, and suitably adds the additive of other necessity.When the aqueous paint composition of pigment is not added in preparation, in the aqueous liquid dispersion of vinylformic acid-fluorine composite polymer particle, add water, film adjuvants, defoamer, thickening material, pH adjusting agent, additive required for other as required, undertaken being uniformly mixed by known method.
As the additive of coating applications, film adjuvants, frostproofer, pigment, weighting agent, pigment dispersing agent, defoamer, flow agent, stream change adjusting agent, sanitas, UV light absorber, antioxidant, matting agent, lubricant, vulcanizing agent etc. can be added as required.
Base material as application aqueous paint composition of the present invention is not particularly limited, and is applicable to following base material: the metal system base materials such as melting coated steel sheet, stainless steel plate, aluminium steel plate; The pottery system base materials such as slate, ceramic industry system sizing (サ イ ジ Application グ) material, foamed concrete, glass; The plastic basis materials such as polychlorovinyl sheet material, PET film, polycarbonate, acrylic film.As melting coated steel sheet, such as hot-dip galvanized steel sheet, molten zinc plating-aluminium-magnesium alloy steel plate, melting can be enumerated and aluminize-zinc steel plate, melting Aludip etc.
As method aqueous paint composition of the present invention being coated on various base material, existing known method and condition can be adopted.Such as, spraying, roller coat, flow coat can be adopted on base material; Based on the coating process such as application of roller, bristle.
Drying means after application is not particularly limited, can seasoning at ambient temperature, also time of drying can be spent carry out the drying under low temperature (5 DEG C ~ 60 DEG C), and for coating composition of the present invention, even if carry out the forced drying under normal temperature ~ 200 DEG C, particularly 60 DEG C ~ 200 DEG C (base material temperature), the film of weathering resistance, water tolerance, intensity, base material adaptation, film-forming properties excellence also can be formed.Time required for forced drying is generally 3 seconds ~ 10 minutes.
As coating composition, the coating composition etc. of coatings composition, office machine or kitchen appliance class inside and outside exterior coating composition, electric product in the weatherability coating composition of weatherability coating composition, particularly building materials, automobile can be exemplified, good from the viewpoint of weathering resistance weather resistance, particularly advantageously can be applied to building materials weatherability coating composition.
Embodiment
Next based on embodiment, the present invention will be described, but the present invention is not limited in these embodiments.
Embodiment 1
(manufacture of the aqueous liquid dispersion of VDF based polymer (A))
Aqueous liquid dispersion (the solid component concentration 45.5 quality %) 659.3g of VdF/TFE/CTFE multipolymer (=72.1/14.9/13 (% by mole)) (VTC) particle as VDF based polymer particle is added in the removable flask of glass system of 2.0L volume, add Newcol707SF (the Japanese emulsifying agent Co., Ltd. manufactures) 37.1g and water 56.8g as emulsifying agent wherein, abundant mixing, prepares aqueous liquid dispersion.
Next, in the glass flask of 1.0L volume, 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 %), prepare monomer solution.
Temperature in removable flask is warming up to 80 DEG C, utilizes within 3 hours, added to by the monomer solution of whole amount in the aqueous liquid dispersion of above-mentioned VDF/TFE/CTFE copolymer pellet.Further, added ammonium persulphate (APS) (the 1 quality % aqueous solution) 41.1g every 30 minutes 7 times in the same time-division dripping monomer solution, be polymerized simultaneously.After 5 hours, reaction soln is cooled to room temperature in polymerization beginning and carrys out termination reaction, obtain the aqueous dispersion (solid component concentration 52.0 quality %) of vinylformic acid-fluorine composite polymer particle.Acrylic portion in the vinylformic acid obtained-fluorine composition polymer consist of MMA/2EHA/MAA/GMA=71.2/19.2/4.1/5.5 (quality % than).In addition, the mass ratio (VDF/ vinylformic acid) of the VDF based polymer part in the vinylformic acid obtained-fluorine composite polymer particle and acrylic portion is 50/50.
(preparation of water-borne coatings)
Use the aqueous liquid dispersion of the vinylformic acid-fluorine composition polymer obtained, utilize triethylamine to be neutralized to pH7.5.Film coalescence aid (diethylene adipate) is added in aqueous liquid dispersion with 5 quality %/solids component, utilizes Three-OneMotor to carry out stirring for 30 minutes, prepare Clear paint use coating composition.
(making of one coat application and test film)
Utilize scraping strip coating machine to be coated with by obtained aqueous paint composition and be filled to Al-Zn coated steel (Japanese Testpanel Co., Ltd. manufactures), at 140 DEG C, carry out drying under the condition of 7 seconds, produce the test film of the transparent coating with thickness 4 μm.
The test film obtained is used 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 % is dropped to test film.After dropping, evaluate to the time produced bubble with following 5 grades.1: produce bubble within 2 minutes after the drop wise addition; 2: after dripping, between 2 ~ 5 minutes, produce bubble; 3: after dripping, between 5 ~ 10 minutes, produce bubble; 4: after dripping, between 10 ~ 15 minutes, produce bubble; 5: produce more than after dripping latter 15 minutes or do not produce bubble.
(outward appearance)
(metewand)
By whether the test film made by visual judgement having agglutinator, 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 within 5; × represent that drum, crackle etc. are more than 5.
(initial stage adaptation)
Placing after 24 hours after dried coating film, is that benchmark carries out checker belt stripping test to test film with JISD0202-1988.Use cellophane tape (" CT24 ", meter Qi Bang Co., Ltd. manufacture), utilize finger belly that it is closely sealed on film, peel off afterwards.Judge to represent without the number of the grid (マ ス order) peeled off in 25 lattice (マ ス).
(weathering resistance)
(test method)
Made test film is inserted in accelerated weathering test machine, use ATR method (Attenuated Total Reflectance) to measure the infrared spectroscopy spectrum after 322 hours.Utilize the C-H stretching vibration (1700cm from acrylate
-1near) rate of fall-off that absorbs to be to evaluate weather resisteant.
Accelerated weathering test machine (SUV): SuperUVTester, Iwasaki Electric Co., Ltd. manufacture
Testing campaign: pure water spraying (every 10 seconds) 1 hour → exposure 11 hours (blackboard temperature 63 DEG C, relative humidity 70%) → condensation 11 hours (blackboard temperature 30 DEG C, relative humidity 100%).Using this circulation as 1 circulation (23 hours).
Test period: 322 hours (14 circulations)
(metewand)
ATR method (Attenuated Total Reflectance) is used to carry out infrared spectroscopy spectrometry to the test film surface element after test.The test film of test film before accelerated weathering test with test rear (after 322 hours) is compared.To 1150cm
-1neighbouring C-F stretching vibration absorbs carries out stdn, confirms 1700cm
-1the neighbouring C-H stretching vibration from acrylate is absorbed in before and after test whether have decay.Zero represents 1700cm compared with before test
-1what the neighbouring C-H stretching vibration from acrylate absorbed decays within 10%; △ represents that decay is greater than 10% and is within 25%; × represent that decay is greater than 25%.
ATR measures: use the FT-IRSpectrometerSpectorum100 that PerkinElmer society manufactures
(making of clear finish (ト ッ プ Network リ ア) application and test film)
In Al-Zn coated steel (Japanese Testpanel society manufactures) upper primer coating: great Jin society manufactures (Zeffle hides hot base coat), intermediate coat: great Jin society manufactures (Zeffle hides hot base coat), obtain coated plate, use the scraping strip coating machine aqueous paint composition that application obtains on this coated plate, carry out drying in 1 day, produce the test film of the transparent coating with thickness 10 μm.
(initial stage closely sealed test)
Be that benchmark carries out checker belt stripping test to test film with JISD0202-1988.Use cellophane tape (" CT24 ", meter Qi Bang Co., Ltd. manufacture), utilize finger belly that it is closely sealed on film, peel off afterwards.Judge to represent without the grid number peeled off in 25 lattice.
(initial stage water resistant test)
By obtained test film immersion process 1 day at 23 DEG C, carry out drum (swollen れ) (JISK5600-8-2), crackle (JISK5600-8-4) after taking-up immediately, peeled off the evaluation of (JISK5600-8-5) grade.
(secondary fitness test)
In addition, taking out after immersion process, after carrying out drying in 1 day, is that benchmark carries out checker belt stripping test with JISD0202-1988 at 23 DEG C.Use cellophane tape (" CT24 ", meter Qi Bang Co., Ltd. manufacture), utilize finger belly that it is closely sealed on film, peel off afterwards.Judge to represent without the number of the grid peeled off in 25 lattice.
(playing drum)
Play the metewand of drum grade (JISK5600-8-2)
Density is divided into grade 0 ~ 5 (density little be 0), and size is divided into grade S1 ~ S5 (size of S1 is little), such as, be recited as 2 (S1).
(crackle)
The metewand of crackle grade (JISK5600-8-4)
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), such as, be recited as 2 (S1) b.
(peeling off)
Peel off the metewand of grade (JISK5600-8-5)
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), such as, be recited as 2 (S1) a.
(general water resistant test)
At 23 DEG C, immersion process in 6 days carried out to test film, after taking-up, carried out drum (JISK5600-8-2), crackle (JISK5600-8-4) immediately, peel off the evaluation of (JISK5600-8-5) grade.
(secondary fitness test)
In addition, taking out after immersion process, after carrying out drying in 1 week, is that benchmark carries out checker belt stripping test with JISD0202-1988 at 23 DEG C.Use cellophane tape (" CT24 ", meter Qi Bang Co., Ltd. manufacture), utilize finger belly that it is closely sealed on film, peel off afterwards.Judge to represent without the number of the grid peeled off in 25 lattice.
(weathering resistance)
Made test film is inserted in accelerated weathering test machine, carry out the mensuration of gloss number, L value, a value, b value every certain circulation.Calculate gloss retention by its result, the weather resisteant of film is evaluated.
Accelerated weathering test machine (SUV): SuperUVTester, Iwasaki Electric Co., Ltd. manufacture
Testing campaign: pure water spraying (every 10 seconds) 1 hour → exposure 11 hours (blackboard temperature 63 DEG C, relative humidity 70%) → condensation 11 hours (blackboard temperature 30 DEG C, relative humidity 100%).Using this circulation 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 seeding polymerization similarly to Example 1, obtain vinylformic acid-fluorine composition polymer respectively.
Use the aqueous liquid dispersion of the vinylformic acid-fluorine composite polymer particle obtained, prepare Clear paint use coating composition similarly to Example 1, form film similarly to Example 1, make test film, various characteristic is studied.The results are shown in table 1.
Comparative example 1
As acrylic acid polymer acrylic monomer mixture, use the comparison monomer mixture of MMA/n-BA/AA=98.0/1.0/1.0 (quality % ratio), in addition, carry out seeding polymerization similarly to Example 1, obtain comparing with vinylformic acid-fluorine composition polymer.Acrylic portion consist of MMA/n-BA/AA=98.0/1.0/1.0 (quality % than).In addition, in the vinylformic acid obtained-fluorine composite polymer particle, the mass ratio (VDF/ vinylformic acid) of VDF based polymer part and acrylic portion is 70/30.
Use the aqueous liquid dispersion of the vinylformic acid-fluorine composite polymer particle obtained, prepare Clear paint use coating composition similarly to Example 1, form film similarly to Example 1, make test film, various characteristic 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
Table 1
As shown in Table 1, the vinylformic acid-fluorine composition polymer containing composition (b1), composition (b2), composition (b3) makes to be improved with the adaptation of base material.
Embodiment 5
As VDF based polymer particle, use the aqueous liquid dispersion (solid component concentration 10.0 quality %) of VdF/TFE multipolymer (=80/20 (% by mole)) (VT) particle, in addition, carry out seeding polymerization similarly to Example 3, obtain vinylformic acid-fluorine composition polymer.
Use the aqueous liquid dispersion of the vinylformic acid-fluorine composite polymer particle obtained, prepare Clear paint use coating composition similarly to Example 1, form film similarly to Example 1, make test film, various characteristic is studied.The results are shown in table 2.
Embodiment 6
As VDF based polymer particle, use the aqueous liquid dispersion (solid component concentration 10.0 quality %) of the particle of VdF/HFP multipolymer (=91/9 (% by mole)) (VH), in addition, carry out seeding polymerization similarly to Example 3, obtain vinylformic acid-fluorine composition polymer.
Use the aqueous liquid dispersion of the vinylformic acid-fluorine composite polymer particle obtained, prepare Clear paint use coating composition similarly to Example 1, form film similarly to Example 1, make test film, various characteristic is studied.The results are shown in table 2.
Table 2
As shown in Table 2, the vinylformic acid-VDF system fluorine composition polymer containing composition (b1), composition (b2), composition (b3) makes to be improved with the adaptation of base material.
Claims (6)
1. an aqueous paint composition, it contains aqueous dispersion, this aqueous dispersion contains vinylformic acid-fluorine composite polymer particle, this vinylformic acid-fluorine composite polymer particle is the vinylformic acid-fluorine composite polymer particle be made up of vinylidene fluoride polymer (A) and crosslinkable acrylic based polymer (B)
Described vinylidene fluoride polymer (A) is containing at least one fluoroolefin unit be selected from the group that is made up of tetrafluoroethylene units, R 1216 unit and trifluorochloroethylene unit and containing vinylidene fluoride units as structural unit;
Described crosslinkable acrylic based polymer (B) containing with this vinylidene fluoride polymer (A) (methyl) acrylic ester unit (b1) that is consistency, with this vinylidene fluoride polymer (A) be non-compatibility (methyl) acrylic ester unit (b2) and (methyl) acrylic monomer unit (b3), described (methyl) acrylic monomer unit (b3) has by heating the crosslinkable groups that can be cross-linked;
Wherein, vinylidene fluoride polymer (A)/crosslinkable acrylic based polymer (B) is 10/90 ~ 90/10 by quality ratio,
(methyl) acrylic ester unit (b2) of described non-compatibility is cyclohexyl methacrylate unit.
2. aqueous paint composition as claimed in claim 1, wherein, vinylidene fluoride polymer (A) is containing tetrafluoroethylene units and trifluorochloroethylene unit.
3. aqueous paint composition as claimed in claim 1, wherein, vinylidene fluoride polymer (A) is vinylidene fluoride/tetrafluoroethylene copolymer.
4. aqueous paint composition as claimed in claim 1, wherein, vinylidene fluoride polymer (A) is vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer.
5. aqueous paint composition as claimed in claim 1, wherein, vinylidene fluoride polymer (A) is vinylidene fluoride/hexafluoropropylene copolymer.
6. the aqueous paint composition as described in any one of Claims 1 to 5, wherein, consistency (methyl) acrylic ester unit (b1) to be (methyl) acrylic acid carbonatoms be 1 ~ 4 chain-like alkyl ester units.
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| JP6222458B2 (en) * | 2013-10-01 | 2017-11-01 | Jsr株式会社 | Paint composition, paint and painted body |
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| 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 |
| US11859075B2 (en) | 2017-12-20 | 2024-01-02 | Daikin Industries, Ltd. | Core-shell type particle, dispersion and powder |
| WO2019170694A1 (en) | 2018-03-08 | 2019-09-12 | Solvay Sa | A process for the preparation of a solid polymer electrolyte useful in batteries |
| US20210070973A1 (en) * | 2018-03-30 | 2021-03-11 | Dai Kin Industries, Ltd. | Aqueous dispersion, coating film, coated article, and method for producing aqueous dispersion |
| JP2022013956A (en) * | 2018-10-29 | 2022-01-19 | Ａｇｃ株式会社 | Aqueous coating composition and coated article |
| WO2020105671A1 (en) * | 2018-11-22 | 2020-05-28 | 東レ・ファインケミカル株式会社 | Fluorine-containing polymer particles |
| JP2024519285A (en) * | 2021-04-19 | 2024-05-10 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Process for Producing Partially Fluorinated Polymers - Patent application |
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