CN1238388C - Fluorine contained multipolymer and coating composition - Google Patents
Fluorine contained multipolymer and coating composition Download PDFInfo
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- CN1238388C CN1238388C CN 03136084 CN03136084A CN1238388C CN 1238388 C CN1238388 C CN 1238388C CN 03136084 CN03136084 CN 03136084 CN 03136084 A CN03136084 A CN 03136084A CN 1238388 C CN1238388 C CN 1238388C
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Abstract
To provide a curable fluorine-containing copolymer excellent in compatibility with other compounds in a coating composition and giving a coating film excellent in weather resistance, hardness, and stain resistance, and to provide the coating composition.The fluorine-containing copolymer comprises (a) a constitutional unit of tetrafluoroethylene, (b) a constitutional unit of a non-aromatic vinyl ester monomer free from hydroxy group and carboxy group, and (c) a constitutional unit of a hydroxy group-containing vinyl monomer free from aromatic group and carboxy group, and further if necessary (d) a constitutional unit of an aromatic group-containing monomer free from hydroxy group and carboxy group, (e) a constitutional unit of a carboxy group-containing monomer free from hydroxy group and aromatic group, and (f) a constitutional unit of another monomer. In the fluorine-containing copolymer, (a) is at least 20 mole% and not more than 49 mole%, (b) is at least 25 mole% and not more than 69.9 mole%, and (c) is at least 8 mole% and not more than 30 mole%, and further (d) is at least 2 mole% and not more than 15 mole%, (e) is at least 0.1 mole% and not more than 2.0 mole%, and (f) is 0 mole% or not more than 10 mole%. The coating composition comprises the fluorine-containing copolymer.(C)2004,JPO&NCIPI.
Description
Technical field
The present invention relates to a kind of novel fluorinated copolymer and contain the coating composition of described fluorinated copolymer.
Background technology
In the prior art, the bond energy height of fluorinated copolymer intramolecularly C-F key, molecular polarity is little, so its weathering resistance, resistance, water and oil-resistant, stain resistance are good, of many uses.Developed in recent years and dissolved in ordinary organic solvents and at room temperature crosslinked fluorine resin paints.For example: the clear 57-34107 communique of TOHKEMY, the multipolymer that discloses fluoroolefin, alkyl vinyl ether and hydroxyalkyl Vinyl Ether is as the coating resin with weathering resistance.In addition, the clear 61-275311 communique of TOHKEMY, multipolymers such as fluoroolefin, vinyl acetate, alkyl vinyl ether, hydroxyalkyl Vinyl Ether are disclosed with 62-7767 communique, the flat 3-121107 communique of TOHKEMY, the flat 6-184243 communique of TOHKEMY and CN1244556 communique.
Yet the TFE copolymer in the above-mentioned multipolymer contains a large amount of unit based on alkyl vinyl ether, so the shortcoming of multipolymer existence and acrylic resin, solidifying agent and dispersion agent intermiscibility difference.Chloride chloro trifluoro-ethylene copolymer intermiscibility is good, but weathering resistance and heat-resisting xanthochromia are poor.In addition, contain the content height of the polymkeric substance of tetrafluoroethylene and aromatics vinyl acetate because of the aromatic vinyl ester, therefore long-term weathering resistance is poor.
Summary of the invention
After inventors of the present invention have carried out research carefully at the problems referred to above, propose by using not chloride fluoroolefin, vinyl acetate, need not or only use a spot of alkyl vinyl ether as polymer monomers, select for use specific non-aromatics vinyl acetate and the polymer monomers that contains functional group to achieve the above object especially.
Promptly the present invention relates to following fluorinated copolymer, described fluorinated copolymer is made of following structural unit: (a) tetrafluoroethylene (TFE) structural unit; (b) the non-aromatics vinyl acetate monomer structural unit of hydroxyl and carboxyl (being designated hereinafter simply as " non-aromatic vinyl acetate monomer unit ") not; (c) do not contain aryl and carboxyl and contain the vinyl monomer structural unit (being designated hereinafter simply as " ethylene monomer unit of hydroxyl ") of hydroxyl and (f) other monomer structure unit.The content of each structural unit is respectively: (a) greater than 20mol%, less than 49mol%, (b) greater than 25mol%, less than 69.9mol%, (c) greater than 8mol%, less than 30mol%, (f) greater than 0mol%, less than 10mol%.Described fluorinated copolymer abbreviates " fluorinated copolymer 1 " as.
In addition, the invention still further relates to following fluorinated copolymer, described fluorinated copolymer is made of following structural unit: (a) TFE unit; (b) non-aromatics vinyl acetate monomer unit; (c) ethylene monomer unit of hydroxyl; (d) not hydroxyl and carboxyl and contain the monomer structure unit (being designated hereinafter simply as " monomeric unit that contains aryl ") of aryl and (f) other monomer structure unit.The content of each structural unit is respectively: (a) greater than 20mol%, less than 49mol%, (b) greater than 25mol%, less than 69.9mol%, (c) greater than 8mol%, less than 30mol%, (d) greater than 2mol%, less than 15mol%, (f) greater than 0mol%, less than 10mol%.Described fluorinated copolymer abbreviates " fluorinated copolymer 2 " as.
In addition, the invention still further relates to following fluorinated copolymer, described fluorinated copolymer is made of following structural unit: (a) TFE unit; (b) non-aromatics vinyl acetate monomer unit; (c) contain the ethylene monomer unit of hydroxyl; (e) not hydroxyl and aryl and contain the monomer structure unit (being designated hereinafter simply as " carboxylic monomeric unit ") of carboxyl and (f) other monomer structure unit.The content of each structural unit is respectively: (a) greater than 20mol%, less than 49mol%, (b) greater than 25mol%, less than 69.9mol%, (c) greater than 8mol%, less than 30mol%, (e) greater than 0.1mol%, less than 2.0mol%, (f) greater than 0mol%, less than 10mol%.Described fluorinated copolymer abbreviates " fluorinated copolymer 3 " as.
In addition, the invention still further relates to following fluorinated copolymer, described fluorinated copolymer is made of following structural unit: (a) TFE unit; (b) non-aromatics vinyl acetate monomer unit; (c) contain the ethylene monomer unit of hydroxyl; (d) contain the monomeric unit of aryl; (e) carboxylic monomeric unit and (f) other monomer structure unit.The content of each structural unit is respectively: (a) greater than 20mol%, less than 49mol%, (b) greater than 25mol%, less than 69.9mol%, (c) greater than 8mol%, less than 30mol%, (d) greater than 2mol%, less than 15mol%, (e) greater than 0.1mol%, less than 2.0mol%, (f) greater than 0mol%, less than 10mol%.Described fluorinated copolymer abbreviates " fluorinated copolymer 4 " as.
Non-aromatics vinyl acetate monomer unit (b) in the above-mentioned fluorinated copolymer 1～4 (below do not have the special section timesharing to claim " fluorinated copolymer ") preferably has the alkanecarboxylic acid vinyl acetate structural unit or the vinyl-acetic ester structural unit of side chain.
The invention still further relates to the coating composition that contains fluorinated copolymer 1～4.Described coating composition can contain acrylic resin.In addition, be mixed into good curable coating composition with solidifying agent.
Embodiment
Fluorinated copolymer 1 of the present invention is made of the vinyl monomer (c) of TFE unit (a), non-aromatics vinyl acetate monomer (b), hydroxyl, and with other monomer structure unit as the arbitrary structures unit.
TFE unit (a) has gives effect to fluorinated copolymer the various characteristics that contains fluoroethylene resin, for example: weathering resistance, solvent resistance, thermotolerance and stain resistance etc.Be limited to 20mol% under it, preferred 30mol%, more preferably 40mol%, especially preferably 42mol%.Be limited to 49mol% on it, preferred 47mol%.Be difficult to obtain the characteristic of fluorine resins such as weathering resistance when being lower than 20mol%.
One or more that the monomer of non-aromatics vinyl acetate unit (b) comprises vinyl-acetic ester, propionate, vinyl butyrate, isopropylformic acid vinyl acetate, new vinyl acetate acid, vinyl caproate, the alkanecarboxylic acid vinyl acetate that side chain is arranged, vinyl laurate, stearic acid vinyl ester, hexahydrobenzoic acid vinyl acetate etc. are provided.Above-mentioned monomer is the non-aromatics monomer of hydroxyl and carboxyl not, has the effect of other composition such as acrylic resin, solidifying agent and the dispersion agent intermiscibility of improvement and multipolymer and coating composition with the fluorinated copolymer preparation coating composition of gained.Consider that from good weathering resistance, intermiscibility and cheap aspect particularly preferred non-aromatics vinyl acetate monomer is alkanecarboxylic acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, hexahydrobenzoic acid vinyl acetate, the vinyl-acetic ester that side chain is arranged.Wherein, consider from the resistance aspect, preferred non-aromatics vinyl carboxylates, special optimization acid contains carbon number greater than 6 vinyl carboxylates, and further the optimization acid contains carbon number greater than 9 vinyl carboxylates.The upper limit that carboxylic acid contains carbon number in the vinyl carboxylates is lower than 20, preferably is lower than 15.Concrete example most preferably has the alkanecarboxylic acid vinyl acetate of side chain.
Be limited to 25mol% under the content of unit (b), preferred 30mol%; On be limited to 69.9mol%, preferred 60mol%, more preferably 43mol%, preferred especially 40mol%.When being lower than 30mol%, poor with the intermiscibility of general mixture acrylic resin, solidifying agent and the dispersion agent of coating.
Provide the monomeric unit (c) of hydroxyl to be not carboxylic non-aromatics monomer, for example formula (I):
CH
2＝CHR
1 (I)
(in the formula, R
1Be usefulness-OR
2Or-CH
2OR
2(R
2Be hydroxyl alkyl) the hydroxyalkyl Vinyl Ether or the hydroxyalkyl aryl ethers etc. of expression.R
2Example be the C that is connected with 1～3 hydroxyl
1～8The straight or branched alkyl, and preferably be connected with 1 hydroxyl.Above-mentioned example comprises one or more of 2-hydroxyethyl Vinyl Ether, 3-hydroxyethyl Vinyl Ether, 2-hydroxypropyl Vinyl Ether, 2-hydroxy-2-methyl propyl vinyl ether, 4-hydroxyl butyl vinyl ether, 4-hydroxy-2-methyl butyl vinyl ether, 5-hydroxyl amyl group Vinyl Ether, 6-hydroxyl hexyl Vinyl Ether, 2-hydroxyethyl aryl ethers, 4-hydroxyethyl aryl ethers, glycerine list aryl ethers etc.Wherein, preferred 4-hydroxyl butyl vinyl ether and 2-hydroxyethyl Vinyl Ether).
Described hydroxyl ethylene monomer unit (c) has the effect that improves coating processibility, shock-resistance and stain resistance, and described coating is made with fluorinated copolymer.
Be limited to 8mol% under the content of unit (c), preferred 10mol%, more preferably 15mol%; On be limited to 30mol%, preferred 20mol%.When being lower than 8mol%, coating hardness and the poor solvent resistance of utilizing described multipolymer to make.
Fluorinated copolymer 1 is (a)+(b)+(c) (can contain multiple multipolymer in each unit) substantially, can also contain the possible monomeric unit (f) of other following multipolymer of 10mol%.The possible monomeric unit (f) of other multipolymer is above-mentioned (a) and (b), (c), contains aryl monomeric unit (d) and contain carboxylic monomer unit (e) monomeric unit in addition.
Provide the monomer of the possible monomeric unit (f) of other multipolymer to comprise alkyl vinyl ether such as ethylene methacrylic ether, ethyl vinyl ether; Fluorine-free alkene such as ethene, propylene, n-butene and iso-butylene.
Copolymerization amount in unit (f) is lower than 10mol%, preferred 5mol%, more preferably 4mol%.For example: can use alkyl vinyl ether as described optional member (f), but when its ratio in multipolymer is too much, as previously mentioned, the intermiscibility variation of described multipolymer and acrylic resin, solidifying agent and dispersion agent.
Fluorinated copolymer 2 of the present invention contains unit (a), unit (b) and unit (c), and contains aryl monomeric unit (d) and be essential structural unit, and unit (f) is optional member.The explanation of fluorinated copolymer 1 is applicable to unit in addition, unit (d).
Unit (d) is for containing the not carboxylic material of aryl, and this point is different with other unit.Contain the characteristic that aryl unit (d) is given fluorinated copolymer high brightness and high intermiscibility.Example particularly is as: M-nitro benzoic acid vinyl acetate, to one or more of M-nitro benzoic acid vinyl acetate monomers such as tertiary butyl M-nitro benzoic acid vinyl acetate, especially preferably to tertiary butyl M-nitro benzoic acid vinyl acetate, and further preferred M-nitro benzoic acid vinyl acetate.
Contain under the ratio of aryl monomeric unit (d) and be limited to 2mol%, preferred 4mol%; On be limited to 15mol%, preferred 10mol%, more preferably 8mol%.When being higher than 15mol%, the weathering resistance of gained fluorinated copolymer is poor.
Fluorinated copolymer 3 of the present invention contains unit (a), unit (b) and unit (c), and contains carboxylic monomer unit (e) and be essential structural unit, and unit (f) is optional member.The explanation of fluorinated copolymer 1 is applicable to unit in addition, unit (e).
Unit (e) is for containing the not material of hydroxyl and aryl of carboxyl, and this point is different with other unit.When the fluorinated copolymer that contains carboxylic monomer unit (e) is mixed with coating composition, can improve fluorinated copolymer to dispersiveness, solidification reactivity and the pigment of water dispersiveness to copolymer solution, can also improve the gained coating brightness, hardness and with contact of primer etc.
The example that contains carboxylic monomer unit (e) has and contains carboxyl vinyl monomer etc. shown in formula (II) or the formula (III).
(in the formula, R
3, R
4And R
5Identical or different, be respectively hydrogen atom, alkyl, carboxyl or ester group, n is 0 or 1);
(in the formula, R
6And R
7Identical or different, be respectively saturated or undersaturated straight chain or cyclic hydrocarbon group, n is 0 or 1, m is 0 or 1)
Object lesson comprises one or more of vinylformic acid, methylacrylic acid, ethene acetate, Ba Dousuan, TRANSCINNAMIC ACID, 3-aryloxy propionic acid, methylene-succinic acid, methylene-succinic acid monoesters, toxilic acid, toxilic acid monoesters, maleic anhydride, fumaric acid, fumaric acid monoesters, phthalandione vinyl acetate, pyromellitic acid vinyl acetate etc.Wherein, the Ba Dousuan of preferred single polymerizability, methylene-succinic acid, toxilic acid, toxilic acid monoesters, fumaric acid, fumaric acid monoesters and 3-aryloxy propionic acid.
Contain under the ratio of carboxylic monomer unit (e) and be limited to 0.1mol%, preferred 0.4mol%; On be limited to 2.0mol%, preferred 1.5mol% is higher than curing speed and useful life phase that 2.0mol% is unfavorable for coating.
Fluorinated copolymer 4 of the present invention contains unit (a), unit (b), unit (c) and unit (d), and unit (e) be essential structural unit, and unit (f) is optional member.For bringing into play above-mentioned every function, the total amount that the ratio of these structural units is chosen in the above-mentioned scope reaches 100mol%.
With the tetrahydrofuran (THF) is elutriant, and the number-average molecular weight scope that records fluorinated copolymer of the present invention with gel permeation chromatography (GPC) is 1,000～1,000,000, preferred 3,000～50,000, and (DSC) records glass transition temp (2 with differential scanning calorimeter
NdRun) be 10～60 ℃, preferred 20～40 ℃.When molecular weight was too small, the coating hardness of preparation coating composition gained was not enough; When molecular weight was excessive, it is big that the viscosity of composition becomes, and is difficult to handle.
Fluorinated copolymer of the present invention normally will offer the unitary monomer of said structure and make by emulsification, suspension or solution polymerization process generation polymerization with polymer solvent or polymerization starter.Polymerization temperature in any polymerization process is generally 0～150 ℃, preferred 5～95 ℃; Polymerization pressure is generally 0.1～10M Pa G (1～100kgf/cm
2G).
The polymer solvent of emulsion polymerization method is a water, and the solvent of suspension polymerization comprises water, the trimethyl carbinol, 1,1,2-three chloro-1,2,2-Halothane and 1,2-two chloro-1,1,2, the mixture of 2-Tetrafluoroethane or above-mentioned substance.The solvent of solution polymerization process comprises ester classes such as methyl acetate, ethyl acetate, propyl acetate, butylacetate; Ketones such as acetone, butanone and pimelinketone; Hydro carbons such as hexane, hexanaphthene, octane, nonane, decane, undecane, dodecane and mineral spirits; Aromatic hydrocarbons such as benzene,toluene,xylene, naphthalene and solvent naphtha; Alcohols such as methyl alcohol, ethanol, the trimethyl carbinol, Virahol, ethylene glycol monoalkyl ether; Ethers such as tetrahydrofuran (THF), tetrahydropyrans and dioxan and, dimethyl sulfoxide (DMSO) equal solvent and composition thereof.
Polymerization starter can be used persulfuric acid salts such as ammonium persulphate, Potassium Persulphate (can also and use with reductive agents such as S-WAT, Sodium Pyrosulfite, cobalt naphthenate and xylidines in case of necessity); The redox initiator class that oxygenant (for example ammonium peroxide and Potassium peroxide etc.), reductive agent (for example S-WAT etc.) and transition metal salt (for example ferric sulfate etc.) are formed; Diacyl peroxide such as acetyl pexoxide, benzoyl peroxide class; Dialkoxy carbonyl peroxides such as isopropoxy carbonyl superoxide, tert-butoxycarbonyl superoxide; Ketone peroxide classes such as butanone peroxide, pimelinketone superoxide; Hydrogen peroxide classes such as tertiary butyl hydrogen peroxide, isopropyl benzene hydrogen peroxide; Dialkyl peroxide classes such as two-tert-butyl peroxide, two-trimethylphenyl superoxide; Alkyl peroxyesters such as tert-butyl hydroperoxide acetic ester, tert-butyl hydroperoxide pivalate; 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2-methyl valeronitrile), 2,2 '-azo two (2-cyclopropyl propionitrile), 2,2 '-azo-bis-iso-dimethyl, 2,2 '-azo two [2-(methylol) propionitrile], 4,4 '-azo two azo compounds such as (4-cyaniding pentenoic acids).
In all polymerization processs, acidic substance such as hydrogen fluoride from monomer or polymkeric substance disengaging in the polymerization process make polymeric solution become acidity, therefore the gelation of polymkeric substance possibility can add inorganic salts such as sodium bicarbonate, yellow soda ash, saleratus, salt of wormwood, sodium phosphate, metal oxide and hydrotalcite in system; Organic amine and basic anion exchange resins such as diethylamine, dibutylamine, triethylamine, acidic substance such as hydrogen fluoride that neutralization breaks away from or hydrogenchloride.
As mentioned above, fluorinated copolymer of the present invention has multiple good characteristic respectively, can be with the variform widespread use.Particularly can be mixed with coating composition as coated component.
Coating composition can use with following form: be dissolved in the solution-based paint in the organic solvent, the forms such as curing composition that are dispersed in the powder-type composition of the aqueous dispersion type composition in the aqueous solvent, non-aqueous dispersion type dispersion, powdered and sneak into solidifying agent formation in above-mentioned substance.
As mentioned above, used solvent species and the condition restriction of fluorinated copolymer of the present invention greatly relaxed.The organic solvent that is applicable to fluorinated copolymer of the present invention comprises ester classes such as ethyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, acetate plug fine jade Suo Fu ester and propylene glycol methyl ether acetate; Ketones such as acetone, butanone, methyl iso-butyl ketone (MIBK), pimelinketone; Cyclic ethers such as tetrahydrofuran (THF), dioxan class; N, amidess such as dinethylformamide, N,N-dimethylacetamide; Aromatic hydrocarbons such as toluene, dimethylbenzene; Alcohols such as propylene glycol monomethyl ether; The mixed solvent of hydro carbons such as hexane, heptane and above-mentioned solvent etc.During the preparation organic solvent solution, the concentration of fluorinated copolymer is 5～95 weight %, preferred 10～70 weight %.
In addition, during preparation aqueous dispersion type composition, if necessary, make it to be distributed in the mixed solvent of water or water and hydrophilic solvent preferred 10～80 weight % of concentration with emulsifying agent.Hydrophilic solvent comprises methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, sec-butyl alcohol, tertiary amyl alcohol, 3-amylalcohol, octanol, 3-methyl-alcohols such as 3-methoxybutanol; Ether alcohol classes such as methyl plug fine jade Suo Fu, plug fine jade Suo Fu, sec.-propyl plug fine jade Suo Fu, butyl plug fine jade Suo Fu, diethylene glycol monomethyl ether; Ketones such as acetone, butanone, methyl second isobutyl ketone; Ethyl acetate, plug fine jade Suo Fu acetic ester, n-butyl acetate, isobutyl acetate, methyl plug fine jade Suo Fu acetic ester and acetate card must ester etc. ester class etc.
In the emulsifying agent, following material can be used as protective colloid and uses: alkylbenzene sulfonate, sulfonated alkyl naphathalene, higher fatty acid salt, alkyl phosphate salt, alkyl ether phosphate salt, phosphate ester salt, to anion surfactants such as fluoroalkyl soaps; Nonionogenic tensides such as alkylphenol ethylene oxide adduct, ethylene oxide-propylene oxide block copolymer etc.In addition, also comprise water-soluble high-molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, Natvosol, methylcellulose gum, hydroxypropylcellulose, sodium polyacrylate and ethene-copolymer-maleic anhydride.
Further, consider, can mix following material: dispersion agents (dispersion stabilizer) such as tripoly phosphate sodium STPP, Sodium hexametaphosphate 99 and sodium polyacrylate from operation or processing aspect; Wetting agents such as above-mentioned nonionogenic tenside; The tackifier such as water-soluble high-molecular compound that above-mentioned protective colloid is used; Silicone oil, mineral wet goods defoamer; Dibutyl phthalate, dioctyl phthalate, phthalandione butyl card must esters and softening agent or film coalescence aid such as methyl plug fine jade Suo Fu; With the titanium oxide is the common tinting material of representative; Common weighting agents such as lime carbonate, kaolin and silicon-dioxide; Common preservatives; Antiseptic-germicide; The pH regulator agent; The homopolymer or the multipolymer that also comprise Acrylic Acid Monomer, vinyl-acetic ester, vinylchlorid etc. in addition; Vinylformic acid-styrol copolymer, vinyl chloride vinyl acetate copolymer, vinyl-vinyl acetate copolymer, ethane-acetic acid ethyenyl ester-vinyl chloride copolymer etc.
Described aqueous dispersion type composition is applicable to normal temperature or heat-curing type coating etc.
During preparation powder-type composition, with fluorinated copolymer according to a conventional method, for example: make the powder that median size is 0.05～10 μ m with the beater type pulverizer.
Described powder-type composition is applicable to thermohardening type powder coating etc.
In addition, multipolymer of the present invention can with other mixed with resin, for example: contain or do not contain cinnamic (methyl) acrylic resin, polyester resin, melamine-formaldehyde resin, polyisocyanate esters resin, Resins, epoxy, vinyl chloride resin (for example vinyl chloride vinyl acetate copolymer etc.), ketone resin, petroleum resin etc., also comprise organic resins such as polyolefins muriate such as polyethylene or polypropylene; Inorganic resin such as silica gel or silicic acid; Can with fluorine resin outside one or more fluorine resins of the present invention (for example the homopolymer of tetrafluoroethylene or chlorotrifluoroethylene or its mix) with other monomeric multipolymer etc., but be not limited thereto.The fluorine resin of the present invention of relative 100 weight parts, the blending ratio of other resin are below 900 weight parts, below preferred 500 weight parts.Be limited to the necessary amounts that obtains the purpose characteristic down, by the kind decision of resin.When being acrylic polymers, usually more than 5 weight parts, more than preferred 10 weight parts.
In the above-mentioned resin, preferred especially intermiscibility is good, with acrylic polymers blended system, make gained coating brightness height, hardness height, finished product outward appearance good.
Acrylic polymers comprises coating material used in the prior art, homopolymer of the preferred especially acrylic acid C1 of (i) (methyl)～10 alkyl esters or multipolymer and (ii) side chain and/or main chain end have (methyl) acrylate copolymer of solidified nature functional group.
Above-mentioned (i) acrylic copolymer comprises the homopolymer or the multipolymer of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, 2-ethylhexyl (methyl) vinylformic acid, (methyl) butyl acrylate, (methyl) cyclohexyl acrylate etc., perhaps with can and the multipolymer of the vinyl unsaturated monomer of above-mentioned substance copolymerization.
Because when using above-mentioned inert solvent as polymer solvent, aspects such as intermiscibility at solvability, weathering resistance, binding property and the fluorine resin of solvent have good properties, so the homopolymer or the multipolymer of preferred (methyl) isobutyl acrylate, 2-ethylhexyl (methyl) vinylformic acid, (methyl) cyclohexyl acrylate etc., perhaps with can and the multipolymer of the vinyl unsaturated monomer of above-mentioned substance copolymerization.The homopolymer or the multipolymer that have (methyl) cyclohexyl acrylate etc. of good character particularly preferably in the aspects such as intermiscibility, resistance and water tolerance of the solvability of solvent, weathering resistance, binding property, fluorine resin, perhaps with can and the multipolymer of the vinyl unsaturated monomer of above-mentioned substance copolymerization.
In addition, the inert solvent in this specification sheets refers to it is the third organic solvent in the law of labour safety and health or the solvent suitable with it.Especially preferably human body and environment had good safety, and during spraying operation, counterdie, former film are difficult for producing detrimentally affect, promptly are difficult for producing the aliphatic solvents that contains of peeling or wrinkling, and aromatic hydrocarbon solvent content less than the solvent of 50 weight % as inert solvent.Polymer solvent can be aliphatic solvents or aromatic hydrocarbon solvent.Commercially available inert solvent comprises SW#310 (the kind oil Co., Ltd. of ball system, trade(brand)name); HAWS and LAWS (being Xie Er chemical company system, trade(brand)name); A SOLVENT (Nippon Oil Co., Ltd's system, trade(brand)name); EXXONNAPHTHA No.6, EXXON NAPHTHA No.5, EXXON NAPHTHANo.3, EXXSOL D40, EXXSOL D80 (being EXXON chemical company system, trade(brand)name); ISOPAR E, ISOPAR G (being Nippon Oil Co., Ltd's system, trade(brand)name); IPSOLVENT 1620, IP SOLVENT2028 (being bright dipping oil Co., Ltd. system, trade(brand)name) etc.
Vinyl unsaturated monomer that can copolymerization comprises (methyl) esters of acrylic acid that contains aryl, the α bit strip has (methyl) esters of acrylic acid of fluorine atom or chlorine atom, the fluoroalkyl that alkyl is replaced by fluorine atom (methyl) esters of acrylic acid, the ethene ethers, vinyl esters, aromatic vinyl monomers classes such as vinylbenzene, olefines such as ethene, propylene, iso-butylene, vinylchlorid, vinylidene chloride, fumaric acid diester class, maleic acid diester class and (methyl) vinyl cyanide etc.
Above-mentioned (ii) acrylic copolymer can be above-mentioned (i) the acrylate copolymer monomer of mentioning and monomeric multipolymer that contains solidified nature functional group.The monomer that contains solidified nature functional group comprises the monomer that contains hydroxyl, carboxyl, epoxy group(ing), amino etc.The concrete example of above-mentioned (ii) acrylic copolymer comprises that (methyl) hydroxyethyl acrylate, (methyl) vinylformic acid 2-hydroxypropyl ester, 2-hydroxyethyl Vinyl Ether, (methyl) vinylformic acid, Racemic glycidol (methyl) acrylate, (methyl) vinylformic acid 2-amino-ethyl ester, (methyl) vinylformic acid 2-aminopropyl ester etc. contain the multipolymer of the alkyl ester of the monomer of solidified nature functional group and 1～10 carbon atom of above-mentioned (methyl) vinylformic acid, but the multipolymer of above-mentioned substance and above-mentioned vinyl unsaturated monomer is not limited thereto.
The content of the alkyl ester of 1～10 carbon atom of (methyl) vinylformic acid was more than 5 weight % during the multipolymer (i) of the alkyl ester of 1～10 carbon atom of (methyl) vinylformic acid reached (ii), be preferably more than the 10 weight %, but from good solvent solubility, weathering resistance, water tolerance, resistance, with the aspects such as intermiscibility of fluorine resin, reaching aspects such as good binding property, weathering resistance, resistance sets out, preferred content is below 98 weight %, more preferably below 96 weight %.Especially when the alkyl ester of 1～10 carbon atom of (methyl) vinylformic acid is (methyl) cyclohexyl acrylate, the content of (methyl) cyclohexyl acrylate is more than 5 weight %, preferably more than 10 weight %, but from good solvent solubility, weathering resistance, binding property, aspects such as intermiscibility, water tolerance, resistance with fluorine resin, and well set out with aspects such as intermiscibility fluorine resin, pliabilities, preferred content is below 90 weight %, more preferably below 80 weight %.At this moment, from aspects such as good solvent solubility, resistance, binding propertys, but the vinyl unsaturated monomer of preferred copolymerization comprises (methyl) esters of acrylic acid that contains aryl, the α bit strip has (methyl) esters of acrylic acid of fluorine atom or chlorine atom, the fluoroalkyl that alkyl is replaced by fluorine atom (methyl) esters of acrylic acid, the ethene ethers, vinyl esters, aromatic vinyl monomers classes such as vinylbenzene, olefines such as ethene, propylene, iso-butylene, vinylchlorid, vinylidene chloride, fumaric acid diester class, maleic acid diester class and (methyl) vinyl cyanide etc.In addition, from aspects such as good binding property, resistance, solidified nature, the monomer that preferably contains solidified nature functional group comprises the monomer that contains hydroxyl, carboxyl, epoxy group(ing), amino etc.Preferred concrete example comprises that (methyl) hydroxyethyl acrylate, (methyl) vinylformic acid 2-hydroxypropyl ester, 2-hydroxyethyl Vinyl Ether, (methyl) vinylformic acid, Racemic glycidol (methyl) acrylate, (methyl) vinylformic acid 2-amino-ethyl ester, (methyl) vinylformic acid 2-aminopropyl ester etc. contain the monomer of solidified nature functional group.From excellent water tolerance, solvent solubility, resistance, weathering resistance, with aspect preferred contents such as the intermiscibility of fluorine resin, binding property below 50 weight %, more preferably 40 weight %, simultaneously also from aspects such as water tolerance, resistance, binding property, weathering resistances, preferred content more selects more than the 4 weight % more than 2 weight %.
The commercially available acrylic copolymer of acrylic copolymer (i) comprises (being Hitachi Chemical Co., Ltd.'s system, trade(brand)name) such as HITALOID 1005, HITALOID 1206, HITALOID 2330-60, HITALOID 4001, HITALOID 1628;-DIANAL LR-1065 ,-(being Mitsubishi Rayon Co., Ltd.'s system, trade(brand)name) such as DIANALLR-90; , PARALOID B-44, PARALOID A-21, PARALOID B-82 etc. (being Rohm ﹠ Haas Corp's system, trade(brand)name) and ELVACITE 2000 etc. (E.I.Du Pont Company's system, trade(brand)name).
Commercially available acrylic copolymer (ii) comprises (being Hitachi Chemical Co., Ltd.'s system, trade(brand)name) such as HITALOID 3004, HITALOID 3018, HITALOID 3046C, HITALOID6500B, HITALOID 6500; (being big Japanese ink and chemical industry Co., Ltd. system, trade(brand)name) such as ACRYDIC A810-45, ACRYDIC A814, ACRYDIC 47-540;-DIANAL LR-620 ,-DIANAL SS-1084 ,-(evenly being Mitsubishi Rayon Co., Ltd.'s system, trade(brand)name) such as DIANAL SS-792; OLESTER-Q166, OLESTER-Q185 etc. (being Mitsui Toatsu Chemicals, Ltd's system, trade(brand)name); HARIACLON 8360G-55, HARIACLON 8360HS-130, HARIACLON 8160 (being Harima Chemical K.K.'s system, trade(brand)name) etc.
The number-average molecular weight that GPC records acrylic polymers is 1,000～200,000, preferred 2,000～100,000.When the molecule quantitative change was big, solvent solubility had the tendency of reduction; When molecular weight diminished, the weathering resistance problem may appear.
Fluorinated copolymer of the present invention and also can disperse form such as thing to use with the mixture of acrylic polymers with above-mentioned organic solvent type composition, aqueous dispersion type composition, powder-type composition and non-aqueous dispersion type.
Fluorinated copolymer of the present invention and solidifying agent mixing energy prepare curable coating composition.Used solidifying agent is and the crosslinked compound that forms of the curing reaction radical reaction of fluorinated copolymer, adopts the silane compound of isocyanates, aminoresin class, anhydrides, polyepoxides and isocyanato group containing etc. usually.
The concrete example of above-mentioned isocyanates comprises 2,4-tolylene diisocyanate, ditane-4,4 '-vulcabond, xylylene vulcabond, different boron vulcabond, lysine methyl ester vulcabond, Methylcyclohexyl diisocyanate, trimethylammonium hexylidene diisocyanate, hexylidene diisocyanate, n-pentyl-1, contain material diisocyanate based more than 2 and block diisocyanates etc. in the trimer of 4-vulcabond, above-mentioned substance, the adducts of above-mentioned substance or biuret, the above-mentioned polymkeric substance, but be not limited thereto.
The concrete example of above-mentioned aminoresin comprises the methylolation melmac of urea resin, melmac, benzene triamino cyanate resin, glycolylurea resin, the generation of melamine methylolation, the alkyl etherificate melmac of methylolation melmac etherificate generation under alcohols effects such as methyl alcohol, ethanol, butanols etc., but is not limited thereto.
The concrete example of acid anhydrides comprises anhydride phthalic acid, PMA and mellitic acid acid anhydride etc., but is not limited thereto.
The silane compound of polyepoxides and isocyanato group containing can adopt the material of records such as flat 2-232250 communique of TOHKEMY and the flat 2-232251 communique of TOHKEMY.Preference comprises following material:
OCNC
3H
6Si(OC
2H
5)
3、OCNC
2H
4Si(OCH
3)
3。
Chemical curing reaction group in the above-mentioned fluorinated copolymer of relative 1 equivalent, the combined amount of solidifying agent is 0.1～5 equivalent, preferred 0.5～1.5 equivalent.Composition of the present invention can solidify in the time about several minutes～10 days down at 0～200 ℃ usually.
Can also mix various additives in the curing composition.Additive comprises curing catalyst, pigment, pigment dispersing agent, levelling agent, defoamer, anti-gelling agent, uv-absorbing agent, oxidation inhibitor, hydrophilizing agent etc.
Curing catalyst includes the reactant of machine tin compound, acid phosphoric acid ester, acid phosphoric acid ester and ammonia, saturated or unsaturated polyvalent carboxylic acid or its acid anhydrides, organic titanate compound, ammoniac compounds and lead octoate 36 etc.
The concrete example of above-mentioned organo-tin compound comprises dibutyl tin laurate, dibutyl tin maleate, maleic acid dioctyl tin, dibutyltin diacetate, phthalandione dibutyl tin, stannous octoate, naphthoic acid tin, dibutyl tin methylate etc.
In addition, above-mentioned acid phosphoric acid ester is the phosphoric acid ester that contains the group that the part following formula represents,
The organic acidity phosphoric acid ester shown in the following formula for example:
(in the formula, b is 1 or 2, R
8Be organic residue), specifically comprise: following material:
Above-mentioned organic titanate compound comprises: titanic acid ester such as tetrabutyl titanate ester, tetra isopropyl titanate and trolamine titanic acid ester.
Further, above-mentioned aminated compounds specifically comprises the reaction product of the low-molecular-weight polyamide resin, excessive polyamine and the epoxy compounds that are generated by salt such as amine substance and carboxylic acid thereof, excessive polyamine and the acid of polybase base etc.Wherein said amine substance is: butylamine, octylame, dibutylamine, monoethanolamine, diethanolamine, trolamine, diethylenetriamine, Triethylenetetramine (TETA), oleyl amine, hexahydroaniline, benzene methanamine, diethylaminopropylamine, benzene two methanediamines, triethylenediamine, guanidine, benzene guanidine, 2,4,6-three (dimethyl aminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo (5,4,0) hendecene-7 aminated compoundss such as (DBU).
Can use one or more curing catalysts.The interpolymer of relative 100 weight parts, the blending ratio of curing catalyst is about 1.0 * 10
-6～1.0 * 10
-2Weight part.Preferred 5.0 * 10
-5～1.0 * 10
-3Weight part.
The object lesson of pigment comprises mineral dyes such as titanium oxide, lime carbonate or carbon black, pigment dyestuffs such as phthalocyanines, quinoline bifurcation ketone or azo class, but be not limited thereto.With respect to 100 weight part multipolymers, the addition of pigment is lower than 200 weight parts usually.
Above-mentioned hydrophilizing agent can adopt the condensation body of methyl silicate, ethyl silicate, fluoroalkyl silicate and above-mentioned substance.The commercially available prod comprises ET 40, the ET48 etc. of Colcoat company limited system, the GH700 of MS56, the MS56S of Mitsubishi Chemical's (strain) system, MS57 etc. and Daikin Industries (strain) system etc.
Described solvent comprises aromatic hydrocarbon solvents such as dimethylbenzene, toluene, solvent naphtha; Fat hydrocarbon solvents such as normal hexane, Skellysolve A, octane, positive nonane, n-decane, n-undecane, n-dodecane and mineral spirits; Esters solvent such as ethyl acetate, butylacetate; Ketones solvents such as methyl iso-butyl ketone (MIBK); Glycol ethers solvents such as ethyl cellosolve; Divinyl glycol ester kind solvents such as acetate carbitol etc., but do not limit therewith.Because above-mentioned reason is especially preferably used inert solvent.
Curing composition can be mixed with above-mentioned organic solvent type composition, aqueous dispersion type composition, powder-type composition and non-aqueous dispersion type and disperse forms such as thing.
The curing composition of using fluorinated copolymer of the present invention has good solubility in solvent, formed coating has the weathering resistance of height, and stain resistance, resistance rerum natura, optical property, mechanical properties, well-behaved with the contact of primer and heat-resisting xanthochromia etc.The same with common curing composition, as indoor coating or outdoor use coating such as building materials, automobile, aircraft, boats and ships and electric car such as building materials and interior packing materials, can be directly used in metal, concrete, plastics etc., perhaps overlapping brushing on priming paints such as wash primer, rust proof paint, epoxy coating, acrylic resin paint and Polyester resin lacquer.Also can be used as sealing agent and film forming agent uses.
The present invention can provide a kind of coating structure, and described coating structure designs the solidified coating of curing composition of the present invention on the primer as outermost layer.The solidified coating of curing composition of the present invention can be directly as primer or as priming paint, in case of necessity can also be with prime coat as the middle layer.The thickness of outermost solidified coating is generally 10～100 μ m, preferred 20～50 μ m.
The known priming paint that priming paint can use fluorine resin paints to use, for example epoxies priming paint and zinc rich primer etc.
The known priming paint that prime coat also can use fluorine resin paints to use, for example acrylic coating, amino formate coating, polyester coating and epoxy resin coating etc.
Primer is different because of the brushing object, comprises above-mentioned metal, concrete, plastics, stone material, timber and paper etc.
To specify the present invention by embodiment below.
Embodiment 1 (fluorinated copolymer 1)
(1) the synthetic and evaluation of fluorinated copolymer
At capacity is alkanecarboxylic acid vinyl acetate (VV9) 638.0g that side chain is arranged, 4-hydroxyl butyl vinyl ether (HBVE) 156.7g that packs into and generated by 2891g butylacetate and C9 carboxylic acid in the autoclave of vinylbenzene system of 6000ml, be cooled to 5 ℃, carry out three decompression nitrogen in the process of cooling and replace operation.And then decompression, tetrafluoroethylene 481.7g packs into.Stirring also is warming up to 65.0 ℃, adds PEROYL355 (trade(brand)name, NOF Corp's system) peroxide polymerization starter again) 12.5g, the beginning polymerization.Simultaneously, the mixture that in 1.5 hours, adds 639.0g VV9 and 156.7gHBVE continuously.Under this temperature, reacted 3 hours after adding initiator, add 12.5gPEROYL355 once more, under this temperature, reacted 4 hours then.When reactor pressure from 1.4MPaG (14.5kgf/cm
2G) reduce to 0.2MPaG (2.1kgf/cm
2G) time, stopped reaction, polymerization yield are 92.3%.With
10F-NMR,
1H-NMR and elemental microanalysis method are analyzed the fluorinated copolymer of gained, and the result shows the tetrafluoroethylene of fluorinated copolymer 1 by 45mol%, and the 4-hydroxyl butyl vinyl ether of the VV9 of 39mol% and 16mol% is formed, and it is 1.5 * 10000 that the GPC method records number-average molecular weight (Mn).The DSC method records glass transition temp (2
NdRun) be 35 ℃.
Mainly studied the intermiscibility of gained fluoropolymer and various coating compounds, the result is as shown in table 1.
(vinylformic acid intermiscibility)
Fluorinated copolymer is dissolved in the butylacetate, and the content that makes solids component is 33 weight %.In described solution, sneak into acrylic resin A, B or C, and the weight ratio of fluorinated copolymer and acrylic resin is 1/1.Described composition is coated on the polyethylene phthalate made membrane, and room temperature is placed, and in the solvent evaporation process, with the naked eye observes coating state.Estimate by following standard.
A: transparent (intermiscibility is good)
B: a small amount of white casse is arranged
C: opaque (intermiscibility is bad)
Acrylic resin A: Mitsubishi Rayon Co., Ltd.'s system-DIANALLR-620, trade(brand)name
Acrylic resin B: Hitachi changes into the HITALOID6500B of Co., Ltd.'s system, trade(brand)name
Acrylic resin C: my society's sample
Be furnished with in the there-necked flask of thermometer, return line, nitrogen ingress pipe and sneak into 27g butyl acrylate, 60g cyclohexyl methacrylate, 12g vinylformic acid 2-hydroxyethyl ester, 1g methacrylic acid and 60g mineral spirits, 40g SOLVESSO 100, stir down, imported nitrogen 1～2 hour by nitrogen ingress pipe.Then, add the 0.5g benzoyl peroxide, reacted 10 hours down, obtain acrylic resin C in 80 ℃.
(elasticity solidifying agent intermiscibility)
Fluorinated copolymer is dissolved in the butylacetate, and the content that makes solids component is 33 weight %.In described solution, sneak into elasticity solidifying agent (big Japanese ink and chemical industry Co., Ltd. system) BURNOCKDN955, trade(brand)name), and hydroxyl/NCO (mol ratio) ratio is 1.1.Described composition is coated on the polyethylene phthalate made membrane, and room temperature is placed, and in the solvent evaporation process, with the naked eye observes coating state.Estimate by following standard.
A: transparent (intermiscibility is good)
B: a small amount of white casse is arranged
C: opaque (intermiscibility is bad)
(dispersion agent intermiscibility)
Fluorinated copolymer is dissolved in the butylacetate, and the content that makes solids component is 33 weight %.In described solution, add pigment dispersing agent (BYK-161 of BYK Japan KCC system, trade(brand)name), and dispersion agent effective constituent/multipolymer (weight ratio) ratio is 0.05.Described composition is coated on the polyethylene phthalate made membrane, and room temperature is placed, and in the solvent evaporation process, with the naked eye observes coating state.Estimate by following standard.
A: transparent (intermiscibility is good)
B: a small amount of white casse is arranged
C: opaque (intermiscibility is bad)
(2) preparation of weathering resistance coating composition and evaluation
Add butylacetate and adjust its concentration in the fluorinated copolymer 1 of gained, making solid component content is 60 weight %.In the described solution of 208g, add CR-95 (trade(brand)name, the titanium oxide of the former industry of stone (strain) system) 250g, butylacetate 100g and granulated glass sphere 800g, with bench grinder with the speed dispersed with stirring of 1500rpm 1 hour.Remove by filter granulated glass sphere, get dispersion liquid 429.4g.
Toward middle butylacetate solution (solid that contains 60 weight %) 224.7g and the butylacetate 115.4g that adds fluorinated copolymer 1 of described dispersion liquid (429.4g), thorough mixing is mixed with whitewash.
Add TAKENATE D-140N (trade(brand)name, the isocyanates solidifying agent of military field pharmaceutical industries (strain) system) 12.7g and butylacetate 80g in the described whitewash of 100g, thorough mixing is mixed with coating composition.
With the spraying squeegee process with described coating composition brushing on aluminium sheet (JIS H4000A-1050PAM-712) (0.5mm is thick), room temperature is placed and 1 week was made the coating drying, makes the coated plate that is coated with the about 40 μ m of thickness.Check brightness, pencil hardness, solvent resistance, resistance rerum natura, the promote weathering resistance and the oily ink contaminative of described coated plate.The result is as shown in table 1.
(brightness)
Carry out according to JIS K 5400.
(pencil hardness)
Carry out according to JIS K 5400.
(solvent resistance)
With the cotton that contains butylacetate with coating friction 100 times after, with the naked eye check the state of coatingsurface, by following standard determination.
A: no abnormal.
B: a small amount of flaw is arranged.
C: coating dissolving or swelling have obvious flaw.
(resistance rerum natura)
Under 35 ℃, after the aqueous sodium hydroxide solution with 10% contacted for 2 weeks with coatingsurface, the washing surface, and observe.
A: no abnormal.
B: a small amount of variable color or bubble are arranged.
C: obvious variable color or bubble are arranged.
(promoting weathering resistance 1)
With SWOM (SUGA trier (strain) system atmospheric exposure test machine: test period is 6000 hours), the initial stage brightness of 60 degree is decided to be 100, represents with the brightness conservation rate after 6000 hours.
(oily ink contaminative)
With red ink felt pen (the SAKURA PEN TOUCH of SAKURA COLOR PRODUCTS CORPORATION system, trade(brand)name) is coated with the coating area of full 10mm * 10mm, after placing 24 hours under 40 ℃, use the ethanol wiping, the Restzustand of the red ink that detects by an unaided eye.Estimate by following rank.
A: remove fully
B: minute quantity is residual
C: small amount of residual
D: obviously residual
(3) preparation of curing composition and evaluation
In the butylacetate solution of 10g gained fluorinated copolymer (concentration is 50 weight %), the CORONATE HX (NCO/OH=1.1) that adds 6.2g Japan's polyurethane (strain) system is mixed with curing composition as solidifying agent.On aluminium sheet (JIS H4000A-1050PAM-712), 80 ℃ were heated 1 hour down, solidify to form blank coating with described composition brushing.Described blank coating is promoted weathering test and acid resisting test.The result is as shown in table 1.
(promoting weathering resistance 2)
EYESUPER-UV tester-W-13 type (Light/Dew/Rest=11/11/1R was 1 week) with rock rugged electric (strain) system carries out promoting weathering test in 500 hours that its outward appearance detects by an unaided eye.Estimate by following standard.
A: no abnormal
B: a small amount of variable color is arranged
C: obviously variable color
Under 50 ℃, with after blank coatingsurface contacted for 1 week, with the surface washing, its condition of surface detects by an unaided eye with the aqueous sulfuric acid of 10 weight %.Estimate by following standard.
A: no abnormal.
B: a small amount of variable color, bubble and flaw are arranged.
C: obvious variable color, bubble and flaw are arranged.
Embodiment 2～9 (fluorinated copolymer 1)
Except that the monomer with table 1 record carries out the copolymerization other and embodiment 1 identical synthetic fluorinated copolymer 1.Number-average molecular weight that the composition of multipolymer (mole %), GPC method record and the glass transition temp that records with DSC are as shown in table 1.In addition, contain ethyl vinyl ether (EVE) unit of 4mol% among the embodiment 7 as optional member (f).
With the various intermiscibilities of embodiment 1 with the fluorinated copolymer 1 of method inspection gained.The result is as shown in table 1.
Press the step preparation coating composition of (2) among the embodiment 1 with the fluorinated copolymer 1 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 1.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 1.
Following monomer is represented in abbreviation in the table 1:
TFE: tetrafluoroethylene
VV9: the alkanecarboxylic acid vinyl acetate (VEOVA9, the trade(brand)name of the C9 aliphatic carboxylic acid vinyl acetate of shell chemical company system) that side chain is arranged
VV10: the alkanecarboxylic acid vinyl acetate (VEOVA10 that side chain is arranged.The trade(brand)name of the C10 aliphatic carboxylic acid vinyl acetate of shell chemical company system)
Vac: vinyl-acetic ester
HBVE: hydroxyl butyl vinyl ether
HEVE: hydroxyethyl Vinyl Ether
Table 1
| Embodiment | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | |
| Structural unit | |||||||||
| (a)TFE | 45 | 44 | 45 | 44 | 43 | 44 | 46 | 46 | 45 |
| (b)VV9 VV10 Vac | 39 | 41 | 40 | 42 | 34 | 33 | 34 | 36 | 38 |
| (c)HBVE HEVE | 16 | 15 | 15 | 14 | 23 | 23 | 16 | 18 | 17 |
| (f)EVE | 4 | ||||||||
| Number-average molecular weight (* 10 3) | 1.2 | 1.3 | 1.1 | 1.2 | 1.1 | 1.2 | 1.3 | 1.3 | 1.3 |
| Glass transition temp (℃) | 35 | 15 | 36 | 12 | 33 | 13 | 34 | 21 | 22 |
| Intermiscibility acrylic resin A acrylic resin B acrylic resin C elasticity solidifying agent dispersion agent | A A A B B | A A A B B | A A A B B | A A A B B | A A A B B | A A A B B | A A A B B | A A A A A | A A A A A |
| Brightness | 78 | 79 | 78 | 77 | 78 | 79 | 78 | 77 | 78 |
| Pencil hardness | H | H | H | H | 2H | 2H | H | H | H |
| Solvent resistance | A | A | A | A | A | A | A | A | A |
| The resistance rerum natura | A | A | A | A | A | A | A | B | B |
| Promote weathering resistance 1 (%) | 88 | 87 | 89 | 90 | 91 | 89 | 89 | 88 | 87 |
| The oily ink contaminative | A | A | A | A | A | A | A | A | A |
| Promote weathering resistance 2 | A | A | A | A | A | A | A | A | A |
| Acid resistance | A | A | B | B | A | A | A | C | C |
Embodiment 10～17 (the synthetic and evaluation of fluorinated copolymer 2)
In the synthetic method of embodiment 1 record, monomer shown in the table 2 is used for structural unit (a)～(c), with described monomer and unit (d) used monomer M-nitro benzoic acid vinyl acetate (VBz) or tertiary butyl M-nitro benzoic acid vinyl acetate (VtBz) copolymerization, synthetic fluorinated copolymer 2.
Number-average molecular weight that the composition of fluorinated copolymer 2 (mole %), GPC method record and the glass transition temp that records with DSC are as shown in table 2.
Various intermiscibilities with the fluorinated copolymer 2 of embodiment 1 identical inspection gained.The result is as shown in table 2.
Press the step preparation coating composition of (2) among the embodiment 1 with the fluorinated copolymer 2 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 2.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 2.
Following monomer is represented in abbreviation in the table 2:
TFE: tetrafluoroethylene
VV9: the alkanecarboxylic acid vinyl acetate (VEOVA9, the trade(brand)name of the C9 aliphatic carboxylic acid vinyl acetate of shell chemical company system) that side chain is arranged
VV10: the alkanecarboxylic acid vinyl acetate (VEOVA10, the trade(brand)name of the C10 aliphatic carboxylic acid vinyl acetate of society of shell chemical company system) that side chain is arranged
Vac: vinyl-acetic ester
HBVE: hydroxyl butyl vinyl ether
HEVE: hydroxyethyl Vinyl Ether
VBz: M-nitro benzoic acid vinyl acetate
VtBz: tertiary butyl M-nitro benzoic acid vinyl acetate
Table 2
| Embodiment | ||||||||
| 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | |
| Structural unit | ||||||||
| (a)TFE | 44 | 45 | 46 | 44 | 44 | 43 | 43 | 44 |
| (b)VV9 VV10 Vac | 36 | 35 | 33 | 34 | 28 | 28 | 27 | 26 |
| (c)HBVE HEVE | 16 | 15 | 15 | 17 | 23 | 22 | 23 | 21 |
| (d)VBz VtBz | 4 | 5 | 6 | 5 | 5 | 7 | 7 | 9 |
| Number-average molecular weight (* 10 3) | 1.2 | 1.3 | 1.2 | 1.2 | 1.2 | 1.1 | 1.2 | 1.2 |
| Glass transition temp (℃) | 33 | 12 | 34 | 16 | 30 | 15 | 20 | 18 |
| Intermiscibility acrylic resin A acrylic resin B acrylic resin C elasticity solidifying agent dispersion agent | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A |
| Brightness | 80 | 83 | 83 | 84 | 84 | 83 | 83 | 82 |
| Pencil hardness | H | H | H | H | 2H | 2H | 2H | 2H |
| Solvent resistance | A | A | A | A | A | A | A | A |
| The resistance rerum natura | A | A | A | A | A | A | A | A |
| Promote weathering resistance 1 (%) | 90 | 89 | 88 | 89 | 88 | 89 | 90 | 89 |
| The oily ink contaminative | A | A | A | A | A | A | A | A |
| Promote weathering resistance 2 | A | A | A | A | A | A | A | A |
| Acid resistance | B | A | A | A | A | A | B | B |
Embodiment 18～26 (the synthetic and evaluation of fluorinated copolymer 3)
In the synthetic method of embodiment 1 record, the monomer shown in the table 3 is used for structural unit (a)～(c), with described monomer and unit (e) used monomer ethylene guanidine-acetic acid (VA), vinylformic acid (AA) or Ba Dousuan (CA) copolymerization, and synthetic fluorinated copolymer 3.In addition, contain ethyl vinyl ether (EVE) unit of 4mol% among the embodiment 24 as optional member (f).
Number-average molecular weight that the composition of fluorinated copolymer 3 (mole %), GPC method record and the glass transition temp that records with DSC are as shown in table 3.
With the various intermiscibilities of embodiment 1 with method inspection gained fluorinated copolymer 3.The result is as shown in table 3.
Press the step preparation coating composition of (2) among the embodiment 1 with gained fluorinated copolymer 3, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 3.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 3.
Following monomer is represented in abbreviation in the table 3:
TFE: tetrafluoroethylene
VV9: the alkanecarboxylic acid vinyl acetate (VEOVA9, the trade(brand)name of the C9 aliphatic carboxylic acid vinyl acetate of shell chemical company system) that side chain is arranged
VV10: the alkanecarboxylic acid vinyl acetate (VEOVA10, the trade(brand)name of the C10 aliphatic carboxylic acid vinyl acetate of shell chemical company system) that side chain is arranged
Vac: vinyl-acetic ester
HBVE: hydroxyl butyl vinyl ether
HEVE: hydroxyethyl Vinyl Ether
VA: vinylacetic acid
AA: vinylformic acid
CA: Ba Dousuan
Table 3
| Embodiment | |||||||||
| 18 | 19 | 20 | 21 | 22 | 23 | 24 | 25 | 26 | |
| Structural unit | |||||||||
| (a)TFE | 45 | 44 | 45 | 45 | 45 | 44 | 46 | 45 | 44 |
| (b)VV9 VV10 Vac | 39.3 | 38.2 | 38.1 | 40.4 | 35.6 | 34.6 | 34.6 | 34.5 | 33.4 |
| (c)HBVE HEVE | 15 | 17 | 16 | 15 | 19 | 21 | 15 | 20 | 22 |
| (e)VA AA CA | 0.7 | 0.8 | 0.9 | 0.6 | 0.4 | 0.4 | 0.4 | 0.5 | 0.6 |
| (f)EVE | 4 | ||||||||
| Number-average molecular weight (* 10 3) | 1.1 | 1.3 | 1.3 | 1.2 | 1.2 | 1.1 | 1.2 | 1.2 | 1.1 |
| Glass transition temp (℃) | 33 | 17 | 30 | 15 | 32 | 18 | 31 | 19 | 20 |
| Intermiscibility acrylic resin A acrylic resin B acrylic resin C elasticity solidifying agent dispersion agent | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A |
| Brightness | 82 | 83 | 82 | 84 | 83 | 82 | 82 | 85 | 83 |
| Pencil hardness | H | H | H | H | H | H | H | 2H | 2H |
| Solvent resistance | A | A | A | A | A | A | A | A | A |
| The resistance rerum natura | A | A | A | A | A | A | A | B | A |
| Promote weathering resistance 1 (%) | 89 | 90 | 89 | 90 | 90 | 89 | 89 | 90 | 91 |
| The oily ink contaminative | A | A | A | A | A | A | A | A | A |
| Promote weathering resistance 2 | A | A | A | A | A | A | A | A | A |
| Acid resistance | A | A | A | A | A | A | A | C | C |
Embodiment 27～34 (the synthetic and evaluation of fluorinated copolymer 4)
In the synthetic method of embodiment 1 record, the monomer shown in the table 4 is used for structural unit (a)～(c), with described monomer and the used monomer copolymerization of unit (d) and unit (e), and synthetic fluorinated copolymer 4.
Number-average molecular weight that the composition of fluorinated copolymer 4 (mole %), GPC method record and the glass transition temp that records with DSC are as shown in table 4.
With the various intermiscibilities of embodiment 1 with the fluorinated copolymer 4 of method inspection gained.The result is as shown in table 4.
Press the step preparation coating composition of (2) among the embodiment 1 with the fluorinated copolymer 4 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 4.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 4.
Following monomer is represented in abbreviation in the table 4:
TFE: tetrafluoroethylene
VV9: the alkanecarboxylic acid vinyl acetate (VEOVA9, the trade(brand)name of the C9 aliphatic carboxylic acid vinyl acetate of shell chemical company system) that side chain is arranged
VV10: the alkanecarboxylic acid vinyl acetate (VEOVA10, the trade(brand)name of the C10 aliphatic carboxylic acid vinyl acetate of shell chemical company system) that side chain is arranged
Vac: vinyl-acetic ester
HBVE: hydroxyl butyl vinyl ether
HEVE: hydroxyethyl Vinyl Ether
VBz: M-nitro benzoic acid vinyl acetate
VtBz: tertiary butyl M-nitro benzoic acid vinyl acetate
VA: vinylacetic acid
AA: vinylformic acid
CA: Ba Dousuan
Table 4
| Embodiment | ||||||||
| 27 | 28 | 29 | 30 | 31 | 32 | 33 | 34 | |
| Structural unit | ||||||||
| (a)TFE | 45 | 43 | 45 | 44 | 45 | 44 | 45 | 44 |
| (b)VV9 VV10 Vac | 34.4 | 36.4 | 32.4 | 28.4 | 31.4 | 28.4 | 30.5 | 29.5 |
| (c)HBVE HEVE | 14 | 14 | 18 | 21 | 15 | 18 | 16 | 17 |
| (d)VBz VtBz | 6 | 6 | 4 | 6 | 8 | 9 | 8 | 9 |
| (e)VA AA CA | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.5 | 0.5 |
| Number-average molecular weight (* 10 3) | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.1 | 1.2 | 1.2 |
| Glass transition temp (℃) | 30 | 17 | 31 | 19 | 20 | 21 | 21 | 22 |
| Intermiscibility acrylic resin A acrylic resin B acrylic resin C elasticity solidifying agent dispersion agent | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A |
| Brightness | 83 | 83 | 83 | 83 | 82 | 83 | 82 | 83 |
| Pencil hardness | H | H | H | H | H | H | H | H |
| Solvent resistance | A | A | A | A | A | A | A | A |
| The resistance rerum natura | A | A | A | A | A | A | A | A |
| Promote weathering resistance 1 (%) | 88 | 90 | 90 | 91 | 89 | 90 | 89 | 90 |
| The oily ink contaminative | A | A | A | A | A | A | A | A |
| Promote weathering resistance 2 | A | A | A | A | A | A | A | A |
| Acid resistance | A | A | A | A | B | B | B | B |
Comparative example 1 (synthetic and evaluation contains the comparison fluorinated copolymer 1 of a small amount of unit (b))
In the synthetic method of embodiment 1 record, the monomer shown in the table 5 is used for structural unit (a)～(c), with described monomer and the used monomer copolymerization of unit (d) and unit (e), and synthetic relatively fluorinated copolymer 1.
Relatively the number-average molecular weight that records of the composition of fluorinated copolymer 1 (mole %), GPC method and the glass transition temp that records with DSC are as shown in table 5.The content of unit (b) is reduced to 23.5mol%.
With the various intermiscibilities of embodiment 1 with the comparison fluorinated copolymer 1 of method inspection gained.The result is as shown in table 5.
Press the step preparation coating composition of (2) among the embodiment 1 with the comparison fluorinated copolymer 1 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 5.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 5.
Comparative example 2 (synthetic and evaluation contains the comparison fluorinated copolymer 2 of a small amount of unit (b))
In the synthetic method of embodiment 1 record, the monomer shown in the table 5 is used for structural unit (a)～(c), with the monomer copolymerization that is used as optional member (f) shown in described monomer and unit (d), unit (e) and the table 5, and synthetic relatively fluorinated copolymer 2.
Relatively the number-average molecular weight that records of the composition of fluorinated copolymer 2 (mole %), GPC method and the glass transition temp that records with DSC are as shown in table 5.The content of unit (b) is reduced to 21mol%, and optional member (f) increases.
With the various intermiscibilities of embodiment 1 with the comparison fluorinated copolymer 2 of method inspection gained.The result is as shown in table 5.
Press the step preparation coating composition of (2) among the embodiment 1 with the comparison fluorinated copolymer 2 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 5.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 5.
Comparative example 3 (synthetic and estimate the comparison fluorinated copolymer 3 that does not contain unit (b) and contain a large amount of unit (f))
In the synthetic method of embodiment 1 record, without structural unit (b), monomer shown in the table 5 is used for structural unit (a) and (c), with shown in described monomer and unit (d), unit (e) and the table 5 as the monomer copolymerization of optional member (f), synthetic relatively fluorinated copolymer 3.
Relatively the number-average molecular weight that records of the composition of fluorinated copolymer 3 (mole %), GPC method and the glass transition temp that records with DSC are as shown in table 5.Do not contain unit (b), the content of optional member (f) (ethyl vinyl ether) increases to 33mol%.
With the various intermiscibilities of embodiment 1 with the comparison fluorinated copolymer 3 of method inspection gained.The result is as shown in table 5.
Press the step preparation coating composition of (2) among the embodiment 1 with the comparison fluorinated copolymer 3 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 5.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 5.
Comparative example 4 (synthetic and estimate the comparison fluorinated copolymer 4 that does not contain unit (b) and contain a large amount of unit (f))
In the synthetic method of embodiment 1 record, without structural unit (b), monomer shown in the table 5 is used for structural unit (a) and (c), with the monomer copolymerization shown in described monomer and unit (d), unit (e) and the table 5 as optional member (f), and synthetic relatively fluorinated copolymer 4.
Relatively the number-average molecular weight that records of the composition of fluorinated copolymer 4 (mole %), GPC method and the glass transition temp that records with DSC are as shown in table 5.Do not contain unit (b), the content of optional member (f) (iso-butylene) increases to 33mol%.
With the various intermiscibilities of embodiment 1 with the comparison fluorinated copolymer 4 of method inspection gained.The result is as shown in table 5.
Press the step preparation coating composition of (2) among the embodiment 1 with the comparison fluorinated copolymer 4 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 5.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 5.
Comparative example 5 (synthetic and evaluation contains the comparison fluorinated copolymer 5 of a small amount of unit (c))
In the synthetic method of embodiment 1 record, the monomer shown in the table 5 is used for structural unit (a)～(c), with the monomer copolymerization shown in described monomer and the table 5 as unit (d) and unit (e), and synthetic relatively fluorinated copolymer 5.
Relatively the number-average molecular weight that records of the composition of fluorinated copolymer 5 (mole %), GPC method and the glass transition temp that records with DSC are as shown in table 5.The content of unit (c) reduces to 7mol%.
With the various intermiscibilities of embodiment 1 with the comparison fluorinated copolymer 5 of method inspection gained.The result is as shown in table 5.
Press the step preparation coating composition of (2) among the embodiment 1 with the comparison fluorinated copolymer 5 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 5.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 5.
Comparative example 6 (synthetic and evaluation contains the comparison fluorinated copolymer 6 of a large amount of unit (d))
In the synthetic method of embodiment 1 record, the monomer shown in the table 5 is used for structural unit (a)～(c), with the monomer copolymerization shown in described monomer and the table 5 as unit (d) and unit (e), and synthetic relatively fluorinated copolymer 6.
Relatively the number-average molecular weight that records of the composition of fluorinated copolymer 6 (mole %), GPC method and the glass transition temp that records with DSC are as shown in table 5.The content of unit (d) increases to 21mol%, and the content of unit (b) and unit (c) reduces.
With the various intermiscibilities of embodiment 1 with the comparison fluorinated copolymer 6 of method inspection gained.The result is as shown in table 5.
Press the step preparation coating composition of (2) among the embodiment 1 with the comparison fluorinated copolymer 6 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 5.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 5.
Comparative example 7 (the synthetic and evaluation comparison fluorinated copolymer 7 of CTFE) as unit (a)
In the synthetic method of embodiment 1 record, replace TFE as unit (a) with chloro trifluoro-ethylene (CTFE), with the monomer copolymerization that is used for structural unit (b)～(c) shown in the table 5, synthetic relatively fluorinated copolymer 7.
Relatively the number-average molecular weight that records of the composition of fluorinated copolymer 7 (mole %), GPC method and the glass transition temp that records with DSC are as shown in table 5.
With the various intermiscibilities of embodiment 1 with the comparison fluorinated copolymer 7 of method inspection gained.The result is as shown in table 5.
Press the step preparation coating composition of (2) among the embodiment 1 with the comparison fluorinated copolymer 7 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 5.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 5.
Comparative example 8 (the synthetic and evaluation comparison fluorinated copolymer 8 of HFP) as unit (a)
In the synthetic method of embodiment 1 record, replace TFE as unit (a) with R 1216 (HFP), with the monomer copolymerization that is used for structural unit (b)～(c) shown in the table 5, synthetic relatively fluorinated copolymer 8.
Relatively the number-average molecular weight that records of the composition of fluorinated copolymer 8 (mole %), GPC method and the glass transition temp that records with DSC are as shown in table 5.
With the various intermiscibilities of embodiment 1 with the comparison fluorinated copolymer 8 of method inspection gained.The result is as shown in table 5.
Press the step preparation coating composition of (2) among the embodiment 1 with the comparison fluorinated copolymer 8 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 5.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 5.
Following monomer is represented in abbreviation in the table 5:
TFE: tetrafluoroethylene
VV9: the alkanecarboxylic acid vinyl acetate (VEOVA9, the trade(brand)name of the C9 aliphatic carboxylic acid vinyl acetate of shell chemical company system) that side chain is arranged
VV10: the alkanecarboxylic acid vinyl acetate (VEOVA10, the trade(brand)name of the C10 aliphatic carboxylic acid vinyl acetate of shell chemical company system) that side chain is arranged
Vac: vinyl-acetic ester
HBVE: hydroxyl butyl vinyl ether
HEVE: hydroxyethyl Vinyl Ether
VBz: M-nitro benzoic acid vinyl acetate
VtBz: tertiary butyl M-nitro benzoic acid vinyl acetate
VA: vinylacetic acid
AA: vinylformic acid
CA: Ba Dousuan
EVE: ethyl vinyl ether
IB: iso-butylene
Table 5
| Comparative example | ||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |
| Structural unit | ||||||||
| (a)TFE CTFE HFP | 46 | 45 | 44 | 45 | 44 | 42 | 49 | 48 |
| (b)VV9 VV10 Vac | 23.5 | 21 | 39.5 | 25.5 | 37 | 37 | ||
| (c)HBVE HEVE | 23 | 16.5 | 14.5 | 16.5 | 7 | 11 | 14 | 15 |
| (d)VBz VtBz | 7 | 7 | 7 | 7 | 9 | 21 | ||
| (e)VA AA CA | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| (f)EVE IB | 10 | 33 | 31 | |||||
| Number-average molecular weight (* 10 3) | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 |
| Glass transition temp (℃) | 21 | 17 | 13 | 14 | 20 | 36 | 19 | 21 |
| Intermiscibility acrylic resin A acrylic resin B acrylic resin C elasticity solidifying agent dispersion agent | C A A C C | C C C C C | C C C C C | C C C C C | A A A A A | A A A A A | A A A A A | C A A C C |
| Brightness | 81 | 81 | 81 | 77 | 83 | 85 | 85 | 75 |
| Pencil hardness | 2H | H | H | H | B | H | H | H |
| Solvent resistance | A | A | A | A | C | A | A | A |
| The resistance rerum natura | A | A | A | A | B | A | A | A |
| Promote weathering resistance 1 (%) | 87 | 88 | 87 | 86 | 89 | 10 | 82 | 82 |
| The oily ink contaminative | A | A | A | A | C | A | C | A |
| Promote weathering resistance 2 | A | A | A | A | A | A | The obvious flavescence of C | A |
| Acid resistance | A | A | A | A | C | A | A | A |
Embodiment 35～44 and comparative example 9～10 (the synthetic and evaluation of fluorinated copolymer 4)
In the synthetic method of embodiment 1 record, the monomer shown in the table 6 is used for structural unit (a)～(c), with the monomer copolymerization shown in described monomer and the table 6 as unit (d) and unit (e), and synthetic fluorinated copolymer 4.
Number-average molecular weight that the composition of fluorinated copolymer 4 (mole %), GPC method record and the glass transition temp that records with DSC are as shown in table 6.
With the various intermiscibilities of embodiment 1 with the fluorinated copolymer 4 of method inspection gained.The result is as shown in table 6.
Press the step preparation coating composition of (2) among the embodiment 1 with the fluorinated copolymer 4 of gained, estimate the coating rerum natura with method with embodiment 1.The result is as shown in table 6.
Further, press the step preparation curing composition of (3) among the embodiment 1, check the promotion weathering resistance and the acid resistance of blank coating with method with embodiment 1.The result is as shown in table 6.
Abbreviation in the table 6 is identical with table 4.
Table 6
| Embodiment | Comparative example | |||||||||||
| 35 | 36 | 37 | 38 | 39 | 40 | 41 | 42 | 43 | 44 | 9 | 10 | |
| Structural unit | ||||||||||||
| (a)TFE | 37 | 36 | 27 | 25 | 35 | 34 | 35 | 24 | 24 | 25 | 15 | 16 |
| (b)VV9 VV10 Vac | 41.4 | 49.5 | 47.3 | 58.5 | 36.3 | 37.5 | 44.4 | 39.5 | 38.4 | 51.5 | 55.5 | 60.5 |
| (c)HBVE HEVE | 21 | 14 | 25 | 16 | 20 | 21 | 15 | 26 | 27 | 14 | 21 | 14 |
| (d)VBz VtBz | 8 | 7 | 5 | 10 | 10 | 9 | 8 | 9 | ||||
| (e)VA AA CA | 0.6 | 0.5 | 0.7 | 0.5 | 0.7 | 0.5 | 0.6 | 0.5 | 0.6 | 0.5 | 0.5 | 0.5 |
| Number-average molecular weight (* 10 3) | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.1 | 1.2 | 12 |
| Glass transition temp (℃) | 34 | 33 | 41 | 35 | 35 | 12 | 34 | 36 | 10 | 32 | 41 | 39 |
| Intermiscibility acrylic resin A acrylic resin B acrylic resin C elasticity solidifying agent dispersion agent | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A | A A A A A |
| Brightness | 83 | 82 | 86 | 87 | 83 | 82 | 83 | 86 | 88 | 87 | 89 | 89 |
| Pencil hardness | 2H | H | 2H | H | 2H | 2H | H | 2H | 2H | H | 2H | H |
| Solvent resistance | A | A | A | A | A | A | A | A | A | A | A | A |
| The resistance rerum natura | A | B | A | B | A | A | A | A | A | A | C | C |
| Promote weathering resistance 1 (%) | 78 | 75 | 68 | 64 | 75 | 77 | 70 | 67 | 68 | 57 | 11 | 12 |
| The oily ink contaminative | A | A | B | B | A | A | A | B | B | B | C | D |
| Promote weathering resistance 2 | A | A | A | A | A | A | A | A | A | A | B | B |
| Acid resistance | A | C | B | C | A | A | C | B | B | C | C | C |
Utilizability on the industry
The result of comparative example in the result of the embodiment of the invention in table 1～4,6 and table 5 and the table 6 is compared as can be known, the intermiscibility of other intermixture is good in fluorinated copolymer of the present invention and the coating composition, and can make coating have good against weather, hardness and stain resistance.
Claims (7)
1, a kind of fluorinated copolymer, described fluorinated copolymer is made of following structural unit: (a) tetrafluoroethylene structural unit, (b) the non-aromatics vinyl acetate monomer structural unit of hydroxyl and carboxyl not, (c) do not contain aryl and carboxyl and contain the vinyl monomer structural unit of hydroxyl, (d) not hydroxyl and carboxyl and contain the monomer structure unit of aryl, (e) not hydroxyl and aryl and contain the monomer structure unit of carboxyl and (f) other monomer structure unit; The content of each structural unit is respectively: (a) greater than 20mol%, less than 49mol%, (b) greater than 25mol%, less than 69.9mol%, (c) greater than 8mol%, less than 30mol%, (d) greater than 2mol%, less than 15mol%, (e) greater than 0.1mol%, less than 2.0mol%, (f) greater than 0mol%, less than 10mol%.
2, fluorinated copolymer as claimed in claim 1, wherein the non-aromatics vinyl acetate monomer structural unit (b) of hydroxyl and carboxyl is not alkanecarboxylic acid vinyl acetate structural unit or the vinyl-acetic ester structural unit that side chain is arranged.
3, a kind of coating composition that forms composition with fluorinated copolymer as coating, wherein, described fluorinated copolymer is made of following structural unit: (a) tetrafluoroethylene structural unit, (b) the non-aromatics vinyl acetate monomer structural unit of hydroxyl and carboxyl not, (c) do not contain aryl and carboxyl and contain the vinyl monomer structural unit of hydroxyl, (d) not hydroxyl and carboxyl and contain the monomer structure unit of aryl, (e) not hydroxyl and aryl and contain the monomer structure unit of carboxyl and (f) other monomer structure unit; The content of each structural unit is respectively: (a) greater than 20mol%, less than 49mol%, (b) greater than 25mol%, less than 69.9mol%, (c) greater than 8mol%, less than 30mol%, (d) greater than 2mol%, less than 15mol%, (e) greater than 0.1mol%, less than 2.0mol%, (f) greater than 0mol%, less than 10mol%.
4, coating composition as claimed in claim 3, wherein the non-aromatics vinyl acetate monomer structural unit (b) of hydroxyl and carboxyl is not alkanecarboxylic acid vinyl acetate structural unit or the vinyl-acetic ester structural unit that side chain is arranged.
5, as claim 3 or 4 described coating compositions, said composition also contains acrylic resin.
6, as claim 3 or 4 described coating compositions, described coating composition is the curable coating composition that contains solidifying agent.
7, coating composition as claimed in claim 5, it is the curable coating composition that contains solidifying agent.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002174183 | 2002-06-14 | ||
| JP174183/2002 | 2002-06-14 | ||
| JP2002312934 | 2002-10-28 | ||
| JP312934/2002 | 2002-10-28 | ||
| JP2003078874A JP4306292B2 (en) | 2002-06-14 | 2003-03-20 | Fluorine-containing copolymer and coating composition |
| JP78874/2003 | 2003-03-20 |
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| CN1467230A CN1467230A (en) | 2004-01-14 |
| CN1238388C true CN1238388C (en) | 2006-01-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006152080A (en) * | 2004-11-26 | 2006-06-15 | Nippon Paint Co Ltd | Weak solvent type fluorine resin coating composition and method for forming coating film |
| WO2008093776A1 (en) | 2007-02-02 | 2008-08-07 | Daikin Industries, Ltd. | Curable resin composition and method for producing the same |
| JP5541276B2 (en) * | 2009-02-23 | 2014-07-09 | 旭硝子株式会社 | Method for producing fluoroolefin copolymer solution and method for producing coating composition |
| WO2012133836A1 (en) * | 2011-03-31 | 2012-10-04 | ダイキン工業株式会社 | Fluorine-containing copolymer |
| WO2013065854A1 (en) | 2011-11-04 | 2013-05-10 | ダイキン工業株式会社 | Backsheet for solar cell module, laminate, and solar cell module |
| JP5828829B2 (en) | 2011-11-04 | 2015-12-09 | ダイキン工業株式会社 | Paint, coating film, solar cell module backsheet, and solar cell module |
| CN103958196B (en) * | 2011-12-15 | 2016-04-20 | 大金工业株式会社 | Solar cell backboard, solar module and solar battery panel |
| EP3110866A4 (en) * | 2014-02-26 | 2017-10-25 | Daikin America, Inc. | Fluoropolymer structures |
| CN105294914B (en) * | 2014-07-18 | 2017-11-21 | 大金工业株式会社 | Fluorinated copolymer and solvent based coating composition |
| US11072153B2 (en) | 2015-03-31 | 2021-07-27 | Daikin Industries, Ltd. | Composition and laminated body |
| WO2017155022A1 (en) * | 2016-03-10 | 2017-09-14 | ダイキン工業株式会社 | Polymer, composition, coating film, layered product, back sheet, and solar cell module |
| WO2018143029A1 (en) * | 2017-02-03 | 2018-08-09 | ダイキン工業株式会社 | Composition and coating film |
| EP3766942A4 (en) | 2018-03-16 | 2021-12-01 | Daikin Industries, Ltd. | Coating film and coated article |
| JP2021152089A (en) * | 2018-06-12 | 2021-09-30 | Ａｇｃ株式会社 | Powdered coating material, production method for the same, production method for base material having coating film, and coated article |
| US20230109353A1 (en) * | 2020-02-25 | 2023-04-06 | Kanto Denka Kogyo Co., Ltd. | Fluorine-containing copolymer composition |
-
2003
- 2003-03-20 JP JP2003078874A patent/JP4306292B2/en not_active Expired - Lifetime
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| CN1467230A (en) | 2004-01-14 |
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