CN1637087A - Normal temperature solidified aqueous composition - Google Patents

Abstract

There is provided a cold curing aqueous composition which has cold curability as a fluorine-containing coating film component of aqueous coating composition and gives excellent coating film characteristics. The cold curing aqueous composition comprises an aqueous curing agent and a fluorine-containing composite resin (B) obtained by emulsion polymerization of a monomer (b1) having an ethylenic un-saturated group in the presence of a fluorine-containing copolymer (A) having an ethylenic un-saturated group and a water soluble functional group in its molecule.

Description

Normal temperature solidified waterborne compositions

Technical field

The present invention relates to normal temperature solidified waterborne compositions, it has the curability at room temperature as the fluoride coating composition of water-based paint compositions, can give superior coating characteristic.

Background technology

In the past, for fluorine-containing aqueous dispersion, for example open in the clear 62-32102 communique the spy, disclosing at vinylidene is in the presence of the aqueous dispersion of fluoro-resin particle, and seeding polymerization (seedpolymerization) acrylate monomer or methacrylate monomer are carried out the technology of compoundization.But the compound resin that obtains is that the intermiscibility of fluoro-resin and (methyl) acrylic resin is low with vinylidene, and, have that to be difficult to the vinylidene as seeding polymerization kind grain be the shortcoming that fluoro-resin is introduced functional groups such as carboxyl, hydroxyl.

Open in the clear 63-314202 communique the spy, the technology that cooperates linking agent in the fluorine-containing aqueous dispersion is disclosed, wherein, fluorine-containing aqueous dispersion be with the fluoropolymer that is combined with carboxyl on the fluoro-alkyl as dispersion stabilizer, and letex polymerization ethylene type unsaturated monomer obtains in this system.But in this technology, the linking agent of cooperation is not normal temperature solidified linking agent, so produce the problem of dry solidification aspect at room temperature.And, do not use the vinyl monomer of weathering resistance as the ethylene type unsaturated monomer, also insufficient aspect weathering resistance.

Open in the flat 7-238253 communique the spy and to disclose the technology that obtains composite water soluble fluoro-resin dispersion, wherein, with fluoroolefins and non-fluorine is the macromonomer copolymerization, this macromonomer have can with fluoroolefins bonded hydrophilic radical, afterwards the fluoro-resin that obtains is carried out letex polymerization, make aqueous dispersion, carry out seeding polymerization, thereby obtain composite water soluble fluoro-resin dispersion to wherein adding vinyl monomer and emulsifying agent.But, owing to be to obtain becoming the fluoro-resin of kind of grain by letex polymerization, so exist water-soluble functional group such as carboxyl and hydroxyl to be difficult to introduce shortcomings such as fluoro-resin.And, because emulsifying agents etc. are many and do not cooperate linking agent, so there are shortcomings such as chemical resistant properties, solvent resistance, hardness of film, the water tolerance of filming are low.

Open in the flat 9-59560 communique the spy, disclose the technology of aqueous paint composition, said composition contains acrylic acid or the like or the methacrylic copolymer dispersion that fluorine resin aqueous dispersion that letex polymerization obtains and letex polymerization obtain.But the intermiscibility of fluorine resin aqueous dispersion and acrylic acid or the like or methacrylic copolymer dispersion is poor, can not full and uniformly mix low shortcomings such as the weathering resistance of filming that existence obtains, adaptation, gloss.And, do not cooperate solidifying agent, have the shortcoming of the problem that stays at aspects such as chemical resistant properties, solvent resistance, hardness of film, water tolerance.

Open in the 2000-129195 communique the spy, disclose and a kind ofly contained fluorine-containing dispersoid and hydrazine is the fluorinated water based coating composition of solidifying agent, wherein, fluorine-containing dispersoid be the aqueous dispersion that obtains in that fluoroolefin, propylene and ethene are carried out letex polymerization in the presence of, seeding polymerization (methyl) acrylate monomer makes acrylic resin and the compound back described fluorine-containing dispersoid that forms of described aqueous dispersion with carbonyl.But the fluoro-resin that obtains according to the document and the intermiscibility of acrylic resin are low, and (methyl) acrylate monomer is insufficient to the penetration of fluoro-resin dispersion during seeding polymerization, consequently have low shortcomings such as the weathering resistance of filming, gloss.

Summary of the invention

The present invention seeks to eliminate above-mentioned shortcoming in the past, being provided at normal temperature can solidified, can give the normal temperature solidified waterborne compositions of superior coating characteristic.

Promptly the present invention relates to normal temperature solidified waterborne compositions, it contains the aqueous dispersion and the waterborne curing agent of fluorine-containing compound resin (B), described fluorine-containing compound resin (B) be intramolecularly have ethylene type unsaturated group and water-soluble functional group fluorinated copolymer (A) in the presence of, the monomer (b1) that letex polymerization contains the ethylene type unsaturated group obtains.

Fluorinated copolymer (A) preferred acid number is 10～250mgKOH/g.

In addition, the water-soluble functional group that has of fluorinated copolymer (A) is preferably with in the alkali and anionic property functional group and the functional group that obtains.

What fluorinated copolymer (A) preferably contained 10～70 moles of % is selected from least a perhalogeno olefin unit in the group of being made up of tetrafluoroethylene, R 1216 and trifluorochloroethylene as the multipolymer of structural unit.

In addition, as the monomer that contains the ethylene type unsaturated group (b1), preferably contain at least a monomer with bridging property functional group and at least aly contain acrylic acid or the like or the monomeric monomer mixture of methacrylic that carbonatoms is 4～10 alkyl.

As this bridging property functional group, preferably be selected from least a group in the group of forming by carbonyl, hydroxyl and carboxyl.

Normal temperature solidified waterborne compositions of the present invention can further contain the emulsion that non-fluorine is synthetic resins (C), and with solid component meter, preferably containing fluorine-containing compound resin of 95～5 weight parts (B) and the non-fluorine of 5～95 weight parts is synthetic resins (C).

In addition, as described waterborne curing agent, use normal temperature solidified solidifying agent, and, list the hydrazide compound that preferred per molecule has at least 2 hydrazide groups, carbodiimide compound or the hydrophilic polyisocyanate that per molecule has at least 2 carbodiimides.

Preferred relative 1 normal fluorine-containing compound resin (B) and non-fluorine are total functional group of synthetic resins (C), cooperate the solidifying agent of 0.1～5 molar equivalent.

According to the present invention, can easily obtain superior filming such as chemical resistant properties, solvent resistance, hardness of film, water tolerance by Air drying (curing).

Embodiment

Normal temperature solidified waterborne compositions of the present invention comprises the aqueous dispersion and the waterborne curing agent of specific fluorine-containing compound resin (B).

This fluorine-containing compound resin (B) be intramolecularly have ethylene type unsaturated group and water-soluble functional group fluorinated copolymer (A) in the presence of, contain by letex polymerization that the monomer (b1) of ethylene type unsaturated group obtains.

Fluorinated copolymer (A) is the fluorinated copolymer that has ethylene type unsaturated group and water-soluble functional group at intramolecularly, preferably contains the fluoroolefin unit.

As fluoroolefin, can enumerate for example tetrafluoroethylene (TFE), trifluoro-ethylene (TrFE), trifluorochloroethylene (CTFE), R 1216 (HFP), ethylene fluoride (VF), vinylidene (VdF) etc., can use in them one or more, especially preferably contain the multipolymer of 10～70 moles of % perhalogeno olefin units.As particularly preferred fluoroolefin, can enumerate perfluoroolefines such as tetrafluoroethylene or R 1216, it can provide fluorine content many fluoropolymers, have filming of excellent fluoro-resin beneficial effect thereby provide, the beneficial effect of described fluoro-resin for example has chemical resistant properties, water tolerance, solvent resistance, stain resistance, weathering resistance etc.

As water-soluble functional group, preferably with the functional group that obtains with anionic property functional group in the alkali.As such anionic property functional group, can the illustration carboxyl, sulfonic group, phosphate etc., good from the water tolerance of filming, the few angle of the corrosion of metal base is considered preferred carboxyl.

As method from anionic property functional group to fluorinated copolymer (A) that introduce, can adopt the method (copolymerization process) that for example makes the monomer copolymerization that contains anionic property functional group and make the polymkeric substance that contains functional groups such as hydroxyl and dibasic acid anhydride etc. has method (high molecular weight reactive method) that the compound of anionic property functional group reacts etc.

Can enumerate the unsaturated carboxylic acid classes such as unsaturated monocarboxylic, unsaturated dicarboxylic acid, its monoesters or acid anhydrides of the formula of using (I) expression etc. as being used for the monomer of copolymerization process introducing as the carboxyl of anionic property functional group.

(in the formula, R ³, R ⁴And R ⁵Identical or different, all represent hydrogen atom, alkyl, carboxyl or ester group, n is 0～20).Preferred R ³And R ⁴All are hydrogen atoms, and preferred n is 3～15.Preferred especially R ³, R ⁴And R ⁵All be that hydrogen atom and n are 6～10.

As the object lesson of the unsaturated carboxylic acid class of formula (I), can enumerate for example vinylformic acid, methacrylic acid, vinylacetic acid, Ba Dousuan, styracin, 3-allyloxy propionic acid, 3-(2-allyloxy ethoxy carbonyl) propionic acid, methylene-succinic acid, the methylene-succinic acid monoesters, toxilic acid, the toxilic acid monoesters, maleic anhydride, fumaric acid, fumaric monoalkylester, the O-phthalic vinyl acetate, the pyromellitic acid vinyl acetate, the 5-hexenoic acid, the 5-heptenoic acid, the 6-heptenoic acid, the 7-octylenic acid, the 8-nonenoic acid, the 9-decylenic acid, the 10-undecylenic acid, the 11-dodecenoic acid, the 17-octadecenoic acid, oleic acid etc.Wherein, the low Ba Dousuan of homopolymerization, methylene-succinic acid, toxilic acid, toxilic acid monoesters, fumaric acid, fumaric monoalkylester, 3-allyloxy propionic acid, 10-undecylenic acid are owing to be difficult to form homopolymer, so be preferred.Particularly the 10-undecylenic acid is preferred at aspects such as polymerisation reactivity are good, difficult water-disintegrable.

Introduce monomeric other examples as being used for copolymerization process, can enumerate the vinyl ether monomers that contains carboxyl represented with formula (II) etc. as the carboxyl of anionic property functional group.

(in the formula, R ⁶And R ⁷Identical or different, all represent saturated or undersaturated straight chain shape or cyclic alkyl, n is 0 or 1, m is 0 or 1)

As the object lesson of the vinyl ether monomers that contains carboxyl of formula (II), for example can enumerate 3-(2-allyloxy ethoxycarbonyl) propionic acid, 3-(2-allyloxy butoxy carbonyl) propionic acid, 3-(2-vinyloxy group ethoxycarbonyl) propionic acid, 3-(2-vinyloxy group butoxy carbonyl) propionic acid etc. one or more.Wherein, consider that from monomeric stability and the good aspect of polymerisation reactivity 3-(2-allyloxy ethoxycarbonyl) propionic acid etc. is favourable, so be preferred.

Introduce sulfonic monomeric object lesson of containing of anionic property functional group as being used to, can enumerate for example vinyl sulfonic acid etc.

In addition,, for example can enumerate when introducing carboxyl, make the fluoroolefin polymkeric substance that contains hydroxyl and the method for diprotic acid or its anhydride reaction as the high molecular weight reactive method.As diprotic acid or its acid anhydrides, can enumerate for example maleic anhydride, succinyl oxide, methylsuccinic acid acid anhydride, adipic anhydride, L-glutamic acid acid anhydride, itaconic anhydride, citraconic anhydride, 1,2-cyclohexane dicarboxylic acid acid anhydride, 4-methyl isophthalic acid, 2-cyclohexane dicarboxylic acid acid anhydride, cis-4-tetrahydrobenzene-1,2-dicarboxylic anhydride, 1-tetrahydrobenzene-1,2-dicarboxylic anhydride etc., wherein preferred 1,2-cyclohexane dicarboxylic acid acid anhydride, 4-methyl isophthalic acid, 2-cyclohexane dicarboxylic acid acid anhydride, cis-4-tetrahydrobenzene-1,2-dicarboxylic anhydride, 1-tetrahydrobenzene-1, the 2-dicarboxylic anhydride.The solvent that can dissolve fluorinated copolymer and dibasic acid anhydride is used in reaction, can carry out under the condition that is added with catalyzer such as carboxylic metallic salt, alkaline carbonate, alkali metal alcoholates, quaternary ammonium salt, tertiary amine when introducing carboxyl.

Narration converts these anionic property functional groups to the method for water-soluble functional group below.

As method from the ethylene type unsaturated double-bond to fluorinated copolymer (A) that introduce, can enumerate the method (copolymerization process) of the monomer copolymerization that makes the ethylene type unsaturated double-bond that has more than 2 or 2, and make and have functional group (carboxyl for example in advance, hydroxyl, amino, oxyethyl group, carbonyl, isocyanate group, silanol group etc.) monomer copolymerization, then make have can with the functional group of these functional group reactionses (carboxyl for example, hydroxyl, silanol group, hydrazide group, amino etc.) and the compound of ethylene type unsaturated double-bond reaction and introduce the method (high molecular weight reactive method) of ethylene type unsaturated double-bond.

As the monomer with 2 or 2 above ethylene type unsaturated double-bonds that can be used for copolymerization process, can the illustration divinyl, isoprene, chloroprene, fluoroprene, cyano group divinyl, phenyl butadiene, diphenyl diethylene, α, diene type monomers such as ω-diolefine; Polyfunctional carboxylic acids vinyl acetate such as hexanodioic acid divinyl ester, vinyl acrylate, methacrylic vinyl acetate, Vinyl crotonate; Ethylene aromatic dicarboxylate esters such as vinyl cinnamate etc.

For the high molecular weight reactive method, the situation that for example with the functional group is carboxyl is that representative describes.Method from carboxyl to multipolymer (A) that introduce can adopt the introducing method of above-mentioned anionic property functional group.

Make the fluoropolymer that contains carboxyl (a1) that obtains and have and to react with the functional group of carboxyl reaction and the compound (a2) of ethylene type unsaturated double-bond.

As can with the functional group of carboxyl reaction, can enumerate isocyanate group, epoxy group(ing), amino, carbodiimide etc., wherein, isocyanate group and epoxy group(ing) are because can be promptly and carboxyl reaction, so be preferred.

As compound (a2), can enumerate the compound that 2-ethyl isocyanate base methacrylic acid ester etc. for example contains isocyanate group; Glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether etc. contain the compound of epoxy group(ing) etc.

Wherein, preferred 2-ethyl isocyanate base methacrylic acid ester, glycidyl methacrylate, glycidyl acrylate etc.

In addition, though isocyanate group also with hydroxyl reaction, but preferential and carboxyl reaction.

The reaction of compound (a2) and fluoropolymer (a1) can be implemented by in organic solvent both being mixed.As preferred reaction conditions, can adopt temperature of reaction is 20～150 ℃, 1～15 hour condition of reaction.

As long as organic solvent can dissolve fluoropolymer and compound, for example can use the organic solvent that in the polymerization of fluoropolymer (a1), uses.

1 mole of carboxyl in the relative fluoropolymer (a1), the functional group of compound (a2) is 1～0.01 mole, is preferably 1～0.1 mole, particularly 1～0.9 mole, determines the amount of the compound (a2) that reaction is required with this.

In addition, fluorinated copolymer (A) can have bridging property functional group, also can not have bridging property functional group, but in order to improve coating strength, water tolerance, solvent resistance, adaptation, hardness of film etc., preferably contains bridging property functional group.

As bridging property functional group, bridging property functional group kind that corresponding aftermentioned solidifying agent is had and non-fluorine are that the bridging property functional group kind that has of synthetic resins etc. is selected, and preferably are selected from least a group in the group of being made up of carboxyl, hydroxyl and carbonyl.Combination for bridging property functional group and solidifying agent will be set forth in the back.

As the monomer that contains bridging property functional group is the monomer that contains carboxyl, and it contains the monomeric object lesson of carboxyl, the monomer of can the above-mentioned introducing anionic property of illustration functional group using that contains carboxyl.That is, carboxyl had both been brought into play the effect of the functional group that gives acid number, brought into play the effect of bridging property functional group again, especially preferably converted water-soluble functional group water-soluble to make (giving acid number) as described later like that to.

As the monomer that contains bridging property functional group is the monomer that contains hydroxyl, and it can enumerate hydroxyalkyl vinyl ether, the hydroxyalkyl allyl ethers of for example using formula (III) expression as the monomeric object lesson that contains hydroxyl,

CH ₂＝CHR ¹?????????(III)

(in the formula, R ¹Expression-OR ²Perhaps-CH ₂OR ², wherein, R ²Be alkyl) with hydroxyl.As R ², for example be to be to connect the group that forms behind 1～3, preferred 1 hydroxyl on 1～8 straight chain shape or the branched-chain alkyl at carbonatoms.As these monomeric examples, can enumerate for example 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methyl propyl vinyl ether, 4-hydroxy butyl vinyl ether, 4-hydroxy-2-methyl butyl vinyl ether, 5-hydroxyl amyl group vinyl ether, 6-hydroxyl hexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxyl butyl allyl ethers, allylin etc.Wherein, the polymerisation reactivity of 4-hydroxy butyl vinyl ether, 2-hydroxyethyl vinyl ether, the solidified nature of functional group are superior, so be preferred.

As the monomer that contains bridging property functional group, it contains the monomeric object lesson of carbonyl, can enumerate the vinyl monomer that contains carbonyl of for example using formula (IV) expression

(in the formula, R ⁶, R ⁷And R ⁸Identical or different, all represent hydrogen atom, alkyl, carboxyl or ester group; N is 0 or 1); Perhaps the vinyl ether type monomer of representing with formula V that contains carbonyl or allyl ethers type monomer etc.

(in the formula, R ⁹And R ¹⁰Identical or different, all represent saturated or undersaturated chain or cyclic divalent alkyl; N is 0 or 1; M is 0 or 1)

As the monomeric object lesson that contains carbonyl, can enumerate for example vinyl alkyl ketone such as propenal, diacetone-acryloamide(DAA), diacetone Methacrylamide, ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone etc.

Wherein, vinyl ether type and allyl ethers type are good with the copolymerization of fluoroolefin, so be preferred.

In fluorinated copolymer (A), as required can copolymerization other can copolymerization monomer.

As other can copolymerization monomer, can enumerate vinyl carboxylates class, alkyl vinyl ethers, non-fluorine is olefines etc.

As the vinyl carboxylates class, can enumerate for example vinyl-acetic ester, propionate, vinyl butyrate, isopropylformic acid vinyl acetate, trimethylacetic acid vinyl acetate, vinyl caproate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, cyclohexane carboxylic acid vinyl acetate, vinyl benzoate, p-tert-butyl benzoic acid vinyl acetate etc., its raising, the glossy that can give intermiscibility improves, the characteristics such as rising of glass transition temp.

As the alkyl vinyl ethers, can enumerate for example methylvinylether, ethyl vinyl ether, butyl vinyl ether etc., it can be given, and glossy improves, the characteristics such as raising of flexibility.

As non-fluorine is olefines, can enumerate for example ethene, propylene, n-butene, iso-butylene etc., can give characteristics such as flexual raising.

For the molecular weight of fluorinated copolymer (A), consider that from the solution polymerization aspect preferred number average molecular weight is smaller or equal to 200,000, and then preferably smaller or equal to 100,000, especially preferably smaller or equal to 50,000; Consider that from the angle of weathering resistance, superior durability preferred number average molecular weight is more than or equal to 1,000, further be preferably greater than and equal 4,000, be preferably greater than especially and equal 8,000.

As previously mentioned, usually the fluorinated copolymer of using with letex polymerization manufactured water-borne coatings that contains functional group directly is modulated into the form (spy open flat 7-238253 communique, spy are opened flat 9-59560 communique, the spy opens the 2000-129195 communique) of aqueous dispersion or emulsion.But, as previously mentioned, adopt emulsion polymerization, copolymerization contains the monomer of water-soluble functional group in large quantities, and the material of macromolecule is only arranged.

Therefore, make fluorinated copolymer (A) to use organic solvent as the solution polymerization process of polymer solvent, whereby, the monomer that contains water-soluble functional group stably can be supplied to polymerization system, can make the water-soluble fluorinated copolymer of expectation, and, also can adjust molecular weight (make molecular weight low).

As technology with the so water-soluble fluorinated copolymer of solution polymerization manufactured, be known (for example spy open clear 62-143915 communique, spy are opened clear 63-152677 communique, the spy opens flat 1-249866 communique etc.) in the field of electroplating coating, also can utilize those methods in the present invention.

More particularly, by with fluoroolefin and contain the monomer of functional group's (water-soluble functional group, ethylene type unsaturated double-bond etc.) and add as required can with monomer polymerization in organic solvent of their copolymerization, make the fluorinated copolymer (A) that uses among the present invention.

As polymerizing condition, preferably in organic solvent, in the presence of polymerization starter, polymerization temperature is 10～90 ℃ of polyreactions of carrying out 1～20 hour.

As organic solvent, can enumerate ester classes such as methyl acetate, ethyl acetate, propyl acetate, butylacetate; Ketones such as acetone, methylethylketone, pimelinketone; Hydro carbons such as hexane, hexanaphthene, octane; Benzene,toluene,xylene, naphthalene etc. are aromatic hydrocarbon based; Alcohols such as methyl alcohol, ethanol, the trimethyl carbinol, Virahol, ethylene glycol monoalkyl ether; Ring-type ethers such as tetrahydrofuran (THF), tetrahydropyrans, diox; Dimethyl sulfoxide (DMSO) etc.; Perhaps their mixture etc.Wherein, acetone, ethyl acetate, Virahol are being favourable aspect the solvability of fluoro-resin, and acetone, ethyl acetate when the preparation of water-based emulsion easily distillation remove, so be most preferred.

As polymerization starter, can use for example diacyl peroxide classes such as peroxidation decoyl, acetyl peroxide, benzoyl peroxide; Dialkoxy carbonyl peroxides such as isopropoxy carbonyl superoxide, tert-butoxycarbonyl superoxide; Ketone peroxide classes such as methyl ethyl ketone peroxide, pimelinketone superoxide; Hydroperoxide kinds such as hydrogen peroxide, tertbutyl peroxide, cumene hydroperoxide; Dialkyl peroxide such as ditertiary butyl peroxide, dicumyl peroxide class; Alkyl peroxyesters such as tert-butyl hydroperoxide acetic ester, tert-butyl hydroperoxide trimethylacetic acid ester; Persulfuric acid such as ammonium persulphate, Potassium Persulphate salt (and also can and using reductive agents such as sodium bisulfite, Sodium Pyrosulfite, cobalt naphthenate, xylidine as required); The redox initiator class that constitutes by oxygenant (for example ammonium peroxide, Potassium peroxide etc.) and reductive agent (for example S-WAT etc.) and transition metal salt (for example ferric sulfate etc.); 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-cyano group pentenoic acids) etc.

And as required, also can use alcohols such as methyl alcohol, ethanol, propyl alcohol etc. as molecular weight regulator.

The fluorinated copolymer that obtains like this (A) can give high acid number, i.e. the acid number of 10～250mgKOH/g.If acid number is less than 10mgKOH/g, then the fluoroolefin multipolymer can not form water-soluble, if just can not be evenly dispersed in the water in fact by dispersion agent or emulsifying agent.

On the other hand, if acid number surpasses 250mgKOH/g, then wetting ability is excessive, reductions such as the water tolerance of filming that obtains, alkali resistance.The lower limit of preferred acid number is 40mgKOH/g, further preferred 50mgKOH/g, preferred especially 55mgKOH/g.In addition, the preferred upper limit is 150mgKOH/g, further preferred 130mgKOH/g, preferred especially 120mgKOH/g.

For the fluorinated copolymer that obtains (A), add in the polymerization liquid by polymerization liquid is dropped in the water or with water, thereby with the organic solvent phase inversion in the polymerization liquid in water, obtain water miscible fluorinated copolymer.At this moment, for improving the water-soluble of fluorinated copolymer,, preferably carry out neutralizing treatment with before anionic property functional group phase inversion is in water or during phase inversion or behind the phase inversion.

As being used for the neutral neutralizing agent, can enumerate ammonia; Organic amines such as diethylamine, ehtylethanolamine, diethanolamine, monoethanolamine, single Propanolamine, Yi Bingchunan, ethylamino ethamine, aminoethyle alcohol, diethylenetriamine; Alkali metal hydroxide such as sodium hydroxide, potassium hydroxide etc.Wherein, ammonia, triethylamine, diethanolamine are preferred at the aspects such as stability of the easiness that obtains, emulsion, and particularly ammonia and triethylamine are favourable aspect easy handling.

Neutralizing agent preferably uses with the form of the aqueous solution, but also can use with the form of gas or solids component.

The neutral result is that anionic property functional group forms the form of ammonium salt, amine salt, an alkali metal salt.

For neutralization, with in the neutralizing agent and acid number be equivalent to more than or equal to 1mgKOH/g, be preferably greater than and equal 2mgKOH/g, and get final product smaller or equal to 250mgKOH/g, the anionic property functional group that preferably has smaller or equal to the 245mgKOH/g multipolymer.

In the present invention, use in the presence of described fluorinated copolymer (A) letex polymerization to contain the monomer (b1) of ethylene type unsaturated group and the fluorine-containing compound resin (B) that obtains.

As the monomer that contains the ethylene type unsaturated group (b1), use monomer to get final product with various characteristics.For example for giving fluorine-containing compound resin (B) water-soluble or water dispersible, use contains carboxyl and/or the sulfonic monomer that contains the ethylene type unsaturated group gets final product, for giving fluorine-containing compound resin (B) adaptation, the such characteristic of pigment-dispersing, use the monomer that contains the ethylene type unsaturated group to get final product with carboxyl, amino, amide group, epoxy group(ing).In addition, use and have bridging property functional group for example hydroxyl, carboxyl, carbonyl, the amino monomer that contains the ethylene type unsaturated group get final product for giving the such characteristic of bridging property.

And then, be to improve weather resisteant, suitable is contains the monomer that contains the ethylene type unsaturated group that carbonatoms is 4～10 alkyl.Special preferably contain at least a monomer with bridging property functional group and at least aly contain acrylic acid or the like or the monomeric monomer mixture of methacrylic that carbonatoms is 4～10 alkyl.

As the object lesson of the monomer that contains the ethylene type unsaturated group (b1), can enumerate for example (methyl) acrylic acid lower alkyl esters classes such as methyl acrylate, n-butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA; (methyl) acrylic acid carbonatomss such as ethyl acrylate, methacrylic acid-2-ethylhexyl, cyclohexyl acrylate, cyclohexyl methacrylate are 4～10 alkyl esters; Unsaturated carboxylic acid classes such as vinylformic acid, methacrylic acid, toxilic acid, Ba Dousuan; Amide compound classes such as acrylamide, Methacrylamide, N methacrylamide, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide, N-methylol methacrylamide, N-methyl acrylamide, N-fourth oxygen methyl acrylamide; Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410 etc. contain the monomer class of hydroxyl; Glycidyl acrylate, glycidyl methacrylate etc. contain the monomer class of epoxy group(ing); γ-Trimethoxy silane methacrylic ester, γ-triethoxyl silane methacrylic ester etc. contains the monomer class of siloxanes; Propenal etc. contain the monomers more than a kind or a kind such as monomer class of aldehyde radical.

Wherein, angle high from polymerizability and that commercially available monomer is abundant is considered preferred (methyl) acrylic monomer.

Letex polymerization is called as so-called seeding polymerization, itself is technique known, for example can open the method for middle records such as 2002-179871 communique with the spy and implement.

The solids component of relative 100 weight part fluorinated copolymers (A), these monomers (b1) that contain the ethylene type unsaturated group preferably use more than or equal to 10 weight parts and then more than or equal to 50 weight parts, particularly more than or equal to 100 weight parts, and smaller or equal to 2000 weight parts and then smaller or equal to 1000 weight parts, particularly smaller or equal to 500 weight parts.

Normal temperature solidified waterborne compositions of the present invention contains the aqueous dispersion of the fluorine-containing compound resin (B) that obtains like this and waterborne curing agent, particularly normal temperature solidified solidifying agent.

Solid component concentration in the aqueous dispersion of fluorine-containing compound resin (B) can be adjusted in the scope of 30～70 weight % usually.

It can be the waterborne curing agent that crosslinking reaction takes place for the bridging property functional group of synthetic resins (C) side (below, only be called " resin side " in the explanation of solidifying agent) with introducing fluorine-containing compound resin (B) or non-fluorine described later that the waterborne curing agent that cooperates adopts.

As waterborne curing agent, can the illustration carbodiimide compound, normal temperature solidified waterborne curing agent such as wetting ability (end-sealed type or non-end-sealed type) isocyanic ester, hydrazide compound, aziridine.

As carbodiimide compound, can use the compound of for example opening record in clear 63-264128 communique, No. 4820863 specification sheets of U.S.'s patent of invention, No. 5108653 specification sheets of U.S.'s patent of invention, No. 5047588 specification sheets of U.S.'s patent of invention, No. 5081173 specification sheets of U.S.'s patent of invention etc. the spy.As water-borne coatings with known Carbojilite E-01, the Carbojilite E-02 that has day to spin (strain) clearly to produce of carbodiimide compound, Carbojilite V-02 etc.

As hydrophilic isocyanate, also can use known blocked isocyanate, but the preferred superior non-blocked isocyanate compound of ambient cure.

As non-blocked isocyanate, suitable the is spy opens flat 11-310700 communique, spy open the non-blocked isocyanate compound after compound modified with polyoxyethylene that flat 7-330861 communique, spy are opened record in the clear 61-291613 communique etc.

In addition, so-called non-blocked isocyanate compound is meant isocyanate compound except that the blocked isocyanate compound that is obtained by alcohol or oxime and isocyanate compound reaction, common.

Specifically, can illustration with non-end-sealed type aliphatic polyisocyanate compound or non-end-sealed type aromatic polyisocyanate compound after the polyoxyethylene compound modification.Wherein, consider preferred non-end-sealed type aliphatic isocyanates compound from the superior angle of weather resisteant.

In the aliphatic polyisocyanate compound, as the chain aliphatic polyisocyanate compound, can illustration trimethylene diisocyanate for example, tetramethylene diisocyanate, 1, the diisocyanate based hexane of 6-(being hexamethylene diisocyanate), pentamethylene diisocyanate, 1, the 2-trimethylene diisocyanate, 1,2-butylidene vulcabond, 2,3-butylidene vulcabond, 1,3-butylidene vulcabond, 2,4,4-or 2,2, the 4-trimethyl hexamethylene diisocyanate, 2, diisocyanates such as 6-vulcabond methylhexanoic acid ester; Methionin ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-is diisocyanate based-4-isocyanic ester methyloctane, 1,3,6-triisocyanate base hexane, 2,5,7-trimethylammonium-1,8-is diisocyanate based-polyisocyanates such as 5-isocyanic ester methyloctane.

In the aliphatic polyisocyanate compound, as the alicyclic polyisocyanates compound, can illustration for example 1,3-cyclopentenes vulcabond, 1,4-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, 1-isocyanate group-3,3,5-trimethylammonium-5-isocyanatomethyl-hexanaphthene (being isophorone diisocyanate), 4,4 '-methylene radical two (cyclohexyl isocyanate), methyl-2,4-cyclohexyl diisocyanate, methyl-2,6-cyclohexyl diisocyanate, 1,3-or 1, diisocyanates such as 4-two (isocyanic ester methyl) hexanaphthene; 1,3,5-three isocyanato cyclohexaness, 1,3,5-trimethylammonium isocyanato cyclohexanes, 2-(3-isocyanic ester propyl group)-2,5-two (isocyanic ester methyl)-two ring (2.2.1) heptane, 2-(3-isocyanic ester propyl group)-2,6-two (isocyanic ester methyl)-two ring (2.2.1) heptane, 3-(3-isocyanic ester propyl group)-2,5-two (isocyanic ester methyl)-two ring (2.2.1) heptane, 5-(2-isocyanic ester ethyl)-2-isocyanic ester methyl-3-(3-isocyanic ester propyl group)-two ring (2.2.1) heptane, 6-(2-isocyanic ester ethyl)-2-isocyanic ester methyl-3-(3-isocyanic ester propyl group)-two ring (2.2.1) heptane, 5-(2-isocyanic ester ethyl)-2-isocyanic ester methyl-2-(3-isocyanic ester propyl group)-two ring (2.2.1) heptane, 6-(2-isocyanic ester ethyl)-polyisocyanates such as 2-isocyanic ester methyl-2-(3-isocyanic ester propyl group)-two ring (2.2.1) heptane.

As aromatic isocyanate compound, can enumerate for example tolylene diisocyanate etc.

These isocyanate compounds can use separately or be used in combination more than 2 kinds or 2 kinds.

Polyoxyethylene compound as properties-correcting agent, can illustration as the known compound of non-ionic emulsifier, as the Voranol EP 2001 class, polyoxyethylene C8～24 alkyl oxides such as polyoxyethylene list Octyl Ether, polyoxyethylene list lauryl ether, polyoxyethylene list decyl ethers, polyoxyethylene list cetyl ether, polyoxyethylene list octadecyl ether, polyoxyethylene list oleyl ether for example, preferred polyoxyethylene C10～22 alkyl oxides, preferred especially polyoxyethylene C12～18 alkyl oxides etc.; Polyoxyethylene monoalkyl aryl ethers is as polyoxyethylene C8～12 alkyl-C6～12 aryl ethers such as polyoxyethylene list octyl phenyl ether, polyoxyethylene list nonylplenyl ether, polyoxyethylene list decyl phenyl ether etc.; Polyoxyethylene sorbitol acid anhydride high-grade aliphatic ester class is as polyoxyethylene sorbitol acid anhydride-lists such as Tween-20, Tween-60, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitol acid anhydride SUNSOFT Q-182S, polyox-yethylene sorbitan tristearate, two or three C10～24 fatty acid esters etc.; Polyoxyethylene list high-grade aliphatic ester class is as polyoxyethylene list C10～24 fatty acid esters such as Vinlub 73, polyoxyl 40 stearate etc.; Or the like.These compounds can use separately or be used in combination more than 2 kinds or 2 kinds.Be easy to angle from water dispersible and consider, preferred compound can be enumerated polyoxyethylene C8～24 alkyl oxides, polyoxyethylene C8～12 alkyl phenyl ethers.

For modification, for example can be undertaken by in solution, isocyanate compound mixed, heat methods such as making its reaction with properties-correcting agent.

For the ratio of described polyisocyanate compound and properties-correcting agent, 1 is normal polyisocyanate-based in the relative polyisocyanate compound, and the active hydrogen atom of properties-correcting agent can be selected in 0.01～0.034 equivalent, preferred 0.015～0.03 normal scope.

As the commercially available product of the non-blocked isocyanate compound that gathers the cyclohexane modification, can enumerate for example Sumitomo Bayer urethane (strain) (Sumitomo Bayer Urethane Co., Ltd.) Bayhydur 3100 of Sheng Chaning, Bayhydur TPLS2150 etc.; The DuranateWB40-100 that Asahi Chemical Industry's (strain) produces etc., but be not limited to these.

Non-blocked isocyanate compound uses with the form of the aqueous solution or aqueous dispersions usually.

As hydrazide compound, can enumerate that the spy opens flat 7-268163 communique, the spy opens the compound of putting down in writing in the flat 9-291186 communique, can enumerate ethylene acid hydrazide, propanedioic acid two hydrazides, amber acid dihydrazide, pentanedioic acid two hydrazides, adipic dihydrazide, m-phthalic acid two hydrazides, sebacic dihydrazide, Malaysia acid dihydrazide, fumaric acid two hydrazides, methylene-succinic acid two hydrazides etc. particularly and contain 2～10, the dicarboxyl acid dihydrazide of 4～6 carbon atoms particularly; Ethene-1,2-two hydrazides, propylene-1,3-two hydrazides, butene-1,4-two hydrazides etc. have aliphatic water-soluble two hydrazides of 2～4 carbon atoms etc., wherein preferred adipic dihydrazide, m-phthalic acid two hydrazides, sebacic dihydrazide.

For example, the combination below can illustration.

(1) the bridging property functional group of resin side is the situation of carboxyl:

Can enumerate for example epoxy compounds, carbodiimide compound, trimeric cyanamide etc.

Wherein, particularly per molecule has carbodiimide compound room temp solidified good of at least 2 carbodiimides, so be preferred.

(2) the bridging property functional group of resin side is the situation of hydroxyl:

Can enumerate hydrophilic isocyanate, trimeric cyanamides etc. such as for example non-blocked isocyanate compound, blocked isocyanate compound.

Wherein, particularly the room temp solidified of hydrophilic polyisocyanate well and as water-borne coatings has good characteristic with solidifying agent, so be preferred.

(3) the bridging property functional group of resin side is the situation of carbonyl:

Can enumerate for example hydrazide compound, Grignard compound etc.

Wherein, particularly per molecule has hydrazide compound room temp solidified good of at least 2 hydrazide groups and has good characteristic as water-borne coatings with solidifying agent, so be preferred.

(4) the bridging property functional group of resin side is the situation of ethylene type unsaturated group:

Can enumerate the low-molecular weight compound that for example contains active methylene group, the resin that contains active methylene group etc.

Wherein, particularly 1, the 3-dicarbonyl compound, contain 1, the resin of 3-dicarbapentaborane room temp solidified good and have good characteristic with solidifying agent as water-borne coatings is so be preferred.

In any case, relative resin side 1 normal bridging property functional group (fluorine-containing compound resin (B) or non-fluorine are whole functional groups of synthetic resins), the use level of waterborne curing agent all preferably cooperates 0.1～5 molar equivalent.

And then, also can cooperate known curing catalyst etc.As curing catalyst, can illustration dibutyl tin dilaurate etc. for example.

In waterborne compositions of the present invention, can also cooperate non-fluorine as required is synthetic resins (C).As fit system, be preferably aqueous liquid dispersion or emulsion.As non-fluorine is synthetic resins, can enumerate for example acrylic resin, urethane resin, vibrin, Resins, epoxy etc., wherein, the weathering resistance of acrylic resin, urethane resin, vibrin, weather resistance, water tolerance, hardness, intensity, bendability, gloss, adaptation are good, so be preferred, the weathering resistance of acrylic resin, gloss, hardness, water tolerance are more superior, so be particularly preferred.

And then non-fluorine is that synthetic resins (C) can have bridging property functional group, also can not have bridging property functional group, but considers from improving aspects such as weathering resistance, water tolerance, hardness, stain resistance, preferably introduces bridging property functional group.About bridging property functional group, can adopt above-mentioned material and comprise the introducing monomer.

With solid component meter, fluorine-containing compound resin (B) and non-fluorine are that the use level of synthetic resins (C) is 95～5 weight parts (B) and 5～95 weight parts (C), are preferably 10～90 weight parts (B) and 90～10 weight parts (C).

Among the present invention,, can obtain weathering resistance, water tolerance, stain resistance, the superior normal temperature solidified waterborne compositions of anti-rain stain contaminative by cooperating waterborne curing agent.

Normal temperature solidified waterborne compositions of the present invention can be modulated into solvent-borne type or water-based paint compositions.At this moment, as the coating additive that can cooperate, except that above-mentioned solidifying agent, can enumerate for example tensio-active agent, pigment, dispersion agent, tackifier, sanitas, UV light absorber, defoamer, smooth agent etc.

As tensio-active agent, can use above-mentioned tensio-active agent.

In addition, can illustration Primal QR708 (Rohm ﹠amp as tackifier; Haas Co., Ltd.) society produces) etc., can illustration Byk023 (BYK Chemie Japan Ltd.) etc. as defoamer, can illustration Byk190 (BYK Chemie Japan Ltd.), SNDISPERANT5027 (SAN NOPCO LIMITED) etc. as dispersion agent.

The aqueous paint composition that obtains can effectively be used as weatherability coating, electroplating coating, coil cord with coating, automotive coating, anti-scribbling with various coating materials such as coating, heavy duty systems.As coating method, can adopt the common coating method that is used for these coating, for example roller coat, dip-coating, brushing, spraying, roller coating etc. or plating covering with paint method etc.

Can make its curing by filming of forming of composition of the present invention at normal temperature.This is the action effect of employed composition, even said composition can be introduced bridging property functional group and also can fully be cured reaction in room temperature in fluorine-containing compound resin morely.In addition, also can heat for promoting to solidify.

Paint film defects such as solidify filming of obtaining and carried out solidifying (crosslinked) fully, compare with the fluoro-resin water-borne coatings that letex polymerization obtains, coating strength, solvent resistance, stain resistance are improved, and outward appearance is also level and smooth, and gloss shifting, color and luster are gloomy have also reduced.

In addition, under the situation that is modulated into the solvent based coating composition, organic solvent, pigment, defoamer, tackifier, dispersion agent, equal paint, solidifying agent etc. be can in containing fluorine graft copolymer, cooperate, its dispersion or dissolving made.

In addition, waterborne compositions of the present invention also can be modulated into binder composition, ink with compositions such as compositions with known method.

Embodiment

Enumerate embodiment below and specifically describe the present invention, but the present invention also only is not limited to these embodiment.

Synthesis example 1

To the VEOVA9 of the stainless steel autoclave adding of 6L 1.25kg acetone, 220g (tertiary ethylene carbonate that shell chemistry society produces), 47g vinyl benzoate, 109g hydroxy butyl vinyl ether, carry out nitrogen replacement, add the 300g tetrafluoroethylene again, be warming up to 61.5 ℃.Then, under agitation add 20g sim peroxides solution (solids component is 70 weight %), reacted stopped reaction when the reaction vessel internal pressure is reduced to 0.25MPaG 5 hours.Reaction mixture is cooled to room temperature, further carries out nitrogen replacement after removing unreacted monomer, obtain 1.8kg reaction product (solids component is 31.6 weight %).The multipolymer that obtains is used ¹⁹The F-nucleus magnetic resonance and ¹The H-nucleus magnetic resonance is analyzed, and tetrafluoroethylene/VEOVA9/ vinyl benzoate/hydroxy butyl vinyl ether is 46/27/7/20 (molar percentage), is 20000 with the number-average molecular weight Mn of gel permeation chromatography, and hydroxyl value is 90mgKOH/g.

Synthesis example 2

Polymkeric substance that contains hydroxyl that in the 3L four-hole boiling flask that has agitator, obtains in the synthesis example 1 of adding 900g and the 4-methyl isophthalic acid of 66g, 2-cyclohexane dicarboxylic acid acid anhydride (the リ カ シ Star De MH700 that new Japanese physics and chemistry (strain) is produced).After further adding the 4g triethylamine, slowly heat up.After solution in the flask reaches 70 ℃, keep this temperature to react.The state that carries out of reaction is followed the trail of with the Infrared spectroscopy device, does not observe the 1860cm of acid anhydrides after 3 hours ^-1And 1790cm ^-1Absorption, at 1733cm ^-1See the strong absorption of ester.In addition, the acid number of this polymkeric substance is 90mgKOH/g.

The 2-ethyl isocyanate ylmethyl acrylate that adds 15.7g in this polymkeric substance 40 ℃ of reactions 3 hours, thereby is introduced the ethylene type unsaturated group.The hydroxyl value of the multipolymer that obtains is 70mgKOH/g.

Then, in this polymers soln, add 28% ammoniacal liquor of 42g, in and the carboxylic acid group.Decompression is slowly removed organic solvent down from the neutralizer that obtains, add 0.82kg water lentamente simultaneously, obtains the uniform aqueous solution (solids component is 30 weight %).

Synthesis example 3

The aqueous solution that adds the fluorinated copolymer that obtains in the 954.6g synthesis example 2 in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler adds the composition of following composition again.

Form:

Diacetone-acryloamide(DAA) 67g

Methyl methacrylate 238.2g

Ethyl acrylate 120g

N-butyl acrylate 243g

Then, adding is dissolved in the 0.7g ammonium persulphate aqueous solution that forms in the 6.3g water, 80 ℃ of polymerizations 2 hours, and then the 10 weight % ammonium persulfate aqueous solutions of dropping 7.7g, further keep making in 2 hours its reaction at 80 ℃, cooling then, then being adjusted to pH with ammoniacal liquor is 8.5, obtains the aqueous dispersion that solids component is 52 weight %.

Synthesis example 4

As synthesis example 1, wherein, the amount of VEOVA9 is set at 183.2g, replaces vinyl benzoate with 22.4g methacrylic vinyl acetate, in addition,, obtain containing the fluorinated copolymer of carboxyl by the operation same with synthesis example 1.This acid number that contains the polymkeric substance of carboxyl is 90mgKOH/g.

Synthesis example 5

The aqueous solution that adds the fluorinated copolymer that obtains in the 954.6g synthesis example 4 in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler adds the composition of following composition again.

Form:

Diacetone-acryloamide(DAA) 67g

Methyl methacrylate 238.2g

2-EHA 120g

N-butyl acrylate 243g

Then, adding is dissolved in the 0.7g ammonium persulphate aqueous solution that forms in the 6.3g water, 80 ℃ of polymerizations 2 hours, and then the 10 weight % ammonium persulfate aqueous solutions of dropping 7.7g, further keep making in 2 hours its reaction at 80 ℃, cooling then, then being adjusted to pH with ammoniacal liquor is 8.5, further add entry, obtain the aqueous dispersion that solids component is 50 weight %.

Embodiment 1 (preparation of normal temperature solidified waterborne compositions)

In 100ml polymerization beaker, cooperate the fluorine-containing compound resin and the 15 weight part adipic dihydrazide (Da mound chemistry (strain) that obtain in the 100 weight part synthesis examples 3 to produce), obtain water-borne coatings with curable composition.

To this water-borne coatings of counting 100 weight parts with solids component with curable composition in, add titanium oxide (titanium white (TIPEK) CR-97 of 50 weight parts as weighting agent, the former industry of stone (strain) is produced), 2 weight parts are as the poly carboxylic acid ammonium salt of NOPCOSPERSE SN5027 (the SAN NOPCO LIMITED) production of dispersion agent), 1 weight part is as the ethylene glycol of frostproofer, 0.5 weight part is as the FS ANTIFOAM 013B (Dow Corning production) of defoamer, 10 weight parts are as the CS-12 (production of Chisso company) of tackifier, use dispersator to mix fully, preparation coating.

Use this coating of material feeder application, place 5 angel's curing of coating, make sample in room temperature.At this sample, investigate following characteristic.The results are shown in the table 1.

Outward appearance: the outward appearance of filming by visual observation.

The gloomy many time marquis of gloss shifting or color and luster are set at C, are set at B when existing gloss shifting or some color and luster gloomy, and lackluster not even color and luster is set at A in the time of gloomy.

Gloss: the mirror surface luster of measuring 60 degree according to JIS K5400.

Water-fast warm nature: will film and flood 24 hours in 50 ℃ warm water, visual observation is subsequently filmed.

Do not have unusual situation to be set at A, see that the situation of some white absurd creatures, delustring is set at B, see that the situation of significant white absurd creature, delustring is set at C, the dissolved situation of filming is set at D.

Solvent-resistance test: use the nonwoven fabric that has flooded dimethylbenzene that film coated surface is carried out wiping operation.Till wiping operation proceeds to and finishes for 100 times repeatedly.

After test stops, find to film and do not find that the situation that dissolving or gloss reduce is set at A, the situation that find to film dissolving a little or gloss reduce is set at B, finds that the situation that significantly dissolving or gloss reduce is set at C.

Atmospheric exposure test: carry out 2000 hours weather-proof accelerated tests by Exposure to Sunlight weather colour fastness instrument (SUGA trier (strain) production).

Luminance difference (Δ E) is set at A more than or equal to 0 less than 2 situation, is set at B more than or equal to 2 less than 4 situation, is set at C more than or equal to 4 less than 6 situation, is set at D more than or equal to 6 less than 10 situation, and the situation more than or equal to 10 is set at E.

Embodiment 2

Except that use the polymkeric substance of producing in the synthesis example 5 as fluorine-containing compound resin, prepare coating similarly to Example 1, make coated plate and then make sample.Similarly to Example 1, the sample that obtains is investigated coating characteristic.The results are shown in the table 1.

Table 1

	Embodiment
			????1	????2
	The fluorine-containing composite dispersion
The synthesis example sequence number			Synthesis example 3	Synthesis example 5
	Use level (solids component weight part)	????100			????100
Solidifying agent (weight part)
	Adipic dihydrazide	????15			????15
The rerum natura of filming
	Outward appearance	????A			????A
Gloss			????80	????82
	The heatproof water-based	????A			????A
Solvent resistance			????A	????A
	Weathering resistance	????A			????A

Synthesis example 6

Trimethylacetic acid vinyl acetate (the JAPAN VAM﹠amp that in the stainless steel autoclave of 6L, adds 1.25kg acetone, 244.4g; POVAL CO., LTD. produces), the 10-undecylenic acid of 192.0g, carry out nitrogen replacement, add the 300g tetrafluoroethylene again, be warming up to 61.5 ℃.Then, under agitation add 11.6g sim peroxides solution (solids component is 70 weight %), reacted stopped reaction when the reaction vessel internal pressure is reduced to 0.25MPaG 8 hours.Reaction mixture is cooled to room temperature, further carries out nitrogen replacement behind the removing unreacted monomer, obtain 2.0kg reaction product (solids component is 35.3 weight %).The multipolymer that obtains is used ¹⁹The F-nucleus magnetic resonance and ¹The H-nucleus magnetic resonance is analyzed, and tetrafluoroethylene/trimethylacetic acid vinyl acetate/10-undecylenic acid is 45/35/20 (molar percentage), is 8000 with the number-average molecular weight Mn of gel permeation chromatography, and acid number is 90mgKOH/g.

Synthesis example 7

In the polymkeric substance that obtains in the 821.5g synthesis example 6 in being positioned over the 3L four-hole boiling flask that has agitator and reflux cooling device, add 8.70g glycidyl methacrylate and 0.87g benzyl triethyl ammonium ammonium, 120 ℃ of reactions 5 hours, the ethylene type unsaturated group is incorporated in the polymkeric substance.

Then, in this polymers soln, add the 47.0g triethylamine, in and the carboxylic acid group.Decompression is slowly removed organic solvent down from the neutralizer that obtains, add 700g water lentamente simultaneously, obtains the uniform aqueous solution (solids component is 30 weight %).

Synthesis example 8

In the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler, add the aqueous solution of the fluorinated copolymer that obtains in the 400g synthesis example 7, add the composition of following composition again.

Form:

Diacetone-acryloamide(DAA) 67g

Methyl methacrylate 117.4g

Cyclohexyl methacrylate 117.5g

N-butyl acrylate 243g

Methacrylic acid 2-ethylhexyl 120g

Vinylformic acid 3.3g

Newcol 707SF (Japanese emulsifying agent (strain) production) 10g

Then, adding is dissolved in the 0.7g ammonium persulphate aqueous solution that forms in the 6.3g water, 80 ℃ of polymerizations 2 hours, and then the 10 weight % ammonium persulfate aqueous solutions of dropping 7.7g, further keep making in 2 hours its reaction at 80 ℃, cooling then, then being adjusted to pH with ammoniacal liquor is 8.5, further add entry, obtain the aqueous dispersion that solids component is 50 weight %.

Synthesis example 9

Add the 10-undecylenic acid of VEOVA9, the 225.9g of 1.25kg acetone, 315.9g to the stainless steel autoclave of 6L, carry out nitrogen replacement, add the 300g tetrafluoroethylene again, be warming up to 61.5 ℃.Then, under agitation add 12g sim peroxides solution (solids component is 70 weight %), reacted stopped reaction when the reaction vessel internal pressure is reduced to 0.25MPaG 8 hours.Reaction mixture is cooled to room temperature, further carries out nitrogen replacement behind the removing unreacted monomer, obtain 2.1kg reaction product (solids component is 39.0 weight %).The multipolymer that obtains is used ¹⁹The F-nucleus magnetic resonance and ¹The H-nucleus magnetic resonance is analyzed, and tetrafluoroethylene/VEOVA9/10-undecylenic acid is 46/30.9/23.1 (molar percentage), is 9000 with the number-average molecular weight Mn of gel permeation chromatography, and acid number is 90mgKOH/g.

Synthesis example 10

In the polymkeric substance that obtains in the 743.6g synthesis example 9 in being positioned over the 3L four-hole boiling flask that has agitator and reflux cooling device, add 8.70g glycidyl methacrylate and 0.87g benzyl triethyl ammonium ammonium, 120 ℃ of reactions 5 hours, the ethylene type unsaturated group is incorporated in the polymkeric substance.

Then, in this polymers soln, add the 47.0g triethylamine, in and the carboxylic acid group.Decompression is slowly removed organic solvent down from the neutralizer that obtains, add 700g water lentamente simultaneously, obtains the uniform aqueous solution (solids component is 30 weight %).

Synthesis example 11

In the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler, add the aqueous solution of the fluorinated copolymer that obtains in the 400g synthesis example 10, add the composition of following composition again.

Form:

Diacetone-acryloamide(DAA) 67g

Methyl methacrylate 117.4g

Cyclohexyl methacrylate 114.2g

N-butyl acrylate 243g

Methacrylic acid-2-ethylhexyl 120g

2-hydroxyethyl methacrylate 3.3g

Vinylformic acid 3.3g

Newcol?707SF????????????????????????????10g

Then, adding is dissolved in the 0.7g ammonium persulphate aqueous solution that forms in the 6.3g water, 80 ℃ of polymerizations 2 hours, and then the 10 weight % ammonium persulfate aqueous solutions of dropping 7.7g, further keep making in 2 hours its reaction at 80 ℃, cooling then, then being adjusted to pH with ammoniacal liquor is 8.5, further add entry, obtain the aqueous dispersion that solids component is 50 weight %.

Synthesis example 12

In the stainless steel autoclave of 6L, add 1.25kg acetone, 373.7g trimethylacetic acid vinyl acetate (JAPAN VAM﹠amp; POVAL CO., LTD. produces), 69.8g vinylformic acid, carry out nitrogen replacement, add the 300g tetrafluoroethylene again, be warming up to 61.5 ℃.Then, under agitation add 9.8g sim peroxides solution (solids component is 70 weight %), reacted stopped reaction when the reaction vessel internal pressure is reduced to 0.25MPaG 8 hours.Reaction mixture is cooled to room temperature, further carries out nitrogen replacement behind the removing unreacted monomer, obtain 2.0kg reaction product (solids component is 32.6 weight %).The multipolymer that obtains is used ¹⁹The F-nucleus magnetic resonance and ¹The H-nucleus magnetic resonance is analyzed, and tetrafluoroethylene/trimethylacetic acid vinyl acetate/vinylformic acid is 45/35/20 (molar percentage), is 6000 with the number-average molecular weight Mn of gel permeation chromatography, and acid number is 90mgKOH/g.

Synthesis example 13

In the polymkeric substance that obtains in the 889.6g synthesis example 12 in being positioned over the 3L four-hole boiling flask that has agitator and reflux cooling device, add 8.70g glycidyl methacrylate and 0.87g benzyl triethyl ammonium ammonium, 120 ℃ of reactions 5 hours, the ethylene type unsaturated group is incorporated in the polymkeric substance.

Then, in this polymers soln, add the 47.0g triethylamine, in and the carboxylic acid group.Decompression is slowly removed organic solvent down from the neutralizer that obtains, add 700g water lentamente simultaneously, obtains the uniform aqueous solution (solids component is 30 weight %).

Synthesis example 14

The aqueous solution that adds the fluorinated copolymer that obtains in the 247.5g synthesis example 13 in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler adds the composition of following composition again.

Form:

Diacetone-acryloamide(DAA) 67g

Methyl methacrylate 117.4g

Cyclohexyl methacrylate 117.5g

N-butyl acrylate 243g

Methacrylic acid-2-ethylhexyl 120g

Vinylformic acid 3.3g

Newcol?707SF?????????????????????????????10g

Then, adding is dissolved in the 0.7g ammonium persulphate aqueous solution that forms in the 6.3g water, 80 ℃ of polymerizations 2 hours, and then the 10 weight % ammonium persulfate aqueous solutions of dropping 7.7g, further keep making in 2 hours its reaction at 80 ℃, cooling then, then being adjusted to pH with ammoniacal liquor is 8.5, further add entry, obtain the aqueous dispersion that solids component is 50 weight %.

Synthesis example 15

The aqueous solution that adds the fluorinated copolymer that obtains in the 954.6g synthesis example 10 in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler adds the composition of following composition again.

Form:

Diacetone-acryloamide(DAA) 67g

Methyl methacrylate 231.6g

N-butyl acrylate 243g

Methacrylic acid-2-ethylhexyl 120g

2-hydroxyethyl methacrylate 3.3g

Vinylformic acid 3.3g

Newcol?707SF????????????????????????????10g

Then, adding is dissolved in the 0.7g ammonium persulphate aqueous solution that forms in the 6.3g water, 80 ℃ of polymerizations 2 hours, and then the 10 weight % ammonium persulfate aqueous solutions of dropping 7.7g, further keep making in 2 hours its reaction at 80 ℃, cooling then, then being adjusted to pH with ammoniacal liquor is 8.5, further add entry, obtain the aqueous dispersion that solids component is 50 weight %.

Synthesis example 16

In the stainless steel autoclave of 6L, add 1.25kg acetone, 212.9g trimethylacetic acid vinyl acetate (JAPAN VAM﹠amp; POVAL CO., LTD. produces), the 10-undecylenic acid of 28.5g hydroxy butyl vinyl ether, 192.0g, carry out nitrogen replacement, add the 300g tetrafluoroethylene again, be warming up to 61.5 ℃.Then, under agitation add 12g sim peroxides solution (solids component is 70 weight %), reacted stopped reaction when the reaction vessel internal pressure is reduced to 0.25MPaG 8 hours.Reaction mixture is cooled to room temperature, further carries out nitrogen replacement behind the removing unreacted monomer, obtain 1.8kg reaction product (solids component is 35.2 weight %).The multipolymer that obtains is used ¹⁹F-nucleus magnetic resonance and 1H-nucleus magnetic resonance are analyzed, tetrafluoroethylene/trimethylacetic acid vinyl acetate/hydroxy butyl vinyl ether/10-undecylenic acid is 45/33.7/4.0/17.3 (molar percentage), number-average molecular weight Mn with gel permeation chromatography is 7000, hydroxyl value is 20mgKOH/g, and acid number is 90mgKOH/g.

Synthesis example 17

In the polymkeric substance that obtains in the 823.9g synthesis example 16 in being positioned over the 3L four-hole boiling flask that has agitator and reflux cooling device, the 2-ethyl isocyanate ylmethyl acrylate that adds 14.5g, 60 ℃ of reactions 1 hour, the ethylene type unsaturated group is incorporated in the polymkeric substance.

Then, in this polymers soln, add the 47.0g triethylamine, in and the carboxylic acid group.Decompression is slowly removed organic solvent down from the neutralizer that obtains, add 700g water lentamente simultaneously, obtains the uniform aqueous solution (solids component is 30 weight %).

Synthesis example 18

The aqueous solution that in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler, adds the fluorinated copolymer that obtains in the 400g synthesis example 17, to the moiety that wherein adds synthesis example 8, carry out same operation and obtain the aqueous dispersion that solids component is 50 weight % again.

Synthesis example 19

Add the hydroxy butyl vinyl ether of VEOVA9, the 32.2g of 1.25kg acetone, 269.9g, the 10-undecylenic acid of 221.0g to the stainless steel autoclave of 6L, carry out nitrogen replacement, add the 300g tetrafluoroethylene again, be warming up to 61.5 ℃.Then, under agitation add 12g sim peroxides solution (solids component is 70 weight %), reacted stopped reaction when the reaction vessel internal pressure is reduced to 0.25MPaG 8 hours.Reaction mixture is cooled to room temperature, further carries out nitrogen replacement behind the removing unreacted monomer, obtain 2.1kg reaction product (solids component is 38.4 weight %).The multipolymer that obtains is used ¹⁹The F-nucleus magnetic resonance and ¹The H-nucleus magnetic resonance is analyzed, tetrafluoroethylene/VEOVA9/ hydroxy butyl vinyl ether/10-undecylenic acid is 46/26.4/5.0/22.6 (molar percentage), number-average molecular weight Mn with gel permeation chromatography is 10000, and hydroxyl value is 20mgKOH/g, and acid number is 90mgKOH/g.

Synthesis example 20

In the polymkeric substance that obtains in the 755.2g synthesis example 19 in being positioned over the 3L four-hole boiling flask that has agitator and reflux cooling device, the 2-ethyl isocyanate ylmethyl acrylate that adds 14.5g, 60 ℃ of reactions 1 hour, the ethylene type unsaturated group is incorporated in the polymkeric substance.

Then, in this polymers soln, add the 47.0g triethylamine, in and the carboxylic acid group.Decompression is slowly removed organic solvent down from the neutralizer that obtains, add 700g water lentamente simultaneously, obtains the uniform aqueous solution (solids component is 30 weight %).

Synthesis example 21

The aqueous solution that in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler, adds the fluorinated copolymer that obtains in the 400g synthesis example 20, to the moiety that wherein adds synthesis example 11, carry out same operation and obtain the aqueous dispersion that solids component is 50 weight % again.

Synthesis example 22

In the stainless steel autoclave of 6L, add 1.25kg acetone, the VEOVA9 of 347g, 23.5g 2-hydroxyethyl methacrylate, 65.4g vinylformic acid, carry out nitrogen replacement, add the 300g tetrafluoroethylene again, be warming up to 61.5 ℃.Then, under agitation add 9.8g sim peroxides solution (solids component is 70 weight %), reacted stopped reaction when the reaction vessel internal pressure is reduced to 0.25MPaG 8 hours.Reaction mixture is cooled to room temperature, further carries out nitrogen replacement behind the removing unreacted monomer, obtain 2.0kg reaction product (solids component is 31.1 weight %).The multipolymer that obtains is used ¹⁹The F-nucleus magnetic resonance and ¹The H-nucleus magnetic resonance is analyzed, tetrafluoroethylene/VEOVA9/ 2-hydroxyethyl methacrylate/vinylformic acid is 30/44.0/4.8/21.2 (molar percentage), number-average molecular weight Mn with gel permeation chromatography is 6000, and hydroxyl value is 20mgKOH/g, and acid number is 90mgKOH/g.

Synthesis example 23

In the polymkeric substance that obtains in the 932.5g synthesis example 22 in being positioned over the 3L four-hole boiling flask that has agitator and reflux cooling device, the 2-ethyl isocyanate ylmethyl acrylate that adds 14.5g, 60 ℃ of reactions 1 hour, the ethylene type unsaturated group is incorporated in the polymkeric substance.

Then, in this polymers soln, add the 47.0g triethylamine, in and the carboxylic acid group.Decompression is slowly removed organic solvent down from the neutralizer that obtains, add 700g water lentamente simultaneously, obtains the uniform aqueous solution (solids component is 30 weight %).

Synthesis example 24

The aqueous solution that in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler, adds the fluorinated copolymer that obtains in the 247.5g synthesis example 23, to the moiety that wherein adds synthesis example 8, carry out same operation and obtain the aqueous dispersion that solids component is 50 weight % again.

Synthesis example 25

The aqueous solution that adds the fluorinated copolymer that obtains in the 954.6g synthesis example 20 in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler adds the composition of following composition again.

Form:

Diacetone-acryloamide(DAA) 67g

Methyl methacrylate 231.6g

N-butyl acrylate 243g

Methacrylic acid-2-ethylhexyl 120g

2-hydroxyethyl methacrylate 3.3g

Vinylformic acid 3.3g

Newcol?707SF?????????????????????????????10g

Then, adding is dissolved in the 0.7g ammonium persulphate aqueous solution that forms in the 6.3g water, 80 ℃ of polymerizations 2 hours, and then the 10 weight % ammonium persulfate aqueous solutions of dropping 7.7g, further keep making in 2 hours its reaction at 80 ℃, cooling then, then being adjusted to pH with ammoniacal liquor is 8.5, further add entry, obtain the aqueous dispersion that solids component is 50 weight %.

Synthesis example 26

The aqueous solution that adds the fluorinated copolymer that obtains in the 954.6g synthesis example 20 in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler adds the composition of following composition again.

Form:

Vinylbenzene 234.9g

N-butyl acrylate 243g

Methacrylic acid-2-ethylhexyl 120g

Vinylformic acid 3.3g

Newcol?707SF????????????????????????????10g

Then, adding is dissolved in the 0.7g ammonium persulphate aqueous solution that forms in the 6.3g water, 80 ℃ of polymerizations 2 hours, and then the 10 weight % ammonium persulfate aqueous solutions of dropping 7.7g, further keep making in 2 hours its reaction at 80 ℃, cooling then, then being adjusted to pH with ammoniacal liquor is 8.5, further add entry, obtain the aqueous dispersion that solids component is 50 weight %.

Embodiment 3～10 and comparative example 1～2

Except that as the polymkeric substance of making in each synthesis example shown in the fluorine-containing compound resin use table 2, prepare coating similarly to Example 1, and then make sample with paired coated plate.The sample that obtains is investigated similarly to Example 1, be the results are shown in the table 2.

Table 2

	Embodiment								Comparative example
												?3	??4	??5	??6	??7	??8	??9	??10	??1	??2
The fluorine-containing composite dispersion
											The synthesis example sequence number	Synthesis example 8	Synthesis example 11	Synthesis example 14	Synthesis example 15	Synthesis example 18	Synthesis example 21	Synthesis example 24	Synthesis example 25	Synthesis example 14	Synthesis example 26
Use level (solids component weight part)	?100	??100	??100	??100	??100	??100	??100	??100	??100	??100
											Solidifying agent (weight part)
The hexanodioic acid hydrazides	?15	??15	??15	??15	??15	??15	??15	??15	??0	??0
											The rerum natura of filming
Outward appearance	?A	??A	??A	??A	??A	??A	??A	??A	??A	??A
											Gloss	?80	??81	??82	??81	??81	??82	??82	??81	??86	??95
The heatproof water-based	?A	??A	??A	??A	??A	??A	??A	??A	??C	??C
											Solvent resistance	?A	??A	??A	??A	??A	??A	??A	??A	??C	??C
Weathering resistance	?A	??A	??A	??A	??A	??A	??A	??A	??A	??D

Synthesis example 27

The 10-undecylenic acid of the VEOVA9 of adding 1.25kg acetone, 306.7g, 5.2g hydroxy butyl vinyl ether, 237.5g carries out nitrogen replacement in the stainless steel autoclave of 6L, adds the 300g tetrafluoroethylene again, is warming up to 61.5 ℃.Then, under agitation add 11.8g sim peroxides solution (solids component is 70 weight %), reacted stopped reaction when the reaction vessel internal pressure is reduced to 0.35MPaG 8 hours.Reaction mixture is cooled to room temperature, further carries out nitrogen replacement behind the removing unreacted monomer, obtain 2.0kg reaction product (solids component is 39.2 weight %).The multipolymer that obtains is used ¹⁹The F-nucleus magnetic resonance and ¹The H-nucleus magnetic resonance is analyzed, tetrafluoroethylene/VEOVA9/ hydroxy butyl vinyl ether/10-undecylenic acid is 46/30/0.8/23.2 (molar percentage), number-average molecular weight Mn with gel permeation chromatography is 8000, and hydroxyl value is 3mgKOH/g, and acid number is 90mgKOH/g.

Synthesis example 28

The 2-ethyl isocyanate ylmethyl acrylate that adds 1.35g in the polymkeric substance that in the 3L four-hole boiling flask that has agitator and reflux cooling device, in 382.6g synthesis example 27, obtains, 60 ℃ of reactions 1 hour, the ethylene type unsaturated group is incorporated in the polymkeric substance.

Then, in this polymers soln, add 28% ammoniacal liquor of 14.5g, in and the carboxylic acid group.Decompression is slowly removed organic solvent down from the neutralizer that obtains, add 750g water lentamente simultaneously, obtains the uniform aqueous solution (solids component is 16.7 weight %).

Synthesis example 29

The water type dispersion that adds the fluorinated copolymer that obtains in the 900g synthesis example 28 in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler adds the composition of following composition again.

Form:

Methyl methacrylate 150.0g

Cyclohexyl acrylate 180.0g

2-EHA 270.0g

Then, adding is dissolved in the 0.6g ammonium persulphate aqueous solution that forms in the 5.4g water, 80 ℃ of polymerizations 2 hours, and then the 10 weight % ammonium persulfate aqueous solutions of dropping 6.0g, further keep making in 2 hours its reaction at 80 ℃, cooling then, then being adjusted to pH with ammoniacal liquor is 8.5, further adds entry and obtains the aqueous dispersion that solids component is 50 weight %.

Synthesis example 30

In the stainless steel autoclave of 6L, the 10-undecylenic acid of the VEOVA9 of adding 1.2kg butylacetate, 420.4g, 152g hydroxy butyl vinyl ether, 241.6g carries out nitrogen replacement, adds the 600g tetrafluoroethylene again, is warming up to 61.5 ℃.Then, under agitation add 19g sim peroxides solution (solids component is 70 weight %), reacted stopped reaction when the reaction vessel internal pressure is reduced to 0.4MPaG 8 hours.Reaction mixture is cooled to room temperature, further carries out nitrogen replacement behind the removing unreacted monomer, obtain 2.4kg reaction product (solids component is 50.3 weight %).The multipolymer that obtains is used ¹⁹The F-nucleus magnetic resonance and ¹The H-nucleus magnetic resonance is analyzed, tetrafluoroethylene/VEOVA9/ hydroxy butyl vinyl ether/10-undecylenic acid is 45/25.6/14.7/14.7 (molar percentage), number-average molecular weight Mn with gel permeation chromatography is 14400, and hydroxyl value is 60mgKOH/g, and acid number is 60mgKOH/g.

Synthesis example 31

The 2-ethyl isocyanate ylmethyl acrylate that adds 3.15g in the polymkeric substance that in the 3L four-hole boiling flask that has agitator and reflux cooling device, in 695.8g synthesis example 30, obtains, 60 ℃ of reactions 1 hour, the ethylene type unsaturated group is incorporated in the polymkeric substance.

Then, in this polymers soln, add the 24.1g triethylamine, in and the carboxylic acid group.Decompression is slowly removed organic solvent down from the neutralizer that obtains, add 700g water lentamente simultaneously, obtains the uniform aqueous solution (solids component is 33.3 weight %).

Synthesis example 32

The aqueous dispersion that adds the fluorinated copolymer that obtains in the 1050g synthesis example 31 in the flask of being furnished with dropping funnel, agitator, rare gas element ingress pipe, thermometer and reflux cooler adds the composition of following composition again.

Form:

Methyl methacrylate 70.0g

Cyclohexyl acrylate 175.0g

Ethyl acrylate 105.0g

Then, adding is dissolved in the 0.35g ammonium persulphate aqueous solution that forms in the 3.15g water, 80 ℃ of polymerizations 2 hours, and then the 10 weight % ammonium persulfate aqueous solutions of dropping 3.5g, further keep making in 2 hours its reaction at 80 ℃, cooling then, then being adjusted to pH with ammoniacal liquor is 8.5, further adds entry and obtains the aqueous dispersion that solids component is 50 weight %.

Embodiment 11 (preparation of normal temperature solidified waterborne compositions)

In 100ml polymerization beaker, cooperate the fluorine-containing compound resin and the 5.0 weight part PERMUTEX XR-2500 (aziridine that Stahl society produces is a solidifying agent) that obtain in the 100 weight part synthesis examples 29, obtain water-borne coatings with curable composition.

Relatively this water-borne coatings of counting 100 weight parts with solids component is with curable composition, add titanium oxide (the TIPEK CR-97 of 50 weight parts as weighting agent, the former industry of stone (strain) is produced), 2 weight parts are as the NOPCOSPERSE SN5027 (the poly carboxylic acid ammonium salt that SAN NOPCO LIMITED produces) of dispersion agent, 1 weight part is as the ethylene glycol of frostproofer, 0.5 weight part is as the FS ANTIFOAM 013B (Dow Corning production) of defoamer, 5 weight parts are as the ADEKANOLUH-420 (rising sun electrochemical industry (strain) production) of tackifier, 7.5 weight part is as the CS-12 (production of Chisso company) of film coalescence aid, use dispersator to mix fully, preparation coating.

Make sample similarly to Example 1.Then investigate coating characteristic similarly to Example 1.The results are shown in the table 3.

Embodiment 12

Except using 20 weight part Carbojilite V-02 (spinning the carbodiimide that (strain) produce day clearly is solidifying agent), to prepare coating similarly to Example 11 as the solidifying agent, and then with paired coated plate making sample.Similarly investigate coating characteristic at sample that obtains and embodiment 11.The results are shown in the table 3.

Embodiment 13

As embodiment 11, wherein fluorine-containing compound resin uses the fluorine-containing compound resin of synthesis example 32 and uses 5 weight part Bayhydur 3100 (the non-blocked isocyanate of polyoxyethylene modification of Sumitomo Bayer urethane (strain) production is a solidifying agent) as solidifying agent, in addition, similarly prepare coating, and then the making sample, investigate coating characteristic.The results are shown in the table 3.

Table 3

	Embodiment
				??11	??12	??13
	Fluorine-containing composite dispersion synthesis example sequence number use level (weight part)	Synthesis example 29 100	Synthesis example 29 100				Synthesis example 32 100
Solidifying agent (weight part) PERMUTEX XR-250 Carbojilite V-02 Bayhydur 3100				??5	??20	??5
	Coating characteristic gloss appearance heatproof water-based solvent resistance weathering resistance	??A ??82 ??A ??A ??A	??A ??81 ??A ??A ??A				??A ??78 ??A ??A ??A

Claims (11)

1, normal temperature solidified waterborne compositions, it contains the aqueous dispersion and the waterborne curing agent of fluorine-containing compound resin (B), described fluorine-containing compound resin (B) be intramolecularly have ethylene type unsaturated group and water-soluble functional group fluorinated copolymer (A) in the presence of, the monomer (b1) that letex polymerization contains the ethylene type unsaturated group obtains.

2, normal temperature solidified waterborne compositions according to claim 1 is characterized in that, the acid number of described fluorinated copolymer (A) is 10～250mgKOH/g.

3, normal temperature solidified waterborne compositions according to claim 1 and 2 is characterized in that, described water-soluble functional group is the functional group that obtains with anionic property functional group with in the alkali.

4, according to each described normal temperature solidified waterborne compositions of claim 1～3, it is characterized in that what described fluorinated copolymer (A) contained 10 moles of %～70 mole % is selected from least a perhalogeno olefin unit in the group of being made up of tetrafluoroethylene, R 1216 and trifluorochloroethylene as structural unit.

5, according to each described normal temperature solidified waterborne compositions of claim 1～4, it is characterized in that the described monomer (b1) that contains the ethylene type unsaturated group contains at least a monomer with bridging property functional group and at least aly has the vinylformic acid system that carbonatoms is 4～10 alkyl or a monomer of methacrylic acid system.

6, normal temperature solidified waterborne compositions according to claim 5 is characterized in that, described bridging property functional group is at least a group that is selected from the group of being made up of carbonyl, hydroxyl and carboxyl.

7, according to each described normal temperature solidified waterborne compositions of claim 1～6, it is characterized in that it also contains the emulsion that non-fluorine is synthetic resins (C).

8, normal temperature solidified waterborne compositions according to claim 7 is characterized in that, with solid component meter, it contains the described fluorine-containing compound resin (B) of 95～5 weight parts and the non-fluorine of 5～95 weight parts is synthetic resins (C).

9, according to each described normal temperature solidified waterborne compositions of claim 1～8, it is characterized in that described waterborne curing agent is normal temperature solidified solidifying agent.

10, according to each described normal temperature solidified waterborne compositions of claim 1～9, it is characterized in that described waterborne curing agent is the hydrazide compound of per molecule with at least 2 hydrazide groups, carbodiimide compound or the hydrophilic polyisocyanate that per molecule has at least 2 carbodiimides.

According to each described normal temperature solidified waterborne compositions of claim 1～10, it is characterized in that 11, relative 1 normal fluorine-containing compound resin (B) and non-fluorine are total functional group of synthetic resins (C), cooperate the described solidifying agent of 0.1～5 molar equivalent.