CN100393828C - Paint composition - Google Patents
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- CN100393828C CN100393828C CNB2005101191967A CN200510119196A CN100393828C CN 100393828 C CN100393828 C CN 100393828C CN B2005101191967 A CNB2005101191967 A CN B2005101191967A CN 200510119196 A CN200510119196 A CN 200510119196A CN 100393828 C CN100393828 C CN 100393828C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides a coating composition containing an unsaturated polyester resin, excellent in water resistance, dryability and adhesion and also good in water-resistant adhesion to steel plate surface. The coating composition comprises (A) an unsaturated polyester resin having polyhydric alcohol allyl ether units, (B) a polymerizable unsaturated compound, (C) a pigment and (D) an antirust agent. In this coating composition, the antirust agent D is contained at 3-50 pts.wt. based on 100 pts.wt. of the total solids of the components A and B.
Description
Technical field
The present invention relates to comprise the coating composition of unsaturated polyester resin, and be particularly related to coating composition the water-fast tack excellence of steel plate face.Coating composition of the present invention is suitable as putty, and is especially suitable for use as automobile and vehicle repairing putty.
Background technology
Usually, compare with other resin, unsaturated polyester resin is cheap, even and also can solidify in the short period of time at normal temperatures, thereby operability excellence, and then can have the physics and the chemical property of various excellences, thereby for example be widely used as automobile and vehicle and repair with putty, carpenter with various uses such as coating, forming composition, sealing materials by the selection of main raw material.The reactive diluent of the unsaturated polyester resin compositions that in these purposes, uses, from aspects such as solidified nature, physical propertiess, many always use vinylbenzene, but in recent years, because the environmental pollution that its foul smell and toxicity cause becomes a problem just gradually.
Relative therewith, proposed to use the low and safe monomer of foul smell to replace cinnamic method etc.For example, in patent documentation 1 and patent documentation 2, proposed to use the high acrylic acid derivative of molecular weight, but their drying property, solidified nature, water-repellancy, chemical-resistant etc. are insufficient, therefore purposes is restricted sometimes.Therefore, in patent documentation 3, disclose and used empty dryness unsaturated polyester, and be 1～4 hydroxyalkyl methacrylate unsaturated polyester resin compositions with the alkyl carbon atoms number as reactive diluent.
[patent documentation 1] spy opens flat 7-216040 communique
[patent documentation 2] spy opens flat 9-151225 communique
[patent documentation 3] spy opens the 2003-82038 communique
Summary of the invention
Although the foul smell of the composition of above-mentioned patent documentation 3 is low and safe and the drying property excellence, its water-repellancy is still insufficient, and particularly when base material was steel plate, its water-fast tack was insufficient, can produce and peel off or blistered problem.
The object of the present invention is to provide a kind of water tolerance, drying property, tack excellent and comprise the coating composition of unsaturated polyester resin, and said composition is to the water-fast tack excellence of steel plate face, and is suitable as putty.
The present invention relates to a kind of coating composition, it is characterized in that comprising the unitary unsaturated polyester resin of allyl ether that (A) have polyvalent alcohol, (B) polymerizable unsaturated compound, (C) pigment and (D) rust-preventive agent, wherein, with respect to the total solids composition is the unsaturated polyester resin (A) and the polymerizable unsaturated compound (B) of 100 weight parts, and the content of this rust-preventive agent (D) is 3～50 weight parts; And relate to a kind of coating process, it is characterized in that this coating composition being coated on substrate surface and making it curing, finish paint coating then.
According to the present invention, can obtain the coating composition that comprises unsaturated polyester resin of water-repellancy, drying property, tack excellence.Coating composition of the present invention is suitable as putty, inner drying property excellence when thick being coated with, and also excellent to the binding property of base material, finish paint coating, particularly the water-fast tack to the steel plate face is very excellent.
Therefore, coating composition of the present invention is especially suitable for use as automobile and rail truck and repairs and use putty, and then also can be used for engineering machinery, carpenter's class with in the putty etc.In addition, be not limited in these purposes, can also be used for buildings or the fissured repairing of furniture chap line, spackling and lining material etc.
As the unsaturated polyester resin (A) that uses in the present invention, get final product so long as have the unitary vibrin of the allyl ether of polyvalent alcohol, and can use normally used vibrin in existing coating, the putty, not special restriction, the vibrin that can use the condensation reaction of polyprotonic acid by comprising unsaturated polyprotonic acid and polyvalent alcohol to obtain usually.
As unsaturated polyprotonic acid, can list for example toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, itaconic anhydride, tetrahydrophthalic acid, tetrahydronaphthalic anhydride, methyltetrahydro Tetra hydro Phthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, hexachloro endoethylene tetrahydrophthalic acid acid anhydride, Poria cocos acid anhydrides etc., these polyprotonic acids can use a kind, also two or more can be mixed and use.
In above-mentioned unsaturated polyprotonic acid, can also mix use with saturated polybasic acid, as this saturated polybasic acid, can list for example phthalic acid, Tetra hydro Phthalic anhydride, the halogenation Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, hexahydro-phthalic acid, hexahydro phthalic anhydride, hexahydroterephthalic acid, the hexahydro-m-phthalic acid, succsinic acid, propanedioic acid, pentanedioic acid, hexanodioic acid, sebacic acid, 1, the 12-dodecanedioic acid, 2, the 6-naphthalic acid, 2, the 7-naphthalic acid, 2, the 3-naphthalic acid, 2, the 3-naphthalic anhydride, 4,4 '-biphenyl dicarboxylic acid, or the dialkyl of these polyprotonic acids etc., these can use wherein a kind, also two or more can be mixed and use.
As polyvalent alcohol, can list for example ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, the 2-methyl isophthalic acid, ammediol, 1, the 3-butyleneglycol, neopentyl glycol, Hydrogenated Bisphenol A, 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, the affixture of dihydroxyphenyl propane and propylene oxide or oxyethane, 1,2,3, the 4-erythritol, glycerine, TriMethylolPropane(TMP), 1, ammediol, 1, the 2-cyclohexanediol, 1, the 3-cyclohexanediol, 1, the 4-cyclohexanediol, 1,4 cyclohexane dimethanol, the p-Xylol glycol, dicyclohexyl-4,4 '-glycol, 2,6-naphthalane glycol, 2,7-naphthalane glycol, terephthalic acid dihydroxy ethyl esters etc., these can use wherein a kind, also two or more can be mixed and use.
In order to improve the surface drying of filming that finally obtains, above-mentioned unsaturated polyester resin (A) has the allyl ether unit of polyvalent alcohol, makes raw material as it, and the allyl ether of hope use polyvalent alcohol etc. has the allylic cpd of hydroxyl.As this allylic cpd, can list glycol monomethyl allyl ether, Diethylene Glycol monoallyl ether, triethylene glycol monoallyl ether, polyoxyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butyleneglycol monoallyl ether, 1, ammediol monoallyl ether, hexylene glycol monoallyl ether, ethohexadiol monoallyl ether, TriMethylolPropane(TMP) diallyl ether, glycerine diallyl ether, tetramethylolmethane three allyl ethers etc.
In addition, as required, can also use lipid acid to above-mentioned unsaturated polyester resin (A) modification.As this lipid acid, be suitably drying oil fatty acid and/or semi-drying oil lipid acid, can enumerate for example fish oil fatty acid, dehydrated castor oil fatty acid, Thistle oil lipid acid, linseed oil fatty acid, soya fatty acid, the acid of sesame oil fat, poppyseed oil lipid acid, perilla oil lipid acid, hempseed oil lipid acid, raisin seed oil lipid acid, corn oil fatty acid, ready denier oil acid, sunflower oil lipid acid, cotton seed oil lipid acid, walnut oil fat acid, rubber seed oil lipid acid, Ha ィ ジ ェ Application lipid acid etc., these lipid acid can use wherein a kind, also two or more can be mixed and use.
In the present invention, as unsaturated polyester resin (A), from the viewpoint of solidified nature, surface drying, the special 5～50mol% that wishes to comprise based on the unitary total mole number of entire infrastructure, the allyl ether unit of the polyvalent alcohol of preferred 10～35mol%.
And then, as unsaturated polyester resin (A),, be particularly suitable for using the vibrin of the allyl ether unit, terephthalic acid units and the ethylene glycol unit that in resin matrix, have imported polyvalent alcohol from viewpoints such as solidified nature and water-repellancy, adaptations.At this moment, from the viewpoint of solidified nature, surface drying, wish to comprise 5～50 moles of %, the allyl ether unit of the polyvalent alcohol of preferred 10～35 moles of % based on entire infrastructure unit total mole number; And, wish to comprise 1～30 mole of % based on the unitary total mole number of entire infrastructure, the terephthalic acid units of preferred 3～20 moles of % from the viewpoint of water-repellancy, adaptation; And, wish to comprise 3～60 moles of % based on the unitary total mole number of entire infrastructure, the ethylene glycol unit of preferred 5～40 moles of % from the synthetic easiness of unsaturated polyester resin.In the situation of using such unsaturated polyester resin, even use the putty of hydroxyl monomer such as methacrylic acid 2-hydroxyl ethyl ester, also can form water-repellancy and not reduce and have good solidification, drying property, particularly the also excellent putty of the adaptation of the steel plate face after exposing filmed as aftermentioned (B) composition.
Allyl ether, terephthalic acid and the ethylene glycol that can pass through to use above-mentioned polyvalent alcohol carry out condensation reaction with other polyprotonic acids or polyvalent alcohol again, thereby these structural units are imported in the unsaturated polyester resin (A) as making raw material.Terephthalic acid units and ethylene glycol unit, from the viewpoint of under the temperature that suppresses the allyl ether radical reaction, carrying out condensation reaction, by using the manufacturing raw material of terephthalic acid dihydroxy ethyl ester, can especially easily in a step, import two kinds of structural units as polyvalent alcohol.As terephthalic acid dihydroxy ethyl ester, can also use the disintegrating and regeneration thing of polyethylene terephthalate (PET).
Above-mentioned unsaturated polyester resin (A) can for example, obtain by make the composition generation condensation reaction that comprises above-mentioned unsaturated polyprotonic acid and polyvalent alcohol under nitrogen atmosphere by the ordinary method manufacturing.From preventing the viewpoint of gelation, the Heating temperature when wishing condensation reaction is 140～250 ℃, is preferably 160～200 ℃.
From viewpoint reactive, tack, the acid number of wishing resulting unsaturated polyester resin (A) is 10～50mg KOH/g, preferred 20～40mg KOH/g.
In addition, wish that the weight-average molecular weight of unsaturated polyester resin (A) is 1000～100000, be preferably 2000～50000.In addition, in the present invention, weight-average molecular weight is by gel permeation chromatography and is converted into the value of polystyrene.The gel permeation chromatography device can use " HLC 8120 GPC ", and (Tosoh company makes, trade(brand)name), and in gel permeation chromatography, as the chromatographic column of using, can use 4 " TSK gel G-4000H * L ", " TSK gel G-3000H * L ", " TSK gel G-2500 H * L ", " TSK gel G-2000H * L " (making trade(brand)name by Tosoh company).
In the present invention, polymerizable unsaturated compound (B) mixes as reactive diluent, can list for example aromatic ethenyl compounds such as vinylbenzene, alpha-methyl styrene, chloro-styrene, Vinyl toluene, t-butyl styrene, Vinylstyrene; (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) isobornyl acrylate, (methyl) vinylformic acid norborneol ester, (methyl) vinylformic acid adamantane esters, trimethylolpropane tris (methyl) acrylate, tetramethylol methane four (methyl) acrylate, tetramethylol methane four (methyl) acrylate, Dipentaerythritol (methyl) acrylate, tristane dimethanol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 2-butyl-2-ethyl-1, ammediol two (methyl) acrylate, two cyclopentenes oxygen base ethyl (methyl) acrylate, 2, two (4-(3-methacryloxy-2-hydroxyl propoxy-)-phenyl) propane of 2-, two (methacryloxyethyl) tri-methyl hexamethylene, two urethanes, 2, (methyl) acrylate of monohydroxy-alcohol such as two (the many ethoxyl phenenyls of 4-methacryloxy) propane of 2-or polyvalent alcohol; (methyl) acrylic acid hydroxy alkyl esters such as (methyl) vinylformic acid 2-hydroxyl ethyl ester; Ethylene glycol bisthioglycolate maleic acid ester, propylene glycol diitaconate etc.; 4-(methyl) acryloxy methoxycarbonyl phthalic acid, 4-(methyl) acryloxy ethoxycarbonyl phthalic acid etc. contain the aromatic polycarboxylic acid and the acid anhydrides thereof of 4-(methyl) acryloxy; Allylic cpds such as Phthalic acid, diallyl ester, diallyl isophthalate, phthalic acid triallyl; Oligopolymer such as epoxy (methyl) acrylate, polyester (methyl) acrylate, polydimethyl silicon two (methyl) acrylate, urethane (methyl) acrylate etc., these compounds can use wherein a kind, also two or more can be mixed and use.
Wherein, viewpoint from toxicity and foul smell, as polymerizable unsaturated compound (B), at least a portion as this composition, wish to comprise hydroxyalkyl methacrylate, 1,9-nonanediol two (methyl) acrylate, (methyl) isobornyl acrylate etc., special hope comprises hydroxyalkyl methacrylates such as methacrylic acid 2-hydroxyl ethyl ester.
The usage ratio of above-mentioned unsaturated polyester resin (A) and this polymerizable unsaturated compound (B) is preferably 90/10～10/90, preferred 80/20～20/80 in the solids component weight ratio.
As being used for pigment of the present invention (C), can use filler pigment and/or tinting pigment, for example can list filler pigments such as talcum, mica, barium sulfate, kaolin, lime carbonate, clay, silicon-dioxide, quartz, glass; Painted pigment such as titanium white, iron oxide red, carbon black, iron oxide black can also comprise glass sphere, baton round etc.These pigment can use wherein a kind, also two or more can be mixed and use.Grinding operation from the putty purposes and finishability aspect, with respect to resin solid composition 100 weight parts that comprised in the composition, the usage quantity of this pigment (c) is 70～500 weight parts, is preferably in the scope of 80～200 weight parts.
In the present invention, from improving the viewpoint of the film forming water-fast tack of shape, mix rust-preventive agent (D).As this rust-preventive agent (D), can list for example phosphoric acid salts such as zinc phosphate, calcium phosphate, zinc phosphite, potassium phosphite, phosphorous acid calcium; Tripyrophosphoric acid classes such as aluminium dihydrogen tripolyphosphate; Molybdic acid such as zinc molybdate, calcium molybdate salt; Phospho-molybdic acid salts such as phospho-molybdic acid aluminium; Borate family; Barium metaborate isogonic borate family; Cyanogen zincamide calcium class; Make the cationic improved silica of porous silica particle in conjunction with calcium, zinc, cobalt, lead, strontium, barium etc., by ion-exchange in conjunction with cationic ion-exchange silicon-dioxide; The aluminum pyrophosphate class; The rust-stabilising pigment of zinc oxide etc. also has 1-(benzothiazole-2-base sulfo-) succsinic acid, (2-[4-morpholinodithio-2-base sulfo-) succsinic acid two (C
12-C
14) benzothiazole compound such as alkylammonium salt; The organic corrosion inhibitors such as ketocarboxylic acid of the addition reaction of the addition reaction of 4-methyl-γ oxo-benzenebutanoic acid and N-ethylmorpholine, 4-methyl-γ oxo-benzenebutanoic acid and zirconium etc., these rust-preventive agent can use wherein a kind, also two or more can be mixed and use.Wherein, from improving the viewpoint of the water-fast tack on the steel plate face,, be preferably selected from least a kind of rust-stabilising pigment in phosphoric acid salt, Tripyrophosphoric acid class, molybdic acid salt, phospho-molybdic acid salt, metaboric acid salt, the cyanogen zincamide calcium class especially as rust-preventive agent (D).
From grinding operation and finishability, solidified nature and drying property, aspects such as the adhesivity of scraper, heat-resisting xanthochromia are considered, total solids composition 100 weight parts with respect to unsaturated polyester resin (A) and polymerizable unsaturated compound (B), the combined amount of above-mentioned rust-preventive agent (D) is 3～50 weight parts, is preferably 5～45 weight parts.
Composition of the present invention comprises above-mentioned (A)～(D) composition as neccessary composition, in addition, in order to improve solidified nature, can mixing cured as required promotor.As curing catalyst, not special restriction, can use existing known curing catalyst, viewpoint from solidified nature, drying property, preferred especially aromatic amine, in addition, from reducing the xanthochromia that the finish paint that is coated with at putty composition is filmed, in this aromatic amine, preferably has the compound of dimethylamino.Specifically, can list the 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid-2-ethylhexyl, the 3-dimethylaminobenzoic acid, 3-dimethylaminobenzoic acid ethyl ester, 3-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 3-dimethylaminobenzoic acid isopentyl ester, 3-dimethylaminobenzoic acid 2-ethylhexyl, the 2-dimethylaminobenzoic acid, 2-dimethylaminobenzoic acid ethyl ester, 2-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 2-dimethylaminobenzoic acid isopentyl ester, 2-dimethylaminobenzoic acid 2-ethylhexyl etc., these compounds can use wherein a kind, also two or more can be mixed and use.Wherein, preferred 4-dimethylaminobenzoic acid, 3-dimethylaminobenzoic acid, preferred especially 4-dimethylaminobenzoic acid.
From the aspects such as heat-resisting xanthochromia that improve working life (gelation time), form the dry air of filming or abrasive property, finish paint is filmed, total solids composition 100 weight parts with respect to above-mentioned unsaturated polyester resin (A) and polymerizable unsaturated compound (B), the usage quantity of above-mentioned aromatic amine is 0.01～2.0 weight part, is preferably 0.05～1.5 weight part.
As other curing catalysts except that above-mentioned aromatic amine, can list for example metal drier such as cobalt naphthenate, copper naphthenate, barium naphthenate, octylenic acid cobalt, octylenic acid manganese, octylenic acid zinc, octylenic acid vanadium; Tertiary amine, quaternary ammonium salt except that the above-mentioned aromatic amine of enumerating, these compounds can use wherein a kind, also two or more can be mixed and use.When stating metal drier in the use, with respect to total solids composition 100 weight parts of unsaturated polyester resin (A) and polymerizable unsaturated compound (B), its usage quantity is preferably 0.01～5 weight part.
In the present composition, can also further as required mixing cured secondary accelerator, stopper, organic solvent, pigment, free radical curing agent etc.
As solidifying secondary accelerator, can list for example aniline, N, accelerine, N, the N-Diethyl Aniline, para-totuidine, N, the N-dimethyl-p-toluidine, N, N-two (2-hydroxyethyl) para-totuidine, 4-(N, the N-dimethylamino) phenyl aldehyde, 4-[N, N-two (2-hydroxyethyl) amino] phenyl aldehyde, 4-(N-methyl-N-hydroxyethyl amino) phenyl aldehyde, N, N-two (2-hydroxypropyl) para-totuidine, N-ethyl-meta-aminotoluene, trolamine, meta-aminotoluene, diethylenetriamine, pyridine, phenylmorpholine, piperidines, N, N-two (hydroxyethyl) aniline, N such as diethanolaniline, the N-substituted aniline, N, N-replaces para-totuidine, amines such as 4-(N, N-substituted-amino) phenyl aldehyde.This curing secondary accelerator can use separately, also two or more can be mixed and use.
As stopper, can list for example three hydrogenation of benzene, three hydrogenation benzoquinones, 14-naphthoquinones, para benzoquinone, quinhydrones, benzoquinones, hydroquinone monomethyl ether, p-ten.-butylcatechol, 2,6 di tert butyl 4 methyl phenol etc.With respect to unsaturated polyester resin compositions, the addition of this stopper is 10～1000ppm.
Can add organic solvent and be used to regulate viscosity,, can list toluene, dimethylbenzene, methyl alcohol, ethanol, propyl alcohol, butanols, vinyl acetic monomer, N-BUTYL ACETATE, acetone, methyl ethyl ketone etc. iff being to enumerate some representational especially solvents.
Preferably before for example using, mix free radical curing agent.As this free radical curing agent; can list organo-peroxide; specifically; can use diacyl peroxide class, peroxy esters class, hydroperoxide type, dialkyl peroxide class, ketone peroxide class, peroxy ketal class, peroxy acid alkyl esters, peroxocarbonate class etc. to have known solidifying agent now; these solidifying agent can use separately, also two or more can be mixed and use.With respect to total solids component 100 weight parts of unsaturated polyester resin (A) and polymerizable unsaturated compound (B), the combined amount of free radical curing agent is preferably 0.1～6 weight part.
In composition of the present invention, can further mix for example air shutoffs such as viscosity modifier, pigment dispersing agent, modifying resin, solvent, thixotropic agent, thixotroping auxiliary agent, defoamer, dye leveller, silane coupling agent, paraffin, aldehyde trapping agents etc. such as ultra-violet stabilizer, UV light absorber, shrinking agent, antioxidant, anti-peeling agent, softening agent, aggregate, fire retardant, stablizer, strengthening material, viscosity depressant as required.
The coating of composition of the present invention can be undertaken by known method.Filming of coating can make until inner curing of filming by carrying out normal temperature or forced drying.As substrate surface, can enumerate tap a blast furnace, metallic surface such as zinc, aluminium or its chemically treated surface, plastics, timber etc., and the old coating film surface that on these materials, is coated with etc., have at coating surface under the situation of damaged portion, as required, it is suitable carrying out sanded in advance around being the center with this damaged portion to it.
In the present invention, can also carry out the finish paint coating to filming of forming by above-mentioned composition, as this finish paint coating, not special restriction can be used the coating of the organic solvent class, water class, powder etc. of normally used acrylic paint, acrylic melamine resene coating, urethane cures type coating, acrylated polyurethane resin class coating, acid-curable epoxide type coating, fluorine type resin coating, Synolac class coating, Synolac melamine resin class coating, polyester melamine resin class coating etc.
Below, by embodiment the present invention is carried out specific description, but the present invention is not limited to these embodiment.In addition, " part " among the following embodiment and " % " represent " weight part " and " weight % " respectively.
Embodiment
The manufacturing of unsaturated polyester resin compositions
Production Example 1
In the four-hole boiling flask of the 2L that is equipped with agitator, gas duct, rectifying tower, thermometer, reliever and reflux exchanger, add 397.5g Diethylene Glycol, 134g dipropylene glycol, 580g fumaric acid, 256g tetramethylolmethane three allyl ethers and 0.5g quinhydrones, and one side is blown into nitrogen, be heated to 150 ℃ on one side, be warmed up to 180 ℃ then.Then change rectifying tower into water separator under uniform temp, backflow toluene also carries out condensation reaction, removes toluene when reaction finishes under reduced pressure, and obtaining acid number is that 35mg KOH/g, weight-average molecular weight are 3000 unsaturated polyester resin (A-1).This resin (A-1) is dissolved in the methacrylic acid 2-hydroxyl ethyl ester, solid component concentration is adjusted to 65%, obtain unsaturated polyester resin solution.Behind 0.25 part of 4-dimethylaminobenzoic acid of 100 parts of these unsaturated polyester resin solution addings, insulation made it be uniformly dispersed, dissolve in 1 hour in 60 ℃ water-bath, obtained unsaturated polyester resin compositions (T-1).
Production Example 2
In Production Example 1, except the different norborneol ester of the vinylformic acid that uses same amount replaces methacrylic acid 2-hydroxyl ethyl ester, use the method identical with Production Example 1, obtain unsaturated polyester resin compositions (T-2).
Production Example 3
In Production Example 1, except use same amount be 17/18 isobornyl acrylate by weight with methacrylic acid 2-hydroxyl ethyl ester replacement methacrylic acid 2-hydroxyl ethyl ester, use the method identical, obtain unsaturated polyester resin compositions (T-3) with Production Example 1.
Production Example 4
Use the device identical with Production Example 1, adding 174.8g Diethylene Glycol, 541.2g tetramethylolmethane three allyl ethers, 184.2g TriMethylolPropane(TMP), 434.8g fumaric acid and 0.6g quinhydrones under nitrogen atmosphere, are heated to 150 ℃, are warmed up to 180 ℃ then.Then change rectifying tower into water separator under uniform temp, backflow toluene also carries out condensation reaction, removes toluene when reaction finishes under reduced pressure, and obtaining acid number is that 31mg KOH/g, weight-average molecular weight are 2900 unsaturated polyester resin (A-2).(A-2) is dissolved in the 2-hydroxyethyl methacrylate with this resin, and solid component concentration is adjusted to 65%, obtains unsaturated polyester resin solution.Phase time adds 0.25 part of 4-dimethylaminobenzoic acid in 100 parts of these unsaturated polyester resins (A-2) solution, and insulation made it be uniformly dispersed, dissolve in 1 hour in 60 ℃ water-bath, obtained unsaturated polyester resin compositions (T-4).
Production Example 5
In Production Example 4, except the isobornyl acrylate of using same amount replaces the 2-hydroxyethyl methacrylate, use the method identical with Production Example 4, obtain unsaturated polyester resin compositions (T-5).
Production Example 6
The unsaturated polyester resin (A-1) that above-mentioned Production Example 1 is made is dissolved in the vinylbenzene, and solid component concentration is adjusted to 65%, obtains unsaturated polyester resin solution.Add 0.25 part of 4-dimethylaminobenzoic acid with respect to 100 parts of these unsaturated polyester resin solution, insulation made it be uniformly dispersed, dissolve in 1 hour in 60 ℃ water-bath, obtained unsaturated polyester resin compositions (T-6).
Production Example 7
In the glass flask of the 2L that is equipped with temperature regulator, reflux cooler, whipping appts, add 232g fumaric acid, 228.6g terephthalic acid dihydroxyl ethyl ester, 93.8g TriMethylolPropane(TMP), 281.6g tetramethylolmethane three allyl ethers and 0.4g para benzoquinone, be warmed up to 180 ℃ and carry out dehydration condensation, when acid number reaches 35mg KOH/g, stop heating, be cooled to 100 ℃.Then add the 421g 2-hydroxyethyl methacrylate, be stirred to and form uniform solution, obtain solid component concentration and be 65% unsaturated polyester resin (A-3) solution.The weight-average molecular weight of this unsaturated polyester resin (A-3) is 3000.Add 0.25 part of 4-dimethylaminobenzoic acid with respect to 100 parts of these unsaturated polyester resins (A-3) solution, insulation made it be uniformly dispersed, dissolve in 1 hour in 60 ℃ water-bath, obtained unsaturated polyester resin compositions (T-7).
Production Example 8
In Production Example 7, replace the 421g 2-hydroxyethyl methacrylate except using 229g isobornyl acrylate and 192g 2-hydroxyethyl methacrylate, the method that use and Production Example 7 are identical obtains unsaturated polyester resin compositions (T-8).
Production Example 9
In Production Example 7, except the isobornyl acrylate of using same amount replaces the 2-hydroxyethyl methacrylate, use the method identical with Production Example 7, obtain unsaturated polyester resin compositions (T-9).
Production Example 10
Use the device identical with Production Example 1, adding 530g Diethylene Glycol, 107g TriMethylolPropane(TMP) diallyl ether, 580g fumaric acid and 0.33g quinhydrones are heated to 150 ℃ under nitrogen atmosphere, be warmed up to 190 ℃ then.Then change rectifying tower into water separator under uniform temp, backflow toluene also carries out condensation reaction, removes toluene when reaction finishes under reduced pressure, and obtaining acid number is that 35mg KOH/g, weight-average molecular weight are 3000 unsaturated polyester resin (A-4).(A-4) is dissolved in the 2-hydroxyethyl methacrylate with this resin, and solid component concentration is adjusted to 65%, obtains unsaturated polyester resin solution.Add 0.25 part of 4-dimethylaminobenzoic acid with respect to 100 parts of these unsaturated polyester resins (A-4) solution, insulation made it be uniformly dispersed, dissolve in 1 hour in 60 ℃ water-bath, obtained unsaturated polyester resin compositions (T-10).
Production Example 11
In Production Example 10, except the isobornyl acrylate of using same amount replaces the 2-hydroxyethyl methacrylate, use the method identical with Production Example 10, obtain unsaturated polyester resin compositions (T-11).
Production Example 12
In Production Example 1, except not mixing the 4-dimethylaminobenzoic acid, use the method identical with Production Example 1, obtain unsaturated polyester resin compositions (T-12).
Production Example 13 (comparative example is used)
Use the device identical with Production Example 1, adding 251g propylene glycol, 286g Diethylene Glycol, 323g maleic anhydride, 326g Tetra hydro Phthalic anhydride and 0.36g quinhydrones are heated to 150 ℃ under nitrogen atmosphere, be warmed up to 190 ℃ then.Then change rectifying tower into water separator under uniform temp, backflow toluene also carries out condensation reaction, removes toluene when reaction finishes under reduced pressure, and obtaining acid number is that 35mg KOH/g, weight-average molecular weight are 2900 unsaturated polyester resin (A-5).(A-5) is dissolved in the 2-hydroxyethyl methacrylate with this resin, and solid component concentration is adjusted to 65%, obtains unsaturated polyester resin solution.Add 0.25 part of 4-dimethylaminobenzoic acid with respect to 100 parts of these unsaturated polyester resins (A-5) solution, insulation made it be uniformly dispersed, dissolve in 1 hour in 60 ℃ water-bath, obtained unsaturated polyester resin compositions (T-13).
The mixing that has provided each unsaturated polyester resin compositions (T～1)～(T～13) in following table 1 is formed.In addition, the scale of each unsaturated polyester resin in the table shows solids component.
Embodiment 1～21 and comparative example 1～5
In each unsaturated polyester resin compositions that 100 parts of (solids component) above-mentioned Production Examples obtain, form according to the mixing shown in the table 2, mix respectively and stir " naphthex cobalt 5% " (trade(brand)name, Japan chemical industry company makes, the naphthenic acid cobalt), quinhydrones, " CR-95 " (trade(brand)name, the former industry of stone society makes, titanium dioxide), " Crawn Talc DR " (trade(brand)name, pine village industry company makes, talcum) and " LF Bowsey M-PSN " (trade(brand)name, KIKUCHI COLOR ﹠amp; CHEMICALS Corp. makes, zinc molybdate) or " BUSAN 11-M1 " (trade(brand)name, Sakai chemical company makes, barium metaborate), " LFBowsey ZK-S2 " (trade(brand)name, KIKUCHI COLOR ﹠amp; CHEMICALS Corp. makes, cyanogen zincamide calcium), " K-WHITE 105 " (trade(brand)name, TAYKA company makes, the mixture of aluminium dihydrogen tripolyphosphate zinc oxide), " EXPERT NP-1007 " (trade(brand)name, east pigment industry company of nation makes, the mixture of zinc phosphate phosphorous acid calcium), " EXPERT NP-1530 " (trade(brand)name, east pigment industry company of nation makes, the mixture of zinc phosphite potassium phosphite), gather 300ml, by high speed mixing roll blending dispersion 20 minutes, obtain each composition.
Use the #240 waterproof abrasive paper to grind the surface of " SPCC-SB " (Japanese Testpanel company limited make trade(brand)name, mild steel plate) gently, be made into substrate surface.In above-mentioned each composition that obtains, add 2% " the general solidifying agent of LUC " (trade(brand)name, principal constituent: the pimelinketone superoxide, Northwest paint company is made) respectively, mixed uniformly mixture is coated on the substrate surface with scraper as putty, and it is thick that coating reaches average 2mm.
Evaluation test
To above-mentioned each constituent that obtains, test according to following evaluation method, benchmark.Its result is as shown in table 2.
(* 1) drying property: under normal temperature (20 ℃), each test coated panel was placed 20 minutes, then, checked viscosity and the inner curing of respectively testing the coated panel surface by the finger contact.(zero: good; △: have some viscosity on the surface but inside solidification is good; *: there is viscosity in the surface, and inside is also solidified not good).
(* 2) are to the adhesivity of scraper: the material that uses uniform mixing solidifying agent in each composition is as putty, and is coated on substrate surface by scraper, checks at this moment extensibility (ノ PVC), scraper sharpness, scraper dispersiveness (さ ば I) etc.(zero: good; △: some is not good; *: not good).
(* 3) working life: the gelation time of under normal temperature (20 ℃), placing after the mixed curing agent.Value is the bigger the better.
The manufacturing of coated panel
At room temperature under (20 ℃) above-mentioned test coated panel was placed drying after 6 hours, use the #400 waterproof abrasive paper to grind this coated face gently, spraying coating " RETAN PG80 WHITEBASE " (trade(brand)name, acrylated polyurethane resin class finish paint coating, Northwest paint company is made) make dry film thickness reach 50 μ m, and, obtain each coated panel at 60 ℃ times dry 30 minutes.
Estimate the tack of above-mentioned each coated panel that obtains according to following method.
(* 4) tack 1: each coated panel is immersed in 40 ℃ the water after 10 days, takes out coated panel and carry out bending from middle body from water, that observes curved part is coated with membrane stage (zero: good; △: film and peel off between steel plate-putty a little; *: film and peel off between steel plate-putty fully).
(* 5) tack 2: each coated panel is immersed in 80 ℃ the warm water after 1 day, from the middle body bending at an angle of 90, that observes curved part is coated with membrane stage (zero: good; △: film and peel off between steel plate-putty a little; *: film and peel off between steel plate-putty fully).
Table 2 (two)
Claims (4)
1. coating composition, it is characterized in that comprising the unitary unsaturated polyester resin of allyl ether that (A) has polyvalent alcohol, (B) contain and be selected from hydroxyalkyl methacrylate, 1,9-nonanediol two (methyl) acrylate, the polymerizable unsaturated compound of at least a at least a portion as its composition of (methyl) isobornyl acrylate, (C) pigment and (D) rust-preventive agent, be to be selected from phosphoric acid salt, Tripyrophosphoric acid, molybdate, phosphomolybdate, metaborate, cyanogen zincamide calcium at least a
And with respect to the total solids composition is the unsaturated polyester resin (A) and the polymerizable unsaturated compound (B) of 100 weight parts, and the content of this rust-preventive agent (D) is 3～50 weight parts.
2. coating composition as claimed in claim 1, wherein the acid number of unsaturated polyester resin (A) is 10～50mg KOH/g.
3. coating composition as claimed in claim 1 or 2, it further comprises aromatic amine.
4. a coating process is characterized in that: each coating composition among the claim 1-3 is coated on substrate surface and makes it and solidify, carry out the finish paint coating then.
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| JP2004379631 | 2004-12-28 | ||
| JP2004379631 | 2004-12-28 | ||
| JP2005293455A JP4657073B2 (en) | 2004-12-28 | 2005-10-06 | Paint composition |
| JP2005293455 | 2005-10-06 |
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| CN100393828C true CN100393828C (en) | 2008-06-11 |
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| JP (1) | JP4657073B2 (en) |
| KR (1) | KR100649074B1 (en) |
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| CN107513300A (en) * | 2010-04-06 | 2017-12-26 | 三菱化学株式会社 | Antifouling paint compositions, the manufacture method of antifouling coat and antifouling coat |
| TWI553068B (en) * | 2010-04-07 | 2016-10-11 | 三菱麗陽股份有限公司 | Antifouling coating composition, manufacturing method of antifouling coating film and antifouling coating film |
| JP5548112B2 (en) * | 2010-12-15 | 2014-07-16 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Room temperature curable organopolysiloxane composition |
| JP2015110486A (en) * | 2012-03-23 | 2015-06-18 | 日産化学工業株式会社 | Method for producing zinc cyanamide |
| CN102702941A (en) * | 2012-06-12 | 2012-10-03 | 天长市巨龙车船涂料有限公司 | Coating composition |
| JP6178679B2 (en) * | 2013-09-17 | 2017-08-09 | 大日本塗料株式会社 | Railcar exterior with laminated coating |
| CN103525271A (en) * | 2013-09-28 | 2014-01-22 | 芜湖中集瑞江汽车有限公司 | Metal rust-removing anti-rust paint and preparation method thereof |
| JP6716274B2 (en) * | 2015-03-24 | 2020-07-01 | 関西ペイント株式会社 | Putty composition and repair coating method using the same |
| JP6607382B2 (en) * | 2015-08-31 | 2019-11-20 | 関西ペイント株式会社 | Putty composition and repair coating method using the same |
| CN105505152A (en) * | 2016-02-02 | 2016-04-20 | 嘉兴市嘉盛绝缘材料有限公司 | Soybean oil modified unsaturated polyester impregnating varnish and preparation method thereof |
| US10308804B2 (en) * | 2016-07-13 | 2019-06-04 | Illinois Tool Works Inc. | Unsaturated polyester composition for autobody repair with improved adhesion to metal substrates |
| CN106675352A (en) * | 2016-11-15 | 2017-05-17 | 惠州市长润发涂料有限公司 | PE whitening-resistant transparent priming paint |
| CN107059106A (en) * | 2017-04-18 | 2017-08-18 | 安徽华辉塑业科技股份有限公司 | A kind of liquid pump blade derusting method |
| CN110741050B (en) * | 2017-06-14 | 2021-05-14 | 综研化学株式会社 | Curable composition for coating and laminate |
| CN107384155A (en) * | 2017-08-04 | 2017-11-24 | 合众（佛山）化工有限公司 | A kind of novel aqueous PE woodcare paints and preparation method thereof |
| CN107686675A (en) * | 2017-09-27 | 2018-02-13 | 广州市阿蒂尔新材料科技有限公司 | Nonflammable atomized ash composition of environmental protection and preparation method thereof and construction method |
| CN108384296A (en) * | 2018-03-02 | 2018-08-10 | 胡小玲 | A kind of automobile-used touch-up paint soil and preparation method thereof |
| KR102035319B1 (en) * | 2019-01-14 | 2019-10-22 | 김유진 | Method of manufacturing putty composition and putty composition manufactured thereby |
| CN112160014A (en) * | 2020-09-17 | 2021-01-01 | 扬州市金杨电镀设备有限公司 | Three-cylinder barrel plating machine |
| JP7284136B2 (en) * | 2020-10-28 | 2023-05-30 | 矢崎総業株式会社 | Anti-corrosion, electric wires with terminals and wire harnesses |
| JP7050882B1 (en) * | 2020-11-16 | 2022-04-08 | 日本ペイント・インダストリアルコ－ティングス株式会社 | Putty paint composition |
| CN113549364B (en) * | 2021-09-02 | 2022-04-12 | 株洲华联高科有限责任公司 | Water-based environment-friendly unsaturated polyester putty for rail transit vehicles and preparation method thereof |
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| JP2006206873A (en) | 2006-08-10 |
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