CN103540250A - Coating compound for plastic - Google Patents
Coating compound for plastic Download PDFInfo
- Publication number
- CN103540250A CN103540250A CN201310289342.5A CN201310289342A CN103540250A CN 103540250 A CN103540250 A CN 103540250A CN 201310289342 A CN201310289342 A CN 201310289342A CN 103540250 A CN103540250 A CN 103540250A
- Authority
- CN
- China
- Prior art keywords
- methyl
- surface conditioner
- hydroxyl
- paint
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
This utility model provides a coating compound for plastic, which is a coating membrane having adhesiveness to plastic raw material, stain resistance (oil resistance acid and milk resistance acid) and finishing. The coating compound for plastic comprises acrylic resin (A) containing hydroxyl, polyisocyanates compound (B), a solidified catalyst (C), a silica surface conditioner (D-1) and an acrylic surface conditioner (D-2). The silica surface conditioner (D-1) and the acrylic surface conditioner (D-2) are coating compound of the necessary surface conditioner (D). The weight-average molecular weight of the acrylic resin (A) containing hydroxyl is 3000-20000 and the hydroxyl value of the acrylic resin (A) containing hydroxyl is from the 100 to 200 mg KOH/g. The coating composition for plastic is characterized in that the drying thick layer of the coating compound is plastered in a 30+-50 Mum means, and the vitrifaction converting temperature is over 100 degrees of the coating membrane which is solidified by baking at temperature of 80 degrees for 20 minutes and the molecular quantity of the junction point is lower than 900g/mol.
Description
Technical field
The present invention relates to paint for plastics composition, its finish and particularly excellent for the stain resistance of lubricant component.
Background technology
In recent years, raw materials for plastics production are expanding as the purposes of Industrial materials.For paint for plastics composition, volatile organic compounds) etc. from the viewpoint of coating cost and low VOCization (VOC: be concerned about that the viewpoint of human body, environment considers, require to cut down or do not contain in fact toluene, dimethylbenzene etc., and realizing tack and film performance by the application based on a painting one roasting (once once baking of coating).
On the other hand, for example, starting material as the interior fitting components of automobile (, instrument panel, central control station, dashboard, door decorations etc.), are used the raw materials for plastics production such as polycarbonate, ABS more.As user to the desired performance of such interior automotive trim parts, be required to meet the finishes such as the Physical properties of coating films such as tack to above-mentioned raw materials for plastics production, water tolerance, weathering resistance and glossiness, and meet take the dirts such as fingerprint and sweat adhere to stain resistance test as imagination object (oil resistant acid and/or resistance to lactate etc.).
A kind of two-pack type coating composition is disclosed in patent documentation 1, it comprises: the number-average molecular weight 2 that (methyl) acrylic compound with the ad hoc structure of secondary hydroxyl is made as to polymerization composition or copolymer composition, 000～15,000, the acrylic resin of the hydroxyl of hydroxyl value 80～150mgKOH/g, second-order transition temperature-30～30 ℃; Polymer based on alicyclic diisocyanate and the polyisocyanates that obtains; Polymer based on aliphatic diisocyanate and the aliphatic polyisocyante that obtains is characterized in that, the softening temperature of filming being formed by this two-pack type coating composition is 60～150 ℃.But this coating composition can not meet the requirement to the tack of coated article and stain resistance.
In addition, in patent documentation 2, disclosing a kind of second-order transition temperature containing more than 20 % by weight is the perspiration resistance plastic basis material coating agent of the polymkeric substance of 110 ℃ of above (methyl) isobornyl acrylate, but in said composition, need fragrant same clan hydrocarbon solvent, can not meet the requirement of stain resistance and finish.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 8-325519 communique
Patent documentation 2: TOHKEMY 2011-184621 communique
Summary of the invention
The problem that invention will solve
The invention provides a kind of paint for plastics composition, even if it is by being once coated with filming of the tack that also can form raw materials for plastics production, stain resistance (oil resistant acid and resistance to lactate) and finish excellence.
For the scheme of dealing with problems
The inventor conducts in-depth research repeatedly in order to address the above problem, found that the following fact, thereby complete the present invention: by containing weight-average molecular weight, be 3, 000～20, 000 and the acrylic resin of the hydroxyl of hydroxyl value in the scope of 100～200mgKOH/g, polyisocyanate compound, curing catalysts, and to take silicon class surface conditioner and acrylic acid or the like surface conditioner be essential surface conditioner, it is more than 100 ℃ making the second-order transition temperature of the cured coating film that obtained by this coating composition, and making molecular weight between cross-linking set is below 900g/mol, thereby can address the above problem.
That is, the invention provides the paint for plastics composition of the following:
1. 1 kinds of paint for plastics compositions of item, it contains weight-average molecular weight is 3, 000～20, 000 and the acrylic resin (A) of the hydroxyl of hydroxyl value in the scope of 100～200mgKOH/g, polyisocyanate compound (B), curing catalysts (C) and to take silicon class surface conditioner (D-1) and acrylic acid or the like surface conditioner (D-2) be essential surface conditioner (D), it is characterized in that, it by this coating composition, according to dry film thickness, is the mode application of 30 ± 5 μ m, and the second-order transition temperature of the cured coating film while solidifying 80 ℃ of bakings 20 minutes is more than 100 ℃, and between the cross-linking set of this cured coating film, molecular weight is below 900g/mol.
2. according to the paint for plastics composition described in item 1, it is characterized in that, it further contains take the acrylic resin (E) that methyl methacrylate 65～90 quality % and other polymerizability unsaturated monomers 10～35 quality % are copolymer composition.
Item 3. is according to the paint for plastics composition described in item 1 or 2, and wherein, curing catalysts (C) includes machine tin compound (C-1), aminated compounds (C-2) and organic acid (C-3).
4. 1 kinds of article of item, it obtains by the paint for plastics composition described in any one in application item 1～3.
The effect of invention
According to paint for plastics composition of the present invention, even by being once coated with filming of the tack that also can form raw materials for plastics production, stain resistance (oil resistant acid and resistance to lactate) and finish excellence.
Embodiment
paint for plastics composition
It is 3 that paint for plastics composition of the present invention contains weight-average molecular weight, 000～20,000 and acrylic resin (A), polyisocyanate compound (B), the curing catalysts (C) of the hydroxyl of hydroxyl value in the scope of 100～200mgKOH/g and to take silicon class surface conditioner (D-1) and acrylic acid or the like surface conditioner (D-2) be essential surface conditioner (D).
the acrylic resin of hydroxyl (A)
It is 3,000～20,000 and the acrylic resin (A) of the hydroxyl of hydroxyl value in the scope of 100～200mgKOH/g that paint for plastics composition of the present invention contains weight-average molecular weight.
From the viewpoint of finish and low VOCization, consider, the weight-average molecular weight of the acrylic resin of hydroxyl (A) is 3,000～20,000, is preferably 5,000～12,000 scope.
From the viewpoint of solidified nature and high crosslink density, consider, the hydroxyl value of the acrylic resin of hydroxyl (A) is 100～200mgKOH/g, is preferably the scope of 100～180mgKOH/g.
Again, in this manual, about the mensuration of weight-average molecular weight (Mw), by gel permeation chromatograph (gel permeation chromatograph: GPC) use the typical curve of polystyrene standard to measure.
As gel permeation chromatograph, can use " HLC-8120GPC " (trade(brand)name, TOSOHCORPORATION system), as chromatographic column, can use 1 " TSKgel G4000HXL ", 2 " TSKgel G3000HXL " and 1 " TSKgel G2000HXL " (trade(brand)name, be all TOSOH CORPORATION system) amount to 4, as detector, can use differential refractometer, can be in moving phase: tetrahydrofuran (THF), measure temperature: under 40 ℃, the condition of flow velocity: 1mL/min, measure.
About the manufacture of the acrylic resin (A) of above-mentioned hydroxyl, for example can be by making the polymerizability unsaturated monomer (a) of hydroxyl and can carrying out copolymerization with other polymerizability unsaturated monomers (b) of the polymerizability unsaturated monomer copolymerization of this hydroxyl and carry out.
For obtaining the copolymerization process of the acrylic resin (A) of above-mentioned hydroxyl, be not particularly limited, list himself known polymerization process, such as mass polymerization, solution polymerization process, carry out body-suspension two-stage polymerization of suspension polymerization etc. after mass polymerization.
Below exemplify used monomer.
the polymerizability unsaturated monomer (a) of hydroxyl
The polymerizability unsaturated monomer of above-mentioned hydroxyl is the compound respectively in a part with more than one hydroxyl and polymerizability unsaturated link(age), such as listing: the monoesters compound of the dibasic alcohol of (methyl) vinylformic acid such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester and carbonatoms 2～8; The 6-caprolactone modification body of the monoesters compound of the dibasic alcohol of this (methyl) vinylformic acid and carbonatoms 2～8; N-hydroxymethyl (methyl) acrylamide; Vinyl carbinol, further there is (methyl) acrylate etc. that molecular end is the polyoxyethylene chain of hydroxyl.
In this manual, " (methyl) acrylate " expression " acrylate or methacrylic ester "." (methyl) vinylformic acid " expression " acrylic or methacrylic acid ", " (methyl) acryl " expression " acryl or methacryloyl ", " (methyl) acrylamide " expression " acrylamide or Methacrylamide ".
other polymerizability unsaturated monomer (b)
Other can with other polymerizability unsaturated monomers of the polymerizability unsaturated monomer copolymerization of above-mentioned hydroxyl can be according to the desired characteristic of the acrylic resin of hydroxyl (A) and choice for use suitably.
The object lesson of this monomer is recited in to (i)～(xix).They can be used alone or are used in combination of two or more.
(i) (methyl) acrylic acid alkyl or cycloalkyl ester: for example, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) vinylformic acid n-octyl, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) tridecyl acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate base ester, (methyl) vinylformic acid iso stearyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) vinylformic acid cyclo-dodecyl ester, (methyl) vinylformic acid tristane base ester etc.
(ii) there is the polymerizability unsaturated monomer of isobornyl: (methyl) isobornyl acrylate etc.
(iii) there is the polymerizability unsaturated monomer of adamantyl: (methyl) vinylformic acid adamantane esters etc.
(iv) there is the polymerizability unsaturated monomer of tricyclic decenyl: (methyl) vinylformic acid tricyclodecenyl ester etc.
(v) the polymerizability unsaturated monomer that contains aromatic nucleus: (methyl) benzyl acrylate, vinylbenzene, alpha-methyl styrene, Vinyl toluene etc.
(vi) there is the polymerizability unsaturated monomer of alkoxysilyl: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxy propyl-triethoxysilicane etc.
(vii) there is the polymerizability unsaturated monomer of fluoro-alkyl: (methyl) perfluoroalkyl acrylate such as (methyl) vinylformic acid perfluoro butyl ethyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, fluoroolefin etc.
(viii) there is the polymerizability unsaturated monomer of the optical polymerism functional groups such as dimaleoyl imino.
(ix) vinyl compound: NVP, ethene, divinyl, chloroprene, propionate, vinyl-acetic ester etc.
(x) the polymerizability unsaturated monomer of phosphorous acidic group: 2-acryloxy ethyl phosphate ester acid, 2-methacryloxyethyl phosphate ester acid, 2-acryloxy propyl group phosphate ester acid, 2-methacryloxypropyl phosphate ester acid etc.
(xi) carboxylic polymerizability unsaturated monomer: (methyl) vinylformic acid, toxilic acid, β-crotonic acid, propenoic acid beta-carboxyl ethyl ester etc.
(xii) nitrogenous polymerizability unsaturated monomer: (methyl) vinyl cyanide, (methyl) acrylamide, (methyl) vinylformic acid N; N-dimethylamino ethyl ester, (methyl) vinylformic acid N; N-diethylamino ethyl ester, N, the affixture of N-dimethylaminopropyl (methyl) acrylamide, methylene-bis (methyl) acrylamide, two (methyl) acrylamides of ethylene, 2-(methacryloyl oxygen base) ethyl-trimethyl salmiac, (methyl) glycidyl acrylate and amine etc.
(xiii) in 1 molecule, there is the polymerizability unsaturated monomer of more than two polymerizability unsaturated group: (methyl) allyl acrylate, 1,6-hexylene glycol two (methyl) acrylate etc.
(xiv) contain the polymerizability unsaturated monomer of epoxy group(ing): (methyl) glycidyl acrylate, (methyl) vinylformic acid Beta-methyl glycidyl ester, (methyl) vinylformic acid 3,4-epoxycyclohexyl methyl esters, (methyl) vinylformic acid 3,4-epoxycyclohexyl ethyl ester, (methyl) vinylformic acid 3,4-epoxycyclohexyl propyl ester, allyl glycidyl ether etc.
(xv) there is (methyl) acrylate that molecular end is the polyethylene oxide chain of alkoxyl group.
(xvi) there is sulfonic polymerizability unsaturated monomer: 2-acrylamido-2-methyl propane sulfonic acid, (methyl) vinylformic acid 2-sulphur ethyl ester, allyl sulphonic acid, 4-styrene sulfonic acid etc., the sodium salt of these sulfonic acid and ammonium salt etc.
(xvii) there is the polymerizability unsaturated monomer of ultraviolet-absorbing functional group: 2-hydroxyl-4-(3-methacryloxy-2-hydroxyl propoxy-) benzophenone, 2-hydroxyl-4-(3-acryloxy-2-hydroxyl propoxy-) benzophenone, 2,2 '-dihydroxyl-4-(3-methacryloxy-2-hydroxyl propoxy-) benzophenone, 2,2 '-dihydroxyl-4-(3-acryloxy-2-hydroxyl propoxy-) benzophenone, 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-2H-benzotriazole etc.
(xviii) UV stable polymerizability unsaturated monomer: 4-(methyl) acryloxy-1, 2, 2, 6, 6-pentamethyl-piperidines, 4-(methyl) acryloxy-2, 2, 6, 6-tetramethyl piperidine, 4-cyano group-4-(methyl) acryl amino-2, 2, 6, 6-tetramethyl piperidine, 1-(methyl) acryl-4-(methyl) acryl amino-2, 2, 6, 6-tetramethyl piperidine, 1-(methyl) acryl-4-cyano group-4-(methyl) acryl amino-2, 2, 6, 6-tetramethyl piperidine, 4-crotons acyloxy-2, 2, 6, 6-tetramethyl piperidine, 4-crotonoyl amino-2, 2, 6, 6-tetramethyl piperidine, 1-crotonoyl-4-crotons acyloxy-2, 2, 6, 6-tetramethyl piperidine etc.
(xix) there is the polymerizability unsaturated monomer of carbonyl: propenal, diacetone-acryloamide(DAA), diacetone Methacrylamide, acetoacetoxyethyl methacrylate, formyl radical vinylbenzene, there is the vinyl alkyl ketone (for example, ethenyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) of 4～7 carbon atoms etc.
As above-mentioned radical polymerization initiator, for example, can list: Cyclohexanone peroxides, 3,3,5-trimethyl hexanone peroxide, the peroxidation ketones such as methyl cyclohexanone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, 1,1-bis(t-butylperoxy) cyclohexane, normal-butyl-4,4-bis(t-butylperoxy) valerate, two (4, the 4-di-tert-butyl peroxide cyclohexyl) propane of 2,2-, two (4,4-, the bis-t-amyl peroxy cyclohexyl) propane of 2,2-, two (the tertiary hexyl peroxidation of 4, the 4-bis-cyclohexyl) propane of 2,2-, two (the tertiary octyl group peroxidation of 4, the 4-bis-cyclohexyl) propane of 2,2-, the ketal peroxide classes such as two (4, the 4-dicumyl peroxidation cyclohexyl) propane of 2,2-, cumene hydroperoxide, 2,5-dimethylhexane-2, the hydroperoxide type such as 5-dihydro-peroxidase, two (a tert-butyl hydroperoxide-sec.-propyl) benzene of 1,3-, 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane, diisopropyl benzene superoxide, the dialkyl peroxide classes such as tertiary butyl cumyl peroxide, caprinoyl superoxide, lauroyl peroxide, benzoyl peroxide, the diacyl peroxide classes such as 2,4 dichlorobenzoyl peroxide, the peroxycarbonates classes such as two (tert-butylcyclohexyl) peroxy dicarbonate, tert butyl peroxy benzoate, 2,5-dimethyl-2, the organo-peroxide Type of Collective initiators such as peroxyesters such as 5-bis-(benzoyl peroxy) hexane, and 2,2 '-Diisopropyl azodicarboxylate, the azo polymerization starters such as 1,1-azo two (hexanaphthene-1-formonitrile HCN).
As the polymerization process based on above-mentioned solution polymerization process, for example can list: by above-mentioned monomer dissolved mixture in or be scattered in organic solvent, and under the existence of above-mentioned radical polymerization initiator, while the temperature 80 ℃～200 ℃ of left and right stirs the method heating conventionally.Reaction times can be made as about 1～24 hour conventionally.
As above-mentioned organic solvent, can list ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, the esters solvents such as butyl carbitol acetate, methylethylketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, the ketones solvents such as pimelinketone, methyl alcohol, ethanol, Virahol, propyl carbinol, sec-butyl alcohol, the alcoholic solvents such as isopropylcarbinol, n-butyl ether, dioxan, ethylene glycol monomethyl ether, the ethers such as ethylene glycol monoethyl ether, SWASOL310, SWASOL1000, SWASOL1500 (more than, be all Cosmo Oil Co., Ltd. make), SHELLSOL A (シ ェ ル ゾ ー Le A, shell chemical company system) the aromatic base crude oil kind solvent etc. such as.These organic solvents can be used a kind of or be used in combination of two or more.
From making the obtained viewpoint consideration of filming hardening and its stain resistance further being improved, the second-order transition temperature (Tg) of the acrylic resin of hydroxyl (A) is 0～90 ℃, is preferably the scope of 20 ℃～80 ℃.
The adjustment of the second-order transition temperature of the acrylic resin of hydroxyl (A) can easily be carried out by changing monomer component and ratio thereof etc.
As the usage rate of the polymerizability unsaturated monomer (a) of hydroxyl, in the monomer composition of the acrylic resin (A) of hydroxyl, more than preferably at least containing 20 quality %, 25～35 quality % more preferably.
About these scopes, full cross-linked owing to making to film, the second-order transition temperature of filming improves, and molecular weight step-down between cross-linking set, thereby makes to film and become fine and close, therefore have meaning aspect the stain resistance of filming (particularly resistance to lactate).
polyisocyanate compound (B)
Paint for plastics composition of the present invention contains polyisocyanate compound (B).
Polyisocyanate compound is the compound in a part with more than two free isocyanate groups, for example, can list: hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, the aliphatic diisocyanate compounds such as lysinediisocyanate, hydrogenated xylene diisocyanate, cyclohexylidene vulcabond, methylene-bis (cyclohexyl isocyanate), the ester ring type diisocyanate cpds such as isophorone diisocyanate, tolylene diisocyanate, phenylene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, Xylene Diisocyanate, tetramethylxylene diisocyanate, the aromatic diisocyanate compounds such as naphthalene diisocyanate, 2-isocyanatoethyl-2,6-bis-isocyanato-capronates, 3-isocyanato-methyl isophthalic acid, 6-hexamethylene diisocyanate, 4-isocyanato-methyl isophthalic acid, the organic multiple isocyanates more than ternary such as 8-eight methylene diisocyanates (common name triaminononane triisocyanate).In addition, also can use dipolymer or the trimer of above-mentioned polyisocyanate compound, polyisocyanate compound and polyvalent alcohol, low molecular weight polyester resin, water etc. be carried out under the excessive condition of isocyanate group to polyurethane-reinforcement reacts and prepolymer of obtaining etc.
Example as the representational commercially available product of above-mentioned polyisocyanate compound, list: " BURNOCK D-750,-800, DN-950,-970 or 15-455 " (be Dainippon Ink Chemicals's system above, trade(brand)name, BURNOCK/ バ ー ノ Star Network Huo バ ー ノ ッ Network is registered trademark), " SUMIDUR N3300, N3390EA " (Sumitomo Bayer Urethane Co., Ltd. make, trade(brand)name, SUMIDUR/ ス ミ ジ ュ ー Le is registered trademark), " TAKENATE D-102,-202,-110 or-123N " (Mitsui Chemicals, Inc.'s system, trade(brand)name, タ ケ ネ ー ト/TAKENATE is registered trademark), " CORONATE EH, L, HL or 203 " (Nippon Polyurethane Industry Co., Ltd. make, trade(brand)name, CORONATE is registered trademark), or " DURANATE TLA-100, DURANATE24A-90CX " (Asahi Kasei Corporation's system, trade(brand)name, デ ュ ラ ネ ー ト/DURANATE is registered trademark) etc.
Among above-mentioned polyisocyanate compound (B), from the viewpoint such as the consistency with other compositions, hardness of film and weathering resistance, consider, be also particularly preferably used as isocyanurate ring affixture, uretdione type affixture and the adducts type affixture of hexamethylene diisocyanate of the isocyanurate ring affixture of aliphatic polyisocyanate compound.
curing catalysts (C)
Paint for plastics composition of the present invention contains curing catalysts (C).
By compounding curing catalysts (C), can promote reacting of hydroxyl and isocyanate group, can more in low temperature shorter time, manifest performance.
Kind as curing catalysts (C), from the processing operation (work-ing life) of curability at low temperatures and coating and the viewpoint of finish, consider, preferably include machine tin compound (C-1), aminated compounds (C-2) and organic acid (C-3).
As organo-tin compound (C-1), such as listing tetrabutyl tin, tributyltin chloride, dibutyl tin dichloride, butyl tin trichloride, tributyl tin-O-phenolate, tributyl tin cyanate, stannous octoate, oleic acid tin, dibutyl tin acetic ester, dibutyl tin two (2-ethylhexanoate), Dibenzyltin two (2-ethylhexanoate), dibutyltin dilaurate etc.
As aminated compounds (C-2), be preferably tertiary amine compounds, for example can use: Trimethylamine 99, triethylamine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, triisobutyl amine, three sec-butylamine, tridodecylamine, N, N '-dimethyl lauryl amine, the tertiary amine level aliphatic alkyl monoamine compounds such as three (hexadecyl) amine, dimethylamino hexanaphthene, 1,5-diazabicyclo [4,3,0]-5-nonene, 1,8-diazabicyclo [5,4,0]-ester ring type aminated compoundss such as 7-undecylene, xylidine, Diethyl Aniline, the aromatic amine compounds such as tribenzylamine, trolamine, methyldiethanolamine, dimethylethanolamine, diethylethanolamine, dibutyl thanomin, two (2-ethylhexyl) thanomin, ethyldiethanolamine, tri-isopropanolamine, the alkanolamine compounds such as dibutyl α-amino isopropyl alcohol, Triethylene Diamine, Tetramethyl Ethylene Diamine, tetramethyl-hexamethylene-diamine, 4-methyl-diaminopropane, the diamine compounds such as five methyl diethylentriamine and three aminated compoundss.
As organic acid (C-3), such as being formic acid, acetic acid, butyric acid, lactic acid, oxalic acid, fumaric acid, succsinic acid, phosphoric acid, citric acid, glyconic acid, propionic acid, butyric acid, caproic acid, stearic acid, lauric acid, ricinolic acid, sad and other aliphatic carboxylic acids etc. arbitrarily.
By using above-mentioned curing catalysts (C), can promote the acrylic resin of hydroxyl and the urethane cures of polyisocyanate compound to react, can improve film whole cross-linking density and the second-order transition temperature of filming, thereby play the also effect of excellence of the processing operation (work-ing life) of stain resistance excellence, coating and finish.
surface conditioner (D)
Paint for plastics composition of the present invention contains surface conditioner (D).
As surface conditioner (D), from the viewpoint of finish and oil resistant acidity, consider, it is essential preferably silicon class surface conditioner (D-1) and these two kinds of surface conditioners of acrylic acid or the like surface conditioner (D-2) to be made as.
Modified silicon that the surface conditioner of silicon class (D-1) lists the organopolysiloxanes such as dimethyl polysiloxane, obtain organopolysiloxane modification etc.As modified silicon, specifically list alkyl-modified polysiloxane, phenyl modified polysiloxane, Siloxane-Oxyalkylene Copolymers etc.They can be used alone or are used in combination of two or more.
Particularly, such as listing: dimethyl polysiloxane, methyl phenyl silicone, polyether-modified polydimethylsiloxane, polyether-modified dimethyl polysiloxane, polyester modification dimethyl polysiloxane, polyester modification polydimethylsiloxane, poly-methyl alkyl siloxane, the poly-methyl alkyl siloxane of polyester modification, the poly-methyl alkyl siloxane of aralkyl modification, the polyether-modified polydimethylsiloxane containing acryl, polyester modification contain the polydimethylsiloxane of acryl etc.
As above-mentioned silicon class surface conditioner (D-1), can use commercially available product.
For example list: DC11PA, ST80PA, DC3074, DC3037, SR2402 (more than, trade(brand)name, Toray Dow Corning company system), KP-321, KP-324, KP-327, KR-9218, X-40-9220 (more than, trade(brand)name, chemical industrial company of SHIN-ETSU HANTOTAI system), TSR165, XR-31B1763 (more than, trade(brand)name, Toshiba Silicone Co., Ltd. make), BYK-341, BYK-344, BYK-306, BYK-307, BYK-325, BYK-315, BYK-320, BYK-322, BYK-323, BYK-300, BYK-302, BYK-330, BYK-333, BYK-335, BYK-370, BYK-SILCLEAN3700 (more than, trade(brand)name, BYK Japan KK system), DISPARLON1711, 1751N, 1761, LS-001, LS-050 (more than, trade(brand)name, Kusumoto Chemicals, Ltd. make), Poly-Flow KL-400HF, KL-401, KL-402, KL-403, KL-404 (more than, trade(brand)name, chemical company of common prosperity society trade(brand)name processed) etc.
As acrylic acid or the like surface conditioner (D-2), for example list: the weight-average molecular weight that (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid alkyl esters are obtained as raw material is 300～50,000 acrylic polymers.In addition, silicon modification and acrylic resin of obtaining etc. are also contained in wherein.
Above-mentioned, as acrylic acid or the like surface conditioner (D-2), can use commercially available product.For example list BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-392 (more than, trade(brand)name, BYK Japan KK system), DISPARLON LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, NSH-8430HF (more than, trade(brand)name, Kusumoto Chemicals, Ltd. make), Poly-Flow No.50EHF, No.54N, No.55, No.77, No.85HF, No.90, No.90D-50, No.95, No.99C (more than, trade(brand)name, chemical company of common prosperity society system) etc.
In addition, paint for plastics composition of the present invention can contain other surface conditioners (D-3) except above-mentioned silicon class surface conditioner (D-1) and acrylic acid or the like surface conditioner (D-2).
As other surface conditioners (D-3), also can use fluorine class, vinyl-based etc.
As commercially available vinyl-based surface conditioner, list DISPARLON LHP-90, LHP-91 (more than, trade(brand)name, Kusumoto Chemicals, Ltd. system) etc.
In addition, as commercially available fluorine class surface conditioner, list BYK-340 (trade(brand)name, BYK Japan KK system) etc.
Can think, by using above-mentioned surface conditioner (D), reduce the oleic acid contact angle of film coated surface, oleic acid becomes and easily soaks expansion, thereby has improved stain resistance.
In addition, the mechanism of action is not clear, but by containing the two or more surface conditioner of silicon class surface conditioner (D-1) and acrylic acid or the like surface conditioner (D-2), thereby play the effect of filming that can obtain stain resistance excellence not only but also finish excellence.
coloring components
In paint for plastics composition of the present invention, in order to obtain the desirable tone of filming, can use a kind of in the following illustrative various coloring components such as tinting pigment, illuminating colour, or be use mixing two or more.But, be not limited only to following illustrative material.
As tinting pigment, such as listing titanium oxide, zinc oxide, carbon black, chrome vermillion, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridine ketone pigment, isoindoline class pigment, intellectual circle's class pigment, perylene class pigment, dioxazine pigment, diketopyrrolopyrroles pigment etc.
In addition, as other tinting pigment, as representational example, list the bright pigment such as aluminium paste, pearl powder, graphite, MIO etc.
These coloring components also can directly make an addition in coating composition, also can mix and disperse, carry out after paste with dispersion agent, dispersion resin, and compounding is in coating.And can use known dispersion agent, dispersion resin, dispersing method.
acrylic resin (E)
Paint for plastics composition of the present invention can contain acrylic resin (E).
About acrylic resin (E), according to the tack with coated article and hardness of film, can preferably use by utilizing the known method of himself, for example, by the solution polymerization process in organic solvent, the total amount of copolymer composition of take is benchmark, methyl methacrylate 65～90 quality % and other polymerizability unsaturated monomer (b) 10～35 quality % is carried out to copolymerization and the acrylic resin manufactured.
Other polymerizability unsaturated monomers (b) can preferably use above-mentioned hydroxyl acrylic resin (A) item in explanation material.
Structure monomer as acrylic resin (E), by among other polymerizability unsaturated monomers (b), the methyl methacrylate that the total amount of copolymer composition of take contains 65～90 quality % as benchmark, thus can form particularly to good the filming of the adhesion of plastic material.
From the viewpoint of the weathering resistance of filming, consider, it is generally 3,000～100,000, particularly 4,000～50 that acrylic resin (E) preferably has, 000, and the further weight-average molecular weight in 5,000～30,000 scope particularly.
other compositions
In paint for plastics composition of the present invention, can be by the resin of the hydroxyl the acrylic resin except hydroxyl (A), pigment extender (for example, calcium carbonate, barium sulfate, silica, barium oxide, talcum, quartzy etc.), UV light absorber (benzotriazole category absorption agent for example, triazines absorption agent, salicyclic acid derivatives class absorption agent, benzophenone absorption agent etc.), photostabilizer (for example, hindered piperidine class etc.), defoamer, softening agent, sedimentation preventing agent, the common additive for coatings such as solvent of dilution use contain individually respectively or two or more combinations are contained.The occasion of the resin of the hydroxyl the acrylic resin (A) containing except hydroxyl, resin solid substance 100 mass parts with respect to the resin of the whole hydroxyl in paint for plastics composition of the present invention, from the viewpoint of stain resistance and finish, consider, can be below compounding 30 mass parts.
In above-mentioned paint for plastics composition, the solvent of contained dilution use is not particularly limited in the present invention, but is preferably the solvent that does not bring dysgenic dilution use to forming drying property, the painting environment of filming.
In addition, preferably use can, by the resin dissolves in paint for plastics composition of the present invention and compatible organic solvent, specifically be preferably at least one organic solvent of selecting in the group from consisting of ester class organic solvent, organic solvent of ketone and ether organic solvent.
As ester class organic solvent, such as listing butylacetate, isobutyl acetate, 2-ethyl hexyl ethanoate, acetic acid-3-methoxyl group butyl ester, hexalin acetate etc., as organic solvent of ketone, list methylethylketone, methyl iso-butyl ketone (MIBK) etc., as ether organic solvent, can list propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic ester, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetic ester etc., they can be used alone or are used in combination.In them, from the viewpoint of the storage stability of coating composition, consider, it is preferred using ester class organic solvent.
the content of each composition of coating composition
The content of above-mentioned each composition in paint for plastics composition of the present invention is not particularly limited, but considers to be preferably following scope from the viewpoint of following film performance and finish.
The solid content of each composition shown below is: in the occasion that comprises the acrylic resin of hydroxyl (A) and acrylic resin (E), take their the total resin solid substance 100 mass parts solid content during as benchmark.
Compounding ratio about polyisocyanate compound (B), from the viewpoint of stain resistance, consider, the mode that the equivalence ratio of the hydroxyl preferably having according to the acrylic resin of the isocyanate group of polyisocyanate compound and hydroxyl (NCO/OH) is generally 0.8～1.5, be in particular in 1.0～1.3 scope is selected.
About the solid content of curing catalysts (C), from the storage stability of coating composition and the viewpoint of the finish of filming and hardness of film, consider, be preferably following ranges.
About the solid content of organo-tin compound (C-1), from the viewpoint of solidified nature and stain resistance, consider, be 0.002～0.5 mass parts, be preferably in the scope of 0.004～0.2 mass parts.
About the solid content of aminated compounds (C-2), from the processing operation (work-ing life) of coating and the viewpoint of stain resistance, consider, be below 5 mass parts, be preferably in the scope of 0.01～2 mass parts.
About the solid content of organic acid (C-3), from the viewpoint of the storage stability of coating, consider, be below 10 mass parts, be preferably in the scope of 0.75～5 mass parts.
About the solid content of surface conditioner (D), from the viewpoint of finish and stain resistance, consider, be 0.1～10 mass parts, more preferably in the scope of 0.2～5 mass parts.
About the solid content of silicon class surface conditioner (D-1), from the viewpoint of finish, consider, be 0.005～5 mass parts, be preferably in the scope of 0.008～0.5 mass parts.
About the solid content of acrylic acid or the like surface conditioner (D-2), viewpoint acid from oil resistant and finish is considered, is 0.01～3 weight part, is preferably in the scope of 0.05～0.8 mass parts.
In the occasion of using other surface conditioners (D-3), its solid content is below 3 mass parts, is preferably in the scope of 0～2 mass parts.
In the occasion of using acrylic resin (E), its solid content, from the viewpoint of the tack of coated article and hardness of film is thought of as below 30 mass parts, is preferably in the scope of 2～20 mass parts.
Occasion using coloring components, if its solid content is in meeting the scope of stain resistance, is not particularly limited.
Paint for plastics composition of the present invention is that the mode application of 30 ± 5 μ m and the second-order transition temperature of the cured coating film when 80 ℃ of bakings are solidified for 20 minutes are more than 100 ℃ according to dry film thickness, and between the cross-linking set of this cured coating film, molecular weight is below 900g/mol.
In specification sheets of the present invention, between second-order transition temperature and cross-linking set, molecular weight is by the measured value of utilizing Measurement of Dynamic Viscoelasticity device to obtain is applicable to the calculated value that theoretical formula is obtained, and can operate as follows and measure.
the second-order transition temperature of cured coating film
The second-order transition temperature of cured coating film of the present invention is: for sample, by using FTRheology Spectra " Rheogel E-400 " (UBM Co., Ltd. system) and in 110 hertz of frequency numbers, 4 ℃/min of Measurement of Dynamic Viscoelasticity that determine of heat-up rate, the dynamic second-order transition temperature determining as the peaked temperature of tan δ (loss Young's modulus/storage Young's modulus) is shown.About sample, the mode that is 30 ± 5 μ m according to curing thickness by paint for plastics composition of the present invention is coated on polypropylene board, by 80 ℃ of conditions of cure of 20 minutes, form cured coating film, then obtained cured coating film is cut to the short strip shape of length 20mm, width 5mm, and the filming as sample freely of the short strip shape obtaining peeling off from polypropylene board.
The second-order transition temperature of the cured coating film being obtained by paint for plastics composition of the present invention is thought of as more than 100 ℃ from the viewpoint of stain resistance, is preferably 100～125 ℃, is further particularly preferably in the scope of 100～120 ℃.
molecular weight between the cross-linking set of cured coating film [Mc]
The molecular weight of the resin between cross-linking set is called to molecular weight between cross-linking set, and cross-linking density more this value that becomes becomes less.
Between the cross-linking set of cured coating film of the present invention, molecular weight is: the mnm. substitution following rubber Theory of Viscoelasticity formula of the storage Young's modulus obtaining in second-order transition temperature at above-mentioned cured coating film is measured and the calculated value obtained.
Formula 1:Mc=3 ρ RT/E
min
Herein, Mc: molecular weight between cross-linking set (g/mol),
ρ: the density (kg/m of coated film of sample
3),
R: gas law constant (8.314J/K/mol),
T: storage Young's modulus is E
mintime absolute temperature (K),
E
min: the mnm. (Pa) of storage Young's modulus.
Between the cross-linking set of cured coating film, molecular weight is thought of as below 900g/mol from the viewpoint of stain resistance, is preferably below 800g/mol, more preferably below 700g/mol.While being greater than 900g/mol, have the significantly reduced situation of stain resistance thereby not preferred.
Paint for plastics composition of the present invention is by the acrylic resin (A) and polyisocyanate compound (B), curing catalysts (C) and the surface conditioner (D) that contain specific hydroxyl, thereby can obtain filming of stain resistance and finish excellence.
Can think, by making the second-order transition temperature of cured coating film, be more than 100 ℃, and to make molecular weight between the cross-linking set of cured coating film be below 900g/mol, in the test of the stain resistance of the applying loads of 80 ℃, pollution substance will be difficult to infiltration, thereby the stain resistance of cured coating film is improved.
Particularly as surface conditioner (D), by containing silicon class surface conditioner (D-1) and this two or more surface conditioner of acrylic acid or the like surface conditioner (D-2), thereby play, can obtain that stain resistance (particularly acidity of oil) not only improves but also the also excellent effect of filming of finish.Further, paint for plastics composition of the present invention, by low-temperature curing, also can meet the effect of desirable Physical properties of coating film and finish even if play once coating.
Paint for plastics composition of the present invention is preferably organic solvent type coating composition.Again, in this manual, organic solvent type coating composition is as the water-free in fact coating of solvent.
About paint for plastics composition of the present invention, from painting operation and the viewpoint of cutting down the organic solvent amount of discharging, consider, preferably when application, use as required in advance thinner, more than solid substance containing ratio is adjusted into 15 quality %, particularly preferably be adjusted in the scope of 25～60 quality %, viscosity be adjusted into 5～30 seconds/Iwata Cup(rock field flow cup) in the scope of 20 ℃.
Paint for plastics composition of the present invention is coated on coated article, can obtains coated article.
Plastic material is not particularly limited, can list: polyethylene, the polyolefin resin of the representatives such as polypropylene, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, the thermoplastic polyesters such as polycarbonate (PC) resin, acrylonitrile styrene resin (AS), acrylonitrile-butadiene-styrene (ABS) (ABS) resin, the styrene resins such as acrylonitrile-styrene-acrylic ester (ASA) resin, and plexiglass, acrylic resin, vinylidene chloride, polyamide resin, polyphenylene oxide resin, polyoxymethylene resin, polybutylene terephthalate resin, urethane resin, epoxy resin etc. or their hybrid resin, the plastic materials (synthetic resin formed product) such as fibre reinforced plastics (Fiber-Reinforced Plastics) etc. and/or engineering resin etc.
Coated article about application paint for plastics composition of the present invention, especially be preferably ABS resin, ASA resin, polyamide resin, acrylic resin, vinylidene resin, PC resin, PBT resin, urethane resin, epoxy resin etc., and the plastic material (synthetic resin formed product) such as their hybrid resin and/or fibre reinforced plastics.
In addition, also metallic substance such as iron, aluminium, brass, copper, stainless steel, tin-coated steel (Block リ キ), galvanized steel, alloying zinc-plated (Zn-A1, Zn-Ni, Zn-Fe etc.) steel and the above-mentioned plastic material material that together moulding forms can be made to coated article.
In addition, also can by such as paper, weave cotton cloth, the fiber-like such as non-woven fabrics etc. is made coated article.Paper is not particularly limited, for example, extensively scope is used the paperboards such as fluting board, yellow plate paper, white board in many aspects, variously cuts front body paper (body paper), surely spends paper (paper using), art paper, printing, glassine paper, kraft paper, synthetic paper, synthetic fibre paper, White Board, converted paper etc.Can suitably carry out skimming treatment according to these starting material, coated article is made in surface treatment.
In addition, as the purposes that is coated with the coated article of paint for plastics composition of the present invention, be not particularly limited, such as the outer board that can list the car bodies such as car, truck, motorcycle, motorbus, trolley part, the outer board of the electrical equipment such as mobile phone, stereo set etc., but the cured coating film of paint for plastics composition of the present invention low VOC and excellent stain resistance (resistance to lactate and oil resistant are acid) because acquisition has, thereby can preferably be used in parts, electric product etc. for automotive interior trim.
The coating process of paint for plastics composition of the present invention is not particularly limited.Such as can be by aerial spraying, without gas blowout mist, rotary-atomizing coating machine, submergence application etc., carry out application.During application, also can carry out static and apply.
Application thickness can be 10～100 μ m according to curing thickness conventionally, is preferably 10～50 μ m, more preferably in the scope of 15～40 μ m.
Heating condition in the coating film-forming methods of paint for plastics composition of the present invention is not particularly limited, but can, by 70～100 ℃, preferably 70～90 ℃ of maintenances, within 10～90 minutes, carry out.About plastic material, because of the heat heating condition of occasion of distortion thereupon, such as using the occasion of ABS resin etc., preferably at 50 ℃～80 ℃, keep 10～90 minutes.
Before being heating and curing as required, also can, in order to reduce the firm application volatile component of filming or removal volatile component afterwards, thereby apply, shape and/or preparation heating.Preparation heating can be undertaken by air blast, IR stove etc.
The curability at low temperatures of paint for plastics composition of the present invention is excellent, and the finish of filming obtaining by paint for plastics composition of the present invention and stain resistance excellence.Especially can preferably be used in the purposes of interior automotive trim parts.
Embodiment
Below enumerate embodiment and further describe the present invention.Again, " part " and " % " is just narrated and is expressed as " mass parts " and " quality % " as long as no other.
The manufacture of the acrylic resin No.1 of (Production Example 1) hydroxyl
To thering is whipping appts, thermometer, reflux exchanger, thermostatted and dripping with in the reaction vessel of pump, add 60 parts of butylacetates, be blown into nitrogen on one side, under whipped state, be warming up to 125 ℃ on one side, utilize to drip with pump the monomer of recording in table 1 and the mixture of polymerization starter to be dripped in reaction vessel in 3 hours with certain speed.Need to drip again for 1 hour the mixture of 10 parts of 0.5 part of identical polymerization starter and butylacetates thereafter.After dropping finishes, in uniform temp, slaking finishes reaction after 3 hours.With butylacetate, the solid substance containing ratio of obtained solution is adjusted into 60%, and obtains the clear solution of the acrylic resin No.1 of hydroxyl.The weight-average molecular weight of multipolymer is about 9,000 in addition, and hydroxyl value is 120mgKOH/g, and second-order transition temperature is 79 ℃.
The manufacture of the acrylic resin No.2～No.4 of (Production Example 2～4) hydroxyl
In Production Example 1, monomer, polymerization starter and temperature of reaction according to the content setting compounding of recording in table 1, in addition, similarly operate with Production Example 1, thereby obtain acrylic resin No.2～No.4 solution of hydroxyl.
Solid substance containing ratio, hydroxyl value and the second-order transition temperature of the acrylic resin of each hydroxyl are shown in to table 1 in the lump.
(noting 1) SWASOL1500: Maruzen Petrochemical Co., Ltd., trade(brand)name, aromatic hydrocarbon solvent.
Table 1
the making > of < test board
(ABS coated article)
With Virahol, the surperficial degreasing of the acrylonitrile-butadiene-styrene (ABS) plate of 100mm * 150mm * 3.0mm is made to ABS coated article.
(PC/ABS coated article)
With Virahol, the surperficial degreasing of polycarbonate-acrylonitrile-butadiene-styrene (ABS) plate of 100mm * 150mm * 3.0m is made to PC/ABS coated article.
the manufacture of coating composition
The manufacture of (embodiment 1) paint for plastics composition No.1
By 158.3 parts of 60% solution of the acrylic resin No.1 of the hydroxyl being obtained by Production Example 1 (95 parts of solid substances), 9.1 parts of 55% solution (5 parts of solid substances) of the acrylic resin No.2 of the hydroxyl being obtained by Production Example 4, 43.5 parts of polyisocyanate compounds (B-1) (noting 2), 0.005 part of dibutyltin dilaurate, 1.00 parts of triethylamines, 0.01 part of BYK-307 (noting 3), 5.0 parts of evenly mixing of 0.40 part of BYK-355 (noting 5) and MONARCH1300 (noting 8), with butylacetate, according to the mode that becomes Cup/20 ℃ of 10 ± 1 seconds/Iwata, solid substance containing ratio adjusted again and obtained paint for plastics composition No.1.The equivalence ratio of the total amount of the hydroxyl (OH) of the acrylic resin composition of the hydroxyl in paint for plastics composition No.1 and the isocyanate group (NCO) of polyisocyanate compound (B) is NCO/OH=1.2.
The manufacture of (embodiment 2～13, comparative example 1～4) paint for plastics composition No.2～No.17
In embodiment 1, the proportioning of each composition is made as to the proportioning shown in table 2, in addition, operation similarly to Example 1, and according to the mode that becomes Cup/20 ℃ of 10 ± 1 seconds/Iwata shown in table 2, with butylacetate, solid substance containing ratio is adjusted and obtained coating composition No.2～No.17.Again, the compounding scale of table 1 shows the compounding amount of solid substance.In addition, molecular weight (Mc) between the work-ing life (working life) of each paint for plastics composition, the second-order transition temperature of filming and cross-linking set is shown in the lump.
(noting 2) SUMIDUR N3300: trade(brand)name, Sumitomo Bayer Urethane Co., Ltd. system, the isocyanurate ring affixture of hexamethylene diisocyanate, solid substance containing ratio 100%, NCO containing ratio 21.8%.
(noting 3) BYK-307: trade(brand)name, BYK Japan KK system, polyether-modified polydimethylsiloxane, surface conditioner,
(noting 4) Shin-Etsu Silicones KP-327: trade(brand)name, chemical industrial company of SHIN-ETSU HANTOTAI system, phenyl methyl polysiloxane, surface conditioner,
(noting 5) BYK-355: trade(brand)name, BYK Japan KK system, acrylic copolymer, surface conditioner,
(noting 6) BYK-350: trade(brand)name, BYK Japan KK system, acrylic copolymer, surface conditioner,
(noting 7) Disparlon NSH8430: trade(brand)name, Kusumoto Chemicals, Ltd. system, acrylic acid or the like (methacrylic ester)-silicon analog copolymer, surface conditioner.
(noting 8) MONARCH1300: trade(brand)name, Cabot company system, charcoal blacks, tinting material.
(noting 9) work-ing life (validity period):
The composition that mensuration is evenly obtained by mixing whole compositions (10 seconds/Iwata of viscosity Cup/20 ℃) is placed the viscosity after 3 hours at 30 degree, and evaluates based on following metewand.
◎: raise less than 2 seconds of viscosity,
Zero: raise 2 seconds～less than 3 seconds of viscosity,
△: raise 3 seconds～less than 10 seconds of viscosity,
*: viscosity has raise more than 10 seconds.
(embodiment 14)
Using aerial spraying, is that the mode of 30 ± 5 μ m is coated with paint for plastics composition No.1 to be contained on ABS coated article according to dry film thickness, shapes at normal temperatures after 5 minutes, then, at 80 ℃, is dried 20 minutes and acquisition coated plate.
(embodiment 15～27 and comparative example 5～8)
In embodiment 14, content setting paint for plastics composition, coated article according to shown in table 3, in addition, carry out operation similarly to Example 14, thereby obtain the coated plate that is coated with each paint for plastics composition.
As above each coated plate that operation obtains is made to test board after standing 24 hours under 23 ℃, the atmosphere of 50% relative humidity, for various tests.
Test-results is as shown in table 3.
(noting 10) tack [initial stage]
On the coated surface of test board, according to JIS K5600-5-6 (1990), at the checker of 100 2mm * 2mm of middle making of filming, after tape sticker is invested to this coated surface and peeling off fast, to residuing in the quantity that the checker of painting face films, evaluate.
◎: residual number/all number=100/100 and there is no edge disappearance,
Zero: residual number/all number=100/100 and there is edge disappearance,
△: residual number/all number=99～90/100,
*: residual number/all number=89 are following/and 100.
(noting 11) finish:
Use orange peel instrument (Wave-scan plus ，BYK Gardner company system, trade(brand)name) to evaluate the finish of film coated surface.About orange peel instrument, the laser radiation of being sent by determinator, in painting face, and is utilized to detector detection of reflected light intensity one by one, can observe the optics of the approaching film coated surface of observation post under naked eyes by catoptrical intensity concavo-convex.By orange peel instrument, measure long wave value (LW) and shortwave value (SW).Long wave value is the index of amplitude of surfaceness of the wavelength of about 1.2～12mm, and it can evaluate the situation of the medium wave striped (medium wave flesh) of painting face.Shortwave value is the index of amplitude of surfaceness of the wavelength of about 0.3～1.2mm, and it can evaluate the situation of the small striped of painting face.In addition, about wave number (WaveScan value), the less level of numerical value is better.Generally speaking the benchmark of wave number in common car is below 15, and the benchmark in senior car is below 10.
(noting 12) stain resistance:
lactate test (test of artificial perspiration's property)
In film coated surface, drip 1 10% lactic acid (dilute with water is 10% solution), in thermostatic bath, carry out the placement of 80 ℃ * 24 hours., wipe drop, and press and state metewand and evaluate outward appearance, tack and scuff resistance thereafter.
the acid lactate test of oil resistant (test of artificial perspiration's property)
In film coated surface, drip 1 10% oleic acid (being 10% solution with gasoline dilution), in thermostatic bath, carry out the placement of 80 ℃ * 24 hours., wipe drop, and press and state metewand and evaluate outward appearance, tack and scratch-resistant thereafter.
outward appearance (visual)
5: there is no drop vestige,
4: there is a little drop vestige,
3: there is drop vestige,
2: on the filming of drop part, there is a little contraction,
1: filming of drop part shrinks, and can see substrate.
tack (after test)
After attaching adhesive tape and peel off fast according to the mode that covers the drop part of the test board after resistance to lactate or oil resistant acid test, whether painting face is peeled off and evaluated.The occasion of being peeled off of filming for *, the occasion of not peeled off of filming is zero.
scuff resistance (after stain resistance test)
As the record in JIS K5600-5-4 (1999), in the drop portion of the test board after the test of resistance to lactate or oil resistant acidity, the angle that the drop portion of take with respect to test board is 45 degree is used pencil (hardness 2H) to filming, to apply wound, to now having or not to peel off, evaluates.Be determined in the thermostatic chamber of 20 ℃ and carry out.
Zero: film and do not peel off,
△: filming, a little peels off,
*: thereby film to peel off, can see substrate.
Claims (4)
1. a paint for plastics composition, it is 3 for containing weight-average molecular weight, 000～20,000 and acrylic resin (A), polyisocyanate compound (B), the curing catalysts (C) of the hydroxyl of hydroxyl value in the scope of 100～200mgKOH/g and the coating composition that silicon class surface conditioner (D-1) and acrylic acid or the like surface conditioner (D-2) be essential surface conditioner (D) of take
It is characterized in that, by this coating composition, according to dry film thickness, be that the mode application of 30 ± 5 μ m and the second-order transition temperature of the cured coating film when 80 ℃ of bakings are solidified for 20 minutes are more than 100 ℃, and between the cross-linking set of this cured coating film, molecular weight is below 900g/mol.
2. paint for plastics composition according to claim 1, is characterized in that, it further contains take the acrylic resin (E) that methyl methacrylate 65～90 quality % and other polymerizability unsaturated monomers 10～35 quality % are copolymer composition.
3. paint for plastics composition according to claim 1 and 2, wherein, curing catalysts (C) includes machine tin compound (C-1), aminated compounds (C-2) and organic acid (C-3).
4. article, it obtains by the paint for plastics composition described in any one in application claim 1～3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-156379 | 2012-07-12 | ||
| JP2012156379A JP2014019714A (en) | 2012-07-12 | 2012-07-12 | Coating composition for plastic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103540250A true CN103540250A (en) | 2014-01-29 |
Family
ID=49964133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310289342.5A Pending CN103540250A (en) | 2012-07-12 | 2013-07-11 | Coating compound for plastic |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2014019714A (en) |
| CN (1) | CN103540250A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109476A (en) * | 2014-07-28 | 2014-10-22 | 广西梧州龙鱼漆业有限公司 | Anti-yellowing terrace coating and construction method thereof |
| CN107033761A (en) * | 2017-03-17 | 2017-08-11 | 广州大学 | A kind of aqueous floride-free anti-fingerprint antifouling polymeric composite coating and its application method |
| CN110713781A (en) * | 2018-07-12 | 2020-01-21 | 荒川化学工业株式会社 | Self-repairable coating agent, cured product, and film |
| CN117402541A (en) * | 2023-08-21 | 2024-01-16 | 巴斯夫涂料有限公司 | Two-component varnish composition, its preparation and use |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098987B (en) * | 2014-07-28 | 2016-06-22 | 广西梧州龙鱼漆业有限公司 | Color inhibition epoxy coating and preparation method thereof |
| JP6977226B2 (en) * | 2018-09-28 | 2021-12-08 | 大日本塗料株式会社 | Paint composition, coating film forming method, and painted body |
| KR20210068064A (en) * | 2018-09-28 | 2021-06-08 | 아라까와 가가꾸 고교 가부시끼가이샤 | Adhesive sheet for surface protection |
| JP7179419B2 (en) * | 2019-01-17 | 2022-11-29 | 関西ペイント株式会社 | Coating film formation method |
| JP7219642B2 (en) * | 2019-03-14 | 2023-02-08 | 三菱ケミカルインフラテック株式会社 | Acrylic resin composition, cured product, paint, coating film and covering material for civil engineering and construction |
| JP6947273B1 (en) * | 2020-10-15 | 2021-10-13 | 荒川化学工業株式会社 | Thermosetting coating agent, cured product, laminate and its manufacturing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08325519A (en) * | 1995-03-31 | 1996-12-10 | Daicel Huels Ltd | Two-part type coating material composition |
| CN1343224A (en) * | 1999-03-12 | 2002-04-03 | 阿克佐诺贝尔公司 | Filler composition |
| CN101245216A (en) * | 2007-02-16 | 2008-08-20 | 关西涂料株式会社 | Colored coating composition |
| CN102292405A (en) * | 2008-10-24 | 2011-12-21 | 关西涂料株式会社 | Coating composition and method for forming coating film |
-
2012
- 2012-07-12 JP JP2012156379A patent/JP2014019714A/en active Pending
-
2013
- 2013-07-11 CN CN201310289342.5A patent/CN103540250A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08325519A (en) * | 1995-03-31 | 1996-12-10 | Daicel Huels Ltd | Two-part type coating material composition |
| CN1343224A (en) * | 1999-03-12 | 2002-04-03 | 阿克佐诺贝尔公司 | Filler composition |
| CN101245216A (en) * | 2007-02-16 | 2008-08-20 | 关西涂料株式会社 | Colored coating composition |
| CN102292405A (en) * | 2008-10-24 | 2011-12-21 | 关西涂料株式会社 | Coating composition and method for forming coating film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109476A (en) * | 2014-07-28 | 2014-10-22 | 广西梧州龙鱼漆业有限公司 | Anti-yellowing terrace coating and construction method thereof |
| CN104109476B (en) * | 2014-07-28 | 2016-04-20 | 广西梧州龙鱼漆业有限公司 | Color inhibition terrace paint and constructional method thereof |
| CN107033761A (en) * | 2017-03-17 | 2017-08-11 | 广州大学 | A kind of aqueous floride-free anti-fingerprint antifouling polymeric composite coating and its application method |
| CN110713781A (en) * | 2018-07-12 | 2020-01-21 | 荒川化学工业株式会社 | Self-repairable coating agent, cured product, and film |
| CN117402541A (en) * | 2023-08-21 | 2024-01-16 | 巴斯夫涂料有限公司 | Two-component varnish composition, its preparation and use |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014019714A (en) | 2014-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103540250A (en) | Coating compound for plastic | |
| US11814470B2 (en) | Omniphobic polyurethane compositions, related articles, and related methods | |
| JP6474834B2 (en) | Adhesion promoter for aqueous coating composition | |
| EP2749583B1 (en) | Siloxane-urethane foul release coatings | |
| JP4844803B2 (en) | Molded laminated sheet | |
| US20210002410A1 (en) | Omniphobic polyurethane compositions, related articles, and related methods | |
| JP6912849B2 (en) | Coating composition and method for forming a multi-layer coating film | |
| CN100471921C (en) | Coating composition and multilayered coating film forming method and coated article using this coating composition | |
| EP3156433B1 (en) | Coating compositions including a polyisocyanate chain extended nh functional prepolymer | |
| JP2015066543A (en) | Coating film formation method | |
| JP2006348172A (en) | Thermosetting coating composition | |
| CN102292405A (en) | Coating composition and method for forming coating film | |
| WO2009024351A1 (en) | Paint compositions, a method of finish-painting and painted objects | |
| CN103509412B (en) | Brightness coating composition | |
| JP2016000770A (en) | Base paint composition | |
| CN112601769B (en) | Polycarbonate-modified acrylic resin, paint, and plastic molded article coated with the paint | |
| JP4482803B2 (en) | Molded laminated sheet | |
| CA3118475A1 (en) | Coating compositions containing phosphorus acid functional polyol polymers and coatings formed therefrom | |
| JP2012172094A (en) | Resin composition for molding, sheet, pressure-sensitive adhesive sheet, method for producing the sheet, and molded body | |
| WO2019188574A1 (en) | Coated body | |
| JP5342457B2 (en) | Multi-layer coating formation method | |
| JP2009149825A (en) | Coating composition and method for forming coated film | |
| JP5060997B2 (en) | COATING COMPOSITION, COATED ARTICLE APPLYING THE SAME, AND METHOD FOR PRODUCING COATING COMPOSITION | |
| KR20170088464A (en) | High glossy paint composition for interial parts | |
| JPH08259887A (en) | Coating composition and coating finish using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140129 |