Summary of the invention
The objective of the invention is advantages such as, good stability low, quick solidifying in conjunction with ultraviolet light polymerization initiator price, with advantage such as security, the penetrance of visible light be good, easy to use, provide a kind of using visible light light source irradiation to cause that solidified contains the visible-light curing metallic paint of radical photoinitiator, to substitute existing traditional metallic paint and ultraviolet light polymerization metallic paint.
Visible-light curing metallic paint of the present invention is formed and content (by weight percentage) is:
The prepolymer 0-20% that contains alkene class unsaturated group
The monomer 20-80% that contains alkene class unsaturated group
Light trigger 1-10%
Aided initiating 0.5-30%
Auxiliary agent 0-10%
Filler and/or pigment 0-40%
Solvent 0-30%
Above-mentioned component according to described mixed, is stirred, promptly prepare visible-light curing metallic paint of the present invention.
The described prepolymer that contains alkene class unsaturated group comprises epoxy (methyl) acrylate, urethane (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) acrylate, acrylic copolymer or their any mixture.
Described epoxy (methyl) acrylate be Resins, epoxy and unsaturated carboxylic acid (for example, vinylformic acid, methacrylic acid) adduct of reaction, comprise epoxy (methyl) acrylate of epoxy (methyl) acrylate, phenol or cresol-novolac epoxy resin of bisphenol A type epoxy resin or (methyl) acrylate of diglycidyl ether.
The reaction product that the reaction of described urethane (methyl) acrylate by hydroxyl (methyl) acrylate and polyvalent alcohol and organic multiple isocyanate makes.(methyl) acrylate of described hydroxyl is (methyl) acrylic acid hydroxy alkyl ester, for example (methyl) 2-hydroxyethyl acrylate or (methyl) vinylformic acid-2-hydroxypropyl ester.Described polyvalent alcohol comprises ethylene glycol, propylene glycol or butyleneglycol etc.Described organic multiple isocyanate comprises tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
Described polyester (methyl) acrylate is polyester polyol and (methyl) acrylic acid dehydrating condensation product.Described polyester polyol is the reaction product of polyvalent alcohol and diprotic acid, wherein polyvalent alcohol comprises ethylene glycol, polypropylene glycol, 1,6-hexylene glycol or TriMethylolPropane(TMP) etc., diprotic acid comprise hexanodioic acid, succsinic acid, phthalic acid, hexahydro-phthalic acid or terephthalic acid etc.
Described polyethers (methyl) acrylate is poly-alkyl diol two (methyl) acrylate, for example polyoxyethylene glycol two (methyl) acrylate or polypropylene glycol two (methyl) acrylate.
Described acrylic copolymer is monomers such as vinylformic acid, acrylate or vinylbenzene, in peroxide initiator (for example, Benzoyl Peroxide) effect down, and by the compounds that Raolical polymerizable obtained.
The described monomer that contains alkene class unsaturated group comprises styrenic, (methyl) esters of acrylic acid, vinyl ethers or their any mixture etc.
Described styrene monomer comprises vinylbenzene or alpha-methyl styrene etc.
Described (methyl) acrylic ester monomer comprises the simple function group monomer, for example butyl acrylate, cyclohexyl acrylate, Isooctyl acrylate monomer, (methyl) vinylformic acid-2-hydroxyl ethyl ester or (methyl) vinylformic acid-2-hydroxypropyl acrylate etc.; The bifunctional monomer, for example 1,6 hexanediol diacrylate (HDDA), tri (propylene glycol) diacrylate (TPGDA), propylene glycol diacrylate (DPGDA), neopentylglycol diacrylate (NPGDA), ethoxylated neopentylglycol diacrylate (PO-NPGDA), bisphenol a diacrylate (DDA), tetraethylene-glycol diacrylate (TEGDA) or PDDA (PDDA) etc.; Trifunctional monomer, for example Viscoat 295 (TMPTA), ethoxylated trimethylolpropane triacrylate (EO-TMPTA), propoxylation Viscoat 295 (PO-TMPTA), pentaerythritol triacrylate (PETA) or three (2-hydroxyethyl) isocyanuric acid triacrylate etc.; Polyfunctional monomer, for example tetramethylol methane tetraacrylate, Dipentaerythritol five acrylate or dipentaerythritol acrylate etc.Usually with one or more the mixture in above-mentioned (methyl) acrylic ester monomer as application.
Described vinyl ethers monomer comprises hexanaphthene dimethyl alcohol divinyl ether, hydroxyethyl vinyl ether or triethylene glycol divinyl ether etc.
The described monomer that contains alkene class unsaturated group further comprises N-vinyl pyrrolidone, N-caprolactam, acryloyl morpholine, N-vinyl formamide or N-vinyl acetamide.
The described monomer that contains alkene class unsaturated group preferably uses polyvalent alcohol many (methyl) acrylate, as two functionality 1,6 hexanediol diacrylates or three-functionality-degree Viscoat 295.1,6 hexanediol diacrylate is a kind of linear chain structure, gives the good snappiness of filming, and contains 3 two keys in the Viscoat 295, can improve curing speed, hardness and the electrical property of filming.
Described light trigger is meant that photochemical reaction can take place produces a free radical or a hydrionic compounds when accepting the special wavelength rayed.Thereby can causing the Raolical polymerizable of system, the free radical that radical photoinitiator produced makes paint solidification.The light trigger of different structure has different absorption spectrums and free radical activity, and the light trigger of selecting comparatively to mate with the light source light spectrum energy distribution will improve curing speed greatly.When the formula for a product of definite purposes of design and using method, may produce synergism from many-sides such as used light source, set time, paint film property and economy screening light trigger and the combination of different light trigger.
Described light trigger comprises benzoin ethers, benzil ketals class, acetophenones, anthraquinone class, thioxanthones, Benzophenones, acyl group see oxygen compound class, benzoates or dicyclo cyclohexadione compounds.
Described benzoin ether photoinitiator is benzoin methyl ether, bitter almond oil camphor ethyl ether or bitter almond oil camphor isopropyl ether etc.
Described benzil ketals photoinitiator is a benzil dimethyl ketal etc.
Described acetophenones light trigger is a methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1, the 1-dichloroacetophenone, the 1-hydroxy acetophenone, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl-1-acetone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-acetone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone or 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone etc.
Described anthraquinone photoinitiator is 2-tertiary butyl anthraquinone, 1-chloroanthraquinone or 2-amyl anthraquinone etc.
Described thioxanthone photoinitiator is 2,4-dimethyl thia anthrone, 2,4-diethyl thioxanthone, 2 (or 4)-isopropyl thioxanthone, 2-chloro thioxanthone or 2,4-di-isopropyl thioxanthone etc.
Described Benzophenones light trigger is benzophenone, 4-chlorobenzophenone, to methyldiphenyl ketone or 4-benzoyl-4 '-dimethyl diphenyl sulfide etc.
The described acyl group oxygen compound photoinitiator of seeing is 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2; 4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, two (2, the 6-dimethylbenzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide or 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide etc.
Described benzoic ether photoinitiator is benzoylbenzoic acid methyl esters or methyl o-benzoylbenzoate etc.
Described dicyclo cyclohexadione compounds is camphorquinone or two imidazoles etc., and wherein camphorquinone has been successfully applied to the visible-light curing dental material.
When metallic paint of the present invention was varnish system, described light trigger accounted for the 1-5wt% of metallic paint gross weight, preferred 2-3wt%.
When metallic paint of the present invention was coloured system, described light trigger accounted for the 1-10wt% of metallic paint gross weight, preferred 2-5wt%.
Described aided initiating comprises the acrylic ester monomer or the prepolymer of alkyl hydroxy aminated compounds, dimethylaminobenzoic acid ester compound or amine modification.
Described alkyl hydroxy amine aided initiating is trolamine, tri-isopropanolamine or methyldiethanolamine.
Described dimethylaminobenzoic acid ester class aided initiating is 4-dimethylamino-ethyl benzoate or the different monooctyl ester of 4-dimethylaminobenzoic acid.
The acrylic ester monomer of described amine modification or prepolymer be aminated compounds (for example, diethylamine) with acrylic ester monomer or prepolymer (for example, Viscoat 295) reaction product that affine substitution reaction obtained taking place, comprises diethylamine modification Viscoat 295 or diethylamine modification ethoxylated trimethylolpropane triacrylate etc.
Described aided initiating has good promoter action to light trigger, and it has the effect that overcomes oxygen inhibition to radical polymerization simultaneously.Because low-molecular-weight aided initiating alkyl hydroxy aminated compounds is easy to from its internal migration to the surface after photo-curing material solidifies, thereby cause " perspiration " or " sending out frost " phenomenon, therefore, the acrylic ester monomer or the prepolymer of preferred dimethylaminobenzoic acid ester class or amine modification among the present invention.The addition of dimethylaminobenzoic acid ester class aided initiating is preferably 0.5-10wt%, more preferably 1-5wt% (accounting for the metallic paint gross weight); The acrylic ester monomer of amine modification or the addition of prepolymer are preferably 5-30wt% (accounting for the metallic paint gross weight), more preferably 10-20wt%.
Described auxiliary agent comprises flow agent, defoamer, wetting dispersing agent and stopper.Wherein the flow agent add-on is the 0-5wt% of prescription gross weight, and defoamer is the 0-2wt% of prescription gross weight, and wetting dispersing agent is the 0-2wt% of prescription gross weight, and stopper is the 0-1wt% of prescription gross weight.
Described flow agent includes organic siloxane type flow agent, for example BYK-306, EFKA-3031, DEUCHEM-432 or HX-3010 etc.; Active organosilicon oxygen alkane type flow agent, for example BYK-373 or EFKA-3883 etc.; Polymer flow agent, for example BYK-358 or EFKA-3277 etc.; Solvent-borne type flow agent, for example HX-3060 etc.Can select wherein one or more mixture.
Described defoamer comprises and does not contain organo-siloxane type defoamer, for example BYK-055, EFKA-2721, DEUCHEM-2700 or HX-2100 etc.; Contain organo-siloxane type defoamer, for example EFKA-2022, DEUCHEM-5600 or HX-2000 etc.Can select wherein one or more mixture.
Described wetting dispersing agent comprises high molecular weight polypropylene acid esters, for example Disperbyk-161 or EFKA-4800 etc.; Macromolecule polyurethane, for example EFKA-4010 etc.; Polymeric carboxylic, for example DEUCHEM-904 etc.; Lower molecular weight is unsaturated, the saturated carboxylic acid amine salt, for example HX-4010 etc.Can select wherein one or more mixture.
Described stopper comprises quinhydrones, Hydroquinone monomethylether, thiodiphenylamine, N-nitrophenyl oxyamine aluminium salt, Resorcinol or MEHQ etc.Can select wherein one or more mixture.
Described filler mainly comprises silicon-dioxide, talcum powder, barium sulfate, Zinic stearas, clay or lime carbonate, and nano materials such as nano silicon or nano titanium oxide, the physical and chemical performance that they can improve paint film to a great extent for example improves hardness of paint film, toughness, wear resistance and weathering resistance etc.; Described pigment comprises mineral dye (for example titanium dioxide, carbon black, copper powder, aluminium powder or pearlescence etc.) or pigment dyestuff (for example phthalocyanine blue, green, the brown chrome yellow of the phthalein mountain valley with clumps of trees and bamboo or bright red etc.).
Described solvent comprises N-BUTYL ACETATE, vinyl acetic monomer, toluene, dimethylbenzene, butanone, pimelinketone or their any mixture.
Coating composition of the present invention is cured with visible light source, if coating composition of the present invention is used for outdoor use, then can utilize sunlight to solidify.Coating of the present invention is pressed the difference of filler in the composition or pigment, is divided into high light varnish, matte varnish, colored paint, pearlescent lacquer and metal flash paint etc.Can be used for the application of various metallic surfaces, mainly comprise metal and alloy materials thereof such as iron and steel, aluminium, aluminium alloy, copper.
The present invention preferably uses the visible light source of spectral range at 360-780nm, comprises sunlight, luminescent lamp, metal halide lamp and xenon lamp etc.More preferably use metal halide lamp, indium lamp especially, its spectral range is at 360-750nm, and its main peak is at 410nm and 450nm, and the most effective spectral range is 400-460nm.
Coating composition of the present invention can be in packaging vessel stably stored more than six months.
Coating composition of the present invention can or be printed on the base material with the method coating known to usually.
Embodiment
Following embodiment and reference examples can illustrate further characteristics of the present invention, but are not subjected to the restriction of these examples.
Embodiment uses 400W indium lamp as visible light source, and test piece and fluorescent tube distance are 10cm, and coating thickness is 40um, but the present invention is not limited thereto.Reference examples uses the 400W high voltage mercury lamp as UV-light (UV) light source, and test piece and fluorescent tube distance are 10cm, and coating thickness is 40um.
Abbreviation among the embodiment has following connotation:
HEA: Hydroxyethyl acrylate
MHEA: hydroxyethyl methylacrylate
EHA: Isooctyl acrylate monomer
HDDA:1,6 hexanediyl esters
PDDA: PDDA
TPGDA: tri (propylene glycol) diacrylate
PO-NPGDA: ethoxylated neopentylglycol diacrylate
TMPTA: Viscoat 295
EO-TMPTA: ethoxylated trimethylolpropane triacrylate
PO-TMPTA: propoxylation Viscoat 295
DEA-TMPTA: diethylamine modification Viscoat 295
184:1-hydroxy-cyclohexyl phenyl ketone
1173:2-hydroxy-2-methyl-1-phenyl-1-acetone
BP: benzophenone
ITX: isopropyl thioxanthone
CTX:2-chloro thioxanthone
TPO:2,4,6-trimethylbenzoyl diphenyl phosphine oxide
819: two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxides
BMS:4-benzoyl-4 '-dimethyl diphenyl sulfide
EDAB:4-dimethylamino-ethyl benzoate
OK-500: silicon-dioxide, as cutting photo etching, German Degussa company product
Embodiment 1
Bisphenol A epoxy acrylate 20wt%
TPGDA????????????????25wt％
TMPTA????????????????37wt％
DEA-TMPTA????????????15wt％
ITX??????????????????3wt％
Above-mentioned component according to described mixed, is stirred, promptly prepare visible-light curing metallic paint.
Purposes: high light varnish
Be 5 seconds the set time of prescription sample under the indium lamp of embodiment 1.
Reference examples 1
Be 6 seconds the set time of prescription sample under the UV lamp of embodiment 1.
Embodiment 2
Bisphenol A epoxy acrylate 15wt%
Urethane acrylate 5wt%
HDDA?????????????????37wt％
TMPTA????????????????25wt％
DEA-TMPTA????????????16wt％
819??????????????????2wt％
Above-mentioned component according to described mixed, is stirred, promptly prepare visible-light curing metallic paint.
Purposes: high light varnish
Be 5 seconds the set time of prescription sample under the indium lamp of embodiment 2.
Reference examples 2
Be 6 seconds the set time of prescription sample under the UV lamp of embodiment 2.
Embodiment 3
Bisphenol A epoxy acrylate 5wt%
Acrylic copolymer 10wt%
PO-NPGDA?????????????20wt％
EO-TMPTA??????25wt％
EHA???????????15wt％
DEA-TMPTA?????18wt％
TPO???????????2wt％
OK-500????????5wt％
Above-mentioned component according to described mixed, is stirred, promptly prepare visible-light curing metallic paint.
Purposes: half matte varnish
Be 6 seconds the set time of prescription sample under the indium lamp of embodiment 3.
Reference examples 3
Be 8 seconds the set time of prescription sample under the UV lamp of embodiment 3.
Embodiment 4
Bisphenol A epoxy acrylate 10wt%
TPGDA????????????????22wt％
TMPTA????????????????40wt％
DEA-TMPTA????????????20wt％
ITX??????????????????2wt％
184??????????????????2wt％
OK-500???????????????4wt％
Above-mentioned component according to described mixed, is stirred, promptly prepare visible-light curing metallic paint.
Purposes: half matte varnish
Be 6 seconds the set time of prescription sample under the indium lamp of embodiment 4.
Reference examples 4
Be 7 seconds the set time of prescription sample under the UV lamp of embodiment 4.
Embodiment 5
Bisphenol A epoxy acrylate 15wt%
Polyester acrylate 5wt%
EO-TMPTA????????????????30wt％
DEA-TMPTA????????36wt％
819??????????????2wt％
1173?????????????2wt％
OK-500???????????10wt％
Above-mentioned component according to described mixed, is stirred, promptly prepare visible-light curing metallic paint.
Purposes: full matte varnish
Be 3 seconds the set time of prescription sample under the indium lamp of embodiment 5.
Reference examples 5
Be 4 seconds the set time of prescription sample under the UV lamp of embodiment 5.
Embodiment 6
Acrylic copolymer 15wt%
HDDA?????????????25wt％
EO-TMPTA?????????15wt％
DEA-TMPTA????????25wt％
TPO??????????????7wt％
184??????????????3wt％
Titanium dioxide 10wt%
Above-mentioned component according to described mixed, is stirred, promptly prepare visible-light curing metallic paint.
Purposes: white paint
Be 10 seconds the set time of prescription sample under the indium lamp of embodiment 6.
Reference examples 6
Be 12 seconds the set time of prescription sample under the UV lamp of embodiment 6.
Embodiment 7
PDDA?????????40wt％
HDDA?????????10wt％
TMPTA????????20wt％
DEA-TMPTA?????18wt％
CTX???????????3wt％
Titanium dioxide 7wt%
Phthalocyanine blue 2wt%
Above-mentioned component according to described mixed, is stirred, promptly prepare visible-light curing metallic paint.
Purposes: blue lacquer
Be 8 seconds the set time of prescription sample under the indium lamp of embodiment 7.
Reference examples 7
Be 10 seconds the set time of prescription sample under the UV lamp of embodiment 7.
Embodiment 8
Bisphenol A epoxy acrylate 3wt%
Acrylic copolymer 7wt%
TPGDA????????????????25wt％
EO-TMPTA?????????????45wt％
DEA-TMPTA????????????15wt％
BMS??????????????????2wt％
EDAB?????????????????1wt％
Pearlescence 2wt%
Above-mentioned component according to described mixed, is stirred, promptly prepare visible-light curing metallic paint.
Purposes: pearlescent lacquer
Be 5 seconds the set time of prescription sample under the indium lamp of embodiment 8.
Reference examples 8
Be 7 seconds the set time of prescription sample under the UV lamp of embodiment 8.
Embodiment 9
Bisphenol A epoxy acrylate 15wt%
Urethane acrylate 5wt%
TPGDA????????????????15wt％
TMPTA????????????30wt％
DEA-TMPTA????????20wt％
ITX??????????????2.5wt％
BP???????????????2wt％
Aluminium powder 0.5wt%
N-BUTYL ACETATE 10wt%
Above-mentioned component according to described mixed, is stirred, promptly prepare visible-light curing metallic paint.
Purposes: flash of light silver paint
Be 7 seconds the set time of prescription sample under the indium lamp of embodiment 9.
Reference examples 9
Be 9 seconds the set time of prescription sample under the UV lamp of embodiment 9.
Initiator content and the test result of embodiments of the invention 1-9 see Table 1.
Initiator combination and the test result of table 1 embodiment 1-9
| Embodiment | Purposes | The initiator combination | Set time | Sticking power | 60 degree gloss | Pencil hardness |
| Embodiment 1 | High light varnish | ??ITX+DEA-TMPTA | ??5s | 0 grade | ??110 | ??3H |
| Embodiment 2 | High light varnish | ??819+DEA-TMPTA | ??5s | 0 grade | ??105 | ??3H |
| Embodiment 3 | Half matte varnish | ??TPO+DEA-TMPTA | ??6s | 0 grade | ??55 | ??2H |
| Embodiment 4 | Half matte varnish | ??ITX+184+DEA-TMPTA | ??6s | 0 grade | ??60 | ??3H |
| Embodiment 5 | Full matte varnish | ??819+1173+DEA-TMPTA | ??3s | 1 grade | ??25 | ??2H |
| Embodiment 6 | White paint | ??TPO+184+DEA-TMPTA | ??10s | 1 grade | ??45 | ??2H |
| Embodiment 7 | Blue lacquer | ??CTX+DEA-TMPTA | ??8s | 1 grade | ??50 | ??2H |
| Embodiment 8 | Pearlescent lacquer | ??BMS+EDAB+DEA-TMPTA | ??5s | 1 grade | ??75 | ??2H |
| Embodiment 9 | The flash of light silver paint | ??ITX+BP+DEA-TMPTA | ??7s | 1 grade | ??80 | ??2H |
| Testing method | ??- | ??- | ??- | ????GB/T9286 | ??GB/T9754 | ??GB/T ??6739 |
From the foregoing description and reference examples as can be seen, light trigger described in the present invention and aided initiating carry out suitable combination, and solidifying with UV-light (high voltage mercury lamp) with visible light (indium lamp) curing ratio needs the shorter time, and has good film performance.The charateristic avsorption band that shows the combined light initiator can move to the visible spectrum zone to the long wave direction from the UV spectrum zone, thereby realizes visible-light curing.Compare with UV-curing technology, visible-light curing is safe ready more, and this will promote photocuring technology to a certain extent and further advance.