Summary of the invention
The purpose of this invention is to provide a kind of new anti-flaming ultraviolet radiation solidifying coating that is used for metal, this coating is at the strong adhesion of metallic surface, and can avoid the coating material solidified inflammable defective of resene.
The technical solution adopted for the present invention to solve the technical problems is:
The anti-flaming ultraviolet radiation solidifying coating that is used for metal mainly is made up of living oligomer, reactive thinner, adhesion promoter, light trigger, thinner etc., and wherein the weight part proportioning of each component is as follows:
20~70 parts of living oligomers, 20~60 parts of reactive thinners, 1~10 part of adhesion promoter, 0.4~2 part of light trigger, 6~20 parts of thinners;
Living oligomer in the said components (prepolymer of ultraviolet-curing paint) is the phosphorous urethane acrylate living oligomer of maleic anhydride modified; Reactive thinner is the compound that contains 1~6 ethylenical unsaturated double bonds.
The weight part proportioning of above-mentioned each component can be preferably:
30~65 parts of living oligomers, 30~50 parts of reactive thinners, 2~8 parts of adhesion promoters, 0.5~2 part of light trigger, 10~20 parts of thinners.
The phosphorous urethane acrylate living oligomer of above-mentioned maleic anhydride modified can make by following method:
Phosphoric acid ester trivalent alcohol and vulcabond and senecioate-hydroxy ester (can be selected from senecioate-hydroxyl ethyl ester or senecioate-hydroxypropyl acrylate; methacrylic acid-beta-hydroxy ethyl ester; methacrylic acid-β-hydroxypropyl acrylate etc.); in molar ratio 1: n: (2n-3); 1.5<n<3 wherein; (can be selected from dibutyltin dilaurate at catalyzer; stannous octoate; N-methylmorpholine; triethylenediamine etc.) under effect and the protection of inert gas; 20~80 ℃ were reacted 6~12 hours; add mass percent again and be 1~8% MALEIC ANHYDRIDE, stir 3~6 hours promptly at 60~80 ℃.
In above-mentioned each component:
Reactive thinner is that a class has chemical reactivity, will participate in the film forming material of polyreaction in the solidification process of above-mentioned anti-flaming ultraviolet radiation solidifying coating, be mainly the compound that contains 1~6 ethylenical unsaturated double bonds in the present invention, can be selected from the compound of single functionality, difunctionality, three-functionality-degree, four functionality and above functionality, wherein:
The single functionality compound can be selected from ethyl propenoate, Jia Jibingxisuanyizhi, butyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, isobornyl acrylate, isobornyl methacrylate, tetrahydrofuran (THF), the vinylformic acid phenoxy ethyl, the methacrylic acid phenoxy ethyl, vinylformic acid hydroxyl-2-ethylhexyl, hydroxyethyl methacrylate-2-ethylhexyl, glycidyl acrylate, glycidyl methacrylate, ethoxy ethoxy ethyl propylene acid esters, the third oxidation neopentyl glycol methyl ether acrylate, in the ring TriMethylolPropane(TMP) methylal acrylate etc. one or more;
The difunctionality compound can be selected from tri (propylene glycol) diacrylate, 1,6-hexanediyl ester, ethoxyquin 1, in 6-hexanediyl ester, propylene glycol diacrylate, dipropylene glycol dimethacrylate, ethoxyquin propylene glycol diacrylate, 1,4 butanediol diacrylate, neopentylglycol diacrylate, the third oxidation neopentylglycol diacrylate, ethoxyquin bisphenol a diacrylate, the ethoxyquin bisphenol a dimethacrylate etc. one or more;
The three-functionality-degree compound can be selected from one or more in Viscoat 295, ethoxyquin Viscoat 295, the third oxidation Viscoat 295, pentaerythritol triacrylate, the glycerol propoxylate triacrylate etc.;
Four functionality and above compound can be selected from one or more in tetramethylol methane tetraacrylate, ethoxyquin tetramethylol methane tetraacrylate, Dipentaerythritol five acrylate, the dipentaerythritol acrylate etc.
Adhesion promoter can be selected from one or more among EM39, EB168, EB170, EB770, SB404, SR9008, SR9012, CD9050, CD9051, Photomer 4846, Photomer 5424, Photomer 4173, KBM603, KBM503, the KBM403, and these trades mark all are conventionally known to one of skill in the art.
Light trigger can be selected from benzophenone, 2-hydroxy-2-methyl-1-phenyl-acetone, benzoin dimethylether, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1, in 2-phenylbenzene ethyl ketone, two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide etc. one or more.
Thinner does not participate in chemical reaction in the preparation process of above-mentioned anti-flaming ultraviolet radiation solidifying coating, can play the effect of solvent in the present invention, and after coating of the present invention being used for metallic surface and curing, this thinner is promptly volatilized; Thinner can be selected from one or more in acetone, butanone, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, isobutyl acetate, tetrahydrofuran (THF), toluene, dimethylbenzene, n-butyl propionate, pimelinketone, ethylene glycol ether acetate, 2-Butoxyethyl acetate, 2-Butoxyethyl acetate, propylene-glycol ethyl ether acetic ester, Virahol, propyl carbinol, diacetone alcohol, propylene glycol butyl ether, the dipropylene glycol methyl ether etc. in the present invention.
The present invention is used for the anti-flaming ultraviolet radiation solidifying coating of metal, except that containing above-mentioned each component, can also contain the weight part proportioning and be 0.1~1 part auxiliary agent.
Described auxiliary agent refers to flow agent, defoamer, lubricant commonly used in the UV coating, can select wherein any one or a few for use.
Described flow agent can be selected from one or more among EFKA3883, EFKA3886, EFKA3600, BYK366, BYK333, BYK307, the DEG0410 etc., and these trade names are conventionally known to one of skill in the art;
Described defoamer can be selected from one or more among EFKA2022, EFKA2527, EFKA2040, BYK352, BYK354, the BYK357 etc., and these trade names are conventionally known to one of skill in the art;
Described lubricant is preferably olefin material, and it can further improve the feel of coating and increase coating gloss.
The present invention is used for the anti-flaming ultraviolet radiation solidifying coating of metal, can adopt following method preparation:
Get the living oligomer of described weight part proportioning, stir the reactive thinner, light trigger, the thinner that add described weight part proportioning down, add in the lump when containing auxiliary agent in the component, stir evenly, promptly obtain the anti-flaming ultraviolet radiation solidifying coating that the present invention is used for metal.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention adopts the prepolymer of the phosphorous urethane acrylate of maleic anhydride modified as ultraviolet-curing paint, owing in urethane acrylate, introduced and had the polar carboxyl, thereby improved the sticking power of filming greatly with metal, and the good flame effect has been played in the existence of phosphorus in the resin.Therefore, ultraviolet-curing paint of the present invention is at the strong adhesion of metallic surface, and can avoid the coating material solidified inflammable defective of resene.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
Present embodiment is the preparation of the phosphorous urethane acrylate of one of ultraviolet-curing paint main raw material of the present invention maleic anhydride modified, and its method is as follows:
Get 50 gram mass percentage concentrations and be 85% phosphate aqueous solution in three-necked bottle, under the argon shield, under ice bath and agitation condition, drip 255 gram propylene oxide, slowly rise to room temperature reaction 2 hours then, revolve to steam to remove and anhydrate and unreacted propylene oxide, obtain 223 gram phosphoric acid ester trivalent alcohols;
In reaction flask, add the above-mentioned phosphoric acid ester trivalent alcohol of 50 grams, add 60 milligrams of dibutyltin dilaurates again as catalyzer, under agitation drip 60 gram diphenylmethanediisocyanates and 25 gram senecioate-hydroxypropyl acrylates (phosphoric acid ester trivalent alcohol, diphenylmethanediisocyanate, senecioate-hydroxypropyl acrylate three mol ratio are 1: 2.5: 2), be warming up to 80 ℃ under the argon shield, reacted 4 hours, and got phosphorous urethane acrylate A; Add 5 gram MALEIC ANHYDRIDE then, stirred 4 hours down, get the phosphorous urethane acrylate B of maleic anhydride modified, as the living oligomer of ultraviolet-curing paint of the present invention at 70 ℃.
Following embodiment 2~9 is the composition of ultraviolet-curing paint of the present invention and compound method:
Embodiment 2
The composition of present embodiment ultraviolet-curing paint and compound method are as follows respectively:
Form (being the weight part proportioning, down together):
60 parts of living oligomers, 21 parts of reactive thinners, 1.2 parts of adhesion promoters, 1.8 parts of light triggers, 14 parts of thinners, 0.3 part of auxiliary agent
Wherein, living oligomer is the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained; Reactive thinner is senecioate-hydroxyl ethyl ester and isobornyl acrylate, is respectively 12 parts and 9 parts; Adhesion promoter is EB168; Light trigger is 2-hydroxy-2-methyl-1-phenyl-acetone; Auxiliary agent comprises flow agent EFKA3883 and defoamer EFKA2527, is respectively 0.2 part and 0.1 part; Thinner is tetrahydrofuran (THF), dimethylbenzene and propylene glycol butyl ether, is respectively 7 parts, 4 parts and 3 parts.
Compound method:
Get 60 gram living oligomers (the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained), stir and add 12 gram senecioate-hydroxyl ethyl esters down, 9 gram isobornyl acrylate, 1.2 gram EB168,1.8 gram light trigger 2-hydroxy-2-methyl-1-phenyl-acetones, 0.2 gram flow agent EFKA3883,0.1 gram defoamer EFKA2527,7 gram tetrahydrofuran (THF)s, 4 gram dimethylbenzene, 3 gram propylene glycol butyl ether obtain the present embodiment anti-flaming ultraviolet radiation solidifying coating.
Embodiment 3
The composition of present embodiment ultraviolet-curing paint and compound method are as follows respectively:
Form:
25 parts of living oligomers, 24 parts of reactive thinners, 2.4 parts of adhesion promoters, 1.2 parts of light triggers, 18 parts of thinners, 0.5 part of auxiliary agent
Wherein, living oligomer is the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained; Reactive thinner is the methacrylic acid-beta-hydroxy ethyl ester and the third oxidation neopentylglycol diacrylate, is respectively 10 parts and 14 parts; Adhesion promoter is EM39; Light trigger is a benzoin dimethylether; Auxiliary agent comprises flow agent DEG0410 and defoamer EFKA2022, is respectively 0.3 part and 0.2 part; Thinner is vinyl acetic monomer, toluene and 2-Butoxyethyl acetate, is respectively 8 parts, 4 parts and 6 parts.
Compound method:
Get 25 gram living oligomers (the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained), stir and add 10 gram methacrylic acid-beta-hydroxy ethyl esters down, 14 grams, the third oxidation neopentylglycol diacrylate, 2.4 gram EM39,1.2 gram light trigger benzoin dimethylethers, 0.3 gram flow agent DEG0410,0.2 gram defoamer EFKA2022,8 gram vinyl acetic monomers, 4 gram toluene, 6 gram 2-Butoxyethyl acetates obtain the present embodiment anti-flaming ultraviolet radiation solidifying coating.
Embodiment 4
The composition of present embodiment ultraviolet-curing paint and compound method are as follows respectively:
Form:
35 parts of living oligomers, 52 parts of reactive thinners, 5 parts of adhesion promoters, 0.4 part of light trigger, 20 parts of thinners, 0.1 part of auxiliary agent
Wherein, living oligomer is the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained; Reactive thinner is the methacrylic acid-β-hydroxypropyl acrylate and the third oxidation neopentyl glycol methyl ether acrylate, is respectively 27 parts and 25 parts; Adhesion promoter is CD9050; Light trigger is 2,2-dimethoxy-1,2-phenylbenzene ethyl ketone; Auxiliary agent comprises flow agent EFKA3600 and defoamer BYK352, is respectively 0.05 part and 0.05 part; Thinner is vinyl acetic monomer, isobutyl acetate and propylene-glycol ethyl ether acetic ester, is respectively 10 parts, 4 parts and 6 parts.
Compound method:
Get 35 gram living oligomers (the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained), stir and add 27 gram methacrylic acid-β-hydroxypropyl acrylates down, 25 grams, the third oxidation neopentyl glycol methyl ether acrylate, 5 gram CD9050,0.4 gram light trigger 2,2-dimethoxy-1,2-phenylbenzene ethyl ketone, 0.05 gram flow agent EFKA3600,0.05 gram defoamer BYK352,10 gram vinyl acetic monomers, 4 gram isobutyl acetates, 6 gram propylene-glycol ethyl ether acetic esters obtain the present embodiment anti-flaming ultraviolet radiation solidifying coating.
Embodiment 5
The composition of present embodiment ultraviolet-curing paint and compound method are as follows respectively:
Form:
20 parts of living oligomers, 60 parts of reactive thinners, 10 parts of adhesion promoters, 0.5 part of light trigger, 10 parts of thinners
Wherein, living oligomer is the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained; Reactive thinner is methacrylic acid phenoxy ethyl and Viscoat 295, is respectively 42 parts and 18 parts; Adhesion promoter is SR9012; Light trigger is a benzoin dimethylether; Thinner is pimelinketone and propyl carbinol, is respectively 6 parts and 4 parts.
Compound method:
Get 20 gram living oligomers (the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained), stir and add 42 gram methacrylic acid phenoxy ethyl down, 18 gram Viscoat 295s, 10 gram SR9012,0.5 gram light trigger benzoin dimethylether, 6 gram pimelinketone, 4 gram propyl carbinols obtain the present embodiment anti-flaming ultraviolet radiation solidifying coating.
Embodiment 6
The composition of present embodiment ultraviolet-curing paint and compound method are as follows respectively:
Form:
70 parts of living oligomers, 20 parts of reactive thinners, 1 part of adhesion promoter, 2 parts of light triggers, 6 parts of thinners
Wherein, living oligomer is the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained; Reactive thinner is methacrylic acid phenoxy ethyl and Viscoat 295, is respectively 12 parts and 8 parts; Adhesion promoter is Photomer 4846; Light trigger is a benzophenone; Thinner is toluene and diacetone alcohol, is respectively 4 parts and 2 parts.
Compound method:
Get 70 gram living oligomers (the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained), stir and add 12 gram methacrylic acid phenoxy ethyl down, 8 gram Viscoat 295s, 1 gram Photomer 4846,2 gram light trigger benzophenone, 4 gram toluene, 2 gram diacetone alcohols obtain the present embodiment anti-flaming ultraviolet radiation solidifying coating.
Embodiment 7
The composition of present embodiment ultraviolet-curing paint and compound method are as follows respectively:
Form:
65 parts of living oligomers, 30 parts of reactive thinners, 8 parts of adhesion promoters,
1 part of light trigger, 15 parts of thinners
Wherein, living oligomer is the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained; Reactive thinner is propylene glycol diacrylate and ethoxyquin tetramethylol methane tetraacrylate, is respectively 12 parts and 18 parts; Adhesion promoter is KBM503; Light trigger is the 1-hydroxycyclohexylphenylketone; Thinner is an acetone.
Compound method:
Get 65 gram living oligomers (the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained), stir and add 12 gram propylene glycol diacrylates down, 18 gram ethoxyquin tetramethylol methane tetraacrylates, 8 gram KBM503,1 gram light trigger 1-hydroxycyclohexylphenylketone, 15 gram acetone obtain the present embodiment anti-flaming ultraviolet radiation solidifying coating.
Embodiment 8
The composition of present embodiment ultraviolet-curing paint and compound method are as follows respectively:
Form:
30 parts of living oligomers, 50 parts of reactive thinners, 2 parts of adhesion promoters, 1.5 parts of light triggers, 12 parts of thinners
Wherein, living oligomer is the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained; Reactive thinner is the tetrahydrofuran (THF) acrylate; Adhesion promoter is SB404; Light trigger is a benzophenone; Thinner is butanone and Virahol, is respectively 7 parts and 5 parts.
Compound method:
Get 30 gram living oligomers (the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained), stir and add 50 gram tetrahydrofuran (THF) acrylate down, 2 gram SB404,1.5 gram light trigger benzophenone, 7 gram butanone, 5 gram Virahols obtain the present embodiment anti-flaming ultraviolet radiation solidifying coating.
Embodiment 9
The composition of present embodiment ultraviolet-curing paint and compound method are as follows respectively:
Form:
50 parts of living oligomers, 40 parts of reactive thinners, 8 parts of adhesion promoters, 2 parts of light triggers, 1 part of 20 parts of auxiliary agent of thinner
Wherein, living oligomer is the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained; Reactive thinner is 1,6 hexanediol diacrylate and glycerol propoxylate triacrylate, is respectively 26 parts and 14 parts; Adhesion promoter is Photomer4173; Light trigger is two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxides; Auxiliary agent is a paraffin; Thinner is a 2-Butoxyethyl acetate.
Compound method:
Get 50 gram living oligomers (the phosphorous urethane acrylate B of the maleic anhydride modified of embodiment 1 gained), stir and add 26 grams 1 down, the 6-hexanediyl ester, 14 gram glycerol propoxylate triacrylates, 8 gram Photomer4173,2 gram light triggers two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide, 1 gram paraffin, 20 gram 2-Butoxyethyl acetates obtain the present embodiment anti-flaming ultraviolet radiation solidifying coating.
Embodiment 10
Present embodiment is the comparative example:
Except that living oligomer was the phosphorous urethane acrylate A without maleic anhydride modified of embodiment 1 gained, all the other components were all identical with embodiment 3 during it was formed.
Compound method is also identical with embodiment 3.
Embodiment 11
Present embodiment carries out the experimental example of film performance test for the anti-flaming ultraviolet radiation solidifying coating product to above-mentioned part embodiment gained:
The contrast UV paint spay-coating that anti-flaming ultraviolet radiation solidifying coating of the present invention that the contriver is prepared with above-mentioned example 2~4 respectively and embodiment 10 are prepared is on the aluminized tinned(sheet)iron of surface vacuum surface, with the ultraviolet lamp of 500W as source of radiation, completion of cure, formed cured film (1~No. 3 sample and No. 4 samples) is carried out every performance test and evaluation, and its result is as shown in table 1:
Table 1 film performance
Sample |
1 |
2 |
3 |
4 |
Outward appearance |
Colourless, transparent, smooth surface, glossiness is good |
Colourless, transparent, smooth surface, glossiness is good |
Colourless, transparent, smooth surface, glossiness is good |
Colourless, transparent, smooth surface, glossiness is good |
Pencil hardness |
3H |
3H |
3H |
3H |
Resistance to boiling water |
Film and do not bubble, any variation does not take place |
Film and do not bubble, any variation does not take place |
Film and do not bubble, any variation does not take place |
The foaming of filming, surface gloss and slickness reduce |
The sticking power rank |
1 |
1 |
1 |
3 |
Flame retardant properties |
Excellent |
Excellent |
Excellent |
Excellent |
As can be seen from Table 1, the film adhesive of 1~No. 3 sample and resistance to boiling water all are better than sample No. 4, showing more can practical requirement as the UV coating of prepolymer with the phosphorous urethane acrylate of maleic anhydride modified, is a kind of very potential anti-flaming ultraviolet radiation solidifying coating.