CN1959530B - Ultraviolet light solidified coating in use for post processing of imaging material - Google Patents

Ultraviolet light solidified coating in use for post processing of imaging material Download PDF

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Publication number
CN1959530B
CN1959530B CN200610102178A CN200610102178A CN1959530B CN 1959530 B CN1959530 B CN 1959530B CN 200610102178 A CN200610102178 A CN 200610102178A CN 200610102178 A CN200610102178 A CN 200610102178A CN 1959530 B CN1959530 B CN 1959530B
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China
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parts
acrylate
ultraviolet
curing paint
trimethylolpropane triacrylate
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CN200610102178A
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Chinese (zh)
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CN1959530A (en
Inventor
郭晓娟
梁笑丛
刘瀛
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中国乐凯胶片集团公司
保定乐凯高分子材料科技发展有限公司
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Abstract

An ultraviolet ray curing coating-material used at post treatment of imaging material is prepared in weight share from 20-60 of propenoic acid ester prepolymer, 20-50 of propenoic acid ester monomer, 3-10 of light initiator, 3-15 of initiating-promotor, 0.3-5 of assistant, 0.5-5 of attaching-promotor and 0-5 of packing material.

Description

A kind of being used for processed the ultraviolet-curing paint of handling behind the image forming material
Technical field
The present invention relates to a kind of ultraviolet-curing paint, particularly a kind of being used for processed the ultraviolet-curing paint of handling behind the image forming material.
Background technology
The radiation curing product have save the energy, be beneficial to environmental protection, economy and characteristics such as efficient, so be widely used in each field.At present, UV-curing technology is used widely in fields such as coating, printing ink, electronic chemical product, bonding agent and medical devices.
At present; being used for one of image forming material surface treatment mode is that unsaturated polyester (A) and the mixing of hardening agent (B) bi-component are coated in image forming material, the PET film is overlying on the AB component, through air dry in tens hours again; remove the PET film, be formed into picture material protection layer.This method is because drying time long (about tens hours, temperature difference, also there is certain difference the time), and production efficiency is low, paint film easily contaminated (staying fingerprint easily).Simultaneously unsaturated polyester (UP) contains a large amount of styrene, and smell is serious, and the harm operator is healthy, environment is polluted, and hardness height behind the curable unsaturated polyester, shrinkage factor is big, and it is frangible to film.Another mode is to adopt film mulching method, promptly with the polyolefin film or the mylar that are coated with pressure sensitive adhesive, is compounded on the image forming material.Though film mulching method is easy, cost height (3~8 yuan/square metre), yield rate is low, and easily produces bubble even come off.
Summary of the invention
Technical matters to be solved by this invention provides a kind of ultraviolet-curing paint that processing is handled behind the image forming material that is used for, and it has, and production cost is low, system cross-linking density height, hardness and anti-wear performance are good, excellent weather resistance and hard; Make the image forming material after the processing have effects such as pebble, flash of light crystal, woven design, frosting, the storage life that has prolonged image forming material.
The technical scheme that addresses the above problem is:
A kind of being used for processed the ultraviolet-curing paint of handling behind the image forming material, and its component is counted by weight:
20~60 parts of acrylate resin performed polymers
20~50 parts of acrylic ester monomers
3~10 parts of light triggers
Cause 3~15 parts of promoter
0.3~5 part of auxiliary agent
0.5~5 part of adhesion promoter
0~5 part of filler.
Above-mentioned being used for processed the ultraviolet-curing paint of handling behind the image forming material, and described acrylate resin performed polymer is the potpourri of epoxy acrylate and urethane acrylate.
Above-mentioned being used for processed the ultraviolet-curing paint of handling behind the image forming material, described acrylic ester monomer is one or more in 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, neopentylglycol diacrylate, PDDA, trimethylolpropane triacrylate, ethoxy trimethylolpropane triacrylate, the propoxyl group trimethylolpropane triacrylate.
Above-mentioned being used for processed the ultraviolet-curing paint of handling behind the image forming material, and described light trigger is one or more in 1-hydroxyl-cyclohexyl benzophenone, benzophenone, 2-hydroxy-2-methyl-1-phenylacetone-1,2-methyl isophthalic acid-(4-methyl mercapto the phenyl)-2-morpholine-1-acetone.
Above-mentioned being used for processed the ultraviolet-curing paint of handling behind the image forming material, and described adhesion promoter is one or more in acrylic acid phosphate, phosphate, acid monofunctional acrylate monomer, the acid polyester acrylate.
Above-mentioned being used for processed the ultraviolet-curing paint of handling behind the image forming material, and described filler is copper bronze (slurry), aluminium silver powder (slurry), pearlescent pigment (slurry), radium-shine or seven colour flashing sheets.
The quick initiated polymerization of ultraviolet light that ultraviolet light polymerization product utilization mercury lamp sends has the energy of saving, is beneficial to characteristics such as environmental protection, economy and high-performance.Ultraviolet-curing paint provided by the invention, be to be the main body component with acrylate resin performed polymer and acrylic ester monomer, light trigger is under UV-irradiation, produce living radical through cracking or hydrogen transfer, living radical is attacked the unsaturated double-bond in acrylate monomer and the acrylate resin, thereby make two keys become singly-bound and make acrylate resin and the crosslinked generation solid superpolymer of acrylate monomer, superpolymer and filler wherein, auxiliary agent etc. are membranaceous attached on the base material, form paint film.
The potpourri that suitable acrylate resin performed polymer of the present invention is Epocryl and polyurethane acrylate resin wherein, adopts the product of epoxy acrylic resin to have characteristics such as high rigidity, high abrasion after solidifying; Adopt the product of polyurethane acrylate resin to have low smell, low volatilization, low irritant and good film forming, its cured article has the wearing quality and the excellent high-temperature stability of high-tensile, brilliance.Epoxy acrylate 6104 and urethane acrylate 6318 as Jiangsu three wooden companies; The epoxy acrylate 6219-100 of Changxing, Taiwan chemical company and urethane acrylate 6112-100; The epoxy acrylate DH306 of the good photochemical Science and Technology Ltd. of Shenzhen ancient cooking vessel and urethane acrylate DH318.
Being fit to acrylate monomer of the present invention can be 1,6-hexanediyl ester (HDDA), O-phthalic acid diethylene glycol diacrylate fat (PDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), ethoxyquin neopentylglycol diacrylate (PO-NPGDA), the third oxidation trimethylolpropane triacrylate (PO-TMPTA), ethoxy trimethylolpropane triacrylate (EO-TMPTA), neopentylglycol diacrylate (NPGDA), pentaerythritol triacrylate, double pentaerythritol C5 methacrylate, ethyl acrylate, butyl acrylate, hydroxy-ethyl acrylate, Isooctyl acrylate monomer etc., the preferred 1,6 hexanediol diacrylate (HDDA) that uses, tripropylene glycol diacrylate (TPGDA), neopentylglycol diacrylate (NPGDA), the third oxidation trimethylolpropane triacrylate (PO-TMPTA), O-phthalic acid diethylene glycol diacrylate fat (PDDA), trimethylolpropane triacrylate (TMPTA), in the ethoxyquin neopentylglycol diacrylate (PO-NPGDA) one or more.Wherein, the tripropylene glycol diacrylate is the low viscosity thinning agent, have remarkable dissolubility and viscosity reduction, O-phthalic acid diethylene glycol diacrylate fat has remarkable curing rate and pliability, trimethylolpropane triacrylate has good curing rate and toughness, and comprehensive collocation makes the paint film after the curing have good flexible and curing rate.
Being fit to light trigger of the present invention can be 1-hydroxyl-cyclohexyl benzophenone (Irgacure 184), o-benzoyl yl benzoic acid methyl esters (OMBB), benzophenone (BP), 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholine-1-acetone (907), 2-hydroxy-2-methyl-1-phenylacetone-1 (Darocur 1173) or their potpourri; preferred 1-hydroxyl-cyclohexyl benzophenone, o-benzoyl yl benzoic acid methyl esters B or their potpourri of using most preferably uses the combination of Irgacure 184 and OMBB.Wherein, Irgacure 184, Darocur 1173 and Irgacure 907 are crack type photoinitiator, and it solidifies fast, help the deep layer of product to solidify, and product is xanthochromia not; BP is a hydrogen transfer type light trigger, and it helps the surface cure of product; OMBB is a kind of initiating agent of low smell, can make paint film odor after the curing help coating for a short time and use on the package that smell is had requirement.
In order to improve the efficiency of initiation of light trigger, added initiation promoter in the coating products provided by the invention, being fit to initiation promoter of the present invention can be the P115 of UCB. S.A. (BE) Bruxelles Belgium, and its principal ingredient is the trimethylolpropane triacrylate tertiary amine, commercially available triethanolamine or reactive amines.
Being fit to auxiliary agent of the present invention can be dimethyl silicone polymer, polyether-modified dimethyl silicone polymer, polyester modification dimethyl silicone polymer, fluorine-carbon modified polyacrylate or its potpourri, Foamex N as German Di Gao company, 6200 of the modest chemistry of Taiwan moral, its principal ingredient are dimethyl silicone polymer; The Glide432 of Di Gao company, the BYK333 of Bi Ke chemistry, its principal ingredient is polyether-modified dimethyl silicone polymer, the EFKA3777 of EFKA company, EFKA3772, its principal ingredient is fluorine-carbon modified polyacrylate; Both adding proportions are 5: 1~1: 5.
For the cross-linking density and hardness, wearing quality and the weatherability that improve coating system of the present invention, the inventor has added adhesion promoter in formulation for coating material provided by the invention.Being fit to adhesion promoter of the present invention can be acrylate phosphate, phosphate, acid monofunctional acrylate monomer, acid polyester acrylate or its potpourri, as EB168, EB170, EB770 and the EB524 of UCB. S.A. (BE) Bruxelles Belgium, its principal ingredient is respectively methacrylated phosphate, acroleic acid esterification phosphate, contain the acid polyester double methacrylate of 40%HEMA and contain the acid polyester of 30%HDDA; The EM39 of Changxing company, its principal ingredient is a methacryl oxyethanol phosphate; The CD9050 of Sartomer company, CD9051, its principal ingredient is respectively acid ester class of trifunctional and the acid ester class of simple function; The Photomer4703 of Cognis company, Photomer5424 and Photomer4173, its principal ingredient is respectively acid monofunctional acrylate monomer, acid polyester acrylate.
In order to improve the effect of coating of the present invention on imaging material, the inventor has added various fillers in coating.Being fit to filler of the present invention can be copper bronze (slurry), aluminium silver powder (slurry), pearlescent pigment (slurry), radium-shine powder or seven color powder.
Ultraviolet-curing paint provided by the invention can prepare by following method:
In proportion acryl resin performed polymer, acrylic ester monomer, light trigger are mixed, be warming up to 50 ± 5 ℃, be stirred to dissolving fully, adding causes promoter and adhesion promoter then, is stirred to mix; Add auxiliary agent and filler again, stir all, cooling is filtered, and obtains ultraviolet-curing paint.
Ultraviolet-curing paint provided by the invention also can prepare by following method:
1. auxiliary agent being joined part propylene acid esters monomer high speed is uniformly dispersed; 2. filler is joined that low speed is uniformly dispersed in the part propylene acid esters monomer; 3. acryl resin performed polymer, remaining acrylate monomer, light trigger are mixed, be warming up to 50 ± 5 ℃, be stirred to dissolving fully, add again and cause promoter and adhesion promoter, stir; 4. with above-mentioned 1., 2., 3. mix and stir, filter, obtain ultraviolet-curing paint.
Being fit to image forming material of the present invention can be silver salt printing paper, air brushing printing paper, canvas, pottery, metal, PP, PET, PVC plastics, art paper, white duplex board etc., these image forming materials can show the formation image at it by known treatment process, by modes such as spraying, roller coat, showering or serigraphys coating of the present invention is coated in these image forming material surfaces then, solidify through medium pressure mercury lamp, make image present the Aero Glass or the flash of light Aero Glass of various homogeneous transparents.
Beneficial effect
Ultraviolet-curing paint provided by the invention does not contain solvent, and to the infringement of human body and little to the pollution of environment, for overlay film, production cost is low, system cross-linking density height, and hardness and anti-wear performance are good, excellent weather resistance and hard; After being coated in the image forming material surface, solidify soon rapidly, adhesion height, weatherability are good, can form various homogeneous transparent Aero Glass or flash of light Aero Glass, have not only prolonged the storage life of image forming material but also have highlighted the graceful quality of product
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
6,104 10 parts
6,318 10 parts
15 parts of PDDA
25 parts of TMPTA
184 10 parts of Irgacure
10 parts of P115
2 parts of Foamex N
3 parts of BYK333
3 parts of EB168
2 parts of EB770
5 parts of copper bronzes (slurry)
1. 15 parts PDDA and 25 parts TMPTA are mixed;
2. the BYK333 of 2 parts FoamexN and 3 parts is joined 1/4 1. in, high speed dispersion is even;
3. 5 parts copper bronze (slurry) is joined 1/4 1. in, stirring at low speed is uniformly dispersed;
4. with 10 parts 6104,10 parts 6318,10 parts Irgacure 184 and remaining 1. mixing, be warming up to 50 ℃, be stirred to dissolving fully, add 10 parts of P115,3 parts of EB168 and 2 parts of EB770 then, stir;
5. will be 2., 3., 4. mix, stir, cooling is filtered, and obtains ultraviolet-curing paint.
The coating that obtains is applied on the silver salt printing paper by the mode that sprays, solidifies through one 3000 watts/centimetre medium pressure mercury lamp irradiation then, make silver salt printing paper surface present transparent starlike sudden strain of a muscle Crystal Gold effect; Also can use roll coating model that the coating that obtains is applied on the silver salt printing paper, again through one 5000 watts/centimetre medium pressure mercury lamp irradiation curing, make silver salt printing paper surface form transparent starlike sudden strain of a muscle Crystal Gold effect behind the infrared levelling of process; Can also be printed on by the mode of showering or silk-screen on the silver salt printing paper, irradiation solidify to form transparent starlike sudden strain of a muscle Crystal Gold effect through medium pressure mercury lamp.
Embodiment 2
20 parts of 6219-100
20 parts of 6112-100
10 parts of PDDA
15 parts of PO-TMPTA
10 parts of TPGDA
184 7 parts of Irgacure
3 parts of OMBB
10 parts of triethanolamines
1 part of Foamex N
4 parts of EFKA3777
0.5 part of Photomer4703
0.5 part in aluminium silver powder (slurry)
More than press the component proportioning, obtain ultraviolet-curing paint by the step among the embodiment 1.
By embodiment 1 coating method the coating that obtains is coated on the PET, obtains the silver-colored Aero Glass of homogeneous transparent.
Embodiment 3
6,104 25 parts
6,318 25 parts
28 parts of HDDA
184 2 parts of Irgacure
4.2 parts of OMBB
15 parts of P115
0.1 part of EFKA3777
0.2 part of Glide432
0.4 part of CD905
0.1 part of CD9051
Radium-shine 3 parts
184,4.2 parts of OMBB of 25 parts of 6104,25 parts of 6318,28 parts of HDDA, 2 parts of Irgacure are mixed, be warming up to 55 ℃, be stirred to dissolving fully, add 15 parts of P115,0.4 part of CD9050,0.1 part of CD9051 then, be stirred to and mix; Add 0.1 part of EFKA3777,0.2 part of Glide432 and 3 parts radium-shine again, stir, cooling is filtered, and obtains ultraviolet-curing paint.
By embodiment 1 coating method the coating that obtains is coated on the canvas, obtains the radium-shine Aero Glass of homogeneous transparent.
Embodiment 4
30 parts of DH306
30 parts of DH318
10 parts of PDDA
5 parts of EO-TMPTA
5 parts of PO-NPGDA
184 3 parts of Irgacure
907 2 parts of Irgacure
9.7 parts of P115
6,200 0.3 parts
5 parts of Photomer5424
3.5 parts of seven colour flashing sheets
More than press the component proportioning, obtain ultraviolet-curing paint by the method among the embodiment 3.
By embodiment 1 coating method the coating that obtains is coated on the PET, obtains seven colour flashing Aero Glass of homogeneous transparent.
Embodiment 5
6,104 25 parts
6,318 15 parts
20 parts of PDDA
20 parts of TMPTA
10 parts of HDDA
1,173 3 parts of Darocur
3 parts of P115
0.3 part of EFKA3772
3 parts of CD9050
2 parts of EB170
More than press the component proportioning, obtain ultraviolet-curing paint by the step among the embodiment 1.
By embodiment 1 coating method the coating that obtains is coated on the white duplex board, obtains the silver-colored Aero Glass of homogeneous transparent.
Embodiment 6
30 parts of DH306
30 parts of DH318
10 parts of HDDA
5 parts of TMPTA
5 parts of TPGDA
184 3 parts of Irgacure
2 parts of OMBB
907 2 parts of Irgacure
10 parts of reactive amines
0.2 part of BYK333
0.1 part of Glide432
0.3 part of CD9051
More than press the component proportioning, obtain ultraviolet-curing paint by the step among the embodiment 1.
By embodiment 1 coating method the coating that obtains is coated on the white duplex board, obtains the silver-colored Aero Glass of homogeneous transparent.
Embodiment 7
30 parts of DH306
30 parts of DH318
10 parts of PDDA
5 parts of TMPTA
5 parts of TPGDA
184 3 parts of Irgacure
2 parts of OMBB
9.7 parts of P115
0.2 part of BYK333
0.1 part of Glide432
5 parts of EB170
2 parts of CD9051
1 part of Photomer4703
More than press the component proportioning, obtain ultraviolet-curing paint by the method among the embodiment 3.
By embodiment 1 coating method the coating that obtains is coated on the PET, obtains seven colour flashing Aero Glass of homogeneous transparent.

Claims (4)

1. one kind is used for processing the ultraviolet-curing paint of handling behind the image forming material, it is characterized in that it is made by the raw material of following parts by weight:
20~60 parts of acrylate resin performed polymers;
20~50 parts of acrylic ester monomers;
3~10 parts of light triggers;
Cause 3~15 parts of promoter;
0.3~5 part of auxiliary agent;
0.5~5 part of adhesion promoter;
0~5 part of filler;
Described acrylate resin performed polymer is the potpourri of epoxy acrylate and urethane acrylate;
Described acrylic ester monomer is one or more in 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, neopentylglycol diacrylate, PDDA, trimethylolpropane triacrylate, ethoxy trimethylolpropane triacrylate, the propoxyl group trimethylolpropane triacrylate.
2. ultraviolet-curing paint according to claim 1, it is characterized in that described light trigger is one or more in 1-hydroxyl-cyclohexyl benzophenone, benzophenone, 2-hydroxy-2-methyl-1-phenylacetone-1,2-methyl isophthalic acid-(4-methyl mercapto the phenyl)-2-morpholine-1-acetone.
3. ultraviolet-curing paint according to claim 2 is characterized in that, described adhesion promoter is one or more in acrylate phosphate, phosphate, acid monofunctional acrylate monomer, the acid polyester acrylate.
4. ultraviolet-curing paint according to claim 3 is characterized in that, described filler is copper bronze or slurry, aluminium silver powder or slurry, pearlescent pigment, radium-shine or seven colour flashing sheets.
CN200610102178A 2006-11-24 2006-11-24 Ultraviolet light solidified coating in use for post processing of imaging material CN1959530B (en)

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