CN101153127A - White composition capable of solidifying by ultraviolet light - Google Patents
White composition capable of solidifying by ultraviolet light Download PDFInfo
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- CN101153127A CN101153127A CNA2007100356923A CN200710035692A CN101153127A CN 101153127 A CN101153127 A CN 101153127A CN A2007100356923 A CNA2007100356923 A CN A2007100356923A CN 200710035692 A CN200710035692 A CN 200710035692A CN 101153127 A CN101153127 A CN 101153127A
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Abstract
The present invention discloses a white composition for ultraviolet solidification. The composition comprises the components with the weight percentages: (1) 10 percent to 40 percent of epoxy acrylate containing carboxyl; (2) 5 percent to 20 percent of polyurethane acrylic ester containing carboxyl; (3) 10 percent to 30 percent of super branching polyester acrylate; (4) 15 percent to 40 percent of acrylic monomer of single- or multi-functional degree; (5) 8 percent to 20 percent of titanium dioxide; (6) 1 percent to 8 percent of light initiator; (7) 0.5 percent to 3 percent of auxiliary aid; and (8) 0.5 percent to 10 percent of adhesive assistant agent. The construction process of the coating of the present invention is simple; the coating can be widely used (not limited) for various density boards, and solid plate materials. After the coating is solidified by ultraviolet irradiation, the coating film has good adhesive capability, high hardness, good covering capability and leveling performances.
Description
Technical field
The present invention relates to a kind of ultraviolet light polymerization white composition, said composition can be widely used in various density board, solid wood board, has good hardness and good opacifying power.
Background technology
Ultraviolet photocureable material is owing to it is efficient, energy-saving and environmental protection have been widely used in the industries such as timber, plastics, metal, paper.Because particularly titanium dioxide (titanium dioxide) is to the absorption of UV-light for mineral dye, it is very difficult always that the design preparation has the ultraviolet light polymerization thick coating material that can hide fully.At present, the ultraviolet photocureable material that commercialization is used is all based on transparent, CN1225642A discloses a kind of photosensitive composition and whitewash, a kind of special photosensitive composition is adopted in this invention, at room temperature be water white, but can make it solidify, bleach, produce a kind of white mass, thereby can be used as whitewash or white ink by UV-irradiation.Obviously, the whitewash that draws by this invention is opacifying property relatively poor to ground, and prices of raw and semifnished materials costliness.Usually, the white pigment titanium dioxide can not well solidify this coating owing to UV-light being had stronger absorption, and base material is difficult to produce and adheres to.
Summary of the invention
Technical problem to be solved by this invention provides a kind of better covering power that has, and can deep layer solidifies and to the white composition of the good uV curable of the sticking power of base material.
The invention provides a kind of white composition of uV curable, contain 1～3 kind of matrix resin, 1～3 kind of acrylate, 2 kinds of light triggers, anatase titanium dioxide, 1～2 kind of adhesion promoter, by weight percentage, it specifically consists of:
(1) carboxylic epoxy acrylate 10-40%;
(2) carboxylic urethane acrylate 5-20%;
(3) hyperbranched polyester acrylate 10-30%;
(4) single functionality or polyfunctional acrylic ester monomer 15-40%;
(5) titanium dioxide 8-20%;
(6) light trigger 1-8%;
(7) auxiliary addition agent 0.5-3%;
(8) adhere to devote every effort to help and advance agent 0.5-10%.
Above-mentioned white composition can solidify rapidly under UV-irradiation, and to common solid wood plate, density board has good adhesive, has higher hardness and wear resistance preferably simultaneously.
Component (1) is carboxylic epoxy acrylic resin, and it is by standard bisphenol type epoxy acrylic resin, and vinylformic acid and MALEIC ANHYDRIDE are synthetic with ordinary method.Compare with the epoxy acrylic resin of routine, carboxylic epoxy acrylic resin proposed by the invention provides sticking power preferably to base material.
Component (2) is carboxylic urethane acrylate, and it is to be made by organic multiple isocyanate, polyvalent alcohol, dimethylol propionic acid, propenoic acid beta-hydroxy ethyl ester reaction.The example of organic multiple isocyanate comprises toluene-isocyanic ester, hexamethylene diisocyanate, isophorone diisocyanate etc., the example of polyvalent alcohol comprises: polyoxyethylene glycol (Mn=1000,2000), polypropylene glycol (Mn=2000), poly-tetramethylene glycol (Mn=1000,2000) etc.Carboxylic urethane acrylate both provided excellent flexibility to system, had promoted adhering to base material simultaneously again.
Component (3) is hyperbranched polyester acrylate, and it has the functionality height, wear resistance is good, viscosity is little, and to characteristics such as pigment wettability are good, concrete example comprises the CN2301 of Sartomer company and the 6361-100 of Changxing, Taiwan company.
Component (4) propylene esters monomer is this area single functionality monomer in common knowledge or polyfunctionality monomer.Specifically comprise hydroxyethyl methylacrylate, the N-vinyl pyrrolidone, the three interior omega-diol diacrylates that contract, 1,6 hexanediol diacrylate, Viscoat 295, pentaerythritol triacrylate, two seasons penta 4 liquor-saturated five acrylate etc.
Selecting for use of component (5) titanium dioxide is the anatase titanium dioxide of median size at 4-6 μ m.
The light trigger example of component (6) comprises 2-hydroxy-2-methyl-1-phenyl-acetone (1173), 1-hydroxycyclohexylphenylketone (184), 1-[4-(methyl sulfo-) phenyl]-2-morpholinyl-propane-1-ketone (907), 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-1-ketone (369), two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide (819).Preferential 1173 and 819 the compound that uses, compound proportion is that 8: 2 left and right sides effects are best.
Auxiliary agent mainly comprises dispersion agent, as BYK-161, and BYK130 etc.; Anti-settling agent is as aerosil or BYK-430 etc.
Adhesion promoter comprises vinylformic acid phosphoric acid ester (PM-2), and the pure acrylic acid resin is as the 6153-1 of Changxing, Taiwan company or the mixture of the two.
The preparation method of the ultraviolet light polymerization white composition that the present invention proposes is with component (1), (2), (3) any in and component (4), (5), after (7) are mixed in proportion, under ℃ condition of temperature≤80 with three roller sand machine sand millings, to system fineness≤30, add other component more in proportion, stir or disperse about 1 hour, filter with 200 order filter clothes and then pack, promptly obtain ultraviolet light polymerization white composition of the present invention.
Coating application technology of the present invention is simple, can be widely used in (but being not limited to) various density board, solid wood board.Coating is after UV-irradiation is solidified, and gained is filmed and had good adhesive, very high hardness, well opacifying power and levelling property.
Embodiment
The invention will be further described below in conjunction with embodiment.
Synthetic carboxylic epoxy acrylate (EP-I):
Agitator is being housed, in the four-hole boiling flask of thermometer and prolong, drop into standard bisphenol type epoxy acrylic resin (oxirane value 0.54～0.56) 550g respectively, vinylformic acid 210g and proper catalyst triethylamine and stopper MEHQ, in 0.5 hour, slowly be warming up to 110～115 ℃ of reactions 4～5 hours, to reaction system acid number≤5mgKOH/g, reaction system is cooled to 40 ℃～60 ℃, add MALEIC ANHYDRIDE 100g, be warming up to 115 ℃ of reactions 1 hour, to system acid value≤55mgKOH/g, cooling, blowing promptly gets carboxylic epoxy acrylate of the present invention (EP-I).
Synthetic carboxylic acrylic acid modified polyurethane resin (YG-I):
Agitator is being housed, in the four-hole boiling flask of thermometer and prolong, drop into 600g polyethers propylene glycol (Mn=2000) respectively, be warmed up to 120 ℃ of following vacuum hydro-extractions 1 hour, be cooled to room temperature, add 40g 2, the 2-dimethylol propionic acid, add appropriate amount of catalysts dibutyl tin laurate and stopper to the methylol methyl-phenoxide, press certain speed after the heating for dissolving and drip the 240g tolylene diisocyanate, treat to be warming up to 55 ℃-65 ℃ reactions 2 hours behind the temperature-stable, add 75g propenoic acid beta-hydroxy ethyl ester reaction 0.5 hour then, be warming up to 84 ℃-88 ℃ reactions 2-2.5 hour again, isocyano-content in reaction system≤0.5%, cooling, blowing promptly gets carboxylic acrylic acid modified polyurethane resin of the present invention (YG-I).
Synthetic carboxylic acrylic acid modified polyurethane resin (YG-II):
Agitator is being housed, in the four-hole boiling flask of thermometer and prolong, drop into 600g polyoxyethylene glycol (Mn=2000) respectively, add 40g 2, the 2-dimethylol propionic acid, add appropriate amount of catalysts dibutyl tin laurate and stopper to the methylol methyl-phenoxide, press certain speed after the heating for dissolving and drip the 265g isophorone diisocyanate, treat to be warming up to 55 ℃-65 ℃ reactions 2 hours behind the temperature-stable, add 75g propenoic acid beta-hydroxy ethyl ester reaction 0.5 hour then, be warming up to 84 ℃-88 ℃ reactions 2-2.5 hour again, isocyano-content in reaction system≤0.5%, cooling, blowing promptly gets carboxylic acrylic acid modified polyurethane resin of the present invention (YG-II).
Embodiment 1:
Carboxylic epoxy acrylic resin (EP-I) 10%
Carboxylic urethane acrylate (YG-I) 20%
Hyperbranched polyester acrylate (6361-100) 30%
1,6-hexylene glycol acrylate 20%
Titanium dioxide 12%
2-hydroxy-2-methyl-1-phenyl-acetone (1173) 3%
Two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide (819) 0.8%
Aerosil 1%
BYK-130 (dispersion agent) 0.2%
6153-1 1.5％
PM-2 1.5％
Any and Acrylic Acid Monomer with above-mentioned three kinds of resins, titanium dioxide and aerosil, dispersion agent mixes in proportion, sand milling adds other component more in proportion to fineness≤30 μ on three-roller, after 40 ℃-20 ℃ abundant down stirring or disperseing, filter with 200 order filter clothes, can get ultraviolet light polymerization white composition of the present invention, this composition is applied to solid wood plate or density board, wet-film thickness is controlled at 20-30 μ, showing light irradiation 3-6 second through the 3000W high pressure, curing is also placed and is surveyed its performance after 24 hours, survey sticking power after 72 hours again, gained the results are shown in Table-1.
Embodiment 2:
Carboxylic epoxy acrylic resin (EP-I) 40%
Carboxylic urethane acrylate (YG-II) 5%
Hyperbranched polyester acrylate (CN2301) 10%
Tripropylene glycol diacrylate (TPGDA) 20%
Hydroxyethyl methylacrylate 6%
Titanium dioxide 8%
2-hydroxy-2-methyl-1-phenyl-acetone (1173) 4%
Two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide (819) 1%
BYK-161 0.4％
PM-2 2.8％
6153-1 2％
Sample making method and condition of cure are with embodiment 1, and test result sees Table-1.
Embodiment 3:
Carboxylic epoxy acrylic resin (EP-1) 15%
Carboxylic urethane acrylate (YG-II) 15%
Hyperbranched polyester acrylate (CN2301) 10%
Pentaerythritol triacrylate (PETA) 15%
Hydroxyethyl methylacrylate 14%
Titanium dioxide 20%
2-hydroxy-2-methyl-1-phenyl-acetone (1173) 4%
Two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide (819) 1%
BYK-130 (dispersion agent) 0.2%
6153-1 5.8％
Sample making method and condition of cure are with embodiment 1, and test result sees Table-1.
Reference examples 1:
Carboxylic epoxy acrylic resin (EP-1) 25%
Hyperbranched polyester acrylate (6361-100) 20%
Pentaerythritol triacrylate (PETA) 8%
1,6-hexylene glycol acrylate (HDDA) 20%
Titanium dioxide 15%
BYK-161 0.2％
2-hydroxy-2-methyl-1-phenyl-acetone (1173) 3%
Two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide (819) 0.8%
PM-2 4％
6153-1 4％
Sample making method and condition of cure are with embodiment 1, and test result sees Table-1.
Table 1 film performance relatively
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Reference examples 1 | ||||
| The solid wood plate | Density board | The solid wood plate | Density board | The solid wood plate | Density board | The solid wood plate | Density board | |
| Set time (second) | 4 | 4 | 5 | 5 | 6 | 6 | 3 | 3 |
| Pencil hardness (H) | 1 | 1 | 1 | 1 | 0 | 1 | 1 | 1 |
| 24 hours postadhesion power (level, cross-hatching) | 0 | 0～1 | 0 | 0～1 | 0 | 0～1 | 1～2 | 2 |
| 72 hours postadhesion power (level, cross-hatching) | 0 | 0 | 0 | 0 | 0 | 0 | 1～2 | 2 |
Claims (8)
1. the white composition of a uV curable is characterized in that: described composition consisting of by weight percentage:
(1) carboxylic epoxy acrylate 10-40%;
(2) carboxylic urethane acrylate 5-20%;
(3) hyperbranched polyester acrylate 10-30%;
(4) single functionality or polyfunctional acrylic ester monomer 15-40%;
(5) titanium dioxide 8-20%;
(6) light trigger 1-8%;
(7) auxiliary addition agent 0.5-3%;
(8) adhere to devote every effort to help and advance agent 0.5-10%.
2. the white composition of uV curable according to claim 1 is characterized in that: the described carboxyl epoxy acrylate that contains is prepared from by chemical reaction for being raw material with standard bisphenol A epoxide resin, vinylformic acid, MALEIC ANHYDRIDE.
3. the white composition of uV curable according to claim 1 and 2 is characterized in that: described carboxylic urethane acrylate is that the acrylate reactions by polyisocyanates and polyvalent alcohol, dimethylol propionic acid, hydroxyl makes.
4. the white composition of uV curable according to claim 1 and 2, it is characterized in that: described hyperbranched polyester acrylate is meant the hyperbranched polyester acrylate of functionality 〉=8.
5. the white composition of uV curable according to claim 1 and 2, it is characterized in that: the single functionality or the polyfunctional acrylic ester monomer of institute's art are selected from 2-EHA, a kind of or several arbitrarily in 1.6-hexanediyl ester, tri (propylene glycol) diacrylate, the third oxidation neopentylglycol diacrylate, ethoxyquin Viscoat 295, Dipentaerythritol five acrylate.
6. the white composition of uV curable according to claim 1 and 2, it is characterized in that: described titanium dioxide is meant the anatase titanium dioxide of average particle size at 4-6 μ m.
7. the white composition of uV curable according to claim 1 and 2, it is characterized in that: described light trigger is by 2-hydroxy-2-methyl-1-phenyl-acetone (Darocur1173), two (2,4,6-Three methyl Benzene formyl) composite the forming of phenyl phosphine oxide (Irgacure819).
8. the white composition of uV curable according to claim 1 and 2, it is characterized in that: described adhesion promoter is vinylformic acid phosphoric acid ester or pure acrylic acid ester resin or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100356923A CN101153127A (en) | 2007-09-06 | 2007-09-06 | White composition capable of solidifying by ultraviolet light |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100356923A CN101153127A (en) | 2007-09-06 | 2007-09-06 | White composition capable of solidifying by ultraviolet light |
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