CN104892798A - Novel thioxanthone photoinitiator and application of UV-LED (ultraviolet-light-emitting diode) light curing - Google Patents
Novel thioxanthone photoinitiator and application of UV-LED (ultraviolet-light-emitting diode) light curing Download PDFInfo
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Abstract
The invention provides a novel thioxanthone photoinitiator applicable to UV-LED (ultraviolet-light-emitting diode) light source curing. The novel thioxanthone photoinitiator has high absorptivity in a long-wavelength region (365-395nm), is applicable to UV-LED light source curing and overcomes the defects of high energy consumption and heavy pollution of conventional curing. Meanwhile, the photoinitiator has low smell, has the advantages of low extractability, low mobility and low volatility after photopolymerization and has great advantages as compared with the similar photoinitiator in the prior art.
Description
Technical field
The present invention relates to a kind of new thioxanthone photoinitiator, this photoinitiator can be used for LED ultraviolet light polymerization.
Background technology
At present, photocuring technology is mainly ultraviolet light polymerization, and light source is high voltage mercury lamp mainly, and the radiation spectrum that high voltage mercury lamp produces haves a wide reach, the radiation quantity highly significant of its middle ultraviolet band, especially UVC, UVB, UVA and UVV region (UVC: 280 below nm; UVB: 280-320 nm; UVA: 320-390 nm; UVV: 390 more than nm).This spectral width can allow people select suitable light trigger according to the kind of material in the type of light source and intensity and formula, and then optimize the solidification of acrylate type ink, coating, tackiness agent, sealing agent and matrix material, thus block or absorb UV-light (such as pigment and filler).
The ray without solidification that tradition mercury lamp gives off accounts for 70% ~ 75%, and wherein maximum is high-octane infrared light, and they can produce a large amount of heats.Typical mercury lamp keeps the nice and cool air-flow needing a large amount of flowing, therefore needs to consume extra energy.The air-flow of high flow capacity like this makes to adopt rare gas element to become do not have practical value (expensive indifferent gas is known from experience along with the cooling of air constantly consumes) to improve surface cure performance.In addition, some obvious defects are also had:
1, the usage quantity of traditional mercury lamp is large, uv equipment use mercury lamp at least 1-2 prop up, 6-8 props up at most;
2, the power of traditional mercury lamp is large, and not etc., current consumption is not huge for 3-20KW;
3, traditional mercury lamp thermal value is very large, selects limitation very large to curing substrate;
4, traditional mercury lamp starts slow, and warm up time is long, is only suitable for non-stop run, causes waste to normal production,
Handiness is very poor;
5, a large amount of use mercury lamps can cause mercury pollution.
And emerging UV-LED light source makes significant progress at present.UV-LED light source utilizes photoelectricity transformation principle, and the electronics in chip and positive charge collide combination and change into luminous energy in moving process, has now many commercial uses, as ink, optical manufacturing, laser and optical communication product manufacturing, medical product bonding etc., more traditional mercury lamp, has many good qualities:
1, cold light source, is energy-conservationly widely used for heat-sensitive substrate material;
2, there is the performance of " namely open and namely close ", without the need to preheating, after start, namely 100% export UV-light, simple to operate;
3, close to single spectrum, spectrum width is very narrow;
4, long service life, more lasting UV light source, can reach more than 25000h;
5, stable output power, continuously adjustabe.
UV-LED light source, because of the huge superiority such as its energy-saving and environmental protection, durable and remarkable luminescent properties, must be the development trend of following photocuring technology.But because UV-LED radiation of light source crest is single, energy accumulating is at certain narrow UV-light spectral coverage, and the crest great majority of UV-LED light source concentrate on 395 ~ 405nm in the market.The ultraviolet initiator matched with UV-LED light source is also very limited, current thioxanthone and acylphosphine oxide photoinitiator can match with UV-LED light source, but the organic compatibility of the two is poor, molecular weight is little, there are more micromolecular shortcomings, therefore urgent need exploitation and UV-LED light source match, there is the light trigger of stronger absorbing ability and Geng Gao initiating activity, especially there is high reactivity, low smell, low volatilization, low migration and the light trigger that can match with existing UV-LED light source, we find that there is the needs that a photoinitiator can meet environment and existing UV-LED light source.
CN200410093977.9 discloses the characteristic that a class thioxanthone-2-carboxylic acid derivative shows low volatilization, low extraction, low migration, but the raw materials cost preparing this compounds is high, its space charge force is also lower than thioxanthone-4-carboxylic acid derivative, and practical application is subject to a definite limitation.The characteristic that CN201010218422.8 discloses thioxanthone-4-carboxylic acid polyoxyethylene glycol-200-dibasic acid esters, thioxanthone-4-carboxylic acid polyoxyethylene glycol-300-dibasic acid esters, thioxanthone-4-carboxylic acid polytetrahydrofuran-250-dibasic acid esters show high reactivity, low volatilization, low extraction, low migration, but the fusing point of this compounds is not high, not easily store, room temperature slightly apperance is difficult to keep, can not continuous seepage; Consistency is not high, adds the difficulty of purification, too increases the difficulty of suitability for industrialized production simultaneously.This two photoinitiator is not all mentioned for UV-LED light source curing.
Summary of the invention
The object of this invention is to provide a photoinitiator overcome existing light trigger poor compatibility, not easily purify, fusing point is low, be difficult to ensure shortcomings such as depositing.
The object of this invention is to provide good, the easy purification of a class consistency, easily preservation, low extractability, low migration and low volatility light trigger, and may be used for the light source curing system of UV-LED.
The invention provides the light trigger of a class high reactivity, low smell, there is the feature of low extractability, low migration and low volatility after photopolymerization, can be used for the wrapping material such as food and medicine.
Light trigger provided by the invention is the compound of the structure with following formula I:
（Ⅰ）
Wherein:
n=2-4；
b=11-20。
Light trigger formula I provided by the invention can keep high reactivity; The at room temperature outward appearance of this compounds can be kept constant simultaneously, ensure to produce regardless of weather continuous industry; Such Compound Phase capacitive is good, easily purifies, and solves difficult problem that industrial production purifies.
Light trigger formula I provided by the invention at room temperature can keep outward appearance constant, convenient storage and transport; Consistency is better, and recrystallization is purified can reach good effect.
Light trigger formula I provided by the invention can prepare easily, and preparation technology is:
In fact, in preparation process, have small portion monoesters formula II generate, the dibasic acid esters formula I generated in experiment proved response process is generally greater than 93%, and the monoesters formula II of generation is less than 5%.
（Ⅱ）
Wherein:
n=2-4；
b=11-20。
Light trigger thioxanthone carboxylic acid dibasic acid esters formula I provided by the invention, in fact the dibasic acid esters of 100% need not be ensured in actual applications, there is a small amount of monoesters formula II can not affect its performance, experiment proves that monoesters is also the light trigger of low extractability, low migration and low volatility, therefore can without separating-purifying dibasic acid esters and monoesters, but used in combination.
Photoinitiator mixtures provided by the invention, it comprises formula I,
（Ⅰ）
Wherein:
n=2-4；
b=11-20；
With the mixing of formula II
（Ⅱ）
Wherein:
n=2-4；
b=11-20。
Light trigger formula I provided by the invention or light trigger formula I and formula II mixed light initiator have stronger absorption in long wave 385-405nm scope, be applicable to high-power UV-LED ultraviolet light polymerization, overcome the shortcoming that traditional mercury lamp solidification power consumption is high, pollution is heavy.
Photocurable composition provided by the invention, it comprises
(a) at least one containing ethylenical unsaturated double bonds compound and
(b) light trigger formula I or light trigger formula I and formula II mixed light initiator.
One or more double bond can be contained containing ethylenical unsaturated double bonds compound.They can be low-molecular-weight
(oligopolymer) of (monomer) or relatively high molecular.Wrapping double bond containing Exemplary monomers is alkyl or hydroxy alkyl acrylate or methacrylic ester, such as, and methyl, ethyl, butyl, 2-ethylhexyl-or 2-hydroxyethylmethacry,ate, iso-bornyl acrylate, or methacrylic acid methyl or ethyl ester; Silicone acrylate; Acrylamide, Methacrylamide, (methyl) acrylamide that N-replaces; Vinyl ester as vinyl-acetic ester, vinyl ether as isobutyl vinyl ether, vinylbenzene, alkyl-and halogenated styrenes, NVP, vinyl chloride or vinylidene chloride.
Containing the monomer of two or more double bond as ethylene glycol, propylene glycol, neo-pentyl ethylene glycol, 1, the diacrylate of 6-hexylene glycol and dihydroxyphenyl propane, 4,4 '-bis-(2-acryloyloxyethoxy) diphenyl propane, Viscoat 295, pentaerythritol triacrylate or tetraacrylate, ethylene propylene acid esters, Vinylstyrene, divinyl succinate, diallyl phthalate, tricresyl phosphate allyl ester, tricarbimide triallyl ester and tricarbimide three (2-acryloyl ethyl) ester.
The example with relative high molecular (oligopolymer) polyunsaturated compounds is epoxy resin and polyethers, the polyurethane(s) of acrylated; Acrylated or the polyester containing vinyl ether group or epoxy group(ing).Unsaturated oligomer can also be unsaturated polyester resin, and they are have toxilic acid mostly, prepared by phthalic acid and one or more glycol and have the molecular weight of about 500-3000.In addition, also can use vinyl ether monomers and vinyl ether oligomers, and take maleic acid ester as terminal, there is the oligopolymer of polyester, polyurethane(s), polyethers, polyvinyl ether and epoxy main chains.
Alefinically unsaturated compounds can also be the ester of ethylenically unsaturated carboxylic acids and polyvalent alcohol epoxy compounds, with the polymkeric substance containing ethylenically unsaturated group on main chain or side chain radical, such as unsaturated polyester, polymeric amide or polyurethane(s) and multipolymer thereof, polyhutadiene or butadienecopolymer, polyisoprene and isoprene copolymer, containing the polymkeric substance of (methyl) acrylic and multipolymer on side chain, containing the polymkeric substance of (methyl) acrylic and multipolymer on side chain, and the mixture of one or more these polymkeric substance.
The example of unsaturated carboxylic acid is that vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid, styracin and unsaturated fatty acids are as linolenic acid and oleic acid.Preferred vinylformic acid and methacrylic acid.
Suitable polyvalent alcohol is aromatic polyol and is especially aliphatic series and Cycloaliphatic polyols.Aromatic polyol as quinhydrones, 4,4 '-dihydroxydiphenyl, 2,2-bis-(4-hydroxy phenyl) propane, and (line style) phenolic varnish and phenol-formaldehyde A.Aliphatic series and Cycloaliphatic polyols are as aklylene glycol, and preferred C2-12, as ethylene glycol, 1,2-or 1, ammediol, 1,2-, 1,3-or 1,4-butyleneglycol, pentanediol, hexylene glycol, ethohexadiol, 12 carbon alkane glycol, glycol ether, triglycol, molecular weight are preferably the polyoxyethylene glycol, 1 of 200-1500,3-ring pentanediol, 1,2-, 1,3-or 1,4-cyclohexanediol, Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), Dipentaerythritol or Sorbitol Powder etc.
There is the method for polymerization in Photocurable composition provided by the invention, comprises the light source by 200-405nm scope
Irradiate, can be used for producing coating material, printing ink, printing plate, dental material, photoengraving agent material and as image recording material.Especially the light source irradiation of 385-405nm can also be used.Therefore Photocurable composition provided by the invention can mate with existing UV-LED light source, can be used for UV-LED photocuring system.
Embodiment
The present invention will by but be not limited only to following embodiment and be described further.
embodiment 1: 2-(2 '-carboxyl-thiophenyl)-benzoic preparation
Be equipped with in churned mechanically 250mL four-hole bottle, adding 47.0g 2-chloro-benzoic acid, 46.2g 2-Thiosalicylic acid, 100ml DMF, 13.2gNaOH, reflux, back flow reaction 5 hours, cooling, steams DMF, add 100mL water, stir lower dropping 50mL concentrated hydrochloric acid, adjust pH=1, a large amount of solid is separated out, and filter, gained solid adds 150mL recrystallizing methanol, obtain the needle-like crystal that 74.0g is yellowish, yield 90%, content >=98%.
1H NMR (DMSO) δ ：7.10（m,2H），7.38（m,2H），7.46（m,2H），7.84（m,2H），13.12（s,2H)。
embodiment 2: the preparation of thioxanthone-4-formic acid:
Be equipped with in churned mechanically 250mL four-hole bottle, adding 40.0g 2-(2 '-carboxyl-thiophenyl)-phenylformic acid, the 3.0g vitriol oil (98%), 30mL dimethylbenzene, reflux is dewatered 5 hours.Cooling, adds 50mL water, and solid is separated out, and filters.Gained solid adds 30mL recrystallizing methanol, obtains 33.6g yellow powder, yield 90%, content >=99%.
1H NMR (DMSO) δ ：7.10-7.80（m,6H），8.40（m,1H），12.81（s,1H）。
embodiment 3: the preparation of thioxanthone-4-carboxylic acid polyoxyethylene glycol-600-dibasic acid esters
To in 250mL four-hole boiling flask, add thioxanthone-4-formic acid (51.20g, 0.2 mol), chlorobenzene (150mL) successively.Mechanical stirring, under room temperature, slowly drips sulfur oxychloride (50mL), is warming up to backflow.TLC monitoring reacts completely to thioxanthone-4-formic acid.Decompression steams unreacted sulfur oxychloride and chlorobenzene, obtains yellow solid crude product, and chlorobenzene washing solid, obtains yellow solid for subsequent use.
To in 250mL four-hole boiling flask, add above-mentioned solid crude product (27.40g, 0.1mol), chlorobenzene (100mL), triethylamine (10mL) successively.Mechanical stirring, under room temperature, slowly drips Polyethylene Glycol-600 (0.12mol), and controlling temperature of reaction is 40 DEG C, and TLC monitoring reacts completely to thioxanthone-4-formyl chloride.Naturally room temperature is down to, suction filtration, by 5% sodium bicarbonate and water washing filtrate extremely neutrality, concentrated, obtain brown color liquid, HPLC purity 95%, HRMS (ESI) m/z calc ' d for C
28+2nh
14+4no
5+ns
2[M+NH
4]
+: 512.0626+44.0262n, found 1040.3756,1084.4032,1128.4294,1172.4556,1216.4818,1260.5080.
embodiment 4: the preparation of thioxanthone-4-carboxylic acid polypropylene glycol-600-dibasic acid esters
To in 250mL four-hole boiling flask, add thioxanthone-4-formic acid (51.20g, 0.2mol), chlorobenzene (150mL) successively.Mechanical stirring, under room temperature, slowly drips sulfur oxychloride (50mL), is warming up to backflow.TLC monitoring reacts completely to thioxanthone-4-formic acid.Decompression steams unreacted sulfur oxychloride and chlorobenzene, obtains yellow solid crude product, and chlorobenzene washing solid, obtains yellow solid for subsequent use.
To in 250mL four-hole boiling flask, add above-mentioned solid crude product (27.40g, 0.1mol), chlorobenzene (100mL), triethylamine (10mL) successively.Mechanical stirring, under room temperature, slowly drip polypropylene glycol 600 (0.12mol), controlling temperature of reaction is 40 DEG C, and TLC monitoring reacts completely to thioxanthone-4-formyl chloride.Naturally room temperature is down to, suction filtration, by 5% sodium bicarbonate and water washing filtrate extremely neutrality, concentrated, obtain brown color liquid, HPLC purity 96%, HRMS (ESI) m/z calc ' d for C
28+3nh
14+6no
5+ns
2[M+Na]
+: 517.0226+58.0419n, found 1213.5254,1271.5673,1329.6092,1387.6511,1445.6930,1503.7349.
embodiment 5: the preparation of thioxanthone-4-carboxylic acid polytetrahydrofuran-850-dibasic acid esters
To in 250mL four-hole boiling flask, add thioxanthone-4-formic acid (51.2g, 0.2mol), chlorobenzene (150mL) successively.Mechanical stirring, under room temperature, slowly drips sulfur oxychloride (50mL), is warming up to backflow.TLC monitoring reacts completely to thioxanthone-4-formic acid.Decompression steams unreacted sulfur oxychloride and chlorobenzene, obtains yellow solid crude product, and chlorobenzene washing solid, obtains yellow solid for subsequent use.
To in 250mL four-hole boiling flask, add above-mentioned solid crude product (27.4g, 0.1mol), chlorobenzene (100mL), triethylamine (10mL) successively.Mechanical stirring, under room temperature, slowly drip polytetrahydrofuran 850 (0.12mol is dissolved in 20mL chlorobenzene), controlling temperature of reaction is 40 DEG C, and TLC monitoring reacts completely to thioxanthone-4-formyl chloride.Naturally room temperature is down to, suction filtration, by 5% sodium bicarbonate and water washing filtrate extremely neutrality, concentrated, obtain brown color liquid, HPLC purity 94%, HRMS (ESI) m/z calc ' d for C
28+4nh
14+8no
5+ns
2[M+Na]
+: 517.0226+72.0419n, found 1165.3997,1237.4416,1309.4835,1381.5254,1453.5673,1525.6092.
embodiment 6: the preparation of thioxanthone-4-carboxylic acid PEG-6000-dibasic acid esters
To in 250mL four-hole boiling flask, add thioxanthone-4-formic acid (51.2g, 0.2mol), chlorobenzene (150mL) successively.Mechanical stirring, under room temperature, slowly drips sulfur oxychloride (50mL), is warming up to backflow.TLC monitoring reacts completely to thioxanthone-4-formic acid.Decompression steams unreacted sulfur oxychloride and chlorobenzene, obtains yellow solid crude product, and chlorobenzene washing solid, obtains yellow solid for subsequent use.
To in 250mL four-hole boiling flask, add above-mentioned solid crude product (27.4g, 0.1mol), chlorobenzene (100mL), triethylamine (10mL) successively.Mechanical stirring, under room temperature, slowly drips cetomacrogol 1000 (0.12mol is dissolved in 50mL chlorobenzene), and controlling temperature of reaction is 40 DEG C, and TLC monitoring reacts completely to thioxanthone-4-formyl chloride.Naturally room temperature is down to, suction filtration, by 5% sodium bicarbonate and water washing filtrate extremely neutrality, concentrated, obtain brown color liquid, HPLC purity 95%, HRMS (ESI) m/z calc ' d for C
28+2nh
14+4no
5+ns
2[M+Na]
+: 517.0226+44.0262n, found 1397.5466,1441.5728,1485.5990,1529.6252,1573.6514,1617.6776.
embodiment 7: light-cured performance evaluation
Test recipe is in table 1.
Table 1:
| Component | Ratio wt % |
| Epoxy acrylic resin | 45.0 |
| TPGDA | 25.0 |
| Phthalocyanine blue BGS | 10.0 |
| Borchi GOL OL17 | 0.5 |
| Embodiment light is carried out the coffin upon burial agent (or ITX) | 2.0 |
| Reactive amines P115 | 17.5 |
Use 40 μm of line rod spreaders on PGA-paper, be coated with the light trigger performance comparing light trigger ITX and embodiment of the present invention light trigger.The sample of coating is installed on tape, under Phoseon 4W 395nm LED, carries this sample.Determine the number of pass times of complete solidified sample under given belt speed.Q-tip method is used to determine to solidify completely.The results are shown in Table 2.
Table 2:
| Radiation-hardenable composition | The number of times passed through when 5m/min | The number of times passed through when 30m/min |
| Embodiment 3 | 1 | 2 |
| Embodiment 4 | 1 | 3 |
| Embodiment 5 | 1 | 3 |
| Embodiment 6 | 2 | 6 |
| ITX | 3 | 6 |
This result shows, it is active that these new light triggers have good light trigger, and can match by LED light source that is good and technology maturation, this photoinitiator has the character of low smell simultaneously, has the feature of low extractability, low migration and low volatility after photopolymerization.Therefore relative to this photoinitiator of prior art, there is sizable advantage.
Claims (7)
1. a thioxanthone photoinitiator, is characterized in that its structure formula I:
（Ⅰ）
Wherein:
n=2-4；
b=11-20。
2. light trigger according to claim 1, is characterized in that they can be used for UV-LED photocuring.
3. photoinitiator mixtures, it comprises at least one formula I compound
（Ⅰ）
Wherein:
n=2-4；
b=11-20；
With at least one formula II compound
（Ⅱ）
Wherein:
n=2-4；
b=11-20。
4. photopolymerizable composition, it comprises:
A) the unsaturated photopolymerization compounds of at least one olefinic and
B) as the mixture of light trigger in formula I compound in light trigger at least one claim 1 or claim 3.
5., containing the photopolymerisable method of compound of ethylenical unsaturated double bonds, it comprises with the composition in the rayed claim 4 of 200-405nm scope.
6., containing the photopolymerisable method of compound of ethylenical unsaturated double bonds, it comprises with the composition in the rayed claim 4 of 385-405nm scope.
7. the method according to claim 5 and 6, is used for producing coating material, printing ink, printing plate, dental material, photoengraving agent material and as image recording material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366755A (en) * | 2016-08-31 | 2017-02-01 | 天津久日新材料股份有限公司 | Photo-cured printing ink composition for food, medicine and cosmetic package |
| CN106810627A (en) * | 2015-12-02 | 2017-06-09 | 天津久日新材料股份有限公司 | UV-LED light sources compounding light trigger |
| CN109880508A (en) * | 2019-01-15 | 2019-06-14 | 东莞市亿森居环保科技有限公司 | A kind of composition, preparation method and the application in photocuring woodcare paint paint field |
| CN109928951A (en) * | 2017-12-19 | 2019-06-25 | 山东久日化学科技有限公司 | The preparation method of 2- isopropyl thioxanthone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5145885A (en) * | 1983-08-15 | 1992-09-08 | Ciba-Geigy Corporation | Photopolymerizable compositions containing aminoaryl ketone photoinitiators |
| CN1660837A (en) * | 2004-12-20 | 2005-08-31 | 天津久日化学工业有限公司 | Light mitiator of thioxanthone-2-carboxylic ester |
| CN101906095A (en) * | 2010-07-06 | 2010-12-08 | 天津久日化学工业有限公司 | Thioxathone-4-carboxylic ester and preparation method as well as photoinitiator composition and application |
-
2015
- 2015-06-23 CN CN201510348211.9A patent/CN104892798B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5145885A (en) * | 1983-08-15 | 1992-09-08 | Ciba-Geigy Corporation | Photopolymerizable compositions containing aminoaryl ketone photoinitiators |
| CN1660837A (en) * | 2004-12-20 | 2005-08-31 | 天津久日化学工业有限公司 | Light mitiator of thioxanthone-2-carboxylic ester |
| CN101906095A (en) * | 2010-07-06 | 2010-12-08 | 天津久日化学工业有限公司 | Thioxathone-4-carboxylic ester and preparation method as well as photoinitiator composition and application |
Non-Patent Citations (1)
| Title |
|---|
| 张里扬等: "含硫杂蒽酮类光引发剂的聚合体系的光固化研究", 《感光科学与光化学》, vol. 15, no. 1, 28 February 1997 (1997-02-28), pages 7 - 12 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106810627A (en) * | 2015-12-02 | 2017-06-09 | 天津久日新材料股份有限公司 | UV-LED light sources compounding light trigger |
| CN106810627B (en) * | 2015-12-02 | 2019-03-01 | 天津久日新材料股份有限公司 | UV-LED light source compounding photoinitiator |
| CN106366755A (en) * | 2016-08-31 | 2017-02-01 | 天津久日新材料股份有限公司 | Photo-cured printing ink composition for food, medicine and cosmetic package |
| CN109928951A (en) * | 2017-12-19 | 2019-06-25 | 山东久日化学科技有限公司 | The preparation method of 2- isopropyl thioxanthone |
| CN109928951B (en) * | 2017-12-19 | 2022-03-08 | 山东久日化学科技有限公司 | Preparation method of 2-isopropyl thioxanthone |
| CN109880508A (en) * | 2019-01-15 | 2019-06-14 | 东莞市亿森居环保科技有限公司 | A kind of composition, preparation method and the application in photocuring woodcare paint paint field |
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|---|---|
| CN104892798B (en) | 2016-11-23 |
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