CN102241792A - Hydrophilic high-molecular polymer photosensitive initiator and preparation method thereof - Google Patents
Hydrophilic high-molecular polymer photosensitive initiator and preparation method thereof Download PDFInfo
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- CN102241792A CN102241792A CN 201010166565 CN201010166565A CN102241792A CN 102241792 A CN102241792 A CN 102241792A CN 201010166565 CN201010166565 CN 201010166565 CN 201010166565 A CN201010166565 A CN 201010166565A CN 102241792 A CN102241792 A CN 102241792A
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- LCSNMSBGUMDVRK-UHFFFAOYSA-N CCC1C=CC(C)=CC1 Chemical compound CCC1C=CC(C)=CC1 LCSNMSBGUMDVRK-UHFFFAOYSA-N 0.000 description 1
- AOIAURCMPYRFGB-UHFFFAOYSA-N Cc1ccc(CC#C)cc1 Chemical compound Cc1ccc(CC#C)cc1 AOIAURCMPYRFGB-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a hydrophilic high-molecular polymer photosensitive initiator, and a preparation method thereof. A repeating structure unit of the hydrophilic high-molecular polymer photosensitive initiator is represented by a formula in the specification, and in the formula, m is 50 to 1000, n is 50 to 1000, R' is selected from hydrogen or alkyl or hydroxyalkyl containing two-four carbon atoms. The photosensitive initiator is an acrylate-4-vinylphenyl-bis(2,4,6-trimethylbenzene benzoyl)phosphine oxide copolymer. The acrylate-4-vinylphenyl-bis(2,4,6-trimethylbenzene benzoyl)phosphine oxide copolymer prepared in the invention has a good hydrophilism which allows the storage stability to be improved, has a macromolecular structure which allows no chemical migration after film forming to be achieved and residual smell of the film to be reduced, and enables the cost to be reduced.
Description
Technical field
The present invention relates to light trigger, specifically, is a kind of hydrophilic high molecular polymer photoinitiator and preparation method thereof.
Background technology
U.S. company has delivered not saturated polyester/vinylbenzene UV-light UV curing technology patent first from nineteen forty-six, photocuring technology is used widely at industrial circles such as photo-cured coating, photoresist material, light-curable ink, electronic package material, tackiness agent, optical media replication, paper glazings, and photocuring technology keeps high speed development.Ultraviolet-curing paint obtains tremendous development on woodenware, major advantage comprises: the first, and rate of drying is fast.Behind the UV coating of constructing, only need UV-irradiation through several seconds, just can be in the moment film forming.The second, disposable one-tenth thickness.UV coating can be made into 100% solid content, has improved production efficiency.The 3rd, lower organic composition volatilization (VOC) is than the more environmental protection of traditional solvent based coating.But because monomer toxicity is big, it is residual still to have small amounts of monomer after the final film forming, and healthy unfavorable to the workmen also has certain influence to environment, the first-elected certainly aqueous woodware paint of product of environmental protection.With water is thinner, nonpoisonous and tasteless, and loopful is protected, and is all harmless to environment and human body, developed rapidly in recent years.Present aqueous woodware paint product is based on single-component, and there are limitation in rate of drying, physicals.Under this overall situation, aqueous wooden ware UV coating arises at the historic moment, and the drying that has the environmental protection that has been equipped with water-miscible paint and UV lacquer concurrently is characteristics fast, do not contain the small molecules acrylate monomer, no chemical transport, and toxic residue is little.Two (2,4, the 6-trimethylbenzoyl)-phenyl-phosphine oxides are current water-based UV efficiency light initiators commonly used, and still, because its lower molecular weight easily produces migration, volatilization in the dry film after construction, the smell extended residual is in paint film; The wetting ability deficiency, that causes initiator after the standing storage separates out the stability of water-based system and the whole drying effect of filming of consistency influence.For the aqueous photo-curing system, after long storage process and film forming, volatilization and migration owing to take place with light solid system consistency difference and reactivity in small molecules type light trigger by force and easily, this has caused the photopolymerization efficiency of initiation low on the one hand, also can cause the product xanthochromia on the other hand, produce smell and toxicity, be difficult to compliance with environmental protection requirements.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of efficient, environmental protection, suitable more aqueous wooden ware UV solidified hydrophilic high molecular polymer photoinitiator and preparation method thereof.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: a kind of hydrophilic high molecular polymer photoinitiator, and the repeated structural unit of hydrophilic high molecular polymer photoinitiator is as follows:
In the formula, m=50-1000, n=50-1000, R ' are selected from hydrogen or contain the alkyl or the hydroxyalkyl of 2-4 carbon atom.
The preparation method of described hydrophilic high molecular polymer photoinitiator may further comprise the steps:
1) preparation of starting raw material 4-ethenylphenyl dichloride phosphine
2) preparation of monomer 4-ethenylphenyl-two (2,4, the 6-trimethylbenzoyl) phosphine oxide
Under the exsiccant nitrogen atmosphere, in toluene, add metallic lithium bits and crystallization naphthalene, stirring at room, reaction mixture becomes aterrimus, continue to stir, drip the toluene solution of 4-ethenylphenyl dichloride phosphine, control reaction temperature is at 20-25 ℃ in the dropping process, dripped in 50 minutes～70 minutes, and continue reaction 0.5 hour～1 hour, then under the ice-water bath cooling and stirring, in reaction mixture, drip 2,4, the toluene solution of 6-tri-methyl chloride dripped in 1.5 hours～2 hours, and at room temperature continue to react 1 hour～1.5 hours, reaction mixture is warmed to 30-40 ℃ then, and the dropping mass percent concentration is 30% aqueous hydrogen peroxide solution under stirring fast, and reacted 0.5 hour～1 hour; Add entry in reaction mixture, stir, filter and separatory, organic phase is 10%NaHCO with mass percent concentration respectively
3Solution and water are respectively washed 2～3 times, anhydrous MgSO
4Dry; After reaching decompression after filtration and down removing solvent, must thick product; Thick product is separated out again through petroleum ether-ethyl acetate, removes solution mutually after vacuum-drying gets faint yellow solid;
3) preparation of acrylic ester copolymer 4-ethenylphenyl-two (2,4,6-trimethylbenzene benzoyl) phosphine oxide
With water, vinylformic acid or acrylate, on go on foot prepared monomer 4-ethenylphenyl-two (2; 4; the 6-trimethylbenzoyl) phosphine oxide and Diisopropyl azodicarboxylate at room temperature mix, and the gained mixture is heated to 60-70 ℃ under stirring fast, reacted 5～7 hours; be cooled to room temperature; through centrifugation, get white copolymer, wash 2～3 times with the petroleum ether-ethyl acetate mixed solvent; through vacuum-drying, get white solid.
Described step 1) is that 4-ethylphenyl dichloride phosphine is through chlorination, high temperature BaCl
2Take off the HCl method under the effect and make 4-ethenylphenyl dichloride phosphine.
Described step 1) is by vinylbenzene and PCl
3At anhydrous AlCl
3Make 4-ethenylphenyl dichloride phosphine under the effect.
Described step 2) be: under the exsiccant nitrogen atmosphere, in 300mL toluene, add metallic lithium bits 0.92mol and crystallization naphthalene 0.008mol, stirring at room 10min, reaction mixture becomes aterrimus, continues to stir; 0.20mol is dissolved in the 120mL toluene with 4-ethenylphenyl dichloride phosphine, the toluene solution that drips 4-ethenylphenyl dichloride phosphine is in above-mentioned solution, control reaction temperature drips about 1 hour at 20-25 ℃ in the dropping process, and continues reaction 0.5 hour; Then under the ice-water bath cooling and stirring, in reaction mixture, drip 2,4, the toluene solution of 6-tri-methyl chloride, described 2,4, the toluene solution of 6-tri-methyl chloride is 2,4, and 6-tri-methyl chloride 0.4mol is dissolved in the 200mL toluene and makes, 1.5 hour drip, and at room temperature continue reaction 1 hour; Reaction mixture is warmed to 30-40 ℃ then, and the dropping mass percent concentration is 30% aqueous hydrogen peroxide solution 0.2mol under stirring fast, and reacted 0.5 hour; Stopped reaction adds 40mL water in reaction mixture, stir, filter and separatory, and organic phase is 10%NaHCO with mass percent concentration respectively
3Solution and water are respectively washed 2 times, anhydrous MgSO
4Drying, after reaching decompression after filtration and down removing solvent, must thick product; Thick product is separated out again through weight ratio 9: 1,120-200mL petroleum ether-ethyl acetate, removes solution mutually after vacuum-drying gets faint yellow solid.
Described step 3) is: with water 50mL, vinylformic acid 10-15g, monomer 4-ethenylphenyl-two (2; 4; the 6-trimethylbenzoyl) phosphine oxide 0.5-0.8g and Diisopropyl azodicarboxylate 0.1-0.2g at room temperature mix; the gained mixture is heated to 60-70 ℃ under stirring fast; reacted 2～6 hours; be cooled to room temperature; through centrifugation; get white copolymer; wash 2 times in order to 2: 1 petroleum ether-ethyl acetate mixed solvent of weight ratio; remove excessive not polymeric acrylate monomer and other impurity,, get white solid through vacuum-drying.
The acrylic ester copolymer 4-ethenylphenyl that the present invention makes-two (2,4,6-trimethylbenzene benzoyl) phosphine oxide has good hydrophilicity and makes stability in storage improve; Macromolecular structure makes does not have chemical transport after the film forming, and the residual smell of filming reduces; Reduce cost.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
One. the preparation of polymer monomer
1) preparation of starting raw material 4-ethenylphenyl dichloride phosphine
4-ethenylphenyl dichloride phosphine can be by literature method (CA:56:46102) by 4-ethylphenyl dichloride phosphine through chlorination, high temperature BaCl
2Taking off the HCl method under the effect makes; Also can adopt other bibliographical information similar approach (J.Chem.Soc.1935,462; J.Chem.Soc.1944,276.) by vinylbenzene and PCl
3At anhydrous AlCl
3Make under the effect.
2) preparation of monomer 4-ethenylphenyl-two (2,4, the 6-trimethylbenzoyl) phosphine oxide
Under the exsiccant nitrogen atmosphere, in 300mL toluene, add the metallic lithium bits (6.5g, 0.92mol) and crystallization naphthalene (1.0g.0.008mol), stirring at room 10min, reaction mixture becomes aterrimus.Continue to stir, (41.0g 0.20mol) is dissolved in the 120mL toluene with 4-ethenylphenyl dichloride phosphine, the toluene solution that drips 4-ethenylphenyl dichloride phosphine is in above-mentioned solution, control reaction temperature drips about 1 hour at 20-25 ℃ in the dropping process, and continues reaction 0.5 hour.Then under the ice-water bath cooling and stirring, in reaction mixture, drip 2,4, the toluene solution of 6-tri-methyl chloride, described 2,4, the toluene solution of 6-tri-methyl chloride is 2,4,6-tri-methyl chloride (73.0g, 0.4mol) be dissolved in the 200mL toluene and make, dripped in 1.5 hours, and at room temperature continue reaction 1 hour.Reaction mixture is warmed to 30-40 ℃ then, and the dropping mass percent concentration is that (23.0g 0.2mol), and reacted 0.5 hour 30% aqueous hydrogen peroxide solution under stirring fast.Stopped reaction.Add 40mL water in reaction mixture, stir, filter and separatory, organic phase is 10%NaHCO with mass percent concentration respectively
3Solution and water are respectively washed 2 times, anhydrous MgSO
4Dry.After reaching decompression after filtration and down removing solvent, must thick product 82.6g.(120-200mL) separate out again, removes solution mutually after vacuum-drying gets faint yellow solid 73.0g (yield 82%), the product structure warp by weight ratio 9: 1 through petroleum ether-ethyl acetate for this thick product
1H,
31P NMR check, purity reaches 95%.
Two. with the preparation of multipolymer-target product acrylic ester copolymer 4-ethenylphenyl-two (2,4,6-trimethylbenzene benzoyl) phosphine oxide (APBPO) of vinylformic acid (ester)
During R '=H, monomer is a vinylformic acid
With vinylformic acid is example:
With water (50mL), vinylformic acid (10g), on go on foot prepared monomer 4-ethenylphenyl-two (2; 4; the 6-trimethylbenzoyl) phosphine oxide (0.5g) and Diisopropyl azodicarboxylate (0.1g) at room temperature mix, and the gained mixture is heated to 60-70 ℃ under stirring fast, reacted 6 hours.Be cooled to room temperature,, get white copolymer, wash (each 10mL) 2 times,, get white solid 9.7g (yield 92%), the product warp through vacuum-drying with petroleum ether-ethyl acetate (2: 1 weight ratios) mixed solvent through centrifugation
1H NMR measures (solvent: DMSO-d
6), the content of photosensitive monomer in multipolymer accounts for 4.9% of weight.After measured, this multipolymer is that solubleness can reach 12g/L (need add NaOH aqueous solution regulator solution pH value) in aqueous medium of 7 at pH, demonstrates better water solubility.
With the ethyl propenoate is example:
With water (50mL), ethyl propenoate (13g), on go on foot prepared monomer 4-ethenylphenyl-two (2; 4; the 6-trimethylbenzoyl) phosphine oxide (0.6g) and Diisopropyl azodicarboxylate (0.2g) at room temperature mix; the gained mixture is heated to 60-70 ℃ under stirring fast, reacted 4 hours.Be cooled to room temperature,, get white copolymer, wash (each 10mL) 2 times,, get white solid 11.2g (yield 81%), the product warp through vacuum-drying with petroleum ether-ethyl acetate (2: 1 weight ratios) mixed solvent through centrifugation
1H NMR measures (solvent: DMSO-d
6), the content of photosensitive monomer in multipolymer accounts for 4.2% of weight.After measured, this multipolymer is solubleness 4g/L (need add NaOH aqueous solution regulator solution pH value) in aqueous medium of 7 at pH, water-soluble decline.
Can certainly select the vinylformic acid glycol ester for use, or the mixture of several acrylate.No longer specifically narrate at this.
Three, the application testing of APBPO in waterborne UV coating
1) test objective: contrast four light-initiated efficiency of initiations
Benzophenone, vapour crust 500, vapour crust 819DW, hydrophilic high molecular polymer photoinitiator (APBPO).
2) test method:
Solidified nature relatively
With 1. benzophenone, 2. vapour crust 500,3. vapour crust 819DW, 4. hydrophilic high molecular polymer photoinitiator (APBPO) is a light trigger, is mixed with corresponding ultraviolet light polymerization varnish preparation.
Table 1
The varnish 1-4 that is mixed with constructs on tinplate with 10 micro wires rod spreader, is cured luminous energy 90mj/cm with 10 meters/minute speed with a power 500W mercury lamp
2Record obtains the surface of good effect and thoroughly solidifies number of times under the needed lamp, the smell maximum be 5 grades, the smell minimum be 1 grade.Huang Du is measured by the full-automatic color difference meter of SC-80C.The result is as shown in table 2
Table 2
| The varnish preparation | All solidify required number of pass times | Oder levels | Huang Du | Store and all solidify required number of pass times after 3 months | Consistency with water |
| Preparation 1 | 5 | 5 | 0.56 | 6 | 5 |
| Preparation 2 | 4 | 3 | 0.55 | 5 | 4 |
| Preparation 3 | 4 | 3 | 0.55 | 4 | 3 |
| Preparation 4 | 2 | 1 | 0.53 | 2 | 1 |
Annotate: 1 is best 5 for the poorest
3) test-results
These results show that the curing speed of compound of the present invention is higher than the curing speed that contrasts initiator.Stink after the varnish of doing light trigger with The compounds of this invention (APBPO) solidifies all is lower than the varnish of making initiator of benzophenone, vapour crust 500, vapour crust 819DW, and the xanthochromia after all varnish curing is also variant.And after the standing storage, with benzophenone and vapour crust 500 varnish of making, all solidifying required number of pass times increases, and initiator wetting ability deficiency is described, that causes initiator after the standing storage separates out the stability of water-based system and the whole drying effect of filming of consistency influence.And vapour crust 819DW makees the varnish of initiator, though efficiency of initiation does not become, smell is also much larger than make the smell that the varnish ultraviolet light polymerization is filmed with APBPO.
4) conclusion
The preparation that the modified oxidized phosphine light trigger of long-chain of the present invention (APBPO) is made; smell, and the consistency of water, curing efficiency, extended storage stability aspect be benzophenone, vapour crust 500, vapour crust 819DW (two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide) make initiator varnish incomparable.Improve the performance of each side, met environmental protection requirement.
Above-described embodiment only is used to illustrate technological thought of the present invention and characteristics, its purpose is to make those skilled in the art can understand content of the present invention and implements according to this, can not only limit claim of the present invention with present embodiment, be equal variation or the modification that all disclosed spirit is done, still drop in the claim of the present invention.
Claims (6)
1. a hydrophilic high molecular polymer photoinitiator is characterized in that, the repeated structural unit of hydrophilic high molecular polymer photoinitiator is as follows:
In the formula, m=50-1000, n=50-1000, R ' are selected from hydrogen or contain the alkyl or the hydroxyalkyl of 2-4 carbon atom.
2. the preparation method of hydrophilic high molecular polymer photoinitiator as claimed in claim 1 is characterized in that, may further comprise the steps:
1) preparation of starting raw material 4-ethenylphenyl dichloride phosphine
2) preparation of monomer 4-ethenylphenyl-two (2,4, the 6-trimethylbenzoyl) phosphine oxide
Under the exsiccant nitrogen atmosphere, in toluene, add metallic lithium bits and crystallization naphthalene, stirring at room, reaction mixture becomes aterrimus, continue to stir, drip the toluene solution of 4-ethenylphenyl dichloride phosphine, control reaction temperature is at 20-25 ℃ in the dropping process, dripped in 50 minutes～70 minutes, and continue reaction 0.5 hour～1 hour, then under the ice-water bath cooling and stirring, in reaction mixture, drip 2,4, the toluene solution of 6-tri-methyl chloride dripped in 1.5 hours～2 hours, and at room temperature continue to react 1 hour～1.5 hours, reaction mixture is warmed to 30-40 ℃ then, and the dropping mass percent concentration is 30% aqueous hydrogen peroxide solution under stirring fast, and reacted 0.5 hour～1 hour; Add entry in reaction mixture, stir, filter and separatory, organic phase is 10%NaHCO with mass percent concentration respectively
3Solution and water are respectively washed 2～3 times, anhydrous MgSO
4Dry; After reaching decompression after filtration and down removing solvent, must thick product; Thick product is separated out again through petroleum ether-ethyl acetate, removes solution mutually after vacuum-drying gets faint yellow solid;
3) preparation of acrylic ester copolymer 4-ethenylphenyl-two (2,4,6-trimethylbenzene benzoyl) phosphine oxide
With water, vinylformic acid or acrylate, on go on foot prepared monomer 4-ethenylphenyl-two (2; 4; the 6-trimethylbenzoyl) phosphine oxide and Diisopropyl azodicarboxylate at room temperature mix, and the gained mixture is heated to 60-70 ℃ under stirring fast, reacted 5～7 hours; be cooled to room temperature; through centrifugation, get white copolymer, wash 2～3 times with the petroleum ether-ethyl acetate mixed solvent; through vacuum-drying, get white solid.
3. the preparation method of hydrophilic high molecular polymer photoinitiator according to claim 2 is characterized in that, described step 1) is that 4-ethylphenyl dichloride phosphine is through chlorination, high temperature BaCl
2Take off the HCl method under the effect and make 4-ethenylphenyl dichloride phosphine.
4. the preparation method of hydrophilic high molecular polymer photoinitiator according to claim 2 is characterized in that, described step 1) is by vinylbenzene and PCl
3At anhydrous AlCl
3Make 4-ethenylphenyl dichloride phosphine under the effect.
5. the preparation method of hydrophilic high molecular polymer photoinitiator according to claim 2, it is characterized in that, described step 2) is: under the exsiccant nitrogen atmosphere, in 300mL toluene, add metallic lithium bits 0.92mol and crystallization naphthalene 0.008mol, stirring at room 10min, reaction mixture becomes aterrimus, continues to stir; 0.20mol is dissolved in the 120mL toluene with 4-ethenylphenyl dichloride phosphine, and the toluene solution that drips 4-ethenylphenyl dichloride phosphine is in above-mentioned solution, and control reaction temperature dripped at 20-25 ℃ in 1 hour in the dropping process, and continued reaction 0.5 hour; Then under the ice-water bath cooling and stirring, in reaction mixture, drip 2,4, the toluene solution of 6-tri-methyl chloride, described 2,4, the toluene solution of 6-tri-methyl chloride is 2,4, and 6-tri-methyl chloride 0.4mol is dissolved in the 200mL toluene and makes, 1.5 hour drip, and at room temperature continue reaction 1 hour; Reaction mixture is warmed to 30-40 ℃ then, and the dropping mass percent concentration is 30% aqueous hydrogen peroxide solution 0.2mol under stirring fast, and reacted 0.5 hour; Stopped reaction adds 40mL water in reaction mixture, stir, filter and separatory, and organic phase is 10%NaHCO with mass percent concentration respectively
3Solution and water are respectively washed 2 times, anhydrous MgSO
4Drying, after reaching decompression after filtration and down removing solvent, must thick product; Thick product is separated out again through weight ratio 9: 1,120-200mL petroleum ether-ethyl acetate, removes solution mutually after vacuum-drying gets faint yellow solid.
6. the preparation method of hydrophilic high molecular polymer photoinitiator according to claim 5; it is characterized in that; described step 3) is: with water 50mL; vinylformic acid 10-15g; monomer 4-ethenylphenyl-two (2; 4; the 6-trimethylbenzoyl) phosphine oxide 0.5-0.8g and Diisopropyl azodicarboxylate 0.1-0.2g at room temperature mix; the gained mixture is heated to 60-70 ℃ under stirring fast; reacted 2～6 hours; be cooled to room temperature,, get white copolymer through centrifugation; wash 2 times in order to 2: 1 petroleum ether-ethyl acetate mixed solvent of weight ratio; remove excessive not polymeric acrylate monomer and other impurity,, get white solid through vacuum-drying.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014051026A1 (en) * | 2012-09-27 | 2014-04-03 | 富士フイルム株式会社 | Ink composition, ink jet recording method, printed material, bisacyl phosphine oxide compound, and monoacyl phosphine oxide compound |
| JP2014185319A (en) * | 2013-02-21 | 2014-10-02 | Fujifilm Corp | Ink composition, inkjet recording method, printed matter and polymer initiator |
| CN105837731A (en) * | 2016-03-30 | 2016-08-10 | 天津市裕北涂料有限公司 | Macromolecular photoinitiator and preparation method thereof |
| CN110144020A (en) * | 2019-06-11 | 2019-08-20 | 长沙新宇高分子科技有限公司 | A kind of Beta-cyclodextrin-based photoinitiator, preparation method and application |
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| CN1348470A (en) * | 1999-03-16 | 2002-05-08 | 法玛西雅格罗宁根有限公司 | Hydrophilic macromolecular compounds |
| CN100436461C (en) * | 2003-07-31 | 2008-11-26 | 巴斯福股份公司 | A process for the preparation of acylphosphines |
| WO2009068590A1 (en) * | 2007-11-29 | 2009-06-04 | Agfa Graphics Nv | Preparation method of copolymerizable photoinitiators |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1348470A (en) * | 1999-03-16 | 2002-05-08 | 法玛西雅格罗宁根有限公司 | Hydrophilic macromolecular compounds |
| CN100436461C (en) * | 2003-07-31 | 2008-11-26 | 巴斯福股份公司 | A process for the preparation of acylphosphines |
| WO2009068590A1 (en) * | 2007-11-29 | 2009-06-04 | Agfa Graphics Nv | Preparation method of copolymerizable photoinitiators |
Non-Patent Citations (1)
| Title |
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| 《Journal of Applied Polymer Science》 19940103 LUIGI ANGIOLINI et al POLYMERIC PHOTOINITIATORS BEARING SIDE-CHAIN BENZOYLDIPHENYLPHOSPHINOXIDE MOIETIES FOR UV CURABLE COATINGS. 第51卷, * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014051026A1 (en) * | 2012-09-27 | 2014-04-03 | 富士フイルム株式会社 | Ink composition, ink jet recording method, printed material, bisacyl phosphine oxide compound, and monoacyl phosphine oxide compound |
| JP2014185319A (en) * | 2013-02-21 | 2014-10-02 | Fujifilm Corp | Ink composition, inkjet recording method, printed matter and polymer initiator |
| EP2960303A4 (en) * | 2013-02-21 | 2016-04-13 | Fujifilm Corp | Ink composition, inkjet recording method, printed matter, and high-molecular-weight polymerization initiator |
| US9902865B2 (en) | 2013-02-21 | 2018-02-27 | Fujifilm Corporation | Ink composition, inkjet recording method, printed matter, and high-molecular-weight polymerization initiator |
| CN105837731A (en) * | 2016-03-30 | 2016-08-10 | 天津市裕北涂料有限公司 | Macromolecular photoinitiator and preparation method thereof |
| CN110144020A (en) * | 2019-06-11 | 2019-08-20 | 长沙新宇高分子科技有限公司 | A kind of Beta-cyclodextrin-based photoinitiator, preparation method and application |
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| CN102241792B (en) | 2012-12-12 |
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