CN101717362A - Novel light initiator - Google Patents
Novel light initiator Download PDFInfo
- Publication number
- CN101717362A CN101717362A CN200910186601A CN200910186601A CN101717362A CN 101717362 A CN101717362 A CN 101717362A CN 200910186601 A CN200910186601 A CN 200910186601A CN 200910186601 A CN200910186601 A CN 200910186601A CN 101717362 A CN101717362 A CN 101717362A
- Authority
- CN
- China
- Prior art keywords
- light trigger
- light initiator
- independently
- light
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Indole Compounds (AREA)
Abstract
The invention relates to a novel light initiator. On the basis of traditional oxime ester compound, another group of diphenyl ketone is initiated. The newly added diphenyl ketone broadens the application range of the light initiator and increases the solubility between the light initiator and a prepolymer. Thus, the invention provides better light initiating effect and stability for compounds.
Description
Technical field
The invention belongs to the light trigger field, particularly relate to a kind of light trigger with oxime ester structure.
Background technology
Light trigger is one of indispensable component of ultraviolet hardening material (main photo-curing material of being made up of unsaturated polyester and monomer material thereof, make it under UV-light, X ray or laser radiation, polymerization curing reaction take place, essential light trigger or the sensitizing agent of adding), sensitivity plays a decisive role to photocuring system for it.Because photo-curing material solvent-free volatilization when solidifying greatly reduce the pollution to environment, thereby photocuring technology obtains vigorous growth in recent years as a kind of eco-friendly green technology.As the important component part of photo-curing material, the effect of light trigger is to produce active free radical or positively charged ion, the polymerization of initiation or corresponding monomer of catalysis or prepolymer after absorbing the luminous energy of certain wavelength.As light trigger, need meet following condition usually: the 1. quantum yield height of Yin Faing; 2. the commensurate in scope of absorption spectrum is in radiation source; 3. Heat stability is good, no dark reaction: 4. consistency is preferably arranged with monomer and prepolymer; 5. the photocuring film forming does not have xanthochromia or variable color; 6. safe and economical.
Put down in writing some oxime ester compounds in the documents such as U.S. Pat 3558309, US 6485885, US2001012596 and European patent EP 810595 and had reactive behavior preferably as light trigger.But, in the practical application in light polymerization technique field, need some reactive behavioies good, be easy to the light trigger of suitability for industrialized production.For example, in order to obtain the high color capability and performance, need to add tinting material in colour filter resist application facet.Along with pigment content increases, it is difficult more that the curing of coloured resist becomes.Thereby need have the more light trigger of hypersensitivity than present initiator system.In addition, this new light trigger also must satisfy under for example hot temperature of industrial relevance matter and the high request of stability in storage.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of novel photoinitiator is provided.
For solving above technical problem, the present invention takes following technical scheme to be:
Compound with general formula (I):
Wherein, R
1, R
2Be unsubstituted or independently optionally by one or more phenyl, halogen, OR
9, SR
9, NO
2, CN, morpholinyl, SO
3R
9Or NR
10R
11The C that replaces
1～C
20Aliphatic group or C
1～C
20Alkoxyl group; Or R
1, R
2Be phenyl independently, it is not substituted or by one or more C
1～C
12Alkyl, phenyl, halogen, OR
9, SR
9, NO
2, CN, morpholinyl, SO
3R
9Or NR
10R
11Replace;
R
3, R
4, R
5, R
6, R
7, R
8Be hydrogen, C independently of one another
1～C
8Alkyl, C
1～C
6Alkoxyl group, phenyl, CN, NO
2Or benzoyl;
R
9, R
10, R
11Be C independently of one another
1～C
8Alkyl.
According to preferred version a: R of the present invention
1, R
2Be C
1～C
12Aliphatic group, more preferably C
1～C
6Aliphatic group, in most typical embodiment, R
1, R
2Be methyl or ethyl.
According to another preferred version of the present invention: R
4, R
5, R
6, R
7, R
8Be hydrogen.
Those of ordinary skill in the art should understand how to obtain compound of the present invention according to existing synthetic method and means.But preferably come to synthesize The compounds of this invention as follows:
At first obtain N-substituted carbazole-3-and replace (substituted 4-benzoyl)-6-ketoxime, react under the organic bases condition by described ketoxime and substituted benzophenone formyl chloride then and produce compound of the present invention.These methods will be explained in detail in the following embodiments.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
The compounds of this invention has been introduced another group benzophenone base on the basis of traditional oxime ester compound, newly-increased benzophenone base has been widened the range of application of light trigger, increase the intermiscibility of light trigger and prepolymer, thereby made compound have better light-initiated effect and stability.
Description of drawings
Fig. 1 is the proton magnetic spectrum figure of embodiment 1 light trigger.
Embodiment
Below the specific embodiment of the present invention is described, but be not limited to these embodiment.
Embodiment 1
According to the light trigger of present embodiment, structural formula is as follows:
The above-claimed cpd synthesis step is as follows:
(1), synthetic N-ethyl carbazole-6-o-methyl-benzene formyl radical-3-ethyl ketone oxime:
1., in the four-hole bottle of 500ml, add 58.5g (0.3mol) N-ethyl carbazole, 40g (0.3mol) AlCl
3And the 200ml methylene dichloride, drip o-methyl-benzene formyl chloride 46.35g (0.3mol), color burn during dropping down at 0～-5 ℃, become green, dropwise, reacted sampling analysis 2 hours, product content is greater than 98%, add aluminum chloride 40g, at 10 ℃～15 ℃ Acetyl Chloride 98Min.s that drip 28.6g (0.36mol) down, after adding, finish reaction about 2 hours, HPLC detects purity 95.00%.Pour reaction product in 300ml water hydrolysis, water 300ml washes 2 times, is washed till pH6～7 with aqueous sodium carbonate again, color is a yellow-green colour, reclaims methylene dichloride, adds 300ml methyl alcohol, be cooled to 20 ℃, filter, 60 ℃ of dryings obtain white virellous crystallization 88.4g, calculated yield 83%, purity 98% (HPLC), fusing point, 161.9 ℃.
2., in the reaction flask of 500ml, add the 1. gained crystallization of 53.5g step, oxammonium hydrochloride 12.51g, sodium-acetate 14.76g and methyl alcohol 300ml, back flow reaction 5～6 hours, sampling analysis, during product content 97%, reaction finishes.Be cooled to 25 ℃, filter, 60 ℃ of dryings obtain white powdery solid 50.4g and are N-ethyl carbazole-6-o-methyl-benzene formyl radical-3-ethyl ketone oxime, and calculated yield is greater than 91%, and purity is greater than 98% (HPLC), fusing point, 169.2 ℃.
(2), the light trigger that synthesizes present embodiment by step (1) gained N-ethyl carbazole-6-o-methyl-benzene formyl radical-3-ethyl ketone oxime:
In the reaction flask of 500ml, add N-ethyl carbazole-6-o-methyl-benzene formyl radical-3-ethyl ketone oxime 100 grams; toluene 500ml; triethylamine 32.3 grams, the 2# catalyzer is a small amount of, is cooled to 0～5 ℃; in feed liquid, drip the toluene solution of o-benzoyl Benzoyl chloride; keep 5～10 ℃ of droppings, 3 hours dropping time is after dropwising; keep 5～10 ℃ to stir sampling after 3～5 hours, qualified after.Prepare hydrolysis, the water of adding 200ml is warming up to 30～35 ℃ in the reaction flask, the washing, layering, anhydrate mutually after, organic phase is washed 2 times again, and each water 200ml tells organic phase, reclaim solvent to the heavy 200g of material, be cooled to 10 ℃, filter crude product, content 98%, wet feed are used 30 ℃ of washings of 200g methyl alcohol once again, be cooled to 20 ℃ filter crude product, the dry target product 98g that must can be used as light trigger, content 98.3%, yield 67%.Fusing point is 192～193 ℃, and its nuclear magnetic spectrogram as shown in Figure 1.
Embodiment 2
According to the light trigger of present embodiment, structural formula is as follows:
The above-claimed cpd synthesis step is as follows: it makes by following step of carrying out successively:
(1), prepares N-ethyl carbazole-6-o-methyl-benzene formyl radical-3-ethyl ketone oxime by the method identical with embodiment 1;
(2), the light trigger that synthesizes present embodiment by step (1) gained N-ethyl carbazole-6-o-methyl-benzene formyl radical-3-ethyl ketone oxime:
In the reaction flask of 500ml, add N-ethyl carbazole-6-o-methyl-benzene formyl radical-3-ethyl ketone oxime 100 grams; toluene 500ml, triethylamine 32.3 grams, the 2# catalyzer is a small amount of; be cooled to 0～5 ℃; in feed liquid, drip toluene solution, keep 5～10 ℃ of droppings, 3 hours dropping time methoxyl group o-benzoyl Benzoyl chloride; after dropwising; after dropwising, keep the 5-10 degree to stir sampling after 3～5 hours, qualified after.Prepare hydrolysis
Add the water of 200ml in the reaction flask, be warming up to 30～35 ℃, washing, layering, anhydrate mutually after, organic phase is washed 2 times again, each water 200ml tells organic phase, reclaims solvent to the heavy 200g of material, be cooled to 10 ℃, filter crude product, content 98%, wet feed is used 30 ℃ of washings of 200g methyl alcohol once again, be cooled to 20 ℃ filter crude product, the dry target product 99g that must can be used as light trigger, content 98.7%, yield 66%.
The photosensitivity test
1., be used for the preparation of the sample composition of photosensitivity test:
The 1# sample: (weight ratio of benzyl methacrylate and methacrylic acid is 4: 1 by the solution of the propylene glycol 1-monomethyl ether 2-acetic ester of 300 weight part benzyl methacrylates and Sipacril 2739OF for it, the content of multipolymer is 25%), 100 parts of dipentaerythritol acrylates (DPHA), 4 parts of light trigger OXE-02 (the novel oxime ester lightlike initiating agent of vapour Bagong department, CAS registration number are 478556-66-0) mix.
The 2# sample: its light trigger by solution (weight ratio of benzyl methacrylate and methacrylic acid is 4: 1, and the content of multipolymer is 25%), 100 parts of dipentaerythritol acrylates (DPHA) and 2.7 parts of embodiment 1 of the propylene glycol 1-monomethyl ether 2-acetic ester of 300 weight part benzyl methacrylates and Sipacril 2739OF mixes.
The 3# sample: its light trigger by solution (weight ratio of benzyl methacrylate and methacrylic acid is 4: 1, and the content of multipolymer is 25%), 100 parts of dipentaerythritol acrylates (DPHA) and 2.7 parts of embodiment 2 of the propylene glycol 1-monomethyl ether 2-acetic ester of 300 weight part benzyl methacrylates and Sipacril 2739OF mixes.
2., photosensitive test: all operations are all implemented under gold-tinted.Utilize electronic applicator that 1# sample composition and 2# sample composition are dragged respectively and be coated on the aluminium sheet, heating 3min drives solvent away in 100 ℃ convection furnace.Build is about 2 microns, puts the stdn test negativity film with the different optical density(OD) of 21 stagewise, and the clearance between film and the resist is 100 microns.Adopt the 250W ultrahigh pressure mercury lamp to expose in the 15cm distance.Total exposure dosage is 1000mj/cm
2(according to light power meter (ORCUV Light Measure Model UV-M02, having the UV-35 detector obtains the mensuration of testing the negativity film) exposed film, the film of exposure adopts 100 seconds (WALTER LEMMEN MODE T21) of spray-type developers development with 1～2% aqueous sodium carbonate at 30 ℃.The highest ladder numerical representation method that the photosensitivity of the initiator system that uses is left with the back of developing.Step values is high more, show tested sample to experience luminosity just high more.The results are shown in Table 1.
Table 1
| Sample | Light sensitivity ladder number |
| ??1# | ??20 |
| ??2# | ??20 |
| ??3# | ??20 |
As seen from Table 1, the embodiment of the invention 1,2 usage quantitys only for 70% o'clock of contrast light trigger OXE-02 usage quantity, can reach identical photosensitive effect, thereby the present invention have more excellent photosensitive property.
Above-described embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; under the prerequisite of original intention of the present invention; those skilled in the art all should be in the protection domain of claims of the present invention to the modification and the improvement of technical solution of the present invention.
Claims (6)
1. the compound that has general formula (I):
Wherein, R
1, R
2Be unsubstituted or independently optionally by one or more phenyl, halogen, OR
9, SR
9, NO
2, CN, morpholinyl, SO
3R
9Or NR
10R
11The C that replaces
1～C
20Aliphatic group or C
1～C
20Alkoxyl group; Or R
1, R
2Be phenyl independently, it is not substituted or by one or more C
1～C
12Alkyl, phenyl, halogen, OR
9, SR
9, NO
2, CN, morpholinyl, SO
3R
9Or NR
10R
11Replace;
R
3, R
4, R
5, R
6, R
7, R
8Be hydrogen, C independently of one another
1～C
8Alkyl, C
1～C
6Alkoxyl group, phenyl, CN, NO
2Or benzoyl;
R
9, R
10, R
11Be C independently of one another
1～C
8Alkyl.
2. compound according to claim 1 is characterized in that: R
1, R
2Be C
1～C
12Aliphatic group.
3. compound according to claim 2 is characterized in that: R
1, R
2Be C
1～C
6Aliphatic group.
4. compound according to claim 3 is characterized in that: R
1, R
2Be methyl or ethyl independently.
5. compound according to claim 1 is characterized in that: R
4, R
5, R
6, R
7, R
8Be hydrogen.
In the claim 1 to 5 each described compound as the purposes of light trigger.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101866015A CN101717362B (en) | 2009-11-25 | 2009-11-25 | Novel light initiator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101866015A CN101717362B (en) | 2009-11-25 | 2009-11-25 | Novel light initiator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101717362A true CN101717362A (en) | 2010-06-02 |
| CN101717362B CN101717362B (en) | 2012-01-04 |
Family
ID=42432006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101866015A Active CN101717362B (en) | 2009-11-25 | 2009-11-25 | Novel light initiator |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101717362B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012068879A1 (en) * | 2010-11-23 | 2012-05-31 | 常州强力先端电子材料有限公司 | High photosensibility carbazole oxime ester photoinitiator,preparation and use thereof |
| CN103204960A (en) * | 2012-12-28 | 2013-07-17 | 南通缔威化工有限公司 | Novel tertiary-amine oxime ester photoinitiator and preparation method thereof |
| CN105504105A (en) * | 2015-12-31 | 2016-04-20 | 天津英吉诺科技有限公司 | Oxime ester photoinitiator and preparation method thereof |
| CN106478843A (en) * | 2016-09-21 | 2017-03-08 | 同济大学 | A kind of double oxime ester lightlike initiating agents containing thiphene ring and its preparation method and application |
| CN108864326A (en) * | 2017-05-12 | 2018-11-23 | 湖北固润科技股份有限公司 | Photocurable composition and its application |
| CN108864136A (en) * | 2017-05-12 | 2018-11-23 | 湖北固润科技股份有限公司 | 3,4- ethylenedioxy thiophene derivative and its preparation method and application |
-
2009
- 2009-11-25 CN CN2009101866015A patent/CN101717362B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012068879A1 (en) * | 2010-11-23 | 2012-05-31 | 常州强力先端电子材料有限公司 | High photosensibility carbazole oxime ester photoinitiator,preparation and use thereof |
| CN103204960A (en) * | 2012-12-28 | 2013-07-17 | 南通缔威化工有限公司 | Novel tertiary-amine oxime ester photoinitiator and preparation method thereof |
| CN105504105A (en) * | 2015-12-31 | 2016-04-20 | 天津英吉诺科技有限公司 | Oxime ester photoinitiator and preparation method thereof |
| CN106478843A (en) * | 2016-09-21 | 2017-03-08 | 同济大学 | A kind of double oxime ester lightlike initiating agents containing thiphene ring and its preparation method and application |
| CN108864326A (en) * | 2017-05-12 | 2018-11-23 | 湖北固润科技股份有限公司 | Photocurable composition and its application |
| CN108864136A (en) * | 2017-05-12 | 2018-11-23 | 湖北固润科技股份有限公司 | 3,4- ethylenedioxy thiophene derivative and its preparation method and application |
| CN108864136B (en) * | 2017-05-12 | 2020-04-24 | 湖北固润科技股份有限公司 | 3, 4-ethylenedioxythiophene derivative and preparation method and application thereof |
| CN108864326B (en) * | 2017-05-12 | 2020-10-13 | 湖北固润科技股份有限公司 | Photocurable composition and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101717362B (en) | 2012-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102020727B (en) | Pyrazole oxime ester photoinitiator with high photosensibility, preparation method and application thereof | |
| CN101717362B (en) | Novel light initiator | |
| EP2845845B1 (en) | Novel oximester fluorine compound, and photopolymerization initiator and photoresist composition comprising same | |
| JP2019528331A (en) | Fluorene photoinitiator, method for producing the same, photocurable composition having the same, and use of fluorene photoinitiator in the field of photocuring | |
| CN103130919B (en) | Carbazole ketone oxime ester high-photosensibility photoinitiator | |
| CN110066225B (en) | Dioxime ester photoinitiator, preparation method, photosensitive resin composition and application | |
| CN101130518A (en) | Ionic liquid photo generated base alkaline agent, preparing method and uses of the same | |
| TW201838968A (en) | Fluorine oxime ester photoinitiator containing polymerisable group, method for preparing the same and the use thereof | |
| CN102492060B (en) | Photoinitiator of diphenyl sulfide oxime esters as well as preparation method and application thereof | |
| JP2013134263A (en) | Photosensitive resin composition for black column spacer, black column spacer, display device, and method for forming black column spacer | |
| CN105085718B (en) | Pyrazoline oxime ester photoinitiator, method for preparing same and application of pyrazoline oxime ester photoinitiator | |
| CN103130833A (en) | Soluble oxime ester and aromatic ketone photo polymerization initiator | |
| WO2020253283A1 (en) | Novel diaroyl carbazole compound and use thereof as sensitising agent | |
| WO2023169520A1 (en) | Use of arylvinyl a-carbonyl acid ester compound as photoinitiator in led photopolymerization and preparation method therefor | |
| CN109503735A (en) | Photoinitiator, the Photocurable composition comprising it and its application | |
| WO2016192610A1 (en) | Acyloxime ester compound used for uv curing material, synthesis method of same, and application of same | |
| CN106478843B (en) | A kind of double oxime ester lightlike initiating agents containing thiphene ring and its preparation method and application | |
| KR101469519B1 (en) | Oxim ester Compound, and Photopolymerization initiator Comprising the Same | |
| WO2021023144A1 (en) | Fluorenoxime ester compound, preparation method therefor, and application thereof | |
| JP6999039B2 (en) | Fluorine-containing fluorene oxime ester-based photoinitiator, photo-curing composition containing it, and its application | |
| WO2016192611A1 (en) | Oxime ester compound, synthesis method of same, and application of same | |
| CN109957046A (en) | Fluorine-containing fluorenes oxime ester lightlike initiating agent, the Photocurable composition comprising it and its application | |
| CN110066352B (en) | Oxime ester photoinitiator, preparation method, photosensitive resin composition and application | |
| CN101723875A (en) | Light trigger | |
| TWI745897B (en) | Photoinitiator composition comprising acylcarbazole derivative and carbazole oxime ester and application thereof in photocurable composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 215421 Shaxi Town, Taicang, Jiangsu Province, Sha Lu Road Patentee after: Excellent new material technology (Suzhou) Co., Ltd. Address before: 215421 Shaxi Town, Taicang, Jiangsu Province, Sha Lu Road Patentee before: Eutec Fine Chemical (Suzhou) Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220120 Address after: 215334 building 6, Huamin Shijia garden, Kunshan Development Zone, Suzhou, Jiangsu Patentee after: Jiangsu yushida New Material Technology Co.,Ltd. Address before: 215421 Taicang, Jiangsu province Shaxi town sand deer Road Patentee before: YOUDI NEW MATERIAL TECHNOLOGY (SUZHOU) Co.,Ltd. |
|
| TR01 | Transfer of patent right |