CN105199018B - Oxime ester photoinitiator as well as preparation and application thereof - Google Patents
Oxime ester photoinitiator as well as preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a novel oxime ester photoinitiator shown as general formulae I and II as well as preparation and an application thereof. The photoinitiator has excellent storage stability, photographic sensitivity, developing performance, pattern integrity and the like.
Description
Technical field
The present invention relates to a kind of new oxime ester lightlike initiating agent, their preparation method, and such compound are used as alkene
The photopolymerization initiator of ethylenically unsaturated compounds system.
Background technology
The photochemical properties of oxime ester compound of Awernerl reported firsts in 1904, oxime esters chemical combination starts within 1970
It is used as light trigger, wherein O-acyl-oxime ester lightlike initiating agent Quantacure PDO（Formulas I）Once by widespread commercial application,
But as its heat endurance is poor, and gradually it is eliminated.Oxime ester compound Recent study is enlivened, and prior art is for example：
Macromol. Symp.2004,217,77；Patent CN101014569A, CN101321727A, CN101679394A,
CN101687794A, CN99108598, CN02811675, CN1800885A, CN1928716A, CN101158812A,
CN101525393A, CN101634807A, and WO2008138733A1, WO0052530A1, WO2007071497A1,
WO2009019173A1, WO2009147031A2, WO2009147033A1 etc. describe the oxime ester of some carbazole structures and phase
Close the oxime ester side chain dimer type compound of structure.Business-like oxime ester compound photoinitiator is occurred in that on this basis
OXE 01 and OXE 02, these compound groups into light sensitivity system particularly have sensitive response to 405 or 365 nanometers of light,
Field is made in the BM and RGB of giant-screen LCD display an important application, the product of similar nature also have CN101565472B and
Oxime ester 305 and 304 disclosed in CN101508744B.Light trigger disclosed in these can meet currently displaying face to varying degrees
The general application requirement of the curing field such as plate and colored filter.
But, the development of electronics technology is maked rapid progress, and existing procucts start to manifest deficiency, product in some applications
Update requirements at the higher level are proposed to light trigger also.For example, the photic erosion agent for being applied to gap control material at present is more
Heat resistance is not good, baking or easily subsides during encapsulation procedure and causes clearance material shrink, and in the processing procedures such as coating, exposure imaging
Deliberately the height of extra clearance control material can increase its cost, and heat blend-out small molecule when subsiding of being heated will pollute liquid crystal.
And for example, in the making of high-end colored filter, one side light trigger need to meet highly dissoluble, good thermal stability it is basic
Require, on the other hand, the qualitative performance requirements of its high color need the highly colored resists of Jing, and with the increasing of pigment content
Plus, the solidification of color resist becomes more difficult, and after its solidification, the definition of image, integrity degree also have higher requirement,
This is accomplished by the initiator of more ISO to solve the above problems.
In curing field, with high photosensitivity, stability it is high, and easily prepared light trigger is still the field
Development is first-selected, and researches and develops the light trigger with higher performance and will be always a core work in the field.
The content of the invention
It is an object of the invention to provide a kind of new oxime ester lightlike initiating agent of excellent performance and its preparation and application.The light
Initiator is not only in aspect excellent performances such as storage stability, speed, aobvious recessive and pattern integrities, and draws with similar light
Send out agent to compare, show the speed and heat endurance for significantly improving.
The present invention realizes that the technical scheme of purpose is as follows：
New oxime ester lightlike initiating agent, which has such as formula I, II：
Wherein,
N=1 or 2；
R1、R2、R3Can be the same or different, be independently selected from the straight or branched alkyl of C1-C20, C3-C8 cycloalkyl,
C7-C10 phenyl substituted alkyls；
R4、R5、R6Can be the same or different, be independently selected from the straight or branched alkyl of C1-C20, C3-C8 cycloalkyl,
The alkyl of C6-C20 aryl, wherein C1-C20 is unsubstituted or is replaced by one or more halogens, phenyl, alkoxyl.
As the preferred version of the present invention, the new oxime ester lightlike initiating agent of above-mentioned formula I, II：
R1、R2、R3It is independently selected from the straight or branched alkyl for being independently expressed as C1-C5, C5-C6 cycloalkyl, C7-C10 benzene
Base replaces alkyl；
R4、R5、R6It is independently selected from the straight or branched alkyl of C1-C5, C3-C8 cycloalkyl, wherein C6-C10 aryl, C1-
The alkyl of C20 is unsubstituted or is replaced by one or more halogens, phenyl, alkoxyl.
The invention further relates to the preparation method of the new oxime ester lightlike initiating agent of above-mentioned formula I, II, comprises the following steps：
1）With triphenylphosphine as raw material, it is acylated on phenyl under the catalysis of alchlor, ferric trichloride or zinc chloride；
2）The acylated product for obtaining obtains phosphine oxide intermediate through oxidation；
3）Phosphine oxide intermediate in the presence of hydrogen chloride, sodium alkoxide or potassium alcoholate with nitrites（Such as：Nitrous ether (ethyl nitrite), Asia
Different monooctyl ester of isoamyl nitrate, nitrous acid etc.）Or nitrite（Such as natrium nitrosum, potassium nitrite etc.）Carry out oximation reaction；
4）The product oxime that oximation reaction is obtained is with acyl chloride reaction into oxime ester；
。
N and R1、R2、R3、R4、R5、R6It is as defined above.
In above-mentioned preparation method, the raw material for using is known compound of the prior art, commercially available or logical
Cross known synthetic method to be prepared from.The preparation method is simple, does not produce contaminative discarded object, and product is pure in preparation process
Degree is high, and yield is good, it is adaptable to industrialized mass production.
The invention further relates to the new oxime ester lightlike initiating agent shown in above-mentioned formula I, II includes in Photocurable composition：
a）At least one olefinic unsaturation photopolymerizable compound and
b）As the compound of at least one formula I, II of light trigger.
Compound containing ethylenical unsaturated double bonds can contain one or more double bonds.They can be low-molecular-weight（It is single
Body）Or relatively high molecular weight（Oligomer）.Double bond containing Exemplary monomers are wrapped for alkyl or hydroxy alkyl acrylate or methyl
Acrylate, for example, methyl, ethyl, butyl, 2- ethylhexyls-or 2- hydroxyethylmethacry,ates, isobornyl acid
Ester, or methacrylic acid methyl or ethyl ester；Silicone acrylate；Acrylamide, Methacrylamide, what N- replaced
（Methyl）Acrylamide；Vinyl esters such as vinyl acetate, vinyl ethers such as isobutylvinyl ether, styrene, alkyl-and halo
Styrene, NVP, vinyl chloride or vinylidene chloride.
Monomer containing two or more double bonds such as ethylene glycol, propane diols, neopentyl ethylene glycol, 1,6- hexylene glycol and bisphenol-A
Diacrylate, 4,4 '-bis-（2- acryloyloxyethoxies）Diphenyl propane, trimethylolpropane trimethacrylate, season
Penta tetrol triacrylate or tetraacrylate, ethylene propylene acid esters, divinylbenzene, divinyl succinate, adjacent benzene
Dioctyl phthalate diallyl ester, phosphoric acid triallyl ester, isocyanuric acid triallyl ester and isocyanuric acid three（2- acryloyl ethyls）
Ester.
With relatively high molecular weight（Oligomer）The example of polyunsaturated compounds is the epoxy resin of propylene acidifying and gathers
Ether, polyurethanes；Propylene is acidified or the polyester containing vinyl ether group or epoxy radicals.Unsaturated oligomers can also be insatiable hunger
And polyester resin, they are have maleic acid mostly, prepared by phthalic acid and one or more glycol and with about
The molecular weight of 500-3000.Alternatively, it is also possible to using vinyl ether monomers and vinyl ether oligomers, and with maleate as end
End, the oligomer with polyester, polyurethanes, polyethers, polyvinylether and epoxy main chains.
Alefinically unsaturated compounds can also be the ester of ethylenically unsaturated carboxylic acids and polyalcohol epoxide, and in main chain
Or the polymer containing ethylenically unsaturated group on side chain radical, such as unsaturated polyester (UP), polyamide or polyurethanes and its altogether
Polymers, polybutadiene or butadiene copolymer, polyisoprene and isoprene copolymer, contain on side chain（Methyl）Acrylic acid
The polymer and copolymer of base, contains on side chain（Methyl）The polymer and copolymer of acrylic, and one or more this gather
The mixture of compound.
The example of unsaturated carboxylic acid is acrylic acid, methacrylic acid, butenoic acid, methylene-succinic acid, cinnamic acid and insatiable hunger
With aliphatic acid such as leukotrienes and oleic acid.It is preferred that acrylic acid and methacrylic acid.
Suitable polyalcohol is aromatic polyol in particular aliphatic and Cycloaliphatic polyols.Aromatic polyol such as hydrogen
Quinone, 4,4 '-dihydroxydiphenyl, 2,2- bis-（4- hydroxy phenyls）Propane, and（Line style）Novolaks and phenol-formaldehyde A.Fat
Race and Cycloaliphatic polyols such as aklylene glycol, preferably C2-12, such as ethylene glycol, 1,2- or 1,3-PD, 1,2-, 1,3-
Or 1,4- butanediols, pentanediol, hexylene glycol, ethohexadiol, 12 carbon alkane glycol, diethylene glycol (DEG), triethylene glycol, molecular weight are preferably 200-
1500 polyethylene glycol, 1,3- ring pentanediols, 1,2-, 1,3- or 1,4- cyclohexanediol, 1,4- hydroxymethyl-cyclohexanes, glycerine,
Pentaerythrite, trimethylolpropane, dipentaerythritol or D-sorbite etc..
The invention further relates to the new oxime ester lightlike initiating agent shown in above-mentioned formula I, II is in Photocurable composition（It is i.e. photosensitive
Property composition）In application.Without limitation, the light trigger can be applicable to chromatic photoresist（RGB）, black photoresistance（BM）, it is empty
Between barrier（Photo-spacer）, dry film, the aspect such as semiconductor light photoresist and ink.
Specific embodiment
The concrete technical scheme of the present invention described further below, is further understood that this in order to those skilled in the art
Invention, and do not constitute the restriction to its right.
Embodiment 1：Compound 1Preparation
1）The preparation of 4,4 ', 4 ' '-triacetyl triphenylphosphine：By triphenylphosphine（52.5g, 0.2mol）It is dissolved in 300ml bis-
In chloromethanes, controlling reaction temperature adds alchlor at 20-30 DEG C（82.7g, 0.62mol）Chloroacetic chloride is added dropwise（48.7,
0.62mol）, the complete stirring 2h of drop, stopping reaction pouring reactant liquor in the watery hydrochloric acid that 800g is made into 130ml concentrated hydrochloric acids into, stir
0.5h, standing separate organic phase, use dichloromethane aqueous phase extracted, merge organic phase, and are washed with 200ml saturated sodium bicarbonate solutions
Wash, to organic phase pH value into neutrality, be dried, precipitation recycling design obtains pale yellow oil, purity 97%, it is also possible to do not reclaim
Solvent directly carries out next step oxidation reaction.
2）To step 1）30% hydrogen peroxide of 22.7g is added in neutral organic phase, 3h is reacted at 60 DEG C, and reaction terminates
Afterwards, it is separately added into sodium sulfite solution and saturated sodium bicarbonate solution is washed, organic phase is finally dried with anhydrous magnesium sulfate, reclaims molten
Agent obtains yellow oil.
3）Hydrogen chloride is dissolved in organic solvent the solution for obtaining hydrogen chloride THF, the THF solution of 200g hydrogen chloride is taken, its
The content of middle hydrogen chloride is selected from 30g, adds step 2）Resulting 4,4 ', 4 ' '-triacetyl triphenylphosphine oxide are stirred molten
Solution, dropwise addition 15.5g nitrite tert-butyls, insulation reaction, recycling design obtains Chinese red oily liquids to raw material reaction completely
72.0g。
4）By step 3）In grease be dissolved in dichloroethanes, be cooled to 0 DEG C, add 47.0g triethylamines, be added dropwise
35.3g chloroacetic chlorides, after raw material reaction is complete, add 3% watery hydrochloric acid condition pH=2 ~ 3, stir 30min, stratification, organic phase water
Wash, be dried, recycling design cools down to obtain yellow oil, through chromatography over CC（EtOAc/hexane=40/1）Obtain colorless oil
Thing, final product structure are confirmed by proton nmr spectra, and embodiments result is as follows：1H-NMR（CDCl3,
400MHz）：δ 7.98 (d, 6H), 7.67 (dd,3J(H, H)=8.3 Hz, 3J (P, H)=11.1 Hz, 6H), 2.48
(s, 9H), 1.90 (s, 9H)；31P-NMR (CDCl3,400 MHz)：δ 27.7 (s).
Embodiment 2：Compound 2Preparation
1）4,4 ', 4 ' ' preparation of-three isobutyryl triphenylphosphines：By triphenylphosphine（52.5g, 0.2mol）It is dissolved in 300ml
In dichloromethane, controlling reaction temperature adds alchlor at 20-30 DEG C（82.7g, 0.62mol）Isobutyryl chloride is added dropwise respectively
（42.6g, 0.40mol）And butyl chloride（16.5g, 0.21mol）, drop finish stirring 2h, stop reaction, by reactant liquor pour into 800g with
In the watery hydrochloric acid that 130ml concentrated hydrochloric acids are made into, 0.5h is stirred, standing separates organic phase, uses dichloromethane aqueous phase extracted, merges organic
Phase, and washed with 200ml saturated sodium bicarbonate solutions, to organic phase pH value into neutrality, it is dried, precipitation recycling design obtains light
Yellow oil, purity 96.7%.
2）To step 1）30% hydrogen peroxide of 22.7g is added in neutral organic phase, 3h is reacted at 60 DEG C, and reaction terminates
Afterwards, it is separately added into sodium sulfite solution and saturated sodium bicarbonate solution is washed, organic phase is finally dried with anhydrous magnesium sulfate, reclaims molten
Agent obtains yellow oil.
3）Hydrogen chloride is dissolved in organic solvent the solution for obtaining hydrogen chloride THF, the THF solution of 200g hydrogen chloride is taken, its
The content of middle hydrogen chloride is selected from 30g, adds step 2）Resulting -4 ', the 4 ' isobutyryl of '-two triphenyl of 4- acetyl group oxidation
Phosphine, stirring and dissolving are added dropwise 15.5g nitrite tert-butyls, and insulation reaction is complete to raw material reaction, and recycling design obtains Chinese red oil
Shape liquid 80.9g.
4）By step 3）In grease be dissolved in dichloroethanes, be cooled to 0 DEG C, add 47.0g triethylamines, be added dropwise
35.3g chloroacetic chlorides, after raw material reaction is complete, add 3% watery hydrochloric acid condition pH=2 ~ 3, stir 30min, stratification, organic phase water
Wash, be dried, recycling design, through chromatography over CC（EtOAc/hexane=40/1）Colorless oil is obtained, final product structure is led to
Cross proton nmr spectra to be confirmed, embodiments result is as follows：
1H-NMR（CDCl3,400MHz）：δ 7.96 (d, 6H), 7.68 (dd,3J(H, H)=8.3 Hz, 3J(P, H)=
11.1 Hz, 6H), 2.08 (s, 9H), 1.90 (s, 3H), 1.79 ~ 1.82 (m, 2H), 1.09 (d, 12H)；31P-NMR
(CDCl3,400 MHz)：δ 27.8 (s).
Embodiment 3：Compound 3Preparation
1）The preparation of 4,4 ', 4 ' '-triacetyl triphenylphosphine：By triphenylphosphine（52.5g, 0.2mol）It is dissolved in 300ml bis-
In chloromethanes, controlling reaction temperature adds alchlor at 20-30 DEG C（82.7g, 0.62mol）Chloroacetic chloride is added dropwise（48.7,
0.62mol）, the complete stirring 2h of drop, stopping reaction pouring reactant liquor in the watery hydrochloric acid that 800g is made into 130ml concentrated hydrochloric acids into, stir
0.5h, standing separate organic phase, use dichloromethane aqueous phase extracted, merge organic phase, and are washed with 200ml saturated sodium bicarbonate solutions
Wash, to organic phase pH value into neutrality, be dried, precipitation recycling design obtains pale yellow oil, purity 97%.
2）To step 1）30% hydrogen peroxide of 22.7g is added in neutral organic phase, 3h is reacted at 60 DEG C, and reaction terminates
Afterwards, it is separately added into sodium sulfite solution and saturated sodium bicarbonate solution is washed, organic phase is finally dried with anhydrous magnesium sulfate, reclaims molten
Agent obtains yellow oil.
3）Hydrogen chloride is dissolved in organic solvent the solution for obtaining hydrogen chloride THF, the THF solution of 200g hydrogen chloride is taken, its
The content of middle hydrogen chloride is selected from 30g, adds step 2）Resulting 4,4 ', 4 ' '-triacetyl triphenylphosphine oxide are stirred molten
Solution, dropwise addition 15.5g nitrite tert-butyls, insulation reaction, recycling design obtains Chinese red oily liquids to raw material reaction completely
72.5g。
4）By step 3）In grease be dissolved in dichloroethanes, be cooled to 0 DEG C, add 47.0g triethylamines, be added dropwise
87.0g chlorobenzoyl chlorides, after raw material reaction is complete, add 3% watery hydrochloric acid condition pH=2 ~ 3, stir 30min, stratification, organic phase
Washing, is dried, and recycling design, through chromatography over CC（EtOAc/hexane=40/1）Obtain colorless oil, final product structure
It is confirmed by proton nmr spectra, embodiments result is as follows：
1H-NMR（CDCl3,400MHz）：δ 8.25 (d, 6H), 7.33 ~ 7.89 (m, 21H), 1.87 (s, 3H)；31P-NMR (CDCl3,400 MHz)：δ 27.8 (s).
The structure of target product and its1H-NMR data are listed in table 1：
Table 1
Embodiment 18：Performance evaluation
By preparing example Photocurable composition, every application performance of light trigger shown in formula of the present invention I, II is entered
Row is evaluated, including aspects such as storage stability, speed, developability, pattern integrities.
1. the preparation of Photocurable composition
Acrylate copolymer 100
（Methacrylic acid Bian ester/methacrylic acid/hydroxyethyl methacrylate（Mol ratio is 70/10/20）Copolymer
（Mw：10,000））
Trimethylolpropane trimethacrylate（TMPTA） 100
Light trigger to be measured 2 ~ 3
PMA solvents 25
In above-mentioned composition, light trigger is the oxime esters chemical combination shown in formula disclosed by the invention I, II
Thing or light trigger well known in the prior art as a comparison, each component are mass parts.
2. exposure imaging
Above-mentioned Photocurable composition lucifuge is stirred, feeding utilizes bar film in PET templates, does at 165 DEG C
Dry 150min removes solvent, forms the film of about 2 μm of film thickness.The substrate for being formed with film is cooled to into room temperature, mask is enclosed
Plate, with high-pressure sodium lamp or LED/light source, is exposed to film in the ultraviolet of 365 ~ 420nm wavelength, with 25 DEG C
20s developments being impregnated in 2.5% sodium carbonate liquor, then using ultrapure washing, air-dried, at 220 DEG C, hard baking 30min makes figure fixed
Shadow, the figure to obtaining are evaluated.
3. the performance evaluation of Photocurable composition
（1）Storage stability
After the Photocurable composition of liquid is stored 3 months at room temperature naturally, visually evaluated according to following standard
The precipitation degree of material：
A：Precipitation is not observed；
B：Slightly it was observed that precipitation；
C：It was observed that obvious sediment.
（2）Speed
During exposure, residual film ratio after the light irradiation zone development in step of exposure is commented in 90% or more minimum exposure amount
Valency is exposure demand, and exposure demand is less to represent that sensitivity is higher.
（3）Developability and pattern integrity
Use SEM（SEM）Observation substrate pattern, to evaluate developability and pattern integrity.
Developability is according to following standard evaluation：
○：Residue is not observed in unexposed portion；
◎：In unexposed portion it was observed that a small amount of residue, but residue can receive；
●：In unexposed portion it was observed that obvious residue.
Pattern integrity is according to following standard evaluation：
◇：Pattern defect is not observed；
□：It was observed that fraction pattern has fewer defects；
◆：Substantially it was observed that many pattern defects.
Evaluation result is as shown in table 2:
Table 2
| Light trigger | Storage stability | Mass color energy mJ/cm2 | Developability | Image integrity |
| Embodiment 1 | A | 40 | ○ | ◇ |
| Embodiment 2 | A | 38 | ○ | ◇ |
| Embodiment 3 | A | 42 | ○ | ◇ |
| Embodiment 4 | A | 43 | ○ | ◇ |
| Embodiment 5 | A | 37 | ○ | ◇ |
| Embodiment 6 | A | 71 | ◎ | □ |
| Embodiment 12 | A | 50 | ○ | ◇ |
| Embodiment 13 | A | 75 | ◎ | □ |
| Embodiment 14 | A | 52 | ◎ | □ |
| Embodiment 16 | A | 55 | ○ | ◇ |
| Embodiment 17 | A | 39 | ○ | ◇ |
| OXE-01 | B | 205 | ◎ | ◆ |
| OXE-02 | B | 185 | ◎ | □ |
New oxime ester lightlike initiating agent by shown in the result of 2 content of table can be seen that comprising formula of the present invention I, II
Photocurable composition has good storage stability, shows splendid speed, developability and pattern integrity.
In sum, the application performance of the new oxime ester lightlike initiating agent shown in formula disclosed by the invention I, II is excellent,
It is applied to the performance that Photocurable composition can greatly improve photocuring product.
Claims (5)
1. oxime ester lightlike initiating agent, which has such as formula I, II structure：
Wherein,
N=1 or 2；
R1、R2、R3Can be the same or different, be independently selected from the straight or branched alkyl of C1-C20, C3-C8 cycloalkyl, C7-
C10 phenyl substituted alkyls；
R4、R5、R6Can be the same or different, be independently selected from the straight or branched alkyl of C1-C20, C3-C8 cycloalkyl, C6-
The alkyl of C20 aryl, wherein C1-C20 is unsubstituted or is replaced by one or more halogens, phenyl, alkoxyl.
2. oxime ester lightlike initiating agent according to claim 1, it is characterised in that：
R1、R2、R3The straight or branched alkyl for being independently expressed as C1-C5 is independently selected from, C5-C6 cycloalkyl, C7-C10 phenyl take
Substituted alkyl；
R4、R5、R6It is independently selected from the straight or branched alkyl of C1-C5, C3-C8 cycloalkyl, C6-C10 aryl.
3. oxime ester lightlike initiating agent according to claim 1, it is characterised in that preparation method is comprised the following steps：
1) with triphenylphosphine as raw material, it is acylated on phenyl under the catalysis of alchlor, ferric trichloride or zinc chloride；
2) in the presence of hydrogen chloride, sodium alkoxide or potassium alcoholate to carry out oximate with nitrites or nitrite anti-for phosphine oxide intermediate
Should；
3) the product oxime that oximation reaction is obtained is with acyl chloride reaction into oxime ester；
4) acylated product for obtaining obtains phosphine oxide intermediate through oxidation；
Wherein：
N=1 or 2；
R1、R2、R3Can be the same or different, be independently selected from the straight or branched alkyl of C1-C20, C3-C8 cycloalkyl, C7-
C10 phenyl substituted alkyls；
R4、R5、R6Can be the same or different, be independently selected from the straight or branched alkyl of C1-C20, C3-C8 cycloalkyl, C6-
The alkyl of C20 aryl, wherein C1-C20 is unsubstituted or is replaced by one or more halogens, phenyl, alkoxyl.
4. oxime ester lightlike initiating agent according to claim 3, it is characterised in that step 2 in its preparation method) nitrous
Acid esters is selected from nitrous ether (ethyl nitrite), isoamyl nitrite, the different monooctyl ester of nitrous acid；Nitrite is selected from natrium nitrosum, potassium nitrite.
5. a kind of Photocurable composition includes：
A) at least one olefinic unsaturation photopolymerizable compound and
B) as light trigger at least one claim 1 described in oxime ester lightlike initiating agent.
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|---|---|---|---|---|
| WO1998054125A1 (en) * | 1997-05-27 | 1998-12-03 | Novartis Ag | O-benzyl oxime ethers and their use as pesticides |
| CN1299812A (en) * | 1999-12-15 | 2001-06-20 | 西巴特殊化学品控股有限公司 | Oximate light initiator |
| US6313344B1 (en) * | 1998-05-27 | 2001-11-06 | Bayer Aktiengesellschaft | Organic compounds |
| CN1514845A (en) * | 2001-06-11 | 2004-07-21 | �������⻯ѧƷ�ع�����˾ | Oxime ester photoinitiatros having combined structure |
| CN104672354A (en) * | 2015-02-04 | 2015-06-03 | 天津墨森科技有限公司 | Dioxime ether photoinitiator as well as preparation method and application thereof |
-
2015
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998054125A1 (en) * | 1997-05-27 | 1998-12-03 | Novartis Ag | O-benzyl oxime ethers and their use as pesticides |
| US6313344B1 (en) * | 1998-05-27 | 2001-11-06 | Bayer Aktiengesellschaft | Organic compounds |
| CN1299812A (en) * | 1999-12-15 | 2001-06-20 | 西巴特殊化学品控股有限公司 | Oximate light initiator |
| CN1514845A (en) * | 2001-06-11 | 2004-07-21 | �������⻯ѧƷ�ع�����˾ | Oxime ester photoinitiatros having combined structure |
| CN104672354A (en) * | 2015-02-04 | 2015-06-03 | 天津墨森科技有限公司 | Dioxime ether photoinitiator as well as preparation method and application thereof |
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