CN105198780B - Oxime ester compound and the optical polymerism composition including the oxime ester compound - Google Patents

Oxime ester compound and the optical polymerism composition including the oxime ester compound Download PDF

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CN105198780B
CN105198780B CN201510338292.4A CN201510338292A CN105198780B CN 105198780 B CN105198780 B CN 105198780B CN 201510338292 A CN201510338292 A CN 201510338292A CN 105198780 B CN105198780 B CN 105198780B
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chemical formula
oxime ester
ester compound
optical polymerism
polymerism composition
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CN105198780A (en
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崔汉永
李宪熙
郑景文
金炫佑
李宗洙
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Dongwoo Fine Chem Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/63—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/30—Sulfides having the sulfur atom of at least one thio group bound to two carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Indole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention discloses a kind of oxime ester compound and a kind of optical polymerism composition including the oxime ester compound, more specifically, the invention discloses a kind of optical polymerism composition including photopolymerizable compound and light trigger, wherein, the light trigger includes oxime ester compound, and the optical polymerism composition has the effect of excellent linearity pattern.

Description

Oxime ester compound and the optical polymerism composition including the oxime ester compound
Technical field
The present invention relates to a kind of oxime ester compound and a kind of optical polymerism composition including the oxime ester compound, and More particularly it relates to a kind of optical polymerism composition including photopolymerizable compound and light trigger, wherein, the light Initiator includes oxime ester compound.
Background technology
Photoactive compounds are widely used to decompose the material for producing chemism atom or molecule by absorbing light Make the light trigger of the various compositions such as light curable inks, light sensitivity printed panel, photoresist.
The Classical examples of known light trigger can be divided into polytype, such as, acetophenone compound, benzophenone chemical combination Thing, compound in triazine class, non-imidazole compound, acylphosphine oxide compound and oxime ester compound, wherein, oxime ester compound Have the following advantages that：Such as absorb ultraviolet and color, free radical generation rate high and photo etching composition material is also hardly presented The superior compatibility and stability of material.
In the case of the light trigger with oxime ester compound, by introducing suitable substitution base, energy in compound Enough it is easily synthesized the adjustable various light triggers in absorption region of light trigger.
Because oxime ester compound to optical polymerism composition, can make with not by by the light radiation of 365nm to 435nm The polymerizable compound polymerization and solidification of saturated bond, so being used for black matrix", colored filter, column spacer, flexibility Dielectric film, the photo etching composition for external coating.
Therefore, it is constantly needed to new light trigger to meet the industrial requirement of various purposes, such as, to such as 365nm extremely The hypersensitivity of the long wavelength light of 435nm, with good solidification reactivity, it is easily fabricated, due to heat endurance higher It is easily processed and storage stability, and there is gratifying dissolving in the solvent of such as propylene glycol methyl ether acetate Degree.
Conventionally known oxime ester compound be US patents 4,255,513 in the oxime ester compound to dialkyl amido benzene Benzophenone in the oxime ester compound and US patents 4,590,145 of the acrylamido substitution in thing, US patents 4,202,697 Oxime ester compound etc..
However, when using known oxime ester compound as light trigger, when exposure is to be attached to mask due to light Caused degraded and cause the pattern form defect of printing process, and cause the reduction of yield.
Additionally, decomposition temperature is less than 240 DEG C, and exist due to after the developing process, light being made in thermal cure step Decomposition of initiator and cause the tack of optical polymerism composition and alkali resistance reduction problem.
Hence it is highly desirable to solve these problems oxime ester compound with new structure and including this have it is new The optical polymerism composition of the oxime ester compound of structure.
[reference listing]
[patent document]
(patent document 1) US patents 4,255,513
(patent document 2) US patents 4,202,697
(patent document 3) US patents 4,590,145
The content of the invention
Therefore, the present invention has been devised to solve the above problems, and it is an object of the invention to provide a kind of new knot The oxime ester compound of structure.
Further, it is poly- it is a further object of the present invention to provide a kind of light including photopolymerizable compound and light trigger Conjunction property composition, wherein, the optical polymerism composition has excellent linear by the oxime ester compound containing new structure The effect of pattern, and the compatibility with other compositions can be improved by good solubility.
To achieve these goals, one aspect of the present invention provides a kind of oxime ester represented by following chemical formula 1 Compound：
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and the integer that n is 6 to 21.
Additionally, the invention provides a kind of optical polymerism composition including photopolymerizable compound and light trigger, the light Initiator includes the oxime ester compound of following chemical formula 1：
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and the integer that n is 6 to 21.
When light radiation to oxime ester compound with new structure of the invention, chain alkyl free radical is produced, and Because the free radical length is long, so that the mobility of the free radical is smaller, so that only occurring on the region of light irradiation solid Change, and the final oxime ester compound with new structure of the invention has the characteristic of excellent pattern linearity.
Additionally, the oxime ester compound with new structure of the invention is due to high-dissolvability, and have with other materials excellent Different compatibility, and absorb ultraviolet color is also hardly presented, so as to for optics purpose be favourable by said composition.
Therefore, the invention provides a kind of optical polymerism composition including photopolymerizable compound and light trigger, its In, the optical polymerism composition has excellent linear graph as light trigger by the oxime ester compound containing new structure The effect of case, and color is hardly presented.
Brief description of the drawings
Fig. 1 is the 1H-NMR spectrograms of the oxime ester compound of the chemical formula 2 prepared in preparation example 1.
Fig. 2 is the 1H-NMR spectrograms of the oxime ester compound of the chemical formula 3 prepared in preparation example 2.
Specific embodiment
Hereinafter, will be described in the present invention.
The present invention relates to the oxime ester compound represented by following chemical formula 1：
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and the integer that n is 6 to 21.
In the oxime ester compound of chemical formula 1, it is preferable that the R in chemical formula 1 is preferably C1 or C6 alkyl.
Additionally, the oxime ester compound of chemical formula 1 may be selected from the group that following chemical formula 2 is constituted to chemical formula 3 Or it is multiple, but not limited to this：
[chemical formula 2]
[chemical formula 3]
The oxime ester compound of new compound chemical formula 1 of the invention can be prepared according to following steps：
(1) the step of making diphenylsulfide be reacted to prepare the compound with acyl group with alkyl carbonyl chlorine；
(2) the step of making the compound with acyl group with nitrite reaction to prepare the compound with oximido；And
(3) compound with oximido is made to be reacted the step of come the oxime ester compound for preparing chemical formula 1 with alkyl carbonyl chlorine, And its reaction mechanism is shown in following reaction equation 1.
Additionally, alkyl according to step (1) and the alkyl carbonyl chlorine of step (3) determines the oxime ester compound of chemical formula 1 R and n.
[reaction equation 1]
The oxime ester compound of new compound chemical formula 1 of the invention includes diphenylsulfide base.Therefore, when light is irradiated to During the oxime ester compound of chemical formula 1, the photoreactivity of the oxime ester compound of chemical formula 1 is improved due to energy transfer, and energy It is enough to improve optical efficiency to greatest extent.Further, since it absorbs ultraviolet is also hardly presented color, so as to by said composition It is favourable for optics purpose.
Therefore, in order to using the oxime ester compound of chemical formula 1, be used the invention provides by the oxime ester compound of chemical formula 1 Make the optical polymerism composition of light trigger.
More specifically, the invention provides a kind of optical polymerism combination including photopolymerizable compound and light trigger Thing, wherein, the light trigger includes the oxime ester compound of following chemical formula 1：
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and the integer that n is 6 to 21.
Used as supplement light efficiency and the composition of color change, the type of photopolymerizable compound is not particularly limited, but It is preferred that having the acrylic compounds oligomer of ethylenic unsaturated bond.
Acrylic compounds oligomer with ethylenic unsaturated bond is unsaturated for introducing precursor and olefinic to be configured to pass The chemical reaction of the monomer of key can just occur light-curable acrylic's class oligomer of UV curing reactions.
Acrylic compounds oligomer precursor can be with (methyl) acrylic monomer and polymerism list with C1 to C14 alkyl Body is copolymerized.The method for preparing acrylic compounds oligomer is not particularly limited, but using commonly used in the art Method, such as polymerisation in bulk, polymerisation in solution, emulsion polymerization or suspension polymerisation prepares acrylic compounds oligomer precursor, and Preferably use polymerisation in bulk.
Additionally, the present invention any solvent usually used during being usable in polymerization, and such as azo, mistake can be used The polymerization initiator of oxide-based, acetals, redox class and hemiacetal class.
The alkyl of (methyl) acrylic monomer with C1 to C14 alkyl includes aliphatic group and aromatic group, And the monomer includes (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) propylene Isopropyl propionate, (methyl) n-butyl acrylate, (methyl) acrylic acid -2- butyl esters, (methyl) tert-butyl acrylate, (methyl) propylene Sour isobutyl ester, (methyl) amyl acrylate, (methyl) EHA, (methyl) acrylic acid ethyl butyl ester, (methyl) third Olefin(e) acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, different camphyl (first Base) acrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate and (methyl) dodecylacrylate etc.. Above-mentioned monomer can be used individually or with two or more combinations.
The instantiation of polymerizable monomer may be, for example, the monomer with hydroxyl, such as (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -2- hydroxy butyl esters, (methyl) acrylic acid -4- hydroxy butyl esters, (methyl) propylene The own ester of acid -6- hydroxyls, 2- hydroxyls ethylene glycol (methyl) acrylate, 2- hydroxyls propane diols (methyl) acrylate and 4- hydroxyl butyl Vinethene etc.；And the monomer with carboxyl, (methyl) acrylic acid, crotonic acid, maleic acid, itaconic acid and fumaric acid etc.； And the like.Polymerizable monomer can be used individually or with two or more combinations.
Monomer type for introducing olefinic unsaturation singly-bound is not particularly limited, it is preferred that using in a molecule Isocyanates monomer with NCO and double bond, the example can be 2- isocyanatoethyls (methyl) acrylate.
The manufacture method of light-curable acrylic's class oligomer is not particularly limited, and the light-cured acrylic class oligomer is excellent Choosing is used as photopolymerizable compound.Specifically, for example, the light-cured acrylic class oligomer can be made by following steps It is standby：Manufacture precursor；The acrylic compounds oligomer precursor of the above-mentioned preparation based on 100 weight portions, adds 0.5 weight portion to 20 weight The isocyanates monomer of part and the catalyst of 0.001 weight portion to 0.5 weight portion, and reacted it.The kind of catalyst Class is not particularly limited, as long as the catalyst can promote the hydroxyl contained in NCO and acrylic compounds oligomer precursor Or the reaction of carboxyl, and for example, organo-tin compound, organic silver compound or their mixture can be used.
The optical polymerism measured by gel permeation chromatography (Gel permeation chromatography, GPC) The weight average molecular weight (polystyrene conversion, Mw) of compound can be 200,000 to 1,000,000.
Additionally, light trigger is characterised by the oxime ester compound represented containing following chemical formula 1：
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and the integer that n is 6 to 21.
In the oxime ester compound of chemical formula 1, the R in chemical formula 1 is preferably C1 or C6 alkyl, and n is preferably 6 to 21 Integer.
Additionally, the oxime ester compound of chemical formula 1 may be selected from the group that following chemical formula 2 is constituted to chemical formula 3 Or it is multiple, but it is not limited to this：
[chemical formula 2]
[chemical formula 3]
Due to the integer that n is 6 to 21, so being used as the chemical formula of light trigger in optical polymerism composition of the invention 1 oxime ester compound has alkyl chain long.Therefore, when light is irradiated to the oxime ester compound of chemical formula 1, chain alkyl is produced Free radical, and because this free radical length is long so as to the mobility of free radical is small, so that only on the region of light irradiation Solidify.Therefore, if carrying out shape using the oxime ester compound containing chemical formula 1 as the photopolymer compositions of light trigger Into pattern, then excellent pattern linearity is able to ensure that.
The solid of the photopolymerizable compound based on 100 weight portions, the content of light trigger is 0.01 weight portion to 10 weights Amount part.If the content is less than 0.01 weight portion, the overall state of cure reduction of optical polymerism composition；If the content is big In 10 weight portions, then the decrease in transmission of ultraviolet light, so as to there is a problem of in the reduction of depths state of cure.
Additionally, optical polymerism composition of the invention can further include solvent, and the present invention is usable in photopolymerization Property composition in the conventional solvent for being used, without any special limitation, as long as the solvent effectively dissolves optical polymerism group Other compositions contained in compound, and specifically, it is preferable to using ethers, arene, ketone, alcohols, esters or amide-type and Analog.
Ethers includes, such as ethylene glycol monoalkyl ether, such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol list third Ether and ethylene glycol monobutyl ether etc.；
Diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, two Butyl cellosolve etc.；
Ethylene glycol alkyl ether acetic acid esters, methylcellosolve acetate, ethyl cellosolve acetate etc.；And
Aklylene glycol alkylether acetates, such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, the third two Alcohol list propyl ether acetic acid esters, methoxybutyl acetic acid esters, methoxypentyl acetic acid esters etc..
Arene includes, such as benzene,toluene,xylene, mesitylene and the like.
Ketone includes, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone and similar Thing.
Alcohols includes ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerine and the like.
Esters include, for example, such as ethyl lactate, butyl lactate, 3- ethoxyl ethyl propionates, 3- methoxy methyl propionates Etc. esters；And the ring-type esters such as gamma-butyrolacton.
It is 100 DEG C to 200 DEG C organic molten more preferably using boiling point for the drying of solvent and coating property aspect Agent, the example of this solvent includes propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, breast Acid butyl ester, 3- ethoxyl ethyl propionates and 3- methoxy methyl propionates and the like.
Above-mentioned solvent can be used alone or is applied in combination with two or more.
Additionally, optical polymerism composition of the invention can further include known additive, such as colouring agent, alkali solubility Resin and surfactant etc..
Optical polymerism composition of the invention is applied to extensive purposes.For example, optical polymerism composition of the invention can Printing-ink, ornament materials, coating material, tackifier/adhesive or the like are applied to, and because it passes through to absorb purple Outer light and cause color be difficult to be noticeable, and can be used as need the transparency the combination for optical imagery display device Thing.
Below, there is provided preferred embodiment more fully understanding the present invention.Although it is disclosed that for illustrating mesh It is of the invention preferred embodiment, but those skilled in the art by what is known are not being departed from such as appended claims Disclosed in scope and spirit of the present invention in the case of, can carry out various modifications, addition and replace.
<The preparation of the oxime ester compound of chemical formula 1>
The preparation of the oxime ester compound of the chemical formula 2 of preparation example 1.
1-1. has the preparation of the compound of acyl group
20g (107.5mmol) diphenylsulfide is added to 100g dichloroethanes and 21.7g (163mmol) aluminium chloride In mixed solution, and 17.4g (107.5mmol) caprylyl chloride is added to above-mentioned solution at a temperature of less than 6 DEG C then In.
Then, stirring reaction liquid 1h, is then put it into frozen water, and oil-moisture is carried out by adding ethyl acetate From.
Hereafter, wash the organic layer of separation with water, anhydrous magnesium sulfate is added into the organic layer and it is dried, then Solvent is removed from organic layer, obtaining 26.3g has the compound of acyl group.
The resulting compound with acyl group is analyzed by 1H-NMR, and determines that it has following chemical formula 4 Structure, its spectrogram is as follows.
[chemical formula 4]
1H-NMR(CDCl3,ppm)：2.01(t,3H),2.55(m,10H),3.65(s,2H),7.00(t,1H),7.07(t, 2H),7.20(d,2H),7.32(d,2H),7.66(d,2H)。
1-2. has the preparation of the compound of oximido
Prepared in example 1-1 made above 5.4g (52mmol) isobutyl nitrite is added to 13g (47.4mmol) Chemical formula 6 the compound with acyl group, the concentrated hydrochloric acid of 3.6g (35mmol) and 50g dimethylformamides mixed solution Afterwards, mixture is stirred at room temperature 3.5 hours.
Then, Oil-water separation is carried out by the way that ethyl acetate and water are added into reactant mixture, is subsequently washed with water The organic layer of separation.
Hereafter, hexane is added into separate organic layer to be settled out solid, filters organic layer, be dried under reduced pressure institute The solid for obtaining, obtaining 10.6g has the compound of oximido.
The compound with oximido obtained by being analyzed by 1H-NMR determines that it has followingization to determine structure The structure of formula 5, its spectrogram is as follows.
[chemical formula 5]
1H-NMR(CDCl3,ppm)：2.01(t,3H),2.65(m,8H),3.25(t,2H),7.02(t,1H),7.09(t, 2H),7.18(d,2H),7.31(d,2H),7.62(d,2H)12.8(s,1H)。
The preparation of the oxime ester compound of 1-3. chemical formulas 2
Compound with oximido, the 2.1g of the chemical formula 5 that 4g (13.2mmol) is obtained in preparation example 1-2 The mixed solution of (27mmol) pyridine and 12g dimethylformamides is maintained in -10 DEG C or less of state, and by 3.6g (15mmol) 4- heptyl chlorobenzoyl chlorides drop to the mixed solution.
Then, the mixture is stirred at 5 DEG C 2 hours afterwards, by ethyl acetate and water add to the solution with carry out oil- Water is separated, and washes the organic layer of separation with water.
Hereafter, anhydrous magnesium sulfate is added to organic layer and it is dried, then remove solvent from organic layer, obtained 3.5g oxime ester compounds.
Oxime ester compound obtained by being analyzed by 1H-NMR determines that it has following chemical formula to determine structure 2 structure, figure 1 illustrates its spectrogram, and its elementary analysis result is as follows.
[chemical formula 2]
Elementary analysis：C,75.12；H,7.58；N,2.57；S,5.91.
The preparation of the oxime ester compound of the chemical formula 3 of preparation example 2.
2-1. has the preparation of the compound of acyl group
20g (107.5mmol) diphenylsulfide is added to 100g (1mol) dichloroethanes and 21.7g (163mmol) chlorine In the mixed solution of change aluminium, and then at a temperature of less than 6 DEG C, the propionyl chloride of 9.94g (107.5mmol) is added supreme In stating solution.
Then, stirring reaction liquid 1h, is then put it into frozen water, and oil-moisture is carried out by adding ethyl acetate From.
Hereafter, wash the organic layer of separation with water, anhydrous magnesium sulfate is added into the organic layer and it is dried, then Solvent is removed from organic layer, obtaining 20.7g has the compound of acyl group.
The structure of the resulting compound with acyl group is following chemical formula 6：
[chemical formula 6]
2-2. has the preparation of the compound of oximido
5.4g (52mmol) isobutyl nitrite is being added the change that is prepared in preparation example 2-1 to 13g (47.4mmol) In the compound with acyl group of formula 6, the concentrated hydrochloric acid of 3.6g (35mmol) and the mixed solution of 50g dimethylformamides it Afterwards, mixture is stirred at room temperature 3.5 hours.
Then, Oil-water separation is carried out by the way that ethyl acetate and water are added into reactant mixture, is subsequently washed with water The organic layer of separation.
Hereafter, hexane is added into separate organic layer to be settled out solid, filters organic layer, be dried under reduced pressure institute The solid for obtaining, then obtaining 19.8g has the compound of oximido.
The structure of the resulting compound with oximido is following chemical formula 7：
[chemical formula 7]
The preparation of the oxime ester compound of 2-3. chemical formulas 3
Compound with oximido, the 2.1g of the chemical formula 7 that 3.6g (13.2mmol) is prepared in preparation example 2-2 The mixed solution of (27mmol) pyridine and 12g dimethylformamides is maintained in -10 DEG C or less of state, and by 3.6g The 4- heptyl chlorobenzoyl chlorides of (15mmol) drop to the mixed solution.
Then, the mixed solution is stirred at 5 DEG C 2 hours afterwards, is added into the solution by by ethyl acetate and water To carry out Oil-water separation, and wash the organic layer of the separation with water.
Hereafter, anhydrous magnesium sulfate is added to organic layer and it is dried, then remove solvent from organic layer, obtained 3.5g oxime ester compounds.
The oxime ester compound of acquisition is analyzed by 1H-NMR to determine structure, and determines that it has following chemical formula 3 Structure, figure 2 illustrates its spectrogram, and its elementary analysis result is as follows.
[chemical formula 3]
Elementary analysis：C,73.51；H,6.61；N,2.94；S,6.74.
<The preparation of optical polymerism composition>
Embodiment 1.
By by bisphenol-A glycerine (1 glycerine/phenol) double methacrylate and 10g dipentaerythritols of the following chemical formulas 8 of 50g The change that six acrylate are prepared as additive, 3g as photopolymerizable compound, 40g carbon blacks (colouring agent) in preparation example 1 The oxime ester compound of formula 2 is added into 100g propylene glycol methyl ether acetate solvents as light trigger, is subsequently agitated for 30 points Clock prepares optical polymerism composition.
[chemical formula 8]
Embodiment 2.
In addition to the oxime ester compound of the chemical formula 3 that will be prepared in preparation example 2 is used as light trigger, with above-described embodiment Identical mode prepares optical polymerism composition in 1.
Comparative example 1.
Except TMDPO (TPO, BASF Co.) is used as outside light trigger, Optical polymerism composition is prepared in identical mode in above-described embodiment 1.
Comparative example 2.
Except by OXE-01 (1,2- octane-dione 1- [4- (thiophenyl) phenyl] -2-O- benzoyl oximes, Ciba Inc.) it is used as outside light trigger, optical polymerism composition is prepared in identical mode in above-described embodiment 1.
Comparative example 3.
Except by OXE-02 (1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -1-O- acetyl group-second Ketoxime, Ciba Inc.) it is used as outside light trigger, optical polymerism combination is prepared in identical mode in above-described embodiment 1 Thing.
The pattern fidelity of the optical polymerism composition of test case 1. and linear evaluation
Using spin coater, by every kind of optical polymerism group of embodiment 1 to embodiment 2 and comparative example 1 to comparative example 3 Compound is coated on the glass substrate with pure surface that thickness is 1mm to form optical polymerism composition film, so that after drying Film thickness is 1.0 μm, and the drying is to be dried 5 minutes at 100 DEG C.
It is following to form black matrix"：Using ultraviolet optical polymerism combination is irradiated through having 20 μm of negative masks of line width Thing film, then at 25 DEG C in 0.5wt% aqueous sodium carbonates spray developing 60 seconds.
Black matrix" is formed with micro- sem observation, the degree of accuracy of pattern is measured and is evaluated the linear of lines, and comment Price card is accurate as follows.
<The evaluation criteria of accuracy>
By obtaining each from subtracting 20 μm using the line width of the pattern film after solidifying with 20 μm of negative masks of line width Value.
When value hour (5 μm smaller), accuracy is evaluated as height.
<Linear evaluation criterion>
When microexamination,
Any slight curves are not observed in pattern lines side or come off：○
It was observed that slight curves or come off, but only observe in part：△
Slight curves are observed in all of pattern or is come off：×.
The accuracy and linear result of pattern are shown in table 1 below：
[table 1]
Classification Accuracy Linearly
Embodiment 1 3μm ○
Embodiment 2 2μm ○
Comparative example 1 7μm △
Comparative example 2 7μm △
Comparative example 3 9μm ×
Be can be seen that for the implementation by the use of oxime ester compound of the invention as light trigger from the result of above-mentioned table 1 Example 1 to embodiment 2 optical polymerism composition prepared by black matrix" pattern, line width minutely increases, and it is in standard Exactness and it is linear in show excellent result, do not observe bending in straight-line pattern side or peel off.
However, for will not be that the oxime ester of compound of the invention is used as the comparative example 1 of light trigger to the light of comparative example 3 The pattern of the black matrix" prepared by polymerizable composition, polymerizable composition, line width is significantly increased, and straight-line pattern side observe bending or Peel off.
It is therefore, it is possible to what is confirmed：By the use of oxime ester compound of the invention as the optical polymerism composition of light trigger There is the effect for producing more exact pattern due to excellent pattern linearity.

Claims (10)

1. a kind of oxime ester compound represented by following chemical formula 1：
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and
N is 6 to 21 integer.
2. oxime ester compound according to claim 1,
Wherein, the R in chemical formula 1 is C1 alkyl or C6 alkyl.
3. oxime ester compound according to claim 1,
Wherein, the chemical formula 1 is one or more in the group constituted to chemical formula 3 selected from following chemical formula 2：
[chemical formula 2]
[chemical formula 3]
4. a kind of optical polymerism composition, the optical polymerism composition includes photopolymerizable compound and light trigger,
Wherein, the light trigger includes the oxime ester compound of following chemical formula 1：
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and
N is 6 to 21 integer.
5. optical polymerism composition according to claim 4,
Wherein, the optical polymerism composition includes the acrylic compounds oligomer with ethylenic unsaturated bond.
6. optical polymerism composition according to claim 5,
Wherein, the acrylic compounds oligomer with ethylenic unsaturated bond has 200,000 to 1,000,000 GPC weights equal Molecular weight.
7. optical polymerism composition according to claim 4,
Wherein, the R in the chemical formula 1 is C1 alkyl or C6 alkyl.
8. optical polymerism composition according to claim 4,
Wherein, the chemical formula 1 is one or more in the group constituted to chemical formula 3 selected from following chemical formula 2：
[chemical formula 2]
[chemical formula 3]
9. optical polymerism composition according to claim 4,
Wherein, the photopolymerizable compound based on 100 weight portions, the content of the light trigger is 0.01 weight portion to 10 Weight portion.
10. optical polymerism composition according to claim 4,
Wherein, the optical polymerism composition further includes solvent.
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