CN105198780A - Oxime ester compound and light-polymerizable composition including same - Google Patents

Oxime ester compound and light-polymerizable composition including same Download PDF

Info

Publication number
CN105198780A
CN105198780A CN201510338292.4A CN201510338292A CN105198780A CN 105198780 A CN105198780 A CN 105198780A CN 201510338292 A CN201510338292 A CN 201510338292A CN 105198780 A CN105198780 A CN 105198780A
Authority
CN
China
Prior art keywords
chemical formula
oxime ester
ester compound
optical polymerism
compound
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
Application number
CN201510338292.4A
Other languages
Chinese (zh)
Other versions
CN105198780B (en
Inventor
崔汉永
李宪熙
郑景文
金炫佑
李宗洙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongwoo Fine Chem Co Ltd
Original Assignee
Dongwoo Fine Chem Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dongwoo Fine Chem Co Ltd filed Critical Dongwoo Fine Chem Co Ltd
Publication of CN105198780A publication Critical patent/CN105198780A/en
Application granted granted Critical
Publication of CN105198780B publication Critical patent/CN105198780B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (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 an oxime ester compound and a light-polymerizable composition including same, and more particularly the invention discloses a light-polymerizable composition which comprises a polymerizable compound and a photoinitiator, wherein the photoinitiator comprises the oxime ester compound. Furthermore the light-polymerizable composition has an excellent linear pattern effect.

Description

Oxime ester compound and comprise the optical polymerism composition of this oxime ester compound
Technical field
The present invention relates to a kind of oxime ester compound and a kind of optical polymerism composition comprising this oxime ester compound, and more specifically, the present invention relates to a kind of optical polymerism composition comprising photopolymerizable compound and light trigger, wherein, this light trigger comprises oxime ester compound.
Background technology
Photoactive compounds is decompose by absorb light the material producing chemically reactive atom or molecule, is widely used as the light trigger of the various compositions such as such as light curable inks, photosensitivity printing plate, photoresist.
The Classical examples of known light trigger can be divided into broad variety; such as; acetophenone compound, benzophenone cpd, compound in triazine class, non-imidazole compound, acylphosphine oxide compound and oxime ester compound; wherein, oxime ester compound tool has the following advantages: such as absorb ultraviolet also present hardly color, high free radical production rate, with the superior compatibility of photo etching composition material and stability.
When having the light trigger of oxime ester compound, by introducing suitable substituting group in compound, the adjustable various light trigger in absorption region of light trigger easily can be synthesized.
Because oxime ester compound passes through the optical radiation of 365nm to 435nm to optical polymerism composition, can make to have polymerizable compound polymerization and the solidification of unsaturated link(age), so be used to black matrix", colored filter, column spacer, flexible insulating film, photo etching composition for external coating (EC).
Therefore, the light trigger that continuous needs are new meets the industrial requirement of various object, such as, to the hypersensitivity of the long wavelength light of such as 365nm to 435nm, there is good solidification reactivity, be easy to manufacture, easily process and stability in storage due to higher thermostability, and there is gratifying solubleness in the solvent of such as propylene glycol methyl ether acetate.
Conventional known oxime ester compound is US patent 4,255, in 513 with the oxime ester compound to dialkyl amido benzene, US patent 4,202, the oxime ester compound that acrylamido in 697 replaces and US patent 4,590, the benzophenone oxime ester compound etc. in 145.
But, when using known oxime ester compound as light trigger, the degraded when exposing to be attached to mask caused by light and cause the pattern form defect of printing process, and cause the reduction of productive rate.
In addition, decomposition temperature lower than 240 DEG C, and exists due to after the developing process, makes light trigger decompose and cause the problem that the tack of optical polymerism composition and alkali resistance reduce in thermal cure step.
Therefore, be starved of the oxime ester compound with novel texture addressed these problems and comprise the optical polymerism composition that this has the oxime ester compound of novel texture.
[reference listing]
[patent documentation]
(patent document 1) US patent 4,255,513
(patent document 2) US patent 4,202,697
(patent document 3) US patent 4,590,145
Summary of the invention
Therefore, devised the present invention and solved the problems referred to above, and the object of this invention is to provide a kind of oxime ester compound of novel texture.
Further, another object of the present invention is to provide a kind of optical polymerism composition comprising photopolymerizable compound and light trigger, wherein, this optical polymerism composition has the effect of excellent linearity pattern by the oxime ester compound containing novel texture, and can be improved the consistency with other composition by good solubleness.
To achieve these goals, one aspect of the present invention provides 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 the integer of 6 to 21.
In addition, this invention provides a kind of optical polymerism composition comprising photopolymerizable compound and light trigger, and this light trigger comprises the oxime ester compound of following chemical formula 1:
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and n is the integer of 6 to 21.
When optical radiation to of the present invention there is the oxime ester compound of novel texture time, produce chain alkyl free radical, and because this free radical length is long, thus the movability of this free radical is less, so make only to solidify on the region of photoirradiation, and finally the oxime ester compound with novel texture of the present invention has the characteristic of excellent pattern linearity.
In addition, the oxime ester compound with novel texture of the present invention due to high-dissolvability, and has excellent consistency with other material, and absorbs ultraviolet and also present color hardly, thus said composition to be used for optics object be favourable.
Therefore, the invention provides a kind of optical polymerism composition comprising photopolymerizable compound and light trigger, wherein, this optical polymerism composition has the effect of excellent linearity pattern by the oxime ester compound containing novel texture as light trigger, and presents color hardly.
Accompanying drawing explanation
Fig. 1 is the 1H-NMR spectrogram of the oxime ester compound of the chemical formula 2 of preparation in preparation example 1.
Fig. 2 is the 1H-NMR spectrogram of the oxime ester compound of the chemical formula 3 of preparation in preparation example 2.
Embodiment
Below, the present invention will be described in detail.
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 n is the integer of 6 to 21.
In the oxime ester compound of chemical formula 1, preferably, the R in chemical formula 1 is preferably C1 or C6 alkyl.
In addition, it is one or more that the oxime ester compound of chemical formula 1 can be selected from the group that chemical formula 2 to chemical formula 3 forms, but be not limited thereto:
[chemical formula 2]
[chemical formula 3]
The oxime ester compound of novel cpd chemical formula 1 of the present invention can be prepared according to following steps:
(1) diphenylsulfide and alkyl carbonyl chlorine is made to react to prepare the step of the compound with acyl group;
(2) step that the compound with oximido is prepared in the compound of acyl group and nitrite reaction is made to have; And
(3) make to have the step that the compound of oximido and alkyl carbonyl chlorine react the oxime ester compound carrying out preparative chemistry formula 1, and in following reaction formula 1, its reaction mechanism has been shown.
In addition, R and n of the oxime ester compound of chemical formula 1 is determined according to the alkyl of the alkyl carbonyl chlorine of step (1) and step (3).
[reaction formula 1]
The oxime ester compound of novel cpd chemical formula 1 of the present invention comprises diphenylsulfide base.Therefore, when photoirradiation is to the oxime ester compound of chemical formula 1, the photoreactivity of the oxime ester compound of chemical formula 1 improves due to energy trasfer, and can improve optical efficiency to greatest extent.In addition, also present color hardly because it absorbs ultraviolet, thus said composition to be used for optics object be favourable.
Therefore, in order to utilize the oxime ester compound of chemical formula 1, the invention provides the optical polymerism composition oxime ester compound of chemical formula 1 being used as light trigger.
More specifically, the invention provides a kind of optical polymerism composition comprising photopolymerizable compound and light trigger, wherein, this light trigger comprises the oxime ester compound of following chemical formula 1:
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and n is the integer of 6 to 21.
The composition of optical efficiency and colour-change as a supplement, the type of photopolymerizable compound is not particularly limited, but preferably has the acrylic acid or the like oligomer of ethylenic unsaturated bond.
The acrylic acid or the like oligomer with ethylenic unsaturated bond is light-curable acrylic's class oligomer that UV curing reaction just can occur for the chemical reaction of the monomer be configured to pass for introducing precursor and ethylenic unsaturated bond.
Acrylic acid or the like oligomer precursor can with (methyl) acrylic monomer and the polymerizable monomer generation copolyreaction with C1 to C14 alkyl.The method preparing acrylic acid or the like oligomer is not particularly limited, but can utilize the method that this area routine uses, and acrylic acid or the like oligomer precursor is prepared in such as mass polymerization, solution polymerization, letex polymerization or suspension polymerization, and preferably uses mass polymerization.
In addition, the present invention can be used in normally used any solvent between polymerization period, and can use the polymerization starter of such as azo, peroxide, acetals, redox class and hemiacetal class.
The alkyl with (methyl) acrylic monomer of C1 to C14 alkyl comprises aliphatic group and aromatic group, and this monomer comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) vinylformic acid-2-butyl ester, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) EHA, (methyl) acrylic acid ethyl butyl ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, different camphyl (methyl) acrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate and (methyl) dodecylacrylate etc.Above-mentioned monomer can use separately or with two or more combinations.
The specific examples of polymerizable monomer can such as having the monomer of hydroxyl, such as (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxy butyl ester, (methyl) vinylformic acid-4-hydroxy butyl ester, the own ester of (methyl) vinylformic acid-6-hydroxyl, 2-hydroxyl ethylene glycol (methyl) acrylate, 2-hydroxyl propylene glycol (methyl) acrylate and 4-hydroxyl butyl vinyl ether etc.; And there is the monomer of carboxyl, such as (methyl) vinylformic acid, β-crotonic acid, toxilic acid, methylene-succinic acid and fumaric acid etc.; And analogue.Polymerizable monomer can use separately or with two or more combinations.
Monomer type for introducing the unsaturated singly-bound of olefinic is not particularly limited, but is preferably used in the isocyanates monomer in a molecule with isocyanate group and double bond, and the example can be 2-isocyanatoethyl (methyl) acrylate.
The manufacture method of light-curable acrylic's class oligomer is not particularly limited, and this light-cured acrylic class oligomer is preferably used as photopolymerizable compound.Particularly, such as, this light-cured acrylic class oligomer is prepared by following steps: manufacture precursor; Based on the acrylic acid or the like oligomer precursor of the above-mentioned preparation of 100 weight parts, add the isocyanates monomer of 0.5 weight part to 20 weight part and the catalyzer of 0.001 weight part to 0.5 weight part, and make it react.The kind of catalyzer is not particularly limited, as long as this catalyzer can promote the reaction of hydroxyl or the carboxyl contained in isocyanate group and acrylic acid or the like oligomer precursor, and organo-tin compound, organic silver compound or their mixture such as, can be used.
The weight-average molecular weight (polystyrene conversion, Mw) of the photopolymerizable compound measured by gel permeation chromatography (Gelpermeationchromatography, GPC) can be 200,000 to 1,000,000.
In addition, the feature of light trigger is the oxime ester compound containing following chemical formula 1 expression:
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and n is the integer of 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 the integer of 6 to 21.
In addition, it is one or more that the oxime ester compound of chemical formula 1 can be selected from the group that chemical formula 2 to chemical formula 3 forms, but be not limited to this:
[chemical formula 2]
[chemical formula 3]
Because n is the integer of 6 to 21, so the oxime ester compound being used as the chemical formula 1 of light trigger in optical polymerism composition of the present invention has long alkyl chain.Therefore, when photoirradiation is to the oxime ester compound of chemical formula 1, produce chain alkyl free radical, and because this free radical length is long thus the movability of free radical is little, so make only to solidify on the region of photoirradiation.Therefore, if use the oxime ester compound containing chemical formula 1 to form pattern as the photopolymer compositions of light trigger, then excellent pattern linearity can be guaranteed.
Based on the solid of the photopolymerizable compound of 100 weight parts, the content of light trigger is 0.01 weight part to 10 weight part.If this content is less than 0.01 weight part, then the overall state of cure of optical polymerism composition reduces; If this content is greater than 10 weight parts, then UV-light is loss of transmission, thus there is the problem reduced in depths state of cure.
In addition, optical polymerism composition of the present invention can comprise solvent further, and the present invention can be used in the conventional solvent used in optical polymerism composition, and it is without any particular limitation, as long as this solvent dissolves other composition contained in optical polymerism composition effectively, particularly, ethers, arene, ketone, alcohols, ester class or amides and analogue is preferably used.
Ethers comprises, such as ethylene glycol monoalkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol 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, dibutyl ethylene glycol ether etc.;
Ethylene glycol alkylether acetates, such as methylcellosolve acetate, ethyl cellosolve acetate etc.; And
Aklylene glycol alkylether acetates, such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester, methoxybutyl acetic ester, methoxypentyl acetic ester etc.
Arene comprises, such as benzene,toluene,xylene, sym-trimethylbenzene and analogue.
Ketone comprises, such as, and methyl ethyl ketone, acetone, Methyl amyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone and analogue.
Alcohols comprises ethanol, propyl alcohol, butanols, hexanol, hexalin, ethylene glycol, glycerol and analogue.
Ester class comprises, such as, and the ester classes such as such as ethyl lactate, n-Butyl lactate, 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate; And the cyclic ester class such as such as gamma-butyrolactone.
With regard to the drying of solvent and coating property aspect, more preferably use boiling point is the organic solvent of 100 DEG C to 200 DEG C, and the example of this solvent comprises propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, pimelinketone, ethyl lactate, n-Butyl lactate, 3-ethoxyl ethyl propionate and 3-methoxy methyl propionate and analogue.
Above-mentioned solvent can be used alone or combinationally uses with two or more.
In addition, optical polymerism composition of the present invention can comprise known additive further, such as tinting material, alkali soluble resins and tensio-active agent etc.
Optical polymerism composition of the present invention is applicable to purposes widely.Such as, optical polymerism composition of the present invention can be applied to printing-ink, finishing material, coated material, tackifier/tackiness agent or analogue, and because it makes color be difficult to be discovered by absorbing UV-light, and the composition for optical imagery display unit of the needs transparency can be used as.
Below, provide preferred embodiment to understand the present invention better.Although what disclosed for illustration of object is preferred embodiment of the present invention, but those skilled in the art are when not departing from as scope and spirit of the present invention disclosed in the accompanying claims by what know, can carry out various amendment, interpolation and replacement.
the preparation > of the oxime ester compound of < chemical formula 1
the preparation of the oxime ester compound of preparation example 1. chemical formula 2
1-1. has the preparation of the compound of acyl group
20g (107.5mmol) diphenylsulfide is added in the mixing solutions of 100g ethylene dichloride and 21.7g (163mmol) aluminum chloride, and subsequently lower than at the temperature of 6 DEG C, 17.4g (107.5mmol) capryl(yl)chloride is added in above-mentioned solution.
Subsequently, stirring reaction liquid 1h, puts it into in frozen water subsequently, carries out Oil-water separation by adding ethyl acetate.
After this, wash the organic layer of separation with water, anhydrous magnesium sulfate added this organic layer and drying is carried out to it, removing solvent from organic layer subsequently, obtain the compound that 26.3g has acyl group.
Analyze the obtained compound with acyl group by 1H-NMR, and determine that it has the structure of following chemical formula 4, its spectrogram is as follows.
[chemical formula 4]
1H-NMR(CDCl 3,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
After 5.4g (52mmol) isobutyl nitrite being added to the compound with acyl group of the chemical formula 6 that 13g (47.4mmol) is prepared in above preparation example 1-1, the concentrated hydrochloric acid of 3.6g (35mmol) and the mixing solutions of 50g dimethyl formamide, mixture is at room temperature stirred 3.5 hours.
Subsequently, carrying out Oil-water separation by ethyl acetate and water being added in reaction mixture, washing the organic layer of separation subsequently with water.
After this, be added to by hexane to be settled out solid in the organic layer of separation, filter organic layer, the solid that drying under reduced pressure obtains, obtains the compound that 10.6g has oximido.
Analyze the obtained compound with oximido to determine structure by 1H-NMR, and determine that it has the structure of following chemical formula 5, its spectrogram is as follows.
[chemical formula 5]
1H-NMR(CDCl 3,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 formula 2
The mixing solutions of the compound with oximido of the chemical formula 5 obtained in preparation example 1-2 by 4g (13.2mmol), 2.1g (27mmol) pyridine and 12g dimethyl formamide maintains in the state of-10 DEG C or following, and 3.6g (15mmol) 4-heptyl benzene formyl chloride is dropped to this mixing solutions.
Subsequently, stir this mixture 2 hours at 5 DEG C after, ethyl acetate and water are added to this solution to carry out Oil-water separation, and wash the organic layer of separation with water.
After this, anhydrous magnesium sulfate be added to organic layer and drying is carried out to it, removing solvent from organic layer subsequently, obtaining 3.5g oxime ester compound.
Analyze obtained oxime ester compound to determine structure by 1H-NMR, and determine that it has the structure of following chemical formula 2, figure 1 illustrates its spectrogram, and its results of elemental analyses is as follows.
[chemical formula 2]
Ultimate analysis: C, 75.12; H, 7.58; N, 2.57; S, 5.91.
the preparation of the oxime ester compound of preparation example 2. chemical formula 3
2-1. has the preparation of the compound of acyl group
20g (107.5mmol) diphenylsulfide is added in the mixing solutions of 100g (1mol) ethylene dichloride and 21.7g (163mmol) aluminum chloride, and subsequently lower than at the temperature of 6 DEG C, the propionyl chloride of 9.94g (107.5mmol) is added in above-mentioned solution.
Subsequently, stirring reaction liquid 1h, puts it into in frozen water subsequently, carries out Oil-water separation by adding ethyl acetate.
After this, wash the organic layer of separation with water, anhydrous magnesium sulfate added this organic layer and drying is carried out to it, removing solvent from organic layer subsequently, obtain the compound that 20.7g has acyl group.
The structure with the compound of acyl group obtained is following chemical formula 6:
[chemical formula 6]
2-2. has the preparation of the compound of oximido
After being added to by 5.4g (52mmol) isobutyl nitrite in the compound with acyl group of the chemical formula 6 that 13g (47.4mmol) is prepared in preparation example 2-1, the concentrated hydrochloric acid of 3.6g (35mmol) and the mixing solutions of 50g dimethyl formamide, mixture is at room temperature stirred 3.5 hours.
Subsequently, carrying out Oil-water separation by ethyl acetate and water being added in reaction mixture, washing the organic layer of separation subsequently with water.
After this, be added to by hexane to be settled out solid in the organic layer of separation, filter organic layer, the solid that drying under reduced pressure obtains, obtains the compound that 19.8g has oximido subsequently.
The structure with the compound of oximido obtained is following chemical formula 7:
[chemical formula 7]
the preparation of the oxime ester compound of 2-3. chemical formula 3
The mixing solutions of the compound with oximido of the chemical formula 7 prepared in preparation example 2-2 by 3.6g (13.2mmol), 2.1g (27mmol) pyridine and 12g dimethyl formamide maintains in the state of-10 DEG C or following, and the 4-heptyl benzene formyl chloride of 3.6g (15mmol) is dropped to this mixing solutions.
Subsequently, stir this mixing solutions 2 hours at 5 DEG C after, carry out Oil-water separation by ethyl acetate and water being added in this solution, and wash the organic layer of this separation with water.
After this, anhydrous magnesium sulfate be added to organic layer and drying is carried out to it, removing solvent from organic layer subsequently, obtaining 3.5g oxime ester compound.
Analyzed the oxime ester compound of acquisition by 1H-NMR to determine structure, and determine that it has the structure of following chemical formula 3, figure 2 illustrates its spectrogram, and its results of elemental analyses is as follows.
[chemical formula 3]
Ultimate analysis: C, 73.51; H, 6.61; N, 2.94; S, 6.74.
the preparation > of < optical polymerism composition
embodiment 1.
Be added in 100g propylene glycol methyl ether acetate solvent by the oxime ester compound of the chemical formula 2 that dihydroxyphenyl propane glycerine (1 glycerine/phenol) double methacrylate of following for 50g chemical formula 8 and 10g dipentaerythritol acrylate are prepared as additive, 3g as photopolymerizable compound, 40g carbon black (tinting material) in preparation example 1 as light trigger, stir subsequently and prepare optical polymerism composition in 30 minutes.
[chemical formula 8]
embodiment 2.
Except the oxime ester compound of the chemical formula 3 of preparation in preparation example 2 is used as, except light trigger, to prepare optical polymerism composition in mode identical in above-described embodiment 1.
comparative example 1.
Except by TMDPO (TPO, BASFCo.) as outside light trigger, prepare optical polymerism composition in mode identical in above-described embodiment 1.
comparative example 2.
Except OXE-01 (1,2-octane-dione 1-[4-(thiophenyl) phenyl]-2-O-benzoyl oximes, CibaInc.), as outside light trigger, is prepared optical polymerism composition in mode identical in above-described embodiment 1.
comparative example 3.
Except by OXE-02 (1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-O-ethanoyl-acetophenone oxime; CibaInc.) as outside light trigger, optical polymerism composition is prepared in mode identical in above-described embodiment 1.
the pattern fidelity of test case 1. optical polymerism composition and linear evaluation
Utilize spin coater, often kind of optical polymerism composition of embodiment 1 to embodiment 2 and comparative example 1 to comparative example 3 is coated on the glass substrate with pure surface that thickness is 1mm and forms optical polymerism composition film, thus dry after film thickness be 1.0 μm, and this drying is drying 5 minutes at 100 DEG C.
Following formation black matrix": utilize ultraviolet to carry out exposure light Polymerizable composition film through the negative mask with 20 μm of live widths, spray developing 60 seconds in 0.5wt% aqueous sodium carbonate at 25 DEG C subsequently.
With black matrix" that microscopic examination is formed, the accuracy of measured pattern and the linear of evaluation lines, and judgement criteria is as follows.
The evaluation criteria > of < accuracy
The live width of the pattern film after being solidified by the negative mask from utilization with 20 μm of live widths deducts 20 μm to obtain each value.
When this value hour (5 μm or less), accuracy is evaluated as height.
The judgement criteria > that < is linear
When microscopic examination,
Do not observe any slight curves in pattern lines side or come off: zero
Observe slight curves or come off, but only observing in part: △
In all patterns, observe slight curves or come off: ×.
Show the accuracy of pattern and linear result 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 ×
As can be seen from the result of above-mentioned table 1, for utilize oxime ester compound of the present invention as embodiment 1 to the embodiment 2 of light trigger optical polymerism composition prepared by the pattern of black matrix", live width increases minutely, and its accuracy and linear in demonstrate excellent result, do not observe in straight-line pattern side bending or peel off.
But for the pattern of black matrix" prepared by the optical polymerism composition oxime ester not being compound of the present invention being used as comparative example 1 to the comparative example 3 of light trigger, live width enlarges markedly, and observes in straight-line pattern side bending or peel off.
Therefore, it is possible to confirm: utilize oxime ester compound of the present invention to have the effect producing more exact pattern due to the pattern linearity of excellence as the optical polymerism composition of light trigger.

Claims (10)

1. the oxime ester compound represented by following chemical formula 1:
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and
N is the integer of 6 to 21.
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, one or more in the group that is selected from following chemical formula 2 to chemical formula 3 and forms of described chemical formula 1:
[chemical formula 2]
[chemical formula 3]
4. an optical polymerism composition, described optical polymerism composition comprises photopolymerizable compound and light trigger,
Wherein, described light trigger comprises the oxime ester compound of following chemical formula 1:
[chemical formula 1]
Wherein, R is C1 to C20 alkyl, and
N is the integer of 6 to 21.
5. optical polymerism composition according to claim 4,
Wherein, described optical polymerism composition comprises the acrylic acid or the like oligomer with ethylenic unsaturated bond.
6. optical polymerism composition according to claim 5,
Wherein, the acrylic acid or the like oligomer described in ethylenic unsaturated bond has 200,000 to 1,000, the GPC weight-average molecular weight of 000.
7. optical polymerism composition according to claim 4,
Wherein, the R in described chemical formula 1 is C1 alkyl or C6 alkyl.
8. optical polymerism composition according to claim 4,
Wherein, one or more in the group that is selected from following chemical formula 2 to chemical formula 3 and forms of described chemical formula 1:
[chemical formula 2]
[chemical formula 3]
9. optical polymerism composition according to claim 4,
Wherein, based on the described photopolymerizable compound of 100 weight parts, the content of described light trigger is 0.01 weight part to 10 weight part.
10. optical polymerism composition according to claim 4,
Wherein, described optical polymerism composition comprises solvent further.
CN201510338292.4A 2014-06-19 2015-06-17 Oxime ester compound and the optical polymerism composition including the oxime ester compound Active CN105198780B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2014-0074751 2014-06-19
KR1020140074751A KR20150145415A (en) 2014-06-19 2014-06-19 Oxime ester compound and a photopolymerizable composition comprising the same

Publications (2)

Publication Number Publication Date
CN105198780A true CN105198780A (en) 2015-12-30
CN105198780B CN105198780B (en) 2017-06-20

Family

ID=54946781

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510338292.4A Active CN105198780B (en) 2014-06-19 2015-06-17 Oxime ester compound and the optical polymerism composition including the oxime ester compound

Country Status (3)

Country Link
KR (1) KR20150145415A (en)
CN (1) CN105198780B (en)
TW (1) TW201600501A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6714533B2 (en) * 2017-03-22 2020-06-24 信越化学工業株式会社 Sulfonium salt, resist composition, and pattern forming method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003307611A (en) * 2002-04-17 2003-10-31 Fujifilm Arch Co Ltd Color filter and method for manufacturing the same
JP2009198710A (en) * 2008-02-20 2009-09-03 Hitachi Chem Co Ltd Photosensitive resin composition, and photosensitive film, resist pattern forming method and permanent resist using the same
JP2009203299A (en) * 2008-02-27 2009-09-10 Toyo Ink Mfg Co Ltd Non-yellowing polymerizable composition and method for producing polymerized material
JP2011159881A (en) * 2010-02-02 2011-08-18 Fujifilm Corp Curable composition for imprint, pattern forming method, and pattern
JP2014149432A (en) * 2013-02-01 2014-08-21 Adeka Corp Alkali developable photosensitive composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003307611A (en) * 2002-04-17 2003-10-31 Fujifilm Arch Co Ltd Color filter and method for manufacturing the same
JP2009198710A (en) * 2008-02-20 2009-09-03 Hitachi Chem Co Ltd Photosensitive resin composition, and photosensitive film, resist pattern forming method and permanent resist using the same
JP2009203299A (en) * 2008-02-27 2009-09-10 Toyo Ink Mfg Co Ltd Non-yellowing polymerizable composition and method for producing polymerized material
JP2011159881A (en) * 2010-02-02 2011-08-18 Fujifilm Corp Curable composition for imprint, pattern forming method, and pattern
JP2014149432A (en) * 2013-02-01 2014-08-21 Adeka Corp Alkali developable photosensitive composition

Also Published As

Publication number Publication date
KR20150145415A (en) 2015-12-30
CN105198780B (en) 2017-06-20
TW201600501A (en) 2016-01-01

Similar Documents

Publication Publication Date Title
JP6196363B2 (en) Novel β-oxime ester fluorene compound, photopolymerization initiator containing the same, and photoresist composition
JP7034175B2 (en) Polymerizable group-containing fluorene oxime ester-based photoinitiator, production method and its application
CN101541837B (en) Curable composition containing hydroxyl group-containing thiol compound and cured product thereof
CN103492948B (en) Light-sensitive compound and comprise its photosensitive resin composition
CN104428713B (en) Photosensitive polymer combination, conductive wires protective film and touch panel component
CN104892512B (en) A kind of pyrazolines sensitizer and its preparation method and application
CN101059656B (en) Photo-sensitive resin composition containing inorganic particle, photo-sensitive film, and process of forming inorganic pattern
JP2009256662A (en) Silsesquioxane derivative and method for producing the same
CN104761661B (en) A kind of water soluble Benzophenone-type light initiator of polymerizable and preparation method thereof
JP5705371B2 (en) Polymer compound containing dye and curable resin composition containing the same
CN104892513B (en) Alkenyl-containing pyrazoline sensitizer as well as preparation method and application thereof
KR20140023224A (en) Photosensitive alkali-soluble resin, method of preparing the same, and color photosensitive resist containing the same
JP6608303B2 (en) Negative photosensitive resin composition, pattern formed from the composition, and image display device
CN106565864A (en) Fluorine-containing oxime ester photoinitiator, synthesis and applications thereof
CN109666088A (en) A kind of diketone oxime ester compound and its manufacturing method and application
TW201802071A (en) Highly sensitive oxime ester photopolymerization initiator and photopolymerizable composition including the same
CN105198779A (en) Oxime ester compound and light-polymerizable composition including same
JP7129006B2 (en) Photopolymerization sensitizer with migration resistance
CN105198780A (en) Oxime ester compound and light-polymerizable composition including same
CN106749776A (en) A kind of oxime ester lightlike initiating agent containing fluorenes
JP2010006982A (en) Photosensitive polyorganosiloxane composition, polyorganosiloxane-cured relief pattern and method for forming the same, and semiconductor device and method for producing the same
KR101570301B1 (en) Oxime ester compound and a photopolymerizable composition comprising the same
CN108503577B (en) Oxime ester compound and photocurable composition containing same
KR20160044204A (en) Oxime ester compound and a photopolymerizable composition comprising the same
KR20210066736A (en) Keto ester photoinitiator and photopolymerizable composition comprising the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant