JP4342886B2 - Photosensitive composition and photosensitive coloring composition - Google Patents

Description

  The present invention relates to a photosensitive composition and a photosensitive coloring composition.

  In the production of color filters using pigments, mainly pigments, methods using the following photosensitive compositions and photosensitive coloring compositions (A) to (C) are known.

  (A) A pigment is dispersed in an acrylic resin by a dispersant or the like (hereinafter referred to as a colored composition in this state), this colored composition is coated on a glass substrate and dried, and then a photosensitive resist material is formed thereon. (Positive resist such as “AZ” manufactured by Hoechst Co., Ltd.) is coated and dried, then exposed using a mask, and then developed to form a resist pattern. Further, a portion without resist is etched. Remove to form a pattern of the colored composition. Then, the resist which became unnecessary on the pattern of a coloring composition is peeled, and the method of completing a color filter (refer Unexamined-Japanese-Patent No. 60-237403).

  (B) In a colored composition similar to (A) above, a photosensitive agent such as a bisazide compound or a diazo compound is added to impart photosensitivity to the colored composition, which is coated on a substrate, dried, A formation method for obtaining a colored pattern by exposure and development (see JP-A-2-181704).

  (C) In the same colored composition as in the above (A), a photopolymerization initiator and a photopolymerizable monomer are added as a photosensitizer to impart photosensitivity to the color composition, and this is coated on a substrate and dried. Thereafter, a method of forming an oxygen barrier film made of PVA or the like, and exposing and developing to obtain a colored pattern (see JP-A-2-144502). In this case, acetophenone, benzyl dimethyl ketal or the like is used as the photopolymerization initiator.

  In the method (C), the oxygen blocking film is formed for the following reason. That is, in this method of adding a photopolymerization initiator to the colored composition, the photopolymerization reaction proceeds in a chain, so that the sensitivity when exposing the colored composition is slightly higher than the type (B). However, since the photopolymerization reaction of the colored composition of the method (C) is inhibited by oxygen, it is difficult to perform patterning in an oxygen atmosphere, and a considerable amount of exposure is required. Therefore, an oxygen barrier film such as PVA is formed so that the colored composition is not affected by this effect.

  However, in the production of the conventional color filter using the composition as described above, in the production method (A), since the colored composition itself is not photosensitive, a photosensitive resist is coated separately from the colored composition. However, there is a manufacturing disadvantage that the patterning, then etching, and the resist that is no longer needed need to be removed, and the process is long and the yield is reduced.

  In the production method of (B), since the coloring composition itself has photosensitivity, there is no disadvantage as in (A). However, since the acrylic resin contains a pigment, the sensitivity is low. There is a drawback that an exposure amount is required. In addition, since an organic solvent is used as a part of the developer, there are some problems such as material cost, waste liquid treatment, and handling method.

  In the production method of (C), a pigment is contained in the acrylic resin as in the case of (B), and the sensitivity is low and a large amount of exposure is required. In addition, it is necessary to form an oxygen barrier film such as PVA, which requires a long process and disadvantageous in production such as a decrease in yield.

  Therefore, as a solution to the above-mentioned problems, a method for producing a polymerization initiator using a photosensitive composition comprising a triazine-based polymerization initiator, a photopolymerizable monomer, an organic polymer conjugate, and a dye (Japanese Patent Application Laid-Open No. 06-2006). However, the photopolymerization initiator used has a problem that a sublimation product is generated and the exposure mask is stained with exposure. Moreover, since the solubility with respect to a solvent is low, when preparing a photosensitive composition, it must be heated or stirred for a long time, and workability | operativity is bad.

  Further, Patent Document 1 proposes to use an oxime ester derivative as an initiator that should solve the problems of the triazine-based initiator. Patent Document 2, Patent Document 3, Patent Document 4, and the like also describe oxime ester compounds. These known oxime ester compounds have insufficient sensitivity.

Patent Document 5, Patent Document 6, and Patent Document 7 propose O-acyloxime photoinitiators having higher reactivity. However, the temporal stability of these oxime ester compounds as photoinitiators is still unsatisfactory. There is also a demand for an initiator that does not contaminate the polymer or apparatus due to volatilization of the decomposition product of the initiator.
US Pat. No. 3,558,309 U.S. Pat. No. 4,255,513 U.S. Pat. No. 4,590,145 US Patent No. 4202697 JP 2000-80068 A JP 2001-233842 A WO02 / 100903 Publication

  The present invention has been made in order to solve such problems, and the subjects thereof are high reliability, high sensitivity, high stability over time, and high solubility. The object is to provide a photosensitive composition and a photosensitive coloring composition which can be well prepared.

  That is, the present invention provides a photosensitive coloring composition comprising (1) a resin, (2) a photopolymerizable monomer, (3) a photopolymerization initiator, (4) a solvent, (5) a coloring pigment, and (6) a dispersant. In (3), the photopolymerization initiator is a dimeric oxime ester compound represented by the following general formula (I).

(Wherein X1 and X1 ′ each represent a halogen atom or an alkyl group, Z represents an oxygen atom or a sulfur atom, m and n each represent a number of 1 to 5, and R1 and R1 ′ each represent R
, OR, COR, SR, CONRR ′ or CN, R2 and R2 ′ represent R, OR, COR, SR, NRR ′, respectively, and R3 and R3 ′ represent R, OR, COR, SR, NRR ′, respectively. R4 represents a diol residue or a dithiol residue, R and R ′ represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which are substituted with a halogen atom and / or a heterocyclic group. Of these, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. )

  The present invention improves the photosensitivity by using the compound represented by the general formula (1) as a main component of the photopolymerization initiator. When this photosensitive composition or photosensitive coloring composition is used, oxygen blocking is achieved. A pattern can be formed without a film, and the accuracy of the pattern can be improved. Moreover, the composition containing the said photoinitiator has the effect excellent in temporal stability.

  Furthermore, the photopolymerization initiator represented by the general formula (1) has high solubility in a solvent and is easy to prepare a photosensitive resin composition, so that workability is good. Therefore, in the method for producing a color filter or the like using the photosensitive composition or the photosensitive coloring composition according to the present invention, the process is shortened and the workability and productivity are improved as compared with the conventional method.

  Hereinafter, the present invention will be described in detail.

  (1) Resin applied in the present invention includes acrylic acrylate, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate and other alkyl acrylates or alkyl methacrylates, cyclic cyclohexyl acrylate or methacrylate Resin synthesized with a molecular weight of about 5000 to 100,000 using about 3 to 5 types of monomers from hydroxyethyl acrylate or methacrylate, styrene and the like. In addition, a resin in which an unsaturated double bond is added to a part of an acrylic resin is obtained by reacting a compound such as the above acrylic resin, an isocyanate ethyl acrylate having at least one vinyl group and an isocyanate group, or methacryloyl isocyanate. The photosensitive copolymer having an acid value of 50 to 150 can be preferably used from the viewpoint of heat resistance, developability and the like.

  Furthermore, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, Ordinary photopolymerizable resins such as epoxy (meth) acrylate obtained by reacting an epoxy resin such as a dihydroxybenzene type epoxy resin and (meth) acrylic acid, or a cardo resin can also be used.

  The (2) photopolymerizable monomer used in the present invention is a polyfunctional (meth) acrylate monomer and forms the main component of the photosensitive resin component of the present invention. For example, ethylene glycol (meth) acrylate, diethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hexane di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycerin tetra (meth) acrylate, tetratrimethylolpropane tri (meth) acrylate, dipentaerythrito Ruhekisa (meth) acrylate and the like, these components are used alone or as a mixture.

  Next, (3) photoinitiator applied in the present invention is

(Wherein X1 and X1 ′ each represent a halogen atom or an alkyl group, Z represents an oxygen atom or a sulfur atom, m and n each represent a number of 1 to 5, and R1 and R1 ′ represent R, OR, respectively. , COR, SR, CONRR ′ or CN, R2 and R2 ′ represent R, OR, COR, SR, NRR ′, respectively, R3 and R3 ′ represent R, OR, COR, SR, NRR ′, respectively. R4 represents a diol residue or a dithiol residue, R and R ′ represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these may be substituted with a halogen atom and / or a heterocyclic group the alkylene moiety of the alkyl group and aralkyl group of these, unsaturated bond, an ether bond, a thioether bond, a compound represented by by an ester bond may be interrupted.) In the general formula (I), examples of the halogen atom represented by X1 and X1 ′ include fluorine, chlorine, bromine and iodine. Examples of the alkyl group represented by X1 and X1 ′ include, for example, methyl , Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl , Vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoro Ethyl, pa Fluoroethyl, 2- (benzoxazol-2'-yl) ethenyl and the like.

Examples of the alkyl group represented by R and R ′ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propylethoxyethoxyethyl, Methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like are mentioned, and the aryl group represented by R and R ′ For example, phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like, and examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, α-methylbenzyl, α , Α-dimethylbenzyl, phenylethyl, phenylethenyl and the like, and examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like, and R and R Examples of the ring that can be formed together with 'include a piperidine ring and a morpholine ring.
The diol residue or dithiol residue represented by R ₄ is not particularly limited and is a group that can be introduced from a diol compound or dithiol compound. Examples of the diol compound include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2, 4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3, Aliphatic diol compounds such as 5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, thiodiethylene glycol, cyclohexanedimethanol, Examples include cycloaliphatic diol, alicyclic diol compounds such as hydrogenated bisphenol A, and aromatic cyclic diol compounds such as p-xylene-α, α'-diol. Examples of the dithiol compound include ethylene dithiol, 1,2- Propanedithiol, 1,3-propanedithiol, 2-methyl-1,3-propanedithiol, 2-butyl-2-ethyl-1,3-propanedithiol, 1,4-butanedithiol, 3-methyl-2,4 -Pentanedithiol, 2,4-pentanedithiol, 1,5-pentanedithiol , 3-methyl-1,5-pentanedithiol, 2-methyl-2,4-pentanedithiol, 2,4-diethyl-1,5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol 3,5-heptanedithiol, 1,8-octanedithiol, 2-methyl-1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol and other aliphatic dithiols, cyclohexanedimethylenethiol, Examples include alicyclic dithiol compounds such as cyclohexanedithiol, and aromatic cyclic dithiols such as p-xylene-α, α′-dithiol.

Among the (3) photoinitiators applied in the present invention, among the above general formula (I), those in which X ₁ and / or X ₁ ′, in particular, X ₁ and X ₁ ′ are chlorine atoms; Or n, in particular m and n are 1; R ₁ and / or R ₁ ′, in particular R ₁ and R ₁ ′ are alkyl groups, in particular methyl groups; R ₂ and / or R ₂ ′, in particular R ₂ and R ₂ ′ are alkyl groups, particularly methyl groups; R ₃ and / or R ₃ ′, especially R ₃ and R ₃ ′ are alkyl groups, especially ethyl groups; R ₄ is an alkylene group or An arylene group, particularly a butylene group or a pentylene group is preferred.

Accordingly, preferred specific examples of the dimer oxime ester compound of the present invention represented by the above general formula (I) include the following compound Nos. 1-No. 4 compounds. However, the present invention is not limited by the following compounds.
(Compound 1)

(Compound 2)

(Compound 3)

(Compound 4)

In addition, as the (3) photopolymerization initiator, one or more known photopolymerization initiators can be used together with the acyloxime ester compound. For example, Ciba-Gaigi, Irgacure 369, 819, 907, 651, 184 (benzyldimethyl ketal), 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.), benzophenone, phenyl biphenyl ketone, 1-hydroxy 1-benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholy-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1 -Chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl -3,6-bis (2'-morpholinoisobutyroyl) carbazole, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s -Triazine, 2-naphthyl-4,6-bis (trichloromethyl) and the like can be used.

  Moreover, in the photosensitive composition containing the compound of the present invention, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; Conventional additives such as fillers can be added.

  (3) Although the usage-amount of a photoinitiator is not specifically limited, When only 1 type or multiple types of dimer oxime ester compounds are used, (2) with respect to 100 weight part of photopolymerizable monomers The dimer oxime ester compound is usually 5 to 50 parts by weight, preferably about 10 to 40 parts by weight. Moreover, when using together a dimer oxime ester compound and a well-known photoinitiator, (2) 1-50 weight part of dimer oxime ester compounds are normally with respect to 100 weight part of photopolymerizable monomers. The amount of the photopolymerization initiator is preferably about 1 to 40 parts by weight, and preferably about 5 to 20 parts by weight.

  Specific examples of the solvent (4) used in the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol, cellosolv solvents such as methoxy alcohol and ethoxy alcohol, methoxy Carbitol solvents such as ethoxyethanol, ethoxyethoxyethanol, ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, ketone solvents such as acetone, methyl isobutyl ketone, cyclohexanone, Cellol acetate acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; carbitol acetates such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate Solvents, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and other ether solvents, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and other aprotic amide solvents, γ-butyrolactone And organic solvents such as unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene, and saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane.

  As a blending method of each component as described above, for example, (6) Dispersant and (5) Colored pigment are kneaded well using two rolls or the like to form a chip, and then (6) Dispersant and (4) The photosensitive coloring composition of the present invention is prepared by adding a solvent to the paste to add a photopolymerizable monomer and a photopolymerizable initiator.

  In the photosensitive coloring composition of the present invention, (5) the coloring pigment is generally C.I. I. No. 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, etc. can be used, and C.I. I. No. 7, 36, etc. can be used, and C.I. I. No. 15, 22, 60, 64, etc. can be used, and C.I. I. No. 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, 168 and the like can be used, and C.I. I. No. 36, 43, 51, 55, 59, 61 etc. can be used, and C.I. I. No. 19, 23, 29, 30, 37, 40, 50, etc. can be used. Of these, only one type may be used, or a plurality of types may be used in combination. In general, two or three kinds of pigments are used in combination for spectral adjustment of the color filter. When carbon black is used as the black pigment, it is desirable that the carbon black has an average particle size of 1.0 μm or less, particularly 0.01 to 0.5 μm, more preferably 0.01 to 0.3 μm. Further, the pH of the aqueous carbon black solution is preferably 8.0 or less. Specific examples of carbon black include Degussa's Printex 3, Printex 25, Printex 30, Printex 35, Printex 40, Printex 45, Printex 200, Printex 300, Printex A, Printex G, Special Black 100, Special Black 250, Special Black 350, CABOT MONARCK 120, MONARCK 280, MONARCK 430, MONARCK460, REGAL 99, REGAL 250, REGAL 330, REGAL 415, Black PEARLS 130, Black PEARLS 480, Raven 410 from Columbian Carbon , Raven 420, Raven 430, Raven 450, Raven 500, Raven 760, Raven 790, Raven 850, Raven 890, Raven 890H, Raven 1000, Raven 1020, Raven 1035, Raven 1040, Raven 1060, MA-made by Mitsubishi Chemical 7, MA-8, MA-11, MA-100, MA-100R, MA-220 and the like.

  (5) Although the usage-amount of a color pigment is not specifically limited, Usually, (1) It shall be about 5-100 weight part with respect to 100 weight part of resin.

  (6) The dispersant can be appropriately selected and used from a wide range, and for example, a surfactant, an intermediate of pigment, an intermediate of dye, or solsperse can be used. Furthermore, the organic dye is a derivative of an organic dye, and the organic dye as a base is an azo, phthalocyanine, quinacridone, anthraquinone, berylene, thioindico, dioxane, or metal complex salt. These organic dyes have a substituent and are effective in dispersing the dye.

  As the substituent, a compound having any one of a hydroxyl group, a carboxyl group, a sulfone group, a carbonamide group, and a sulfonamide group can also be used. Furthermore, in order to improve the dispersibility, elastomers such as polyurethane, polyester, polyamide, polystyrene, and polyolefin may be added.

  (6) Although the usage-amount of a dispersing agent is not specifically limited, Usually, it is about 1-100 weight part with respect to 100 weight part of (5) coloring pigments.

  The photosensitive coloring composition of the present invention thus obtained is useful for the production of color filters, and particularly useful for the production of color filters for use in color liquid crystal displays, color video cameras, image scanners, and the like. It becomes. Moreover, it is not restricted to this, The photosensitive coloring composition of this invention can be widely used as UV ink, a photosensitive coating material, etc.

  And the process of apply | coating the photosensitive coloring composition of this invention on a board | substrate, the pattern exposure of the photosensitive coloring composition apply | coated to the board | substrate, the process of photocuring the photosensitive coloring composition of an exposure part, the pattern exposure photosensitive The color filter can be produced from the step of leaving the colored layer in which the photosensitive coloring composition is cured by developing the photosensitive coloring composition and then heating it in a pattern on the substrate.

  In the step of producing a color filter using the photosensitive coloring composition of the present invention, the step of forming the oxygen blocking film is not necessarily required, but may be provided as necessary. As methods for producing color filters, the methods described in JP-A-3-53201, JP-A-2-199403, JP-A-2-199404, and JP-A-2-144502 are known. The color filter of the invention can be produced in the same manner as these methods as long as the photosensitive coloring composition of the invention is used.

  The color filter obtained as described above is suitable as a color filter used in a liquid crystal cell of a color liquid crystal display device, and in particular, a TN (twisted nematic) type liquid crystal, a GH (guest host) type liquid crystal, and an FLC (ferroelectric property). It is suitable as a color filter for use in a full color liquid crystal display device using liquid crystal. Further, it is also suitable as a color separation color filter used for a solid-state imaging device such as a color video camera or an image scanner.

  As described above, the photosensitive composition and the photosensitive coloring composition of the present invention are highly reliable and sensitive by using a dimer oxime ester compound (Chemical Formula 1) as a photopolymerization initiator, Since it has high stability over time and high solubility, it can be formulated with good workability. Furthermore, the phenomenon of crying out to the photosensitive layer can be suppressed and the stability over time is good.

Preparation of photosensitive coloring composition Acrylic resin (20 parts of methacrylic acid, 10 parts of methyl methacrylate, 55 parts of butyl methacrylate, 15 parts of hydroxyethyl methacrylate are dissolved in 300 g of ethyl cellosolve, and 0.75 parts of azobisisobutylnitrile under nitrogen atmosphere The acrylic resin obtained by the reaction at 70 ° C. for 5 hours was diluted with ethyl cellosolve so that the resin concentration became 10%.

To 90.1 g of this diluted resin, 9.0 g of pigment and 0.9 g of a dispersant were added and kneaded sufficiently with three rolls to prepare blue, red, green and black varnishes.
For 100 g of each colored resin,
Compound 1-0.02 g
Trimethylolpropane acrylate-0.4g
And stirred well to obtain a photosensitive coloring composition.

Subsequently, r-glycidoxypropylmethylethoxysilane was spin-coated on the substrate and spin-dried well, and the photosensitive composition was spin-coated (1000 rpm, 40 seconds) and dried. After pre-baking at 70 ° C. for 20 minutes, exposure was performed using a mask having a pixel size of 30 μm × 100 μm. Next, after developing with a 2.5% sodium carbonate solution, it was washed well with water, further washed with water and dried, and then baked at 230 ° C. for 1 hour to fix the pattern. The exposure amount was 30 mJ / cm ² .

  Further, no photopolymerization initiator was deposited even after standing for 10 days or more after spin coating of the photosensitive composition.

Styrene-acrylic photosensitive copolymer [(a) 26.3 parts by weight of styrene, (b) 43.8 parts by weight of 2-hydroxymethacrylate, (c) 35 parts by weight of methacrylic acid, (d) 70 parts by weight of ethyl methacrylate A portion was dissolved in 175 parts by weight of ethyl cellosolve, 0.75 part by weight of azobisisobutylnitrile was added under a nitrogen atmosphere, and the mixture was reacted at 90 ° C. for 5 hours. Next, a solution of 23.5 parts by weight of isocyanate ethyl methacrylate and 0.11 part by weight of tin octylate dissolved in 20 parts by weight of ethyl cellosolve was dropped in about 10 minutes, followed by reaction for 2 hours, and the resulting styrene-acrylic against the system photosensitive copolymer, by adding a pigment and a dispersant to obtain a blue, red, green, each colored resin black. The colored resin was added with trimethylolpropane acrylated preparative Compound 2 thoroughly stirred to obtain a photosensitive coloring composition.

Subsequently, r-glycidoxypropylmethylethoxysilane was spin-coated on the substrate and spin-dried well, and the photosensitive composition was spin-coated (1000 rpm, 40 seconds) and dried. After pre-baking at 70 ° C. for 20 minutes, exposure was performed using a mask having a pixel size of 30 μm × 100 μm. Next, after developing with a 2.5% sodium carbonate solution, it was washed well with water, further washed with water and dried, and then baked at 230 ° C. for 1 hour to fix the pattern. The exposure amount was 30 mJ / cm ² .

  Further, no photopolymerization initiator was deposited even after standing for 10 days or more after spin coating of the photosensitive composition.

  Compound 2 was replaced with compound 4, and a photosensitive composition was obtained with the same blending ratio and production conditions as in Example 2.

Then, r-glycidoxypropylmethylethoxysilane was spin-coated on the substrate and spin-dried well, and the photosensitive composition was spin-coated (1000 r.p.m, 40 seconds) and dried. After pre-baking at 70 ° C. for 20 minutes, exposure was performed using a mask having a pixel size of 30 μm × 100 μm. Next, after developing with a 2.5% sodium carbonate solution, it was washed well with water, further washed with water and dried, and then baked at 230 ° C. for 1 hour to fix the pattern. The exposure amount was 30 mJ / cm ² .

Further, no photopolymerization initiator was deposited even after standing for 10 days or more after spin coating of the photosensitive composition.
[Comparative Example 1]
An acrylic copolymer was produced under the same conditions as in Example 1.
(Compound 5)

Next, 0.02 g of dipentaerythritol penta and hexaacrylate and compound 5 was added to 100 g of the acrylic copolymer, and the mixture was stirred well to obtain a photosensitive composition.

Next, r-glycidoxypropylmethylethoxysilane was spin-coated on the substrate and spin-dried well, and each photosensitive composition was spin-coated (1300 rpm, 50 seconds) and dried. After pre-baking at 70 ° C. for 20 minutes, a 5% polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, the film was exposed using a predetermined mask, developed with a 2.5% sodium carbonate solution, and then thoroughly washed with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. In addition, the exposure amount of each color was blue: 100 mJ / cm ² , green: 120 mJ / cm ² , red: 120 mJ / cm ² , and the pattern obtained was unclear and the sensitivity was not so good .

  In addition, this photosensitive coloring composition has the same characteristic as the photosensitive coloring composition which concerns on the comparative example 1, and a sensitivity is not good compared with Example 2. FIG. Further, after spin coating the photosensitive composition, it was confirmed that the photopolymerization initiator was precipitated when left for 10 days or longer.

Claims (9)

In the photosensitive composition comprising (1) resin, (2) photopolymerizable monomer, (3) photopolymerization initiator, and (4) solvent, the above (3) photopolymerization initiator is represented by the following general formula (I): A photosensitive composition, which is a dimer oxime ester compound that can be expressed.
(Wherein X1 and X1 ′ each represent a halogen atom or an alkyl group, Z represents an oxygen atom or a sulfur atom, m and n each represent a number of 1 to 5, and R1 and R1 ′ represent R, OR, respectively. , COR, SR, CONRR ′ or CN, R2 and R2 ′ represent R, OR, COR, SR, NRR ′, respectively, R3 and R3 ′ represent R, OR, COR, SR, NRR ′, respectively. R4 represents a diol residue or a dithiol residue, R and R ′ represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these may be substituted with a halogen atom and / or a heterocyclic group Of these, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.)
The photosensitive composition according to claim _1, wherein X ₁ and / or X ₁ ′ in the general formula (I) is a chlorine atom.   3. The photosensitive composition according to claim 1 or 2, wherein m and / or n in the general formula (I) is 1. The photosensitive composition according to claim _1, wherein R ₁ and / or R ₁ ′ in the general formula (I) is an alkyl group. R < ₂ > and / or R < ₂ '> in general formula (I) is an alkyl group, The photosensitive composition in any one of Claims 1-4 characterized by the above-mentioned. The photosensitive composition according to claim 1, wherein R ₃ and / or R ₃ ′ in the general formula (I) is an alkyl group. R < ₄ > in general formula (I) is an alkylene group, The photosensitive composition in any one of Claims 1-6 characterized by the above-mentioned. R < ₄ > in general formula (I) is an arylene group, The photosensitive composition in any one of Claims 1-6 characterized by the above-mentioned. The photosensitive composition according to claim 1, further on, (5) worn color pigment, (6) a photosensitive coloring composition, characterized in that to incorporate a dispersing agent.