TWI662366B - Photosensitive composition - Google Patents

Abstract

The present invention provides a pattern that can form a high sensitivity, and has excellent straightness and adhesion to a substrate. Even if the photosensitive composition contains a light-shielding agent or an insufficient exposure amount, it can suppress the development after development. A photosensitive composition having an undercut pattern, and a color filter and a display device using the composition.

In a photosensitive composition containing a photopolymerizable compound and a photopolymerization initiator, a carbazole-3-ylcarbonyl group having a specific substituent at the 6-position on the carbazole ring and a cycloalkylalkyl bond having a specific structure An oxime-based compound bound to an oxime carbon is used as a photopolymerization initiator.

Description

Photosensitive composition

The present invention relates to a photosensitive composition, a color filter using the same, and a display device.

A display device such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates formed with electrodes facing each other in pairs. A color filter composed of pixel regions of each color, such as red (R), green (G), and blue (B), is formed inside one of the substrates. This color filter generally forms a black matrix in order to distinguish each pixel region such as red, green, and blue.

Generally, a color filter is manufactured by a lithography method. That is, first, a black photosensitive composition is coated on a substrate, dried, and then exposed and developed to form a black matrix. Next, the photosensitive composition of each color, such as red, green, and blue, is repeatedly coated, dried, exposed, and developed to form a pixel region of each color at a specific position to produce a color filter.

The black matrix is a pattern made of a photosensitive composition containing a light-shielding agent. It helps to obtain light by suppressing light leakage from each pixel region. The contrast of the display device is improved or the color development is good. In addition, as described above, the black matrix formed in the initial stage of color filter production also plays the role of forming recesses for embedding the photosensitive composition for coloring each pixel region thereafter, and forming each color pixel region at a specific position. .

In recent years, in the manufacture of liquid crystal displays, attempts have been made to improve the light-shielding properties through the black matrix, and to further improve the contrast of the images displayed by the liquid crystal displays. Therefore, the photosensitive composition for forming a black matrix must contain a large amount of a light-shielding agent. However, when the photosensitive composition contains a large amount of a light-shielding agent as described above, when the film of the photosensitive composition formed on the substrate is exposed, the light for curing the photosensitive composition hardly reaches the bottom of the film. Leading to poor hardening as the sensitivity of the photosensitive composition decreases significantly.

The photopolymerization initiator contained in the photosensitive composition as a part of the composition causes radicals to be generated by exposure, and this radical polymerizes and hardens the polymerizable compound contained in the photosensitive composition. Therefore, it is known that the sensitivity of the photosensitive composition is affected by the type of the photopolymerization initiator contained in the photosensitive composition. In addition, in recent years, the number of liquid crystal displays has increased, and the production volume of color filters has also increased. From the viewpoint of further improving productivity, it is expected that a photosensitive composition with high sensitivity can be formed at a low exposure. In this case, a photopolymerization initiator which can make the sensitivity of the photosensitive composition good is proposed in Patent Document 1 as an oxime ester compound having a cycloalkyl group. The examples described in Patent Document 1 specifically disclose compounds represented by the following chemical formulae (a) and (b).

[Prior technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 101508744

[Invention Summary]

By using the compounds represented by the chemical formulae (a) and (b) as a photopolymerization initiator, a highly sensitive photosensitive composition can be produced. However, the sensitivity of a photosensitive composition containing a compound represented by the above-mentioned chemical formulae (a) and (b) as a photopolymerization initiator may not necessarily correspond to the effect of low exposure quantification in pattern formation during production of a display or the like. The photosensitive composition needs to be further improved in sensitivity.

In addition, these compounds are used as photopolymerization initiators. When forming a black matrix, the sensitivity is good, but on the contrary, The pattern shape causes the following problems.

Generally, when a pattern of a color filter for a liquid crystal display is formed using a photosensitive composition, as shown in FIG. 1 (a), generally, the closer the cross section 1 of the cross section of the pattern in the width direction is to the bottom 1a, the wider it becomes, the closer it is to the top edge 1b, the narrower the trapezoidal shape becomes. At this time, the angle θ formed between the patterned section 1 and the color filter substrate (not shown) becomes an acute angle.

However, when a black matrix is formed using a photosensitive composition containing a compound represented by the above chemical formula (a) or (b) as a photopolymerization initiator, as shown in FIG. 1 (b), the bottom of the pattern is accompanied by development. Some of them are dissolved, and undercuts 21 may be generated at both ends of the bottom edge 2a in the cross section 2 which is the cross section in the pattern width direction. At this time, an angle θ formed between the cross section 2 of the pattern and a color filter substrate (not shown) is an obtuse angle. As described above, when the angle θ becomes an obtuse angle, when the pixel regions of red, green, blue, and the like adjacent to the black matrix are formed, bubbles are generated in the undercut 21 portion. That is, in the case of a film adjacent to the photosensitive composition for forming a black matrix-forming pixel region, the photosensitive composition does not enter the space existing in the form of undercut 21, and the space remains as a bubble. When such bubbles exist in a color filter, there is a problem because the image quality of the liquid crystal display device is greatly impaired. This problem is particularly noticeable in the case of development when the black matrix pattern is formed, and in the case of a slight excessive overdevelopment.

In addition, when a photosensitive composition containing a compound represented by the above-mentioned chemical formulae (a) and (b) as a photopolymerization initiator is used to form a pattern, it may be difficult to form a pattern having excellent straightness, or a pattern may be easily generated after development. Type peeling from the substrate.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a pattern that can form a high sensitivity, and has excellent straightness and adhesion to a substrate, even if the photosensitive composition contains a light-shielding agent or an insufficient exposure amount. In this case, it is also possible to suppress a photosensitive composition that undercuts the pattern after development, a color filter and a display device using the composition.

As a result of careful review in order to solve the above problems, the present inventors have found that in a photosensitive composition containing a photopolymerizable compound and a photopolymerization initiator, a carbazole having a specific substituent at the 6-position on the carbazole ring An oxime-based compound in which a -3-ylcarbonyl group and a cycloalkylalkyl group having a specific structure are bonded to an oxime carbon is used as a photopolymerization initiator, which can solve the above-mentioned problems and complete the present invention.

A first aspect of the present invention is a photosensitive composition containing (A) a photopolymerizable compound and (B) an oxime-based photopolymerization initiator represented by the following formula (1).

(In the above formula (1), l is an integer of 1 to 5, m is an integer of 0 to (l + 3), n is an integer of 1 to 8, R ¹ is an alkyl group of 1 to 11 carbon atoms, or An aryl group which may have a substituent, R ² is any of the substituents represented by the following formulae (2) to (5), R ³ is an alkyl group, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms .)

The second aspect of the present invention is the photosensitive composition of the first aspect, and a color filter formed using the photosensitive composition containing a colorant (C).

A third aspect of the present invention is a display device using the color filter of the second aspect of the present invention.

According to the present invention, it is possible to provide a pattern that can form a high sensitivity, and has excellent straightness and adhesion to a substrate. Even if the photosensitive composition contains a light-shielding agent or an insufficient exposure amount, it can suppress the development after development. A photosensitive composition with an undercut pattern, a color filter and a display device using the composition.

1‧‧‧ Wide cross-section in an undercut pattern

2‧‧‧ undercut in wide direction

[Fig. 1] A schematic diagram showing a cross-sectional shape in the width direction of a pattern formed from a photosensitive composition, (a) a diagram showing a cross-sectional shape of a normal pattern, and (b) a cross-section of a pattern generating undercut 21. Shaped figure.

[Photosensitive composition]

The photosensitive composition contains at least (A) a photopolymerizable compound and (B) an oxime-based photopolymerization initiator represented by the above formula (1). Hereinafter, each component contained in the photosensitive composition of this invention is demonstrated in detail.

<(A) Photopolymerizable compound>

The (A) photopolymerizable compound contained in the photosensitive composition of the present invention is not particularly limited, and conventionally known photopolymerizable compounds can be used. Among them, a resin or monomer having an ethylenically unsaturated group is preferred, and a combination of these is more preferred. By combining a resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group, the curability of the photosensitive composition can be improved and a pattern can be easily formed.

[Resin with ethylenically unsaturated group]

Examples of the resin having an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, and 2-hydroxyethyl (meth) acrylate. Ester, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methyl Acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylenedi Alcohol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate Ester, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (methyl) Oligomers obtained by polymerizing acrylate, 1,6-hexanediol di (meth) acrylate, cardo epoxy diacrylate, etc .; polyesters obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid Prepolymer, polyester (meth) acrylate obtained by reacting with (meth) acrylic acid; polyamine group obtained by reacting polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid Formate (meth) acrylate; make bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol or cresol novolac epoxy resin, resol type ring Oxygen resin, trisphenol methane epoxy resin, polypropylene carbonate, polyol polypropylene oxide, fat Epoxy or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin, the obtained reacted with the epoxy (meth) acrylate, (meth) acrylate resin and the like. In addition, a resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be used. The "(meth) acrylic acid" in this specification means "acrylic or methacrylic acid".

In addition, the resin having an ethylenically unsaturated group is more preferably a resin obtained by reacting an epoxy compound with a reactant of an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride.

Among them, a compound represented by the following formula (a1) is preferred. The compound represented by the formula (a1) is more stable than good.

In the formula (a1), X represents a group represented by the following formula (a2).

In the formula (a2), R ^1a each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^2a each independently represents a hydrogen atom or a methyl group, and W represents a single bond or the following formula (a3) The base of representation.

In the formula (a1), Y represents a residue in which an acid anhydride group (-CO-O-CO-) is removed from a dicarboxylic anhydride. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylmethylenetetrahydroxylylene. Acid anhydride (methyl endo-methylene-tetrahydrophthalic anhydride), chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride and the like.

In the formula (a1), Z represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and diphenyl ether tetracarboxylic dianhydride.

In the formula (a1), m represents an integer of 0 to 20.

The acid value of the resin having an ethylenically unsaturated group is preferably 10 to 150 mgKOH / g, and more preferably 70 to 110 mgKOH / g based on the solid content of the resin. When the acid value is 10 mgKOH / g or more, sufficient solubility in a developing solution can be obtained, which is preferable. In addition, when the acid value is 150 mgKOH / g or less, sufficient hardenability can be obtained, and surface properties can be improved, which is preferable.

The mass average molecular weight of the resin having an ethylenically unsaturated group is preferably 1,000 to 40,000, and more preferably 2,000 to 30,000. When the mass average molecular weight is 1,000 or more, it is preferable because good heat resistance and film strength can be obtained. Moreover, it is preferable to set a mass average molecular weight to 40,000 or less in order to obtain favorable developability.

[Monomer with ethylenically unsaturated group]

Monoethylenically unsaturated monomers include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (meth) acrylamine Amine, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- Hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2- Acrylamido-2-methylpropanesulfonic acid, tertiary butylacrylamidosulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, (formaldehyde) Tetrahydrofurfuryl acrylate, dimethylamino (meth) acrylate, epoxypropyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, (meth) 2,2,3,3-tetrafluoropropyl acrylic acid, semi- (meth) acrylic acid esters of phthalic acid derivatives, etc. These monofunctional monomers may be used alone or in combination of two or more kinds.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propylene glycol di (methyl). Acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (methyl) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- ((Meth) acryloxydiethoxyphenyl) Propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, Diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate , Glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), trimethylhexamethylene diisocyanate Reactant with hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyol and N -A polyfunctional monomer such as a condensate of hydroxymethyl (meth) acrylamide, or methylal triacrylate. These polyfunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable compound of the component (A) is 100 parts by mass with respect to the total of the solid content of the photosensitive composition, and preferably 10 to 99.9 parts by mass. When the content of the component (A) is 10 parts by mass or more with respect to 100 parts by mass of the total solid content, sufficient heat resistance and chemical resistance of the pattern to be formed can be expected.

<(B) oxime-based photopolymerization initiator>

The oxime-based photopolymerization initiator contained in the photosensitive composition of the present invention is a compound represented by the following formula (1).

(In the above formula (1), l is an integer of 1 to 5, m is an integer of 0 to (l + 3), n is an integer of 1 to 8, R ¹ is an alkyl group of 1 to 11 carbon atoms, or An aryl group which may have a substituent, R ² is any of the substituents represented by the following formulae (2) to (5), R ³ is an alkyl group, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms .)

In the above formula (1), R ^{1 is} preferably exemplified by methyl, ethyl, propyl, isopropyl, butyl, phenyl, methylphenyl, naphthyl, and the like. Among them, methyl is more preferable. Or phenyl.

In the formula (1), R ³ is an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. R ^{3 is} preferably exemplified by methyl, ethyl, propyl, isopropyl, butyl and the like, and among these, methyl is more preferable.

In the formula (1), R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In the above formula (1), R ^{4 is} preferably exemplified by a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Among these, n-pentyl, n-hexyl, 3-methylbutyl, and the like are more preferably ethyl.

In the above formula (1), l is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the above formula (1), m is 0 to (l + 3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the above formula (1), n is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

Among the compounds represented by formula (1), preferable compounds include the following compounds.

The method for synthesizing the compound represented by the formula (1) is not particularly limited. The compound represented by the formula (1) can be synthesized according to the following Scheme ( Scheme ) , for example.

<Composite icon>

Specifically, first, a carbazole compound represented by the formula (i) is subjected to nitration or Friedel-Crafts Acylation according to a conventional method to obtain a carbazole represented by the formula (ii). Compound. Next, the carbazole compound represented by the formula (ii) is subjected to Friedel-Crafts aberration using the carboxylic acid halide represented by the formula (iii) to obtain a ketone compound represented by the formula (iv).

Next, a ketone compound represented by the formula (iv) is reacted with a nitrite in the presence of hydrochloric acid to obtain an oxime compound represented by the formula (v). The obtained oxime compound (v) is tritiated with an acid halide (R ¹ COHal), an acid anhydride ((R ¹ CO) ₂ O), or the like to obtain a compound represented by the formula (1).

In the above formulae (i) to (v), R ¹ , R ² , R ³ , R ⁴ , m, n, and l are the same as defined in the formula (1). In the above synthesis scheme, Hal represents a halogen atom. Examples of the halogen include chlorine, bromine, and iodine, and chlorine is preferred.

The oxime-based photopolymerization initiator represented by the above formula (1) provides a pattern capable of forming a high sensitivity, excellent straightness, and excellent adhesion to a substrate. Even if the photosensitive composition contains a light-shielding agent, the exposure amount is insufficient. It is also preferable to suppress the photosensitive composition that undercuts the pattern after development.

The oxime-based photopolymerization initiator represented by the formula (1) is also preferable in that it is easily soluble in propylene glycol monomethyl ether acetate (PM). PM is safe and unlimited in use. It is widely used as a solvent for materials used to form various structures in the process of manufacturing color filters or LCDs. Therefore, a photopolymerization initiator that is well soluble in PM can be used as an additive added to a photosensitive composition (photoresist material).

The content of the oxime-based photopolymerization initiator of the component (B) is 100 parts by mass with respect to the total solid content of the photosensitive composition, preferably 0.1 to 50 parts by mass, and more preferably 1 to 45 parts by mass. Within the above range, sufficient heat resistance and chemical resistance can be obtained, and at the same time, the coating film forming energy can be improved, and photohardening defects can be suppressed.

The oxime-based photopolymerization initiator represented by the above formula (1), in which the photosensitive composition contains only the component (B), is preferably used as the photopolymerization initiator. However, the oxime-based photopolymerization initiator represented by the above formula (1) as the component (B) can be used in combination with a photopolymerization initiator having a structure other than the formula (1) as long as the object of the present invention is not hindered. In this case, compared with the photopolymerization contained in the photosensitive composition, When the total mass of the initiator is, the mass of the oxime-based photopolymerization initiator of the component (B) is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass. Above mass%.

Specific examples of the photopolymerization initiator having a structure other than the formula (1) include, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one, bis (4-dimethylaminophenyl) ketone, 2 , 4,6-trimethylbenzylidene diphenylphosphine oxide, 4-benzylidene-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-di Methyl methylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoate, 4 -Dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2 -(o-ethoxycarbonyl) oxime, o-benzylidene benzoate methyl ester, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone , 1-chloro-4-propoxythioxanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthine, 2-methylthioxanthone, 2-isopropyl Thiothan, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, Benzoyl Peroxide ), Cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimerization Compounds, 2- (o-chlorophenyl) -4,5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer , 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenyl Diimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e., Michelin), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Michelin), 4,4'-dichlorobenzophenone, 3,3-dimethyl 4-Methoxybenzophenone, Benzil, Benzoin, Benzoin Methyl Ether, Benzoin Ether, Benzoin Isopropyl Ether, Benzoin-n-Butyl Ether, Benzoin Butyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropylacetophenone, dichloroacetophenone , Trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone Ketone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, pentyl-4 -Dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridyl) heptane, 1,5-bis- (9-acridyl) pentane, 1,3-bis- (9-acridyl) propane, p-methoxytriazine, 2,4,6-ginseng (trichloromethyl) ) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloro (Methyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxybenzene ) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-tri Hydrazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3- Bromo-4-methoxy) styrylphenyl-s- Triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE "369", "IRGACURE 651", "IRGACURE 907" (trade name: made by BASF), "NCI-831" (trade name: made by ADEKA), etc. These photopolymerization initiators can be used alone or in combination of two or more.

<(C) Colorant>

The photosensitive composition of the present invention may further contain (C) a colorant. The photosensitive composition contains a (C) component, and can be used suitably as a color filter formation application of a liquid crystal display, for example. The photosensitive composition of the present invention can be suitably used as a black matrix forming application in a color filter of a display device, for example, by containing a light-shielding agent as a colorant.

The (C) colorant contained in the photosensitive composition of the present invention is not particularly limited, but it is preferable to use a compound classified as a pigment in, for example, the CI (issued by The Society of Dyers and Colourists). , Specifically, as shown below with a color index (CI) number.

CI Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same, only the number is described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185; CI Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same, only the number is described), 5, 13, 14, 16 , 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73; CI Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same, only Description number), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; CI Pigment Red 1 (hereinafter, "CI Pigment Red" is the same, only the number is described), 2, 3, 4 , 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 15, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42 , 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2 , 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113 , 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190 , 192, 193, 194, 202, 206, 207 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265; CI Pigment Blue 1 (hereinafter, "CI Pigment Blue" Similarly, only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37; C.I.Pigment Brown 23, C.I.Pigment Brown 25, C.I.Pigment Brown 26, C.I.Pigment Brown 28; C.I.Pigment Black 1, C.I.Pigment Black 7.

When a colorant is used as a light-shielding agent, a black pigment is preferably used as the light-shielding agent. Examples of the black pigment include carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides, metal sulfates, and metal carbonates. , Not limited to organic, inorganic pigments. Among these, it is preferable to use carbon black having high light shielding properties. By using the component (B), as a photopolymerization initiator, even if a black pigment having a high light-shielding property is used, the undercut of the pattern after development can be suppressed.

As the carbon black, well-known carbon blacks such as groove black, furnace black, heat black, and lamp black can be used, and it is preferable to use groove black having excellent light shielding properties. Alternatively, a resin-coated carbon black may be used.

Compared with non-resin-coated carbon black, resin-coated carbon black has lower electrical conductivity. Therefore, when used as a liquid crystal display element such as a liquid crystal display or a black matrix, it can produce a low power consumption with low leakage current and high reliability. monitor.

Moreover, in order to adjust the hue of carbon black, the above-mentioned organic pigment can be suitably added as a supplementary pigment.

In order to uniformly disperse the colorant in the photosensitive composition, a dispersant may be further used. Such a dispersant is preferably a polymer dispersant of polyethyleneimine type, urethane resin type, or acrylic resin type. In particular, when carbon black is used as the colorant, and propylene is used as the dispersant. An acid resin-based dispersant is preferred.

In addition, each of the inorganic pigment and the organic pigment may be used alone or in combination of two or more kinds. However, when used in combination, the organic pigment is preferably used in the range of 10 to 80 parts by mass relative to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is more preferably used in a range of 20 to 40 parts by mass.

The use amount of the coloring agent in the photosensitive composition may be appropriately determined in accordance with the use of the photosensitive composition, but for example, it is preferably 5 to 70 masses with respect to 100 parts by mass of the total solid content of the photosensitive composition. Parts, more preferably 25 to 60 parts by mass. By setting it within the above range, a black matrix or each colored layer can be formed in a desired pattern, which is preferable.

In particular, when a black matrix is formed using a photosensitive composition, it is preferable to adjust the amount of the light-shielding agent in the photosensitive composition so that the OD value of the film of the black matrix in units of 1 μm becomes 4 or more. When the OD value of the film in the black matrix is 1 or more in units of 4 μm, a sufficient display contrast can be obtained in the case of the black matrix used in a liquid crystal display.

The colorant is preferably added to the photosensitive composition using a dispersant to form a dispersion liquid dispersed at an appropriate concentration.

<(D) Alkali soluble resin>

The photosensitive composition of the present invention may further contain (D) an alkali-soluble resin. The (A) photopolymerizable compound may be an alkali-soluble resin, but the (D) alkali-soluble resin is similar to (A) light in a resin that does not contain a photopolymerizable functional group such as an ethylenically unsaturated double bond. The polymerizable compounds are different.

(D) Alkali-soluble resin (hereinafter also referred to as "(D) component") means a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass to form a film thickness of 1 μm on a substrate When the resin film is immersed in a KOH aqueous solution having a concentration of 0.05% by mass for 1 minute, the thickness of the film is 0.01 μm or more.

(D) The alkali-soluble resin is not particularly limited as long as it is a resin that exhibits the above-mentioned alkali solubility and does not have a photopolymerizable functional group such as an ethylenically unsaturated double bond, and a conventionally known resin can be appropriately selected and used. (D) The alkali-soluble resin is preferably a polymer of a monomer having an ethylenically unsaturated double bond, and is a resin containing a unit derived from an unsaturated carboxylic acid. Hereinafter, a polymer of a monomer having an ethylenically unsaturated double bond and a resin containing a unit derived from an unsaturated carboxylic acid is also referred to as a (D1) copolymer.

Examples of unsaturated carboxylic acids include (meth) acrylic acid; ammonium (meth) acrylate; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like. Anhydrides of carboxylic acids. The amount of the unit derived from an unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has desired alkali-solubility. The amount of the unit derived from an unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably 5 to 25% by mass and more preferably 8 to 16% by mass relative to the mass of the resin.

Among (D1) copolymers, the balance of transparency, film-forming property, and hardness of the formed film is good. Therefore, it is preferable to contain (meth) acrylic acid and one or more kinds selected from (meth) acrylic acid esters. Body of polymer. In the following, a description is given of a composition containing (meth) acrylic acid and one or more monomers selected from (meth) acrylic acid esters. polymer.

The (meth) acrylate used for the preparation of a polymer containing (meth) acrylic acid and one or more monomers selected from (meth) acrylic acid esters is not particularly limited as long as it does not hinder the object of the present invention. It is limited, and a well-known (meth) acrylate can be selected suitably.

Preferable examples of the (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and (meth) ) Alkyl (meth) acrylates, linear or branched, such as third octyl acrylate; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, ( 2-hydroxyethyl methacrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate; (meth) with epoxy groups Acrylate; (meth) acrylate with alicyclic skeleton. The details of the (meth) acrylate having an epoxy group and the (meth) acrylate having an alicyclic skeleton group will be described later.

The monomer used for the preparation of the polymer containing (meth) acrylic acid and one or more monomers selected from (meth) acrylic acid esters may include other than (meth) acrylic acid and (meth) acrylic acid esters. Monomers having other ethylenically unsaturated double bonds.

Monomers having other ethylenically unsaturated double bonds other than (meth) acrylic acid and (meth) acrylates include, for example, (meth) acrylamide, acrylic compounds, vinyl ethers, and vinyl esters , Styrenes, etc. These compounds can be used alone or in combination of two or more.

Examples of (meth) acrylamide include (meth) acrylamine Amine, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (methyl) ) Acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, and the like.

Examples of the allyl compound include allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, Allyl acetate such as allyl acetate, allyl lactate; allyloxyethanol; etc.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, Chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, Alkyl ethylene, such as dimethylamino ethyl vinyl ether, diethyl amino ethyl vinyl ether, butyl amino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether Ether; vinyl vinyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether, etc. Aryl ethers; etc.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, and dichloride. Vinyl acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, ethyl acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, water Vinyl salicylate, vinyl chlorobenzoate, four Vinyl chlorobenzoate, vinyl naphthalate and the like.

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, and hexyl Alkane of styrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, ethoxymethylstyrene, etc. Styrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene , Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro- Halostyrene such as 3-trifluoromethylstyrene; etc.

Among polymers containing (meth) acrylic acid and one or more monomers selected from (meth) acrylic acid esters, from the viewpoint of transparency or mechanical properties of a film formed using a photosensitive composition, it is preferred that A polymer of (meth) acrylic acid and a monomer composed of one or more kinds selected from (meth) acrylic acid esters.

Among polymers composed of (meth) acrylic acid and one or more monomers selected from (meth) acrylic acid esters, a film formed from a photosensitive composition is excellent in adhesion to a substrate or mechanical strength. From the viewpoint of a resin, it is preferable to contain a resin derived from a unit containing a (meth) acrylate having a group having an epoxy group.

The (meth) acrylate containing a group having an epoxy group may be a (meth) acrylate containing a group having a chain aliphatic epoxy group, or may contain an alicyclic epoxy group as described later (Meth) acrylic acid ester.

The (meth) acrylate containing an epoxy group may contain an aromatic group. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of the (meth) acrylate having an aromatic group and containing a group having an epoxy group include, for example, 4-glycidoxyphenyl (meth) acrylate and 3-glycidoxybenzene (Meth) acrylate, 2-glycidoxyphenyl (meth) acrylate, 4-glycidoxyphenyl methyl (meth) acrylate, 3-glycidoxybenzene Methyl (meth) acrylate, 2-glycidoxyphenylmethyl (meth) acrylate, and the like.

From the viewpoint of transparency of a film formed using a photosensitive composition, the (meth) acrylic acid containing an epoxy group-containing group is preferably one which does not contain an aromatic group.

Examples of the (meth) acrylate containing a chain-like aliphatic epoxy group include epoxyalkyl (meth) acrylate and epoxyalkoxyalkyl (meth) acrylate A (meth) acrylate in which an oxy group (-O-) in an ester group (-O-CO-) of an ester is bonded to a chain aliphatic epoxy group. The (meth) acrylic acid ester may have one or more oxygen groups (-O-) in the chain of the aliphatic aliphatic epoxy group. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

Specific examples of the (meth) acrylate containing a chain-like aliphatic epoxy group include, for example, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate , 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, etc. epoxy alkyl (meth) acrylate; 2-epoxy Propoxyethyl (meth) acrylate, 3-epoxy Propoxy-n-propyl (meth) acrylate, 4-glycidoxy-n-butyl (meth) acrylate, 5-glycidoxy-n-hexyl (meth) acrylic acid Ester, 6-glycidoxy-n-hexyl (meth) acrylate, and the like, epoxy alkoxyalkyl (meth) acrylate.

A polymer containing a unit derived from (meth) acrylic acid and one or more selected from (meth) acrylic acid ester-containing units derived from a unit containing a (meth) acrylate having an epoxy group, derived from The content of the unit containing the (meth) acrylate having an epoxy group is based on the weight of the resin, preferably 1 to 95% by mass, and more preferably 30 to 70% by mass.

In addition, a polymer composed of (meth) acrylic acid and a monomer selected from one or more kinds of (meth) acrylic acid esters can easily form an insulating film having excellent transparency using a photosensitive composition. A resin containing a unit of (meth) acrylate having a alicyclic skeleton group is also preferable.

In the (meth) acrylic acid ester containing a group having an alicyclic skeleton, the group having an alicyclic skeleton may be a group having an alicyclic hydrocarbon group or a group having an alicyclic epoxy group. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl, isofluorenyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

Among the (meth) acrylates having a group having an alicyclic skeleton, and the (meth) acrylates having a group having an alicyclic hydrocarbon group, examples thereof include the following formulae (d1-1) to (d1-8) ). Among these, compounds represented by the following formulae (d1-3) to (a1-8) are preferred, and compounds represented by the following formulae (d1-3) or (d1-4) are more preferred.

In the above formula, R ^d1 represents a hydrogen atom or a methyl group, R ^d2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^d3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^d2 is a single bond, straight chain or branched chain alkylene, for example, methylene, ethylene, propyl, tetramethylene, ethylethylene, pentamethylene, Hexamethylene. R ^{d3 is} preferably a methyl group or an ethyl group.

Specific examples of the (meth) acrylate containing a group having an alicyclic skeleton and the (meth) acrylate containing a group having an alicyclic epoxy group include the following formula (d2-1) The compound represented by ~ (d2-15). this Among others, in order to make the developability of the photosensitive composition moderate, the compounds represented by the following formulae (d2-1) to (d2-5) are preferred, and the following formulae (d2-1) to The compound represented by (d2-3).

In the above formula, R ^d4 represents a hydrogen atom or a methyl group, R ^d5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^d6 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and p represents 0 to 10 Integer. R ^d5 is a linear or branched alkylene group, for example, methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentamethylene, and hexamethylene are preferred base. R ^{d6 is} preferably, for example, methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentamethylene, hexamethylene, phenylene, cyclohexyl, -CH _2- Ph-CH _2- (Ph stands for phenylene).

A polymer of (meth) acrylic acid and a monomer selected from one or more kinds of (meth) acrylic acid esters is a resin containing a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton. Case, resin The amount of the unit containing (meth) acrylate having a alicyclic skeleton-based group is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and still more preferably 30 to 70% by mass.

In addition, a polymer containing a unit derived from (meth) acrylic acid and a monomer selected from one or more kinds of (meth) acrylic acid esters containing units derived from a (meth) acrylic acid ester having a alicyclic skeleton Among them, a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylate containing an alicyclic epoxy group is preferred. This resin has excellent adhesion to a substrate. When such a resin is used, the carboxyl group contained in the resin can react with the alicyclic epoxy group on its own. Therefore, when using a photosensitive composition containing such a resin, by using a method such as heating a film, a carboxyl group can react with an alicyclic epoxy group on its own, thereby improving mechanical properties such as hardness of the formed film.

The amount of the unit derived from (meth) acrylic acid in the resin containing the unit derived from (meth) acrylic acid and the unit derived from (meth) acrylic acid ester having a cycloaliphatic epoxy group is preferable It is 1 to 95% by mass, and more preferably 10 to 50% by mass. Among resins containing units derived from (meth) acrylic acid and units derived from (meth) acrylic acid esters having a group having an alicyclic epoxy group, resins containing units derived from a group having an alicyclic epoxy group ( The amount of the unit of meth) acrylate is preferably 1 to 95% by mass, and more preferably 30 to 70% by mass.

A unit containing (meth) acrylic acid-derived units and a unit containing (meth) acrylic acid esters having an alicyclic epoxy group is composed of (meth) acrylic acid and one or more selected from (meth) acrylates Aggregate of monomers Among the compounds, a unit derived from (meth) acrylic acid and a unit derived from (meth) acrylate having an alicyclic hydrocarbon group and a unit derived from (meth) containing an alicyclic epoxy group are preferred. Resin in acrylate units.

In a resin containing a unit derived from (meth) acrylic acid and a unit derived from (meth) acrylate having an alicyclic hydrocarbon group and a unit derived from (meth) acrylate having an alicyclic epoxy group, The amount of the unit derived from (meth) acrylic acid in the resin is preferably 1 to 95% by mass, and more preferably 10 to 50% by mass. In a resin containing a unit derived from (meth) acrylic acid and a unit derived from (meth) acrylate having an alicyclic hydrocarbon group and a unit derived from (meth) acrylate having an alicyclic epoxy group, The amount of the unit derived from the (meth) acrylate having an alicyclic hydrocarbon group in the resin is preferably 1 to 95% by mass, and more preferably 10 to 70% by mass. In a resin containing a unit derived from (meth) acrylic acid and a unit derived from (meth) acrylate having an alicyclic hydrocarbon group and a unit derived from (meth) acrylate having an alicyclic epoxy group, The amount of the unit derived from the (meth) acrylic acid ester containing a group having an alicyclic epoxy group in the resin is preferably 1 to 95% by mass, and more preferably 30 to 70% by mass.

(D1) The mass average molecular weight of the copolymer (Mw: measured value in terms of polystyrene in gel permeation chromatography (GPC). The same in this specification) is preferably 2000 to 200,000, and more preferably 5,000 to 30,000. By setting it in the said range, there exists a tendency for the balance of the film-forming ability of a photosensitive composition, and the developability after exposure to become easy easily.

(D) The content of the alkali-soluble resin is preferably 30 to 80% by mass, and more preferably 50 to 60% by mass relative to the solid content of the photosensitive composition. %. By setting it in the said range, there exists a tendency for the balance of developability to be easily achieved.

<Other ingredients>

Various additives can be added to the photosensitive composition of the present invention as necessary. Specific examples are solvents, sensitizers, hardening accelerators, photocrosslinkers, photosensitizers, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anticoagulants, and thermal polymerization inhibitors. , Defoamer, surfactant, etc.

Examples of the solvent used in the photosensitive composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. ) Alkanediol monoalkane ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol (Poly) alkanediol monoalkyl ether acetates such as monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether , Tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionate methyl ester, 2- Propanoate group of lactic acid alkyl esters and the like; hydroxy-2-methylpropionate, methyl 3-methoxy propionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methyl Methyl butyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetate Butyl, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methylpyruvate Esters, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-oxobutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and other amidines. These solvents may be used alone or in combination of two or more.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, Cyclohexanone and 3-methoxybutyl acetate have excellent solubility in the above-mentioned (A) component, (B) component, and (D) component, and at the same time, the dispersibility of the above-mentioned (C) component is good, so Preferably, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferably used. The solvent may be appropriately determined depending on the use of the photosensitive composition, and an example of the solvent is about 50 to 900 parts by mass based on 100 parts by mass of the total solid content of the photosensitive composition.

Examples of the thermal polymerization inhibitor used in the photosensitive composition of the present invention include hydroquinone and hydroquinone monoethyl ether. Examples of the defoaming agent include compounds of the silicone type and fluorine type, and examples of the surfactant include compounds of the anionic type, cationic type, and nonionic type.

"Method for preparing photosensitive composition"

The photosensitive composition of the present invention can be prepared by mixing all the above components with a blender. In addition, it is also possible to use a filter to make the prepared photosensitive composition uniform.

"Pattern Formation Method"

When forming a pattern using the photosensitive composition of the present invention, first, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a spin coater (a spin coater) is used. ), A non-contact coating device such as a curtain coater, etc., which coats a photosensitive composition on a substrate.

Next, the coated photosensitive composition is dried to form a coating film. The drying method is not particularly limited, and examples thereof include (1) a method of drying on a hot plate at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C for 60 to 120 seconds, and (2) standing at room temperature for several seconds. A method from hours to several days, (3) a method of removing a solvent by leaving it in a warm air heater or an infrared heater for several tens of minutes to several hours.

Next, the coating film is irradiated with active energy rays such as ultraviolet rays, excimer laser light, and the like through a negative-type mask, and is partially exposed. The amount of energy ray to be irradiated varies depending on the composition of the photosensitive composition, but is preferably about 30 to 2000 mJ / cm ² , for example.

Next, the exposed film is developed with a developing solution and patterned into a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spray method, or the like can be used. Examples of the developing solution include monoethanolamine and diethanol. Organic solvents such as amines and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. As described above, by using the photosensitive composition of the present invention, undercuts in a pattern formed after development can be suppressed. Therefore, if the photosensitive composition of the present invention is used, for example, when a color filter for a display device is manufactured, it is preferable to prevent bubbles from entering the vicinity of each pixel boundary portion.

Next, for the developed pattern, post-baking is preferably performed at about 200 ° C to 250 ° C.

The pattern thus formed can be suitably used as a pixel or a black matrix of a color filter in a display device such as a liquid crystal display. Such a color filter or a display device using the same is also one of the present invention.

[Example]

The following examples illustrate the present invention in more detail, but the scope of the present invention is not limited to those examples.

In Examples and Comparative Examples, the following PI-1 to PI-12 were used as the photopolymerization initiator. PI ~ 1 ~ PI-6 are compounds having a structure represented by the aforementioned formula (1), and P1-7 ~ PI-12 are compounds without a structure represented by the aforementioned formula (1).

The aforementioned PI-1 to PI-6 were synthesized according to the following Synthesis Examples 1 to 6.

[Synthesis example 1]

(Synthesis of PI-1)

5.00 g (16.37 mmol) of 3- (thien-2-ylcarbonyl) -9-ethylcarbazole and 3.14 g (18.00 mmol) of 3-cyclohexylpropanoic acid chloride in the presence of 2.62 g of aluminum chloride at In 50 ml of a dichloromethane solvent, the reaction was performed under ice-cooling for 1 hour. The reaction mixture was poured into ice water, and the organic layer was separated. (separate). The recovered organic layer was dried over anhydrous magnesium sulfate and evaporated. The residue was purified on a silica gel column with an eluent of ethyl acetate / hexane = 1/2 to obtain 3- (thien-2-ylcarbonyl) -6- (3-cyclohexylpropanyl) -9-ethyl. Carbazole 6.90 g (15.55 mmol). 6.90 g (15.55 mmol) of 3- (thien-2-ylcarbonyl) -6- (3-cyclohexylpropanyl) -9-ethylcarbazole and 1.60 g (15.55 mmol) of concentrated hydrochloric acid were added to isobutyl nitrite In the presence of 2.42 g (23.33 mmol) of the ester, 25 ml of a dimethylformamide solvent was reacted under ice-cooling for 3 hours. The reaction solution was evaporated, ethyl acetate was added to the residue, the mixture was washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to obtain 3- (thien-2-ylcarbonyl) -6- (3-cyclohexyl-2- Hydroxyimidopropanyl) -9-ethylcarbazole 5.51 g (11.67 mmol). 5.51 g (11.67 mmol) of 3- (thien-2-ylcarbonyl) -6- (3-cyclohexyl-2-hydroxyiminopropionyl) -9-ethylcarbazole, 1.43 g of acetic anhydride (13.42 mmol), 1.36 g (13.42 mmol) of triethylamine, and 45.00 ml of dimethylformamide solvent, and stirred at 35 ° C. for 3 hours. After cooling to room temperature, ethyl acetate was added to the reaction solution, washed with water, dried over anhydrous magnesium sulfate, and evaporated. The residue was purified by a silica gel column with an eluent of ethyl acetate / hexane = 2/1 to obtain PI-1, 5.40 g (10.50 mmol).

[Synthesis example 2]

(Synthesis of PI-2)

Except changing 5.00 g (16.37 mmol) of 3- (thien-2-ylcarbonyl) -9-ethylcarbazole to 4.74 g (16.37 mmol) of 3- (furan-3-ylcarbonyl) -9-ethylcarbazole In addition, PI-2 and PI-2 were obtained in the same manner as in Synthesis Example 1. 5.15 g (10.32 mmol).

[Synthesis example 3]

(Synthesis of PI-3)

Except changing 3.14 g (18.00 mmol) of 3-cyclohexylpropanoic acid chloride to 3.14 g (18.00 mmol) of 4-cyclopentylbutyric acid chloride, PI-3 and 5.28 g (10.26 mmol) were obtained in the same manner as in Synthesis Example 1. ).

[Synthesis example 4]

(Synthesis of PI-4)

Except changing 5.00 g (16.37 mmol) of 3- (thien-2-ylcarbonyl) -9-ethylcarbazole to 4.74 g (16.37 mmol) of 3- (furan-3-ylcarbonyl) -9-ethylcarbazole And except that 3.14 g (18.00 mmol) of 3-cyclohexylpropanoic acid chloride was changed to 3.14 g (18.00 mmol) of 4-cyclopentylbutyric acid chloride, PI-4 and 5.17 g (10.36) were obtained in the same manner as in Synthesis Example 1. mmol).

[Synthesis example 5]

(Synthesis of PI-5)

Except changing 5.00 g (16.37 mmol) of 3- (thien-2-ylcarbonyl) -9-ethylcarbazole to 3.93 g (16.37 mmol) of 3-nitro-9-ethylcarbazole, it was the same as in Synthesis Example 1 Similarly, PI-5 and 4.85 g (10.80 mmol) were obtained.

[Synthesis example 6]

(Synthesis of PI-6)

Except changing 5.00 g (16.37 mmol) of 3- (thien-2-ylcarbonyl) -9-ethylcarbazole to 5.72 g (16.37 mmol) of 3- (naphthalene-1-ylcarbonyl) -9-ethylcarbazole Except that, in the same manner as in Synthesis Example 1, PI-6 and 6.02 g (10.78 mmol) were obtained.

The measurement results of ¹ H NMR of PI-1 to PI-6 obtained in Synthesis Examples 1 to 6 are shown below.

(PI-1)

¹ H NMR (CDCl ₃ , 600 MHz, δ in ppm) 8.9 (s, 1H); 8.7 (s, 1H); 8.3 (d, 1H); 8.1 (d, 1H); 7.7 (dd, 2H); 7.5 ( dd, 2H); 7.2 (t, 1H); 4.4 (q, 2H); 2.8 (d, 2H); 2.3 (s, 3H); 1.6-1.8 (m, 6H); 1.5 (t, 3H); 1.0 -1.2 (m, 5H).

(PI-2)

¹ H NMR (CDCL ₃ , 600 MHz, δ in ppm) 9.0 (s, 1H); 8.9 (a, 1H); 8.3 (d, 1H); 8.2 (d, 1H); 7.8 (s, 1H); 7.4 ( dd, 2H); 7.3 (d, 1H); 6.6 (d, 1H); 4.4 (q, 2H); 2.8 (d, 2H); 2.3 (s, 3H); 1.6-1.8 (m, 6H); 1.5 (t, 3H); 1.1-1.3 (m, 5H).

(PI-3)

¹ H NMR (CDCl ₃ , 600 MHz, δ in ppm) 8.9 (s, 1H); 8.7 (s, 1H); 8.3 (d, 1H); 8.1 (d, 1H); 7.7 (dd, 2H); 7.5 ( dd, 2H); 7.2 (t, 1H); 4.4 (q, 2H); 3.0 (t, 2H); 2.3 (s, 3H); 1.8-1.9 (m, 3H); 1.5-1.6 (m, 9H) ; 1.1 (m, 2H).

(PI-4)

¹ H NMR (CDCl ₃ , 600 MHz, δ in ppm) 9.0 (s, 1H); 8.9 (s, 1H); 8.3 (d, 1H); 8.2 (d, 1H); 7.8 (dd, 2H); 7.4 ( dd, 2H); 7.3 (t, 1H); 6.6 (d, 1H); 4.4 (q, 2H); 3.0 (t, 2H); 2.3 (s, 3H); 1.8-1.9 (m, 3H); 1.5 -1.6 (m, 9H); 1.1 (m, 2H).

(PI-5)

¹ H NMR (CDCl ₃ , 600 MHz, δ in ppm) 9.1 (s, 1H); 8.6 (s, 1H); 8.5 (d, 1H); 8.2 (d, 1H); 7.5 (m, 2H); 4.4 ( q, 2H); 2.8 (d, 2H); 2.3 (s, 3H); 1.6-1.8 (m, 6H); 1.5 (t, 3H); 1.0-1.2 (m, 5H).

(PI-6)

¹ H NMR (CDCl ₃ , 600 MHz, δ in ppm) 8.7 (s, 1H); 8.5 (s, 1H); 7.9-8.1 (m, 5H); 7.4-7.7 (m, 6H); 4.4 (q, 2H ); 2.8 (d, 2H); 2.3 (s, 3H); 1.6-1.8 (m, 6H); 1.5 (t, 3H); 1.0-1.2 (m, 5H).

[Examples 1 to 6 and Comparative Examples 1 to 6]

About the transparent photosensitive composition which does not contain a coloring agent, it evaluates based on Examples 1-6 and Comparative Examples 1-6 below.

In Examples 1 to 6 and Comparative Examples 1 to 6, dipentaerythritol hexaacrylate was used as the photopolymerizable compound. In Examples 1 to 6 and Comparative Examples 1 to 6, as the alkali-soluble resin, a resin having the following structure having a mass average molecular weight of 15,000 was used. In the following structure, the numerical value at the bottom right of the parentheses in each constituent unit represents the content (mass%) of each constituent unit in the resin.

59.3 parts by mass of an alkali-soluble resin, 40 parts by mass of a photopolymerizable compound, and 0.7 parts by mass of a photopolymerization initiator of the kind described in Table 1 were uniformly dissolved in 60% by mass of diethylene glycol methyl ether and propylene glycol monomethyl In a mixed solvent composed of 40% by mass of ether acetate, the solid content concentration was 15% by mass, and the photosensitive compositions of Examples 1 to 6 and Comparative Examples 1 to 6 were obtained. The pattern formed using the obtained photosensitive composition was evaluated for straightness, pattern peeling, and cross-sectional shape (taper angle) of the pattern. In addition, the photopolymerization initiator used for the preparation of the photosensitive composition in each of Examples and Comparative Examples evaluated the solubility of propylene glycol monomethyl ether acetate (PM). The results of these evaluations are shown in Table 1.

<Optimal exposure>

Using a spin coater, the photosensitive compositions of Examples and Comparative Examples were coated on a glass substrate (100 mm × 100 mm), and pre-baked at 90 ° C. for 120 seconds to form a coating film having a film thickness of 1.0 μm. Next, a mirror projection exposure machine (product name: TME-150RTO, manufactured by TOPCON Corporation) was used, and the exposure gap was 50 μm. The exposure amount was changed to 15, 30, 45 through a negative mask with a line pattern of 10 μm formed. 4 steps of 60 mJ / cm ² , the coating film is irradiated with ultraviolet rays. The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C for 40 seconds, and then post-baked at 230 ° C for 30 minutes to form a line pattern. The size of the line pattern formed by each exposure amount is measured, and from the relationship between the exposure amount and the formed line width, the optimal exposure amount necessary to form a pattern having a line with a width of 10 μm is obtained.

<Pattern straightness evaluation>

Using a spin coater, the photosensitive compositions of Examples and Comparative Examples were coated on a glass substrate (100 mm × 100 mm), and pre-baked at 90 ° C. for 120 seconds to form a coating film having a film thickness of 1.0 μm. Next, using a mirror projection exposure machine (product name: TME-150RTO, manufactured by TOPCON Corporation), the exposure gap was 50 μm, and a negative mask with a line pattern of 10 μm was formed, and the exposure was 15, 30, 45, 60 mJ The coating film was irradiated with ultraviolet rays at four stages per cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C for 40 seconds, and then post-baked at 230 ° C for 30 minutes to form a line pattern.

The formed line pattern was observed by an optical microscope, and the straightness of the pattern was evaluated. Graphic straightness is based on the evaluation of the line's edge without deformation (wobble) The price is "○" and those with deformation are evaluated as "×".

<Pattern adhesion evaluation>

In the evaluation of the pattern straightness, the formed line pattern was observed by an optical microscope to evaluate the pattern adhesion. The pattern adhesion is not peeled from the substrate, and a line pattern is evaluated as "○", and a line pattern defect is evaluated as "x".

<Evaluation of the sectional shape (taper angle) of the pattern>

As in the pattern straightness evaluation, a coating film of a photosensitive composition having a film thickness of 1.0 μm was formed on a glass substrate (10 cm × 10 cm). Then, using a specular projection exposure machine (product name: TME-150RTO, manufactured by TOPCON Corporation), the coating film was exposed at an exposure amount of 4045 mJ / cm ² through a negative mask formed with a line pattern of 10 μm. The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C for 50 seconds, and then subjected to a firing treatment at 230 ° C for 30 minutes. A scanning electron microscope was used to measure the bonding angle between the pattern and the substrate (cone angle).

This cone angle corresponds to the angle θ in Figs. 1 (a) and (b). When the cone angle is acute, it means that the pattern has no undercut, and when the cone angle is obtuse, it means that the pattern has undercut.

Based on the measured cone angle, follow the following criteria to evaluate the cross-sectional shape of the pattern.

◎: Above 70 ° and below 85 °

○: More than 85 ° and less than 90 °

△: More than 90 ° and less than 100 °

×: more than 100 °

<Propylene glycol monomethyl ether acetate (PM) solubility>

Because it is safe and has no restrictions on use, PM is widely used as a solvent for materials for structural formation in the manufacturing steps of color filters or LCDs. Therefore, a photopolymerization initiator added to a photoresist is expected to dissolve PM well.

Therefore, the solubility of the photopolymerization initiator in PM was evaluated according to the following method.

At 23 ° C., 1 g of the powder of the photopolymerization initiator was added with any amount of a PM solvent in a range that would not completely dissolve the photopolymerization initiator, and stirred for 5 minutes. After the stirred liquid was allowed to stand, the concentration of the photopolymerization initiator was measured with respect to the upper liquid. The concentration of the photopolymerization initiator in the upper clear solution was measured, and the PM solubility of the photopolymerization initiator was evaluated according to the following criteria.

◎: More than 6% by mass

○: More than 3% by mass and less than 6% by mass

△: More than 1% by mass and less than 3% by mass

×: 1% by mass or less

According to Examples 1 to 6, it was found that when a photosensitive composition containing a photopolymerizable compound and the oxime-based photopolymerization initiator represented by the formula (1) is used, a straightness can be formed with a low exposure and a substrate can be formed. A pattern with excellent adhesion and suppressed undercuts.

According to Comparative Examples 1 to 6, it was found that when a photosensitive composition containing a photopolymerizable compound and a photopolymerization initiator having a structure other than the aforementioned formula (1) was used, it was difficult to form a straightness and a substrate with a low exposure amount. Patterns with excellent adhesion, and undercuts easily occur in the formed patterns.

[Examples 7 to 12 and Comparative Examples 7 to 12]

The photosensitive composition containing a coloring agent was evaluated below with Examples 7-12 and Comparative Examples 7-12.

In Examples 7 to 12 and Comparative Examples 7 to 12, photopolymerization As the composition, Resin A and dipentaerythritol hexaacrylate obtained in Synthesis Example 7 described below were used. In Examples 7 to 12 and Comparative Examples 7 to 12, a carbon black dispersion liquid (solid content concentration: 50% by mass, solvent: 3-methoxybutyl acetate) was used as a coloring agent.

[Synthesis example 7]

First, in a 500 ml four-necked flask, 235 g of a bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, and 100 mg of 2,6-di-tert-butyl-4-methylphenol were charged. And 72.0 g of acrylic acid, while blowing air into it at a speed of 25 ml / minute, and heating and dissolving at 90 to 100 ° C. Next, the solution was gradually heated while the solution was cloudy, and heated to 120 ° C to completely dissolve. At this time, the solution gradually became transparent and thick, but stirring was continued in this state. At this time, the acid value was measured, and heating and stirring were continued until it reached 1.0 mgKOH / g. It takes 12 hours for the acid value to reach the target value. Then, it cooled to room temperature and obtained the colorless transparent solid bisphenol fluorene type epoxy acrylate represented by following formula (a4).

Next, the above-mentioned bisphenol fluorene type epoxy propylene 600 g of 3-methoxybutyl acetate was added to 307.0 g of the acid ester, and after dissolving, 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was gradually raised to 110-115 The reaction was carried out at 4 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain resin A. The disappearance of the acid anhydride group was confirmed by IR spectrum.

This resin A corresponds to a resin represented by the above formula (a-1).

30 parts by mass of the resin A, 17 parts by mass of pentaerythritol hexaacrylate, 3 parts by mass of a photopolymerization initiator of the type described in Table 1, and 50 parts by mass of a carbon black dispersion were uniformly dissolved and dispersed in a 3-methoxy group. In a mixed solvent consisting of 60% by mass of butyl acetate, 20% by mass of propylene glycol monomethyl ether acetate, and 20% by mass of cyclohexanone, the solid content concentration was 15% by mass. Examples 7 to 12, and And the photosensitive compositions of Comparative Examples 7 to 12. The pattern formed using the obtained photosensitive composition was evaluated for straightness, pattern peeling, and cross-sectional shape (taper angle) of the pattern in the same manner as in Examples 1 to 6 and Comparative Examples 1 to 6. The results of these evaluations are shown in Table 1.

According to Examples 7 to 12, it was found that when a photosensitive composition containing a photopolymerizable compound, the oxime-based photopolymerization initiator represented by the formula (1), and a coloring agent was used, a straightness can be formed with a low exposure amount. Patterns with excellent adhesion to the substrate, and patterns with undercuts suppressed.

According to Comparative Examples 7 to 12, it was found that when a photosensitive composition containing a photopolymerizable compound, a photopolymerization initiator having a structure other than the formula (1), and a coloring agent was used, it was difficult to form a straightness at a low exposure. And patterns with excellent adhesion to the substrate, and undercuts are easily generated in the formed patterns.

Claims (6)

A photosensitive composition containing (A) a photopolymerizable compound and (B) an oxime-based photopolymerization initiator represented by the following formula (1), wherein the (A) photopolymerizable compound includes the following formula ( a1), (In the above formula (1), l is an integer of 1 to 5, m is an integer of 0 to (l + 3), n is an integer of 1 to 8, R ¹ is an alkyl group of 1 to 11 carbon atoms, or An aryl group which may have a substituent, R ² is any of the substituents represented by the following formulae (2) to (5), R ³ is an alkyl group, and R ⁴ is a hydrogen atom or an alkane having 1 to 10 carbon atoms base) (In the above formula (a1), X represents a group represented by the following formula (a2), and in the above formula (a1), Y represents a residue from which the acid anhydride group (-CO-O-CO-) is removed from the dicarboxylic anhydride, and In the formula (a1), Z represents a residue in which two acid anhydride groups are removed from the tetracarboxylic dianhydride, and in the formula (a1), m represents an integer of 0 to 20) (In the above formula (a2), R ^1a each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^2a each independently represents a hydrogen atom or a methyl group, and W represents a single bond or the following formula (a3 ) Said the base, A photosensitive composition comprising (A) a photopolymerizable compound, (B) an oxime-based photopolymerization initiator represented by the following formula (1), and (D) an alkali-soluble resin, (D) the alkali-soluble The resin includes a polymer containing at least one monomer selected from the group consisting of a (meth) acrylate having an epoxy group and a (meth) acrylate having an alicyclic skeleton, (In the above formula (1), l is an integer of 1 to 5, m is an integer of 0 to (l + 3), n is an integer of 1 to 8, R ¹ is an alkyl group of 1 to 11 carbon atoms, or An aryl group which may have a substituent, R ² is any of the substituents represented by the following formulae (2) to (5), R ³ is an alkyl group, and R ⁴ is a hydrogen atom or an alkane having 1 to 10 carbon atoms base) For example, the photosensitive composition according to item 1 or 2 of the patent application scope further contains a colorant (C). For example, the photosensitive composition of claim 3, wherein the colorant is a light-shielding agent. A color filter is formed by using a photosensitive composition such as item 3 or 4 of the scope of patent application. A display device uses a color filter such as the fifth item in the patent application scope.