KR20070027445A - Photosensitive composition - Google Patents

Abstract

A photosensitive composition is provided to have favorable linearity, be hardly released, and be capable of forming black matrix patterns with less residues by comprising a photo-polymerization initiator consisting of the oxime ester based compound having fluorene backbone and benzoyl group. The composition includes a photo-polymeric compound, a photo-polymerization initiator and a coloring agent. The photo-polymerization initiator contains a compound represented by a formula(1), wherein A is -R1, -OR1, -COR1, -SR1 or -NR1R2; B is -R1, -OR1, -COR1, -SR1, -CONR1R2 or -CN; G is hydrogen, -R1, -OR1, -COR1, -SR1 or -NR1R2; D is same or different and halogen atom or hydrocarbon group that contains hetero atoms having C1 to C20; E is same or different and alkyl group having C1 to C20, alkoxy group having C1 to C20, cycloalkyl group having C3 to C20, -OR3 or -NR4R5; and at least one of E is a group with molecular weight of at least 30; m is integer of 0 to 5, n is integer of 0 to 3 and m+n is more than 1. The photo-polymeric compound has at least one of ethylene double bond. The photo-polymerization initiator is mercaptoimidazol. The coloring agent includes carbon black.

Description

Photosensitive Composition

The present invention relates to a photosensitive composition for forming a black matrix of a liquid crystal display panel.

In a display such as a liquid crystal display, a liquid crystal layer is sandwiched between two substrates, a pair of electrodes facing each other of the two substrates is disposed, and a red (R) and green color is opposite to the liquid crystal layer inside one substrate. The color filter layer which consists of each pixel (G), blue (B), and black is arrange | positioned. In addition, the black pixels serve to prevent mixing of different colors or to hide patterns of electrodes, and are generally called a black matrix because they are arranged in a matrix to partition pixels of R, G, and B colors.

In general, color filters are formed by lithography. Specifically, the coating liquid of the composition which disperse | distributed or disperse | distributed or disperse | distributed the organic pigment, dye, or carbon black uniformly in the photosensitive resin component is apply | coated on a board | substrate, and is dried, and exposure according to the various patterns which comprise a color filter is performed. Subsequently, the pixel pattern obtained by developing this with alkali developing solution etc. is heat-processed and the mechanical strength as a permanent film is provided. This process is repeated for each color of R, G, and B to form a color filter layer.

The black matrix of a color filter has conventionally used the thing which patterned the chromium thin film deposited by the lithographic method. The black matrix made of this chromium thin film has high dimensional accuracy and high reliability. However, in order to form a chromium thin film, a vacuum film manufacturing process called deposition or sputtering is required as described above. Since the enlargement of the substrate is accompanied by the enlargement of the machine, it is difficult to cope with the enlargement of the substrate.

In addition, as for the chromium thin film, a resin film formed of a photocurable composition in which a black colorant was dispersed in the same manner as a color filter of another color was used (Japanese Patent Laid-Open No. 11-84125). Carbon black, titanium black, etc. are known as a black coloring agent for materials of these black matrices. Among them, carbon black is most commonly used.

Japanese Patent Laid-Open No. 11-84125 discloses a photopolymerizable composition containing a compound containing at least one ethylenically unsaturated double bond capable of addition polymerization, a photopolymerization initiator, a metal oxide, and the like, and substantially free of halogen atoms. Is disclosed. This composition makes it possible to provide a color filter which is excellent in heat resistance and substantially high in electrical insulation resistance by substantially removing halogen atoms.

However, in order to give a high light-shielding property to a black matrix, content of a light-shielding material must be raised. As a result, the optical density is increased, so that light does not reach the depth of the film during exposure, and the photocuring (photoreaction) may not proceed sufficiently. As a result, development margin narrowed and the linearity of a pattern might become low, a pattern might peel off from a board | substrate, or residue might generate | occur | produce on a board | substrate.

Moreover, when manufacturing a color filter, depending on the coloring photosensitive resin used, a sublimation may generate | occur | produce from a coloring pattern when heat-processing in a bake furnace after exposure and image development. If this sublimate is mixed as foreign matter in the coloring pattern, it may cause product defects.

In view of the above problems, an object of the present invention is to provide a photosensitive composition which can form a black matrix pattern which has good linearity, is difficult to peel off, and has little residue in a color filter of a liquid crystal display. Moreover, it aims at providing the photosensitive composition which can form the black-matrix pattern with few generation | occurrence | production of a sublimation in the heating after image development.

MEANS TO SOLVE THE PROBLEM The present inventors can use the oxime type compound which has a fluorene skeleton and benzoyl as a photoinitiator of a photosensitive composition, and can provide the photosensitive composition which can form the black-matrix pattern which has favorable linearity, is hard to peel off, and has few debris. Found. Furthermore, the present inventors found that when the benzoyl moiety is a bulky group, it becomes possible to suppress the generation of a sublimation in heating after development.

More specifically, the present invention provides the following.

(1) It contains a photopolymerizable compound, a photoinitiator, and a coloring agent,

A photosensitive composition containing a compound represented by the following Chemical Formula 1 as the photopolymerization initiator:

Wherein A represents -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ , or -NR ₁ R ₂ , and B represents -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ ,- CONR ₁ R ₂ or -CN, G represents a hydrogen atom, -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ , or -NR ₁ R ₂ , wherein R ₁ and R ₂ are each independently An alkyl group, an aryl group, an aralkyl group, or a heterocyclic group may be represented, and these may be substituted by at least any one of a halogen atom or a heterocyclic group, and among these, the alkylene part of an alkyl group and an aralkyl group may be an unsaturated bond, an ether bond, a thioether It may be interrupted by a bond or an ester bond, and R ₁ and R ₂ may be integrated to form a ring, and D may be the same or different and may be a halogen atom or a C 1 or more and 20 or less containing a hetero atom. Represents a hydrocarbon group which may be present, and E is an egg having 1 to 20 carbon atoms which may be the same or different. Group, having 1 to 20 carbon atoms in the alkoxy group, a cycloalkyl group having a carbon number of ₃ ~ 20, -OR 3, -NR ₄ R ₅ represents a, where R ₃ is optionally an alkyl group (part of carbon atoms of 1 to 20 carbon atoms substituted by heteroatoms like), even if a cycloalkyl group (part of carbon atoms of 3 to 20 carbon atoms are substituted by heteroatoms like) to indicate, R _4, R ₅ are the same or different good each other carbons alkyl of 1 to 20, an alkoxycarbonyl group of 2 to 20 carbon atoms Or R ₄ and R ₅ may be integrated to form a ring having 3 to 20 carbon atoms; when a ring is formed, a portion of the carbon atoms may be substituted with a hetero atom, and at least one of E has a molecular weight of 30 or more; Group, m is an integer of 0-5, n is an integer of 0-3, and m + n> 1 is satisfied).

According to invention of (1), by making a photoinitiator into the said structure, the sensitivity to light can be improved. For this reason, it can be activated by a very small amount of light and harden | cures a photosensitive composition. As a result, it is possible to provide a black matrix pattern having high linearity and no peeling off or debris. In addition, when at least one of E is a group having a molecular weight of 30 or more, the decrease in the film thickness is small, and it is possible to further suppress the generation of the sublimation without impairing the sensitivity to light.

(2) E is a photosensitive composition according to group (1) of any one selected from the group consisting of cycloalkyl group having 3 to 20 carbon atoms in the alkyl group, having 3 to 20 carbon atoms, -OR _3, or -NR ₄ R _5.

According to the invention of (2), E is an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, -OR ₃ , or -NR ₄ R ₅ , and the like. It is possible to provide a photosensitive composition capable of forming a small black matrix pattern.

(3) The photosensitive composition as described in (1) or (2) whose m is 1 or more and n is 0.

According to the invention of (3), by setting the value of n to 0, the sensitivity to light can be further improved.

(4) The photosensitive composition as described in (1) whose E is an alkyl group having 7 to 12 carbon atoms.

According to invention of (4), when E is a C7-C12 alkyl group, E becomes a bulky structure. Therefore, generation | occurrence | production of a sublimation can be suppressed more, without impairing the sensitivity to light.

(5) The photosensitive composition as described in (1) whose compound represented by the said General formula (1) is a compound represented by following General formula (2).

According to the invention of (5), by adding a pyranyl group to the benzoyl moiety of the compound represented by the general formula (1), the benzoyl moiety can be made into a bulky structure without impairing the sensitivity to light. For this reason, the photosensitive compound which can suppress generation | occurrence | production of a sublimation can be provided.

(6) The photosensitive composition as described in (1) whose compound represented by the said General formula (1) is a compound represented by following General formula (3).

According to the invention of (6), as shown by the general formula (3), by adding a specific group to the benzoyl moiety of the compound represented by the general formula (1), similarly to the invention of (5), the benzoyl moiety is not impaired without impairing sensitivity to light. Can be made into a large structure. For this reason, the photosensitive compound which can suppress generation | occurrence | production of a sublimation can be provided. It is also possible to suppress the reduction in the film thickness of the formed film.

(7) The photosensitive composition as described in (1) in which the said photoinitiator further contains the compound represented by following formula (4).

According to the invention of (7), by containing the compound as a photopolymerization initiator, it can be efficiently activated by a very small dose of light. This is because a compound having a different electron band spectrum coexists, and thus, the photopolymerization initiator broadens a substantial wavelength region of light having high sensitivity, or at least two compounds interact with each other. Therefore, by using the photoinitiator which concerns on the said invention together with the compound represented by General formula (4), the sensitivity and image development margin of a photosensitive composition become high further, and it is more preferable to make a black matrix pattern into a favorable form with high linearity and few peelings or debris. Easier

(8) The photosensitive composition as described in (1) in which the said photoinitiator further contains the compound represented by following formula (5).

According to the invention of (8), similarly to the invention as described in (7), by using the photopolymerization initiator according to the invention in combination with the compound represented by the formula (5), the linearity is higher, and there is no peeling or residue generation. Matrix patterns can be provided.

(9) The photosensitive composition as described in (1), wherein the photopolymerization initiator further comprises mercaptobenzimidazole.

According to the invention of (9), similarly to the inventions of (7) and (8), by using in combination, it is possible to provide a black matrix pattern having a higher linearity and no peeling or residues. In addition, since mercaptobenzimidazole also acts as an antioxidant, it is possible to more reliably prevent peeling and generation of residues by further adding as a photopolymerization initiator.

(10) The photosensitive composition according to (1), wherein the photopolymerizable compound is a compound having at least one ethylenic double bond in a molecule.

According to the invention of (10), by using a photopolymerizable compound having an ethylenic double bond in a molecule as a photopolymerizable compound, the absorbance concentration of the photosensitive composition can be increased in a wide wavelength range, and the light can be activated even with a very small dose of light. have. As a result, it is possible to easily form a good black matrix pattern having high light shielding properties and high linearity and no peeling or residue.

On the other hand, the "compound which has at least one ethylenic double bond in a molecule | numerator" contains a monomer, an oligomer, a prepolymer, etc., It is preferable to select at least 1 type from these, and to use.

(11) The photosensitive composition as described in (1), wherein the photopolymerizable compound is an acrylic resin.

According to the invention of (11), by using the photopolymerizable compound as an acrylic resin, the weather resistance and chemical resistance of the photosensitive composition can be improved. As the 'acrylic resin', acrylic acid, methacrylic acid and derivatives thereof such as acrylamide, acrylonitrile and the like can be used.

(12) The photosensitive composition according to (1), wherein the photopolymerizable compound has a cardo structure in the molecule and contains a resin having at least one ethylenic double bond in the molecule.

According to the invention of (12), heat resistance and chemical resistance of the photosensitive composition can be improved by using the photopolymerizable compound as a resin having a cardo structure in the molecule.

(13) The photosensitive composition as described in (1), wherein the coloring agent contains carbon black.

According to the invention of (13), by using the colorant as carbon black, a black matrix pattern having a thin film and high light shielding property can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

The photosensitive composition according to the present invention contains a photopolymerizable compound, a photopolymerization initiator, and a colorant.

[Photopolymerization Initiator]

A "photoinitiator" is a component of a photocurable composition, and means the compound which superposes | polymerizes and polymerizes a composition by irradiation, such as an ultraviolet-ray or an electron beam. In the present invention, a compound represented by the following Chemical Formula 1 can be used as the photopolymerization initiator.

[Formula 1]

Wherein A represents -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ , or -NR ₁ R ₂ , and B represents -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ ,- CONR ₁ R ₂ or -CN, G represents a hydrogen atom, -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ , or -NR ₁ R ₂ , wherein R ₁ and R ₂ are each independently An alkyl group, an aryl group, an aralkyl group, or a heterocyclic group may be represented, and these may be substituted by at least any one of a halogen atom or a heterocyclic group, and among these, the alkylene part of an alkyl group and an aralkyl group may be an unsaturated bond, an ether bond, a thioether It may be interrupted by a bond or an ester bond, and R ₁ and R ₂ may be integrated to form a ring, and D may be the same or different and may be a halogen atom or a C 1 or more and 20 or less containing a hetero atom. Represents a hydrocarbon group which may be present, and E is an egg having 1 to 20 carbon atoms which may be the same or different. Group, denotes a cycloalkyl group, -OR _3, -NR ₄ R having 1 to 20 carbon atoms an alkoxy group, having 3 to 20 carbon atoms of the _5, wherein R ₃ is an alkyl group or a (part of carbon atoms of 1 to 20 carbon atoms substituted by heteroatoms Or an ester bond), a cycloalkyl group having 3 to 20 carbon atoms (some of the carbon atoms may be substituted with a hetero atom, or substituted with an ester bond), and R ₄ and R ₅ may be the same or different. An alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, or R ₄ and R ₅ may be integrated to form a ring having 3 to 20 carbon atoms, and in the case of forming a ring, a portion of the carbon atoms is substituted with a hetero atom. And at least one of E represents a group having a molecular weight of 30 or more, m is an integer of 0 to 5, n is an integer of 0 to 3, and satisfies m + n> 1).

Among these, A represents -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ , or -NR ₁ R ₂ , and it is more preferable to use -R ₁ . In addition, B represents -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ , -CONR ₁ R _2, or -CN, and it is more preferable to use -R ₁ as in A. In addition, G represents a hydrogen atom, -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ , or -NR ₁ R ₂ , and it is more preferable to use -R ₁ like A and B.

As said alkyl group represented by R <_1> and R <_2> among the said A, B, G, a C1-C20 thing is preferable, and a C1-C5 thing is more preferable. For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, third butyl group, amyl group, isoamyl group, third amyl group, hexyl group, hep And linear or branched saturated hydrocarbon groups such as a methyl group, octyl group, isooctyl group, 2-ethylhexyl group, third octyl group, nonyl group, isononyl group, decyl group and isodecyl group. Especially, it is preferable to use a C1-Cmethyl group.

As an aryl group represented by R <_1> and R <_2> , it is preferable that it is C6-C20, and it is more preferable that it is C6-C10. For example, a phenyl group, a tril group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, phenanthryl group, etc. are mentioned.

As an aralkyl group represented by R <_1> and R <_2> , it is preferable that it is C7-20, and it is more preferable that it is C7-12. For example, a benzyl group, the (alpha)-methyl benzyl group, the (alpha), (alpha)-dimethyl benzyl group, the phenyl ethyl group, the phenylethenyl group, etc. are mentioned.

As the heterocyclic group represented by R ₁ and R ₂ , a 5 or more ring, preferably 5 or 7 membered heterocyclic group containing at least one atom of a nitrogen atom (N), a sulfur atom (S) and an oxygen atom (O) Can be mentioned. Condensed ring may be contained in this heterocyclic group, For example, a pyridyl group, a pyrimidyl group, a furyl group, a thiophenyl group, etc. are mentioned.

In addition, these R <_1> and R <_2> may be substituted by the halogen atom. For example, a monofluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluoroethyl group, chlorophenyl group, chlorobenzyl group, etc. are mentioned.

Moreover, the alkylene part of the alkyl group and the aralkyl group in these R <_1> and R <_2> may be interrupted by an unsaturated bond, an ether bond, a thioether bond, and an ester bond. Specifically, you may have a linear or branched unsaturated hydrocarbon group or substituents, such as a vinyl group, an allyl group, butenyl group, an ethynyl group, and a propynyl group.

As such, the group represented by A or B is methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, methoxypropyl group, 2- (benzooxazol-2'-yl) ethenyl group, etc. are mentioned. Can be.

Moreover, a heterocyclic ring is mentioned as a ring which R <_1> and R <_2> may form integrally. Examples of the heterocyclic ring include five or more ring, preferably five to seven membered heterocyclic groups containing at least one atom of nitrogen atom (N), sulfur atom (S) and oxygen atom (O). Condensed ring may be contained in this heterocyclic group, For example, a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, etc. are mentioned.

In addition, D represents a halogen atom which may be the same or different, or a hydrocarbon group which may contain a hetero atom as 1 to 20 carbon atoms. As such a C1-C20 hydrocarbon group containing an oxy group, a thio group, a dithio group, an imino group, a nitrino group, a hydrazo group, an azo group, etc. are mentioned. In addition, an unsaturated bond may be included and the ring may be formed.

It is preferable that molecular weight is group of 30 or more, and, as for at least 1 group of E has, it is more preferable that molecular weight is 50 or more. Moreover, as an upper limit of the group, 250 or less are preferable in consideration of a sensitivity, solubility to a solvent, etc., and it is more preferable that it is 150 or less. Especially, it is more preferable to use a hydropyranyl group.

In addition, E may be the same or different and also represents a cycloalkyl group having 1 to 20 carbon alkyl group, an alkoxy group having 1 to 20 carbon atoms, 3 to 20 carbon atoms of, -OR _3, -NR ₄ R ₅ with each other. Especially, it is preferable to use -OR <_3> . As the alkyl group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, third butyl group, amyl group, isoamyl group, Linear or branched saturation such as a third amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, third octyl group, nonyl group, isononyl group, decyl group and isodecyl group Hydrocarbon group is mentioned.

Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, isopropoxy group and isobutoxy group.

Moreover, as a C3-C20 cycloalkyl group, a cyclopropyl group, a cyclohexyl group, a cyclohexyl group, etc. are mentioned.

In addition, R <_3> of -OR <_3> represents a C1-C20 alkyl group, a C3-C20 cycloalkyl group, and a heterocyclic group. As the alkyl group, the methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, third butyl group, amyl group, isoamyl group, third amyl group, hexyl group, Linear or branched saturated hydrocarbon groups such as heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, third octyl group, nonyl group, isononyl group, decyl group and isodecyl group. These alkyl groups may contain an oxy group, a thio group, a dithio group, an imino group, a nitrino group, a hydrazo group, an azo group, etc.

Moreover, a cyclopropyl group, a cyclohexyl group, etc. are mentioned as a cycloalkyl group. As mentioned above, these cycloalkyl groups may also contain an oxy group, a thio group, a dithio group, an imino group, a nitrino group, a hydrazo group, an azo group, etc. For example, a tetrahydrofuryl ring, a tetrahydropyranyl ring, etc. are mentioned. In addition, these groups may be substituted by a C1-C6 alkyl group, a C1-C6 alkoxy group, etc. In addition, in consideration of the solubility in a solvent, a part of the carbon atoms of the alkyl group and the cycloalkyl group is particularly preferably substituted with an ether bond or an ester bond. It is preferable that 1 to 6 of these ether bonds and ester bonds are contained in the said alkyl group and cycloalkyl group, and it is more preferable that 2 to 4 are contained. Moreover, as a solvent at this time, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, ethers, ketones, and esters are preferable, and propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are used. It is particularly preferable to.

As a heterocyclic ring, the heterocyclic group of 5 or more rings, preferably 5-7 membered rings containing at least 1 atom of a nitrogen atom (N), a sulfur atom (S), and an oxygen atom (O) is mentioned. In addition, the heterocyclic group may contain the condensed ring.

In addition, -NR ₄ R ₅ for R ₄ and R ₅ are the same and also different even if it is an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group, or R ₄ and R ₅ are any of 2 to 20 carbon atoms having a carbon number of 3 to 20 rings may be formed. As the alkyl group, the methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, third butyl group, amyl group, isoamyl group, third amyl group, hexyl group, Linear or branched saturated hydrocarbon groups such as heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, third octyl group, nonyl group, isononyl group, decyl group and isodecyl group.

Moreover, as an alkoxy carbonyl group, linear, branched form, such as a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, or cyclohexyloxycarbonyl group, or the like Cyclic groups are mentioned.

When R <_4> and R <_5> form the ring integrally, a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, etc. are mentioned, for example. In addition, these rings may be substituted by a C1-C6 alkyl group, a C1-C6 alkoxy group, etc.

In addition, in the formula (1), it is preferable to use a compound in which m is 1 or more and n is 0.

As a compound which has such a structure, it is preferable that it is a compound represented by following formula (2). By setting A and B to a methyl group, G to an ethyl group, and n to 0, the sensitivity to light is improved. In addition, by adding a bulky pyranyl group to E, it is possible to reduce the generation of a sublimation at the time of exposure.

[Formula 2]

When using the compound as a photopolymerization initiator, 1 part by mass to 150 parts by mass, preferably 5 parts by mass to 100 parts by mass, and more preferably 10 parts by mass to 50 parts by mass based on 100 parts by mass of the total photopolymerizable compound. It is contained in a negative range. Sufficient heat resistance and chemical resistance can be anticipated by making content into 150 mass parts or less. In addition, it is because the coating film formation ability can be improved by setting it as 1 mass part or more, and the photocuring defect can be prevented.

R ₁ may be a group having a bulky skeleton in addition to a pyranyl group. For example, you may use the compound represented by following formula (3).

[Formula 3]

When using the compound as a photopolymerization initiator, 1 part by mass to 150 parts by mass, preferably 5 parts by mass to 100 parts by mass, and more preferably 10 parts by mass to 50 parts by mass based on 100 parts by mass of the total photopolymerizable compound. It is contained in a negative range. It is because sufficient heat resistance and chemical resistance can be anticipated when content is 150 mass parts or less, and when it is 1 mass part or more, coating film formation ability can be improved and a photocuring defect can be prevented.

In addition, you may use a photoinitiator combining various types of the compound represented by the said Formula (1) with another compound (photoinitiator). Such compounds include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone. Benzophenones such as leucine, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether Sulfur compounds such as benzoin ether, benzyl dimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene and 2-isopropylthioxanthene; Anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone, and organic such as azobisisobutyronitrile, benzoyl peroxide and cumene peroxide Peroxide or 2-mercaptobenzoimidazole Thiol compounds such as 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl Imidazolyl compounds such as dimers, triazine compounds such as p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenol) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine And halomethyl groups such as 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Which is a triazine compound, 2-benzyl-1- (4-morpholinophenyl) - there may be mentioned amino ketone compounds, such as butane -1-one.

In such a compound, it is preferable to use a metcaptobenzimidazole or a triazine compound, but it is more preferable to use the compound represented by following formula (4). It is because the sensitivity to light can be improved further by using this compound together.

[Formula 4]

In addition, the sensitivity to light can be further improved by using the compound represented by the following formula (5).

[Formula 5]

When the compound is used in combination with the compound represented by the formula (1) as a photopolymerization initiator, 1 part by mass to 150 parts by mass, preferably 5 parts by mass to 100 parts by mass, based on 100 parts by mass of the total photopolymerizable compound, More preferably, it is contained in the range of 10 mass parts to 50 mass parts. This is because sufficient heat resistance and chemical resistance can be expected when the content is 150 parts by mass or less, and when the content is 1 part by mass or more, the coating film forming ability can be improved and photocuring defects can be prevented.

In addition, in the case of using a compound represented by the formula (1) and a compound other than the compound represented by the formula (1, in particular, the formulas 4 and 5 and metcaptobenzimidazole, etc.), the mass ratio is 10:90 to 90:10. It is preferable, especially 50:50 to 70:30. By carrying out the compounding ratio of the compound represented by General formula (1) and compounds other than the compound represented by General formula (1) in the above-mentioned range, two compounds may interact effectively, and the sensitivity and image development margin of a photosensitive composition can be improved further.

As an example of the manufacturing method of the photoinitiator which concerns on this invention, the following synthetic reaction formula is mentioned. In addition, this synthesis reaction formula is a synthesis example in case n of D is zero. Here, in formula, R <_1> corresponds to B in this invention, and R <_2> corresponds to the phenyl group containing E in this invention. In addition, R <_3> corresponds to A in this invention, and R is equivalent to G in this invention.

[Photopolymerizable compound]

The "photopolymerizable compound" refers to a substance which is polymerized and cured by irradiation with light such as ultraviolet rays. As a photopolymerizable compound, the compound which has an ethylenic double bond is preferable, Specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl acrylate, 2-hydroxyethyl Methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylic acid amide, Methacrylate amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl Methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol di Methacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethyl Roll propane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate Monomers, oligomers such as dihydrate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxy diacrylate Ryu; After (meth) acrylic acid is reacted with a polyester (meth) acrylate obtained by reacting (meth) acrylic acid to a polyester prepolymer obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid, a compound having a polyol group and two isocyanate groups Polyurethane (meth) acrylate obtained by reacting; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycol Epoxy (meth) acrylate resin etc. which are obtained by reacting (meth) acrylic acid with epoxy resins, such as a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, and a dihydroxy benzene type epoxy resin, are mentioned. Furthermore, the resin which made polybasic acid anhydride react with the said epoxy (meth) acrylate resin can be used.

Especially, it is preferable to use resin which has a cardo structure in an acrylic resin or a molecule | numerator. Since the resin having a cardo structure has high heat resistance and chemical resistance, the heat resistance and chemical resistance of the photosensitive composition can be improved by using a photopolymerizable compound. Specifically, it is preferable to use resin having the following structure.

Here, X of the compound represented by general formula (6) is a group represented by general formula (7).

In the formula, Y is maleic anhydride, succinic anhydride, itaconic acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, chlorendic acid anhydride, methyltetrahydro anhydride It is a residue which removed the carboxylic anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride called phthalic acid and glutaric anhydride.

In addition, Z is a residue remove | excluding two carboxylic anhydride groups from tetracarboxylic dianhydride, such as a pyromellitic dianhydride, a benzophenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, and a biphenyl ether tetracarboxylic dianhydride.

The photopolymerizable compound is contained in a range of 60 parts by mass to 99.9 parts by mass based on 100 parts by mass in total of the photopolymerizable composition. This is because sufficient heat resistance and chemical resistance can be expected by setting the content to 99.9 parts by mass or less, and by setting the content to 60 parts by mass or more, the coating film forming ability can be improved and the photocuring defect can be prevented.

[coloring agent]

A "coloring agent" means the component contained as one of the photosensitive resin components, and coloring on a board | substrate. For example, a compound classified as a pigment in the color index (C.I., published by The Society of Dyers and Colourists), and specifically, the one labeled with the following color index (C.I.) number.

C.I. Pigment Yellow 1 (hereinafter 'CI Pigment Yellow' is the same and only numbers are listed), 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;

C.I. Pigment Orange 1 (hereinafter 'CI Pigment Orange' is the same and only numbers are listed), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55 59, 61, 63, 64, 71, 73;

C.I. Pigment Violet 1 (hereinafter 'C.I. Pigment Violet' is the same and lists only the numbers), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

C.I. Pigment Red 1 (hereinafter 'CI Pigment Red' is the same and only numbers are listed), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 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;

C.I. Pigment Blue 1 (hereinafter 'C.I. Pigment Blue' is the same and lists only the numbers), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. 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.

Moreover, carbon black is also preferable as a black pigment.

Since the photosensitive composition which concerns on this invention has high sensitivity, it is especially preferable for black matrix formation. That is, light-shielding agents, such as carbon black, can be used suitably as a coloring agent. Specifically, the carbon black dispersion liquid etc. which were disperse | distributed to the carbon black and acrylic dispersion liquid are mentioned. In addition, inorganic pigments such as metal oxides such as titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, composite oxides, metal sulfides, lead metal sulfates, and metal carbonates may also be mentioned. It is more preferable to use carbon black which has light-shielding property among these coloring agents.

As carbon black, well-known carbon black, such as channel black, furnace black, thermal black, lamp black, can be used, but channel black excellent in light-shielding property is especially preferable. Moreover, you may use resin-coated carbon black.

This resin-coated carbon black has lower conductivity compared to carbon black without resin coating, and therefore, when used as a color filter (black matrix) such as a liquid crystal display, there is little leakage of current, thereby forming a highly reliable low power display. Can be.

In addition, an organic pigment may be further added as an auxiliary pigment of carbon black. This is because the organic pigment can erase the red group of carbon black by appropriately selecting and adding the complementary color of the inorganic pigment. For example, a phthalocyanine pigment, an azo pigment, a basic dye lake pigment, etc. are mentioned.

The organic pigment is preferably used in the range of 10 parts by mass to 80 parts by mass, and more preferably in the range of 20 parts by mass to 40 parts by mass with respect to 100 parts by mass of the total of the inorganic pigment and the organic pigment. The inorganic pigments and organic pigments may be used a solution dispersed in a suitable concentration using a dispersant.

As the dispersant, it is preferable to use a polymer dispersant of polyethyleneimine, urethane resin, or acrylic resin.

[Composition of Photosensitive Composition]

In the photosensitive composition according to the present invention, a photopolymerizable compound, a photopolymerization initiator, and a coloring agent are added, and in 100 parts by mass, 20 parts by mass to 60 parts by mass of the photopolymerizable compound, 0.5 parts by mass to 30 parts by mass of the photopolymerization initiator, and 10 parts by mass of the colorant It is preferable to contain in the range of 70 mass parts by weight. By making a coloring agent 10 mass parts or more, the light-shielding performance of the formed black pattern can fully be obtained. Moreover, it is because curability can be improved when irradiating the light ray of a predetermined wavelength by making a coloring agent into 70 mass parts or less.

On the other hand, in the said composition ratio, although the coloring agent may be only inorganic pigments, such as carbon black and titanium black, it may contain auxiliary pigments.

In addition, it is preferable to adjust the density | concentration of a coloring agent so that OD (Optical Density) value per 1 micrometer of film thickness of a photosensitive composition may be 3.5 or more, when forming a black matrix using the photosensitive composition which concerns on this invention as mentioned later. Do. When the OD value per 1 micrometer of the film thickness of the photosensitive composition is 3.5 or more, when used for the black matrix of a liquid crystal display, sufficient display contrast can be obtained.

In addition, when forming a black-matrix pattern using the photosensitive composition which concerns on this invention, a photosensitive composition of this invention is apply | coated and dried on a board | substrate as mentioned later, and a film is formed. In order to improve the coating property at this time and to improve the physical properties after photocuring, a polymer binder may be further contained as a binder in addition to the above components. The binder may be appropriately selected depending on the purpose of improvement such as compatibility, film formability, developability, and adhesiveness.

The thickness of the black matrix pattern formed on the substrate can usually be set within the range of 0.1 µm to 10.0 µm, preferably 0.2 µm to 5.0 µm, more preferably 0.2 µm to 3.0 µm.

Moreover, the photosensitive composition which concerns on this invention may add the solvent for dilution, a thermal polymerization inhibitor, an antifoamer, surfactant, etc.

Here, as a solvent which can be added to the photosensitive composition, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono Methyl 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 mono (Poly) alkylene glycol monoalkyl ethers such as ethyl ether; (Poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Lactic acid alkyl esters such as ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone, methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxy acetate, 2 Methyl hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate -Butyl, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyridate, ethyl pyrrate, Other esters such as n-propyl vinate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutyrate; Aromatic hydrocarbons such as toluene and xylene; Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetoamide, and the like. These solvents can be used 1 type or in mixture of 2 or more types.

Among them, 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 ethyl ether, cyclohexanone, 3-methoxy Butyl acetate is preferable since it shows excellent solubility with respect to a photopolymerizable compound and a photoinitiator, and can make the dispersibility of insoluble components, such as a black pigment, favorable, and is propylene glycol monomethyl ether acetate and 3-methoxy butyl acetate. Particular preference is given to using. A solvent can be used in 50 mass parts-500 mass parts with respect to a total of 100 mass parts of a photopolymerizable compound, a photoinitiator, and a coloring agent.

Moreover, hydroquinone, hydroquinone monoethyl ether, etc. can be used as a thermal polymerization inhibitor. As the antifoaming agent, a variety of known thermal polymerization inhibitors such as silicone-based and fluorine-based compounds and anionic, cationic and non-ion-based compounds can be used as the surfactant.

As a manufacturing method of the photosensitive composition which concerns on this invention, it is obtained by mixing the photopolymerizable compound mentioned above, a photoinitiator, a coloring agent, and all with a stirrer. In addition, you may filter using a filter so that the obtained mixture may become uniform.

<Formation method of color filter>

Hereinafter, the example of the method of forming a color filter using the photosensitive composition which concerns on this invention is demonstrated.

[Formation of Black Matrix (Black Color Layer)]

First, a photosensitive composition (including a black colorant) is applied onto a substrate using a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. As the substrate, a substrate having light transparency is used. On the other hand, in this embodiment, the case where the glass substrate of thickness 0.5mm-1.1mm is used is considered.

In order to improve the adhesiveness of a glass substrate and a photosensitive composition, you may apply a silane coupling agent on a glass substrate previously. Alternatively, a silane coupling agent may be added at the time of preparing the photosensitive composition.

After apply | coating this photosensitive composition, it dries and removes a solvent. The drying method is not particularly limited, and for example, (1) drying in a hot plate at a temperature of 80 ° C to 120 ° C, preferably 90 ° C to 100 ° C for 60 seconds to 120 seconds, and (2) water at room temperature You may use either the method of leaving for several days in time, (3) the method of removing a solvent in a hot air heater or an infrared heater in tens of minutes for several hours.

Subsequently, active energy rays such as ultraviolet rays and excimer laser light are irradiated and partially exposed through the negative mask. Although the energy dose to irradiate changes with the composition of the photosensitive composition, about 30 mJ / cm <^2> -2000mJ / cm <^2> is preferable, for example.

Subsequently, the film | membrane after exposure is developed with a developing solution, and it patterned to a desired shape. The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. Examples of the developing solution include organic compounds such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

Next, post-development patterning is post-baked at about 200 degreeC. In addition, it is preferable to expose the formed pattern to the whole surface.

[Formation of Other Colored Layers]

On the glass substrate on which the black matrix formed by the above method was formed, the photosensitive composition was applied, dried, exposed, and developed in the same manner as the above method, and a colored layer of a predetermined color was patterned (striped or dots) at a predetermined position (opening) of the black matrix. Etc.) are formed. For example, when manufacturing an RGB color filter, using the photosensitive composition of each of R, G, and B, repeating the said process, three color layers are formed and a color filter is formed.

<Example 1>

Synthesis of Photopolymerizable Compound

As a photopolymerizable compound having an ethylenically unsaturated bond, methacrylic acid / benzyl methacrylate / 1-hydroxyethyl methacrylate copolymer (hereinafter referred to as compound 1) was synthesized. First, a 500 ml inlet flask containing 400 g of propylene glycol monomethyl ether acetate (PGMEA), 75 g of methacrylic acid, 210 g of benzyl methacrylate, 15 g of 2-hydroxyethyl methacrylate, and azobisisobutyro 5 g of nitriles were added thereto, and the mixture was kept at 65 ° C and 70 ° C while blowing nitrogen into the mixture, followed by stirring for 3 hours.

[Photopolymerization Initiator]

The photoinitiator was made into a compound having a structure represented by the following formula (2). This compound was prepared according to the synthesis scheme described above.

[Formula 2]

In synthesizing this compound, a compound of Formula 8 was prepared according to the following scheme.

(In formula, R <_2> corresponds to R <_2> in the reaction formula mentioned above and corresponds to the phenyl group containing E in this invention.).

As said compound 1 and a monomer, pentaerythritol tetraacrylate (PETTA) was used as a photopolymerizable compound, and the photosensitive composition which concerns on this invention was adjusted to the compound of Table 1. At this time, a carbon dispersion (CF black EX-1455, containing 24 mass% of high-resistance carbon, manufactured by Japan Mikuni Color Co., Ltd.) was used as a pigment, and 3-methoxybutyl acetate was used as a solvent. All of these were mixed with a stirrer for 2 hours and filtered with a 5 micrometer membrane filter to adjust the photosensitive composition which concerns on this invention.

<Example 2>

The photosensitive composition was adjusted in the same procedure as in Example 1 except that the photopolymerizable compound was used as a compound having the structure represented by the following formula (Compound 2) (see Table 1).

Synthesis of Photopolymerizable Compound

A cardo resin having a structure represented by the following formula (6) was synthesized.

[Formula 6]

In the formula, X is a group having a structure represented by the formula (7).

[Formula 7]

25 ml of 235 g of bisphenol fluorene type epoxy resin (235 equivalents of epoxy equivalent), 110 mg of tetramethylammonium chloride, 100 mg of 2, 6- di-tert butyl- 4-methyl phenols, and 72.0 g of acrylic acid were put into the flask of 500 ml of 4 inlets. It melt | dissolved by heating from 90 degreeC to 100 degreeC, blowing air at the rate of / min.

Subsequently, the solution was slowly warmed up to 120 ° C in a cloudy state and completely dissolved. At this time, the solution became transparent viscous in order, but stirring was continued as it was. In the meantime, the acid value was measured and heating stirring was continued for about 12 hours until it became less than 1.0 mgKOH / g. Then, it cooled to room temperature and obtained the colorless transparent solid bisphenol fluorene type epoxy acrylate represented by following formula (9).

Subsequently, 600 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained, followed by dissolution. Then, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of emulsified tetraethylammonium were mixed, It was made to react at 110 degreeC-115 degreeC 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 a cardo resin represented by the above formula (7). In addition, the loss | disappearance of the acid anhydride group was confirmed by IR spectrum. This cardo resin was made into compound 2.

Here, compound 2 is a compound represented by the formula (6), X is a group represented by the formula (7), Y is an acid anhydride group (-CO-O-CO in 1,2,3,6-tetrahydrophthalic anhydride dianhydride) The residue from which-) is removed, Z is a residue from which the acid anhydride is removed from the 3,3 ', 4,4'-benzophenonetetracarboxylic acid office water, and the Y / Z molar ratio is 50.0 / 50.0.

<Example 3>

In addition to the photopolymerization initiator of Example 2, the compound 2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -2- (phenylmethyl) -1-butanone (photopolymerization) Initiator 2: The photosensitive composition which concerns on this invention was adjusted in the same combination and procedure as Example 2 except having added the brand name Monocure 269 and the product made by Chiba Co., Ltd. (refer Table 1).

[Formula 4]

<Example 4>

The photosensitive composition which concerns on this invention was adjusted in the procedure similar to Example 2 except having added mercaptobenzimidazole (photoinitiator 3) further to the photoinitiator of Example 2 (refer Table 1).

Comparative Example 1

The photosensitive composition was adjusted in the same procedure as in Example 1 except that the photopolymerization initiator was used as a compound represented by the following formula (Photopolymerization initiator 4: Nippon Chivas Specialty Chemical Co., Ltd., CGI242) (see Table 1).

[Formula 5]

Photopolymerizable compound Photopolymerization Initiator Carbon dispersion solvent Suzy Monomer Example 1 Compound 1: 150 parts by mass PETTA: 30 parts by mass Photopolymerization initiator 1: 12 parts by mass 700 parts by mass 3-methoxybutyl acetate: 300 parts by mass Example 2 Compound 2: 150 parts by mass PETTA: 30 parts by mass Photopolymerization initiator 1: 12 parts by mass 700 parts by mass 3-methoxybutyl acetate: 300 parts by mass Example 3 Compound 2: 150 parts by mass PETTA: 30 parts by mass Photopolymerization Initiator 1: 12 parts by mass Photopolymerization Initiator 2: 6 parts by mass 700 parts by mass 3-methoxybutyl acetate: 300 parts by mass Example 4 Compound 2: 150 parts by mass PETTA: 30 parts by mass Photopolymerization Initiator 1: 12 parts by mass Photopolymerization Initiator 3: 6 parts by mass 700 parts by mass 3-methoxybutyl acetate: 300 parts by mass Comparative Example 1 Compound 2: 150 parts by mass PETTA: 30 parts by mass Photoinitiator 4: 12 parts by mass 700 parts by mass 3-methoxybutyl acetate: 300 parts by mass

<Evaluation>

The photosensitive composition was coated on a glass substrate having a clean surface having a thickness of 1 mm, using a spin coater (TR 25000, Tokyo-Okago Kogyo Co., Ltd.) so as to have a dry film thickness of 1.2 μm, and dried at 90 ° C. for 2 minutes. The film (photosensitive layer) of the photosensitive composition was formed. This film was then selectively irradiated with ultraviolet light through a negative mast. The exposure amount was set to four stages of 40, 45, 50, and 60 mJ.

Then, a black matrix pattern including a line having a line width of 10 μm was formed by spray development at 25 ° C. for 60 seconds with an aqueous 0.5 mass% sodium carbonate solution. Thereafter, it was post-baked in a circulation oven at 220 ° C. for 30 minutes. The film thickness of the created black matrix was 1.0 micrometer, and OD value was measured with the OD measuring apparatus (D-200II, GretagMacbeth company make). The results are shown in Table 2.

Straightness of the pattern Pattern peeling  leftover  OD value Exposure amount (mJ / cm ² ) 40 45 50 60 40 45 50 60 Example 1 Bad Good Good Good has exist none none none none 4.0 Example 2 Good Good Good Good none none none none none 4.0 Example 3 Good Good Good Good none none none none none 4.0 Example 4 Good Good Good Good none none none none none 4.0 Comparative Example 1 Bad Good Good Good has exist none none none none 4.0

The straightness of the pattern was visually determined whether the edge of the 10 micron line (the line of 10 mu m width) was irregular. In addition, the pattern peeling visually determined whether peeling and omission in a 5 micron line (line of 5 micrometers in width) did not generate | occur | produce. The residue was visually determined whether the residue of the pigment remained on the glass. Thereby, the pattern obtained in Examples 2-4 was excellent in linearity, and peeling with a pigment dreg and a board | substrate was not confirmed. On the other hand, Comparative Example 1 was found to have a lot of pattern peeling at a low exposure dose, and the straightness was also poor.

Moreover, about Example 2 and the comparative example 1, the result of having compared the residual film ratio at the time of setting the temperature of a post base as 200 degreeC and 220 degreeC is shown in Table 3. The residual ratio refers to the ratio of the film thickness after the postbase to the film thickness before the exposure and the postbaking. As a result, it was shown that the use of the photosensitive composition according to the present invention had a high residual film ratio of about 2%, thereby suppressing the generation of a sublimation after the postbase.

Example 2 Comparative Example 1 200 ℃ 86.80% 84.20% 220 ℃ 85.10% 82.90%

In addition, Example 2 and Comparative Example 1 examined the sublimation generation during exposure. After exposure at 70 sheets 100 (mJ / cm ² ), the mask was cleaned using an amount of tetrahydrofuran (THF). Subsequently, the mask deposit was quantified using gel permeation chromatography (manufactured by Shimadzu Seisakusho, Japan). The comparison of the amount of sublimation generation was judged from the peak area near 16 minutes of the chart. The results are shown in Table 4. As a result, it was shown that the one using the photosensitive composition according to the present invention can suppress the generation of sublimation.

Example 2 Comparative Example 1 Area% 36 41 Peak height% 41.1 47.9

According to the present invention, it is possible to easily form a black matrix pattern having excellent linearity, less peeling and residue, and excellent display contrast by using a photopolymerization initiator having excellent sensitivity to light. In addition, even with a high light-shielding resist, it is possible to provide a black matrix pattern having high development margin and high resolution with high sensitivity. Furthermore, by using the polymerization initiator according to the present invention, it is possible to provide a photosensitive composition capable of forming a black matrix pattern with less generation of sublimation in heating after development.

Claims (13)

It contains a photopolymerizable compound, a photoinitiator, and a coloring agent, A photosensitive composition containing a compound represented by the following Chemical Formula 1 as the photopolymerization initiator: [Formula 1]

Wherein A represents -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ , or -NR ₁ R ₂ , and B represents -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ ,- CONR ₁ R ₂ or -CN, G represents a hydrogen atom, -R ₁ , -OR ₁ , -COR ₁ , -SR ₁ , or -NR ₁ R ₂ , wherein R ₁ and R ₂ are each independently An alkyl group, an aryl group, an aralkyl group, or a heterocyclic group may be represented, and these may be substituted by at least any one of a halogen atom or a heterocyclic group, of which the alkylene portion of the alkyl group and the aralkyl group is an unsaturated bond, an ether bond, a thioether It may be interrupted by a bond or an ester bond, and R ₁ and R ₂ may be integrated to form a ring, and D may be the same or different and may be a halogen atom or a C 1 or more and 20 or less containing a hetero atom. Represents a hydrocarbon group which may be present, and E is an egg having 1 to 20 carbon atoms which may be the same or different. Group, having 1 to 20 carbon atoms in the alkoxy group, a cycloalkyl group having a carbon number of ₃ ~ 20, -OR 3, -NR ₄ R ₅ represents a, where R ₃ is optionally an alkyl group (part of carbon atoms of 1 to 20 carbon atoms substituted by heteroatoms Good), a C3-C20 cycloalkyl group (some of the carbon atoms may be substituted with a hetero atom), R ₄ , R ₅ may be the same or different, a C 1-20 alkyl group, a C 2-20 alkoxycarbonyl group Or R ₄ and R ₅ may be integrated to form a ring having 3 to 20 carbon atoms; when a ring is formed, a portion of the carbon atoms may be substituted with a hetero atom, and at least one of E has a molecular weight of 30 or more; Group, m is an integer of 0-5, n is an integer of 0-3, and m + n> 1 is satisfied). The method of claim 1, E is a photosensitive composition of any one group selected from the group consisting of an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, -OR ₃ , or -NR ₄ R ₅ . The method according to claim 1 or 2, m is 1 or more and n is 0. The photosensitive composition. The method of claim 1, E is a photosensitive composition which is a C7-C12 alkyl group. The method of claim 1, The compound represented by Formula 1 is a compound represented by the following formula (2) photosensitive composition: [Formula 2]

. The method of claim 1, Compound represented by Formula 1 is a compound represented by the following formula (3): [Formula 3]

. The method of claim 1, The photopolymerization initiator further comprises a compound represented by the following formula (4): [Formula 4]

. The method of claim 1, The photopolymerization initiator further comprises a compound represented by the following formula (5): [Formula 5]

. The method of claim 1, The photopolymerization initiator further comprises a mercaptobenzimidazole. The method of claim 1, The photopolymerizable compound is a compound having at least one ethylenic double bond in the molecule. The method of claim 1, The photopolymerizable compound is an acrylic resin. The method of claim 1, The photopolymerizable compound includes a resin having a cardo structure in the molecule and at least one ethylenic double bond in the molecule. The method of claim 1, The colorant comprises a carbon black photosensitive composition.