KR20070027446A - Photosensitive composition - Google Patents

Abstract

A photosensitive composition including acyloxime ester based compound is provided to have favorable linearity, be hardly released and be capable of forming black matrix patterns with less residues by comprising the acyloxime ester based compound with carbazole backbone as photo-polymerization initiator. The composition includes a photo-polymeric compound, a photo-polymerization initiator and a coloring agent. The photo-polymerization initiator comprises acyloxime ester based compound represented by a formula(1), wherein R1 is lower alkyl group containing C1 to C5, A is selected from hydrocarbon group, -CN and -NO2, Ar is carbazole group or substituent thereof, or benzoyl group that has substitutional group. R1 is methyl or ethyl group. The initiator further contains mercaptobenzimidazole. The photo-polymeric compound is acryl resin and has at least one ethylene double bond in a molecule.

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, and carbon black is the most common among them.

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.

The present inventors have found that by using an acyl oxime ester compound as the photopolymerization initiator of the photosensitive composition, it is possible to provide a photosensitive composition having good linearity, being hard to peel off, and capable of forming a black matrix pattern with little residue.

More specifically, the present invention provides the following.

(1) The photosensitive composition containing a photopolymerizable compound, a photoinitiator, and a coloring agent, and containing the acyl oxime ester type compound represented by following General formula (1) as said photoinitiator.

(Wherein R ₁ represents a lower alkyl group having 1 to 5 carbon atoms, A represents a group selected from a hydrocarbon group, -CN, -NO ₂ , and Ar represents a group having a carbazole or a substituent or a substituent) Benzoyl group).

According to the invention of (1), the starting efficiency of the photopolymerization initiator can be improved by using the photopolymerization initiator as a lower alkyl group having the above structure, in particular, R ₁ having 1 to 5 carbon atoms. For this reason, it can activate efficiently by the light of a very small irradiation amount, and can harden a photopolymerizable compound, and the sensitivity to light of a photosensitive composition can be improved. As a result, it is possible to provide a black matrix pattern having high linearity and less generation of peelings and debris.

(2) Ar is photosensitive composition as described in (1) which is group represented by following formula (2) or formula (3).

(Wherein, B is equal to or different from each other also represents a group that is a hydrogen atom, a halogen atom, selected from alkyl, phenyl, C ₆ H ₅ S- having a carbon number of 1 ~ 12, k is an integer of 0-5.

G may be the same or different from each other, a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C3-C20 cycloalkyl group, -OR ₂ , -NR ₃ R ₄ M is an integer of 0-5.

R ₂ represents an alkyl group having 1 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms) or a cycloalkyl group having 3 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms),

R <_3> , R <_4> may represent the same or different C1-C20 alkyl group, C2-C20 alkoxycarbonyl group, or R <_3> and R <_4> may be integrated and may form a C3-C20 ring, When the ring is formed, part of the carbon atoms may be substituted with hetero atoms.

D represents a group selected from the same or different hydrogen atoms, halogen atoms, and hydrocarbon groups which may contain hetero atoms with 1 to 20 carbon atoms, and n is an integer of 0 to 3.

E represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a phenyl group).

According to the invention of (2), by making Ar be benzoyl, the sensitivity to light can be further improved. In addition, as shown in the general formula (3), when the third position of the benzene ring is substituted with benzoyl, and further used a carbazole ring having a few substituents, the sensitivity to light can be further improved, and the heat resistance is also improved. It becomes possible.

(3) The photosensitive composition as described in (1) or (2) whose R <_1> is a methyl group or an ethyl group.

According to the invention of (3), when R ₁ is a methyl group or an ethyl group, the sensitivity to light can be further improved. Therefore, it can activate efficiently by the light of very small irradiation amount, and can harden a photoinitiator. As a result, it is possible to provide a black matrix pattern having a higher linearity and less generation of peeling and debris. Moreover, since the structure of the photoinitiator which concerns on this invention can be made simpler, a manufacturing process can also be simplified.

(4) The photosensitive composition according to any one of (1) to (3), wherein the compound represented by the formula (1) is a compound represented by the following formula (4).

(Wherein A represents a group selected from a hydrocarbon group, -CN, and -NO ₂ , G represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, which may be the same or different from each other, It represents a group selected from a cycloalkyl group having a carbon number of _{3 ~ 20, -OR 2, -NR} 3 R 4, m is an integer from 0-5.

R ₂ represents an alkyl group having 1 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms) or a cycloalkyl group having 3 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms),

R <_3> , R <_4> may represent the same or different C1-C20 alkyl group, C2-C20 alkoxycarbonyl group, or R <_3> and R <_4> may be integrated and may form a C3-C20 ring, When a ring is formed, part of the carbon atoms may be substituted with hetero atoms).

According to the invention of (4), by using the photopolymerization initiator as a structure of formula (4), it is possible to provide a photosensitive composition which can form a black matrix pattern having high heat resistance and higher linearity and less generation of peeling and debris. have.

(5) The photosensitive composition according to any one of (1) to (4), wherein the photopolymerization initiator is a mixture of a compound represented by the formula (1) and a compound represented by the following formula (5).

According to the invention of (5), 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 together the photoinitiator which concerns on invention as described in (1)-(4), and the compound represented by General formula (5), the sensitivity and image development margin of a photosensitive composition become further high, the linearity of a black matrix pattern is high, and peeling and dregs are It is easier to make a good form with less number.

(6) The photosensitive composition according to any one of (1) to (5), wherein the photopolymerization initiator further contains mercaptobenzimidazole.

According to the invention of (6), similarly to the invention of (5), by using in combination, a black matrix pattern having a higher linearity and less occurrence of peeling and debris can be provided. 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.

(7) The photosensitive composition according to any one of (1) to (6), wherein the photopolymerizable compound is a compound having at least one ethylenic double bond in a molecule.

According to the invention of (7), 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 at a very low dose. 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.

(8) The photosensitive composition as described in any one of (1)-(7) whose said photopolymerizable compound is an acrylic resin.

According to the invention of (8), 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.

(9) The photosensitive composition according to any one of (1) to (8), wherein the photopolymerizable compound is a resin having a cardo structure in its molecule.

According to the invention of (9), by using the photopolymerizable compound as a resin having a cardo structure in the molecule, the heat resistance and chemical resistance of the photosensitive composition can be improved.

(10) The photosensitive composition according to any one of (1) to (9), wherein the colorant contains carbon black.

According to the invention of (10), by using the colorant as carbon black, a black matrix pattern having high light blocking property can be provided in a thin film.

(11) The photosensitive composition in any one of (1)-(10) used as a black resist which comprises the black matrix which comprises a liquid crystal display.

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 R ₁ represents a lower alkyl group having 1 to 5 carbon atoms, A represents a group selected from a hydrocarbon group, -CN, -NO ₂ , and Ar represents a group having a carbazole or a substituent or a substituent) Benzoyl group).

R ₁ represents a lower alkyl group having 1 to 5 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group and pentyl group. . Especially, it is preferable to use a methyl group and an ethyl group.

Examples of A include a group selected from a hydrocarbon group, -CN, and -NO ₂ . As a hydrocarbon group, a C1-C20 alkyl group, a C1-C4 haloalkyl group, a phenyl group, etc. are mentioned. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, third butyl group, amyl group, isoamyl group, and third Linear or branched saturated hydrocarbon groups such as amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl and isodecyl; As mentioned above, it is preferable to use a methyl group of 1 carbon among these.

As a C1-C4 haloalkyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are mentioned, for example.

Ar is either carbazole or a group having a substituent or a benzoyl group which may have a substituent, and among these, it is preferable to use a carbazole or a group having the substituent, but as described later, It is more preferable that the 3rd position is substituted by the benzoyl group which has a substituent G.

Moreover, the thing represented by following formula (2) is mentioned specifically as a benzoyl group which may have a substituent.

[Formula 2]

(Wherein, B is equal to or different from each other also represents a group that is a hydrogen atom, a halogen atom, an alkyl group of 1 to 12 carbon atoms, selected from phenyl, C ₆ H ₅ S-, k is an integer from 0 to 5)

Among these, B represents a group selected from the same or different hydrogen atoms, halogen atoms, alkyl groups having 1 to 12 carbon atoms, phenyl groups and C ₆ H ₅ S-. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, third butyl group, amyl group, isoamyl group, and third Straight or branched saturated hydrocarbon groups, such as amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl and isodecyl groups Can be mentioned. In addition, k is an integer of 0-5.

Moreover, as a group which has the structure of the group which has a carbazole substituent, and the benzoyl group which may have a substituent, the structure specifically, represented by General formula (3) is mentioned.

[Formula 3]

In the formula, G may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, -OR ₂ , -NR ₃ R ₄ Represents group selected from, and m is an integer of 0-5.

R ₂ represents an alkyl group having 1 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms) or a cycloalkyl group having 3 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms),

R <_3> , R <_4> may represent the same or different C1-C20 alkyl group, C2-C20 alkoxycarbonyl group, or R <_3> and R <_4> may integrate and form a C3-C20 ring, When the ring is formed, part of the carbon atoms may be substituted with hetero atoms.

D represents a group selected from the same or different hydrogen atoms, halogen atoms, and hydrocarbon groups which may contain hetero atoms with 1 to 20 carbon atoms, and n is an integer of 0 to 3.

E represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a phenyl group)

G is the same or different hydrogen atom, halogen atom, alkyl group of 1 to 20 carbon atoms, alkoxy group of 1 to 20 carbon atoms, cycloalkyl group of 3 to 20 carbon atoms, -OR ₂ , -NR ₃ R ₄ Preference is given to using groups having 3 or more carbon atoms. This is because by setting the bulky structure of G, it is possible to suppress the generation of a sublimation during exposure and to reduce the decrease in the film thickness.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, third butyl group, amyl group, isoamyl group, and third Linear or branched saturated hydrocarbon groups such as 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 Can be 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, a cyclopropyl group, a cyclohexyl group, etc. are mentioned as a C3-C20 cycloalkyl group. In addition, m is an integer of 0-5.

In addition, R <_2> of -OR <_2> is a C1-C20 alkyl group (a part of carbon atoms may be substituted by the hetero atom, or may be substituted by the ester bond), and a C3-C20 cycloalkyl group (a part of carbon atoms is a hetero atom) It may be substituted or may be substituted by the ester bond).

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. 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.

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, Saturated hydrocarbon groups, such as a heptyl group, an octyl group, an isooctyl group, 2-ethylhexyl group, a third octyl group, a nonyl group, isononyl group, a decyl group, and an isodecyl group, are mentioned.

Moreover, as an alkoxy carbonyl group, linear, branched form, or ring, such as a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, or cyclohexyloxycarbonyl group, etc. A group of shape is 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.

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, this hydrocarbon group may contain the unsaturated bond and may form the ring.

In addition, E represents a hydrogen atom, a halogen atom, a C1-C20 alkyl group, or a phenyl group. Especially, it is preferable to use an alkyl group. As the alkyl group having 1 to 12 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. As mentioned above, it is preferable to use a C2 ethyl group especially.

It is preferable that it is a compound represented by General formula (4) as a compound which has such a structure. Having a skeleton of both carbazole and benzoyl improves sensitivity to light. Moreover, heat resistance improves by having a carbazole skeleton.

[Formula 4]

(Wherein A represents a group selected from a hydrocarbon group, -CN, and -NO ₂ , G represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, which may be the same or different from each other, It represents a group selected from a cycloalkyl group having a carbon number of _{3 ~ 20, -OR 2, -NR} 3 R 4, m is an integer from 0-5.

R ₂ represents an alkyl group having 1 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms) or a cycloalkyl group having 3 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms),

R <_3> , R <_4> may represent the same or different C1-C20 alkyl group, C2-C20 alkoxycarbonyl group, or R <_3> and R <_4> may be integrated and may form a C3-C20 ring, When a ring is formed, part of the carbon atoms may be substituted with hetero atoms).

More specifically, it is more preferable to use a compound represented by the following formula (6) in which A is a methyl group, Ar is a group represented by the formula (3), G is a methyl group, n is 0 and E is an ethyl group.

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. This is because sufficient heat resistance and chemical resistance can be expected by setting the content to 150 parts by mass or less, and by setting the content to 1 part by mass or more, the coating film forming ability can be improved to prevent photocuring defects.

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 and 2-mercaptobenzoimida 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.

Among these compounds, it is preferable to use a metcaptobenzimidazole or a triazine compound, but it is more preferable to use a compound represented by the following formula (5). It is because the sensitivity to light can be improved further by using this compound together.

[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 by setting the content to 150 parts by mass or less, and by setting the content to 1 part by mass or more, the coating film forming ability can be improved to prevent photocuring defects.

When the compound represented by the formula (1) and a compound other than the compound represented by the formula (1), in particular, formula (5) and metcaptobenzimidazole, etc. are used in combination, the mass ratio is preferably 10:90 to 90:10. In particular, it is preferable that it is 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 A in this invention, and R <_2> corresponds to the phenyl group containing G in this invention. In addition, R <_3> corresponds to R <_1> in this invention, and R is equivalent to E 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. 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 a resin represented by the following formula (7).

In the formula, X is a group represented by the following formula (8).

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 photopolymerization composition. If the content is less than 60 parts by mass, sufficient heat resistance and chemical resistance cannot be expected, and by setting it as 99.9 parts by mass or less, the coating film forming ability can be improved, and photocuring defects 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 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 rack, can be used, but channel black excellent in light-shielding property is especially preferable. Moreover, you may use resin-coated carbon black.

Since the resin-coated carbon black has lower conductivity than carbon black without resin coating, when used as a color filter such as a liquid crystal display, there is little leakage of current, and a highly reliable low power display can be formed.

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]

The photosensitive composition according to the present invention has a photopolymerizable compound, a photopolymerization initiator, and a colorant 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, when a coloring agent is 70 mass parts or less, hardening defect can be suppressed when irradiating the light ray of a predetermined wavelength.

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 hair Ethyl ether and (poly) alkylene glycol monoalkyl 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 Hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 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 pyrrate, ethyl pyrrate, Other esters such as n-propyl pyrvinate, 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 because 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, cyclohexanone, 3- Methoxybutyl acetate is particularly preferred. 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 light shielding material.

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. On the other hand, you may filter using a filter so that the obtained mixture may be 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. Energy dose of irradiation varies depending on the composition of the photosensitive composition, for example, it is 2000mJ / cm ² preferably at about 30mJ / cm ^2.

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

First, the cardo resin represented by the following formula (7) is synthesized.

[Formula 7]

In the formula, X is a group represented by the following formula (8).

[Formula 8]

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 (9). In addition, the loss | disappearance of the acid anhydride group was confirmed by IR spectrum. This cardo resin was made into compound 1.

Here, Compound 1 is a compound represented by the formula (7), X is a group represented by the formula (8), 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.

[Photopolymerization Initiator]

The compound represented by following formula (6) was made into the photoinitiator 1 (CGI242, the Japanese Chiba Specialty Chemicals company) concerning this invention.

[Formula 6]

Using the pentaerythritol tetraacrylate as the photopolymerizable compound as the compound 1 and the monomer, the photosensitive composition according to the present invention was adjusted as shown in 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 the stirrer for 2 hours, and it filtered by the 5 micrometer membrane filter, and adjusted the photosensitive composition.

<Example 2>

The photosensitive composition according to the present invention was adjusted in the same manner as in Example 1 except that the photopolymerization initiator was used as a compound having a structure represented by the following formula (10) (see Table 1). On the other hand, this compound was prepared according to the above-described synthetic scheme.

In synthesizing this compound, a compound represented by the following Formula 11 was prepared according to Scheme 2 below.

(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 the stirrer for 2 hours, and it filtered by the 5 micrometer membrane filter, and adjusted the photosensitive composition.

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 having the following formula (12, manufactured by Chiba Specialty Chemical Co., Ltd., CGI242: Photopolymerization Initiator 3).

Comparative Example 2

The photosensitive composition was adjusted in the same procedure as in Example 1 except that the photopolymerization initiator was a compound having the following formula (13) (photopolymerization initiator 4) (see Table 1). In addition, this photoinitiator 4 was synthesize | combined with following Reaction Formula 3.

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: 1 part by mass 500 parts by mass 3-methoxybutyl acetate: 300 parts by mass Example 2 Compound 1: 150 parts by mass PETTA: 30 parts by mass Photoinitiator 2: 1 part by mass 500 parts by mass 3-methoxybutyl acetate: 300 parts by mass Comparative Example 1 Compound 1: 150 parts by mass PETTA: 30 parts by mass Photopolymerization Initiator 3: 1 parts by mass 500 parts by mass 3-methoxybutyl acetate: 300 parts by mass Comparative Example 2 Compound 1: 150 parts by mass PETTA: 30 parts by mass Photoinitiator 4: 1 part by mass 500 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 made into four steps of 50, 80, 100, and 120 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 it 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 ) 50 80 100 120 50 80 100 120 Example 1 Good Good Good Good none none none none none 3.5 Example 2 Good Good Good Good none none none none none 3.5 Comparative Example 1 Bad Bad Bad Good has exist has exist has exist none none 3.5 Comparative Example 2 Bad Bad Good Good has exist has exist none none none 3.5

The linearity 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 patterns obtained in Examples 1 and 2 were excellent in linearity, and peeling with pigment dregs and a board | substrate was not confirmed. On the other hand, Comparative Examples 1 and 2 were found to have many pattern peelings at low exposure doses, and showed poor linearity.

According to the present invention, by using a photoinitiator excellent in light sensitivity, it is possible to easily form a black matrix pattern having excellent linearity, low peeling and residue, and excellent display contrast on a substrate. 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.

Claims (11)

It contains a photopolymerizable compound, a photoinitiator, and a coloring agent, A photosensitive composition containing the acyl oxime ester compound represented by the following formula (1) as the photopolymerization initiator: [Formula 1]

(Wherein R ₁ represents a lower alkyl group having 1 to 5 carbon atoms, A represents a group selected from a hydrocarbon group, -CN, -NO ₂ , and Ar represents a group having a carbazole or a substituent or a substituent) Benzoyl group). The method of claim 1, Ar is a group of the photosensitive composition represented by the following formula (2) or (3): [Formula 2]

[Formula 3]

(Wherein B represents any one kind of group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group and C ₆ H ₅ S- which may be the same or different from each other, and k is 0 to Is an integer of 5. G may be the same or different from each other in the group consisting of a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C3-C20 cycloalkyl group, -OR ₂ , -NR ₃ R ₄ Any 1 group selected is represented and m is an integer of 0-5. R ₂ represents an alkyl group having 1 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms) or a cycloalkyl group having 3 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms), R <_3> , R <_4> may represent the same or different C1-C20 alkyl group, C2-C20 alkoxycarbonyl group, or R <_3> and R <_4> may be integrated and may form a C3-C20 ring, When the ring is formed, part of the carbon atoms may be substituted with hetero atoms. D represents the same or different hydrogen atoms, halogen atoms, and any one group selected from the group consisting of hydrocarbon groups which may contain hetero atoms with 1 to 20 carbon atoms, and n is an integer of 0 to 3. E represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a phenyl group). The method according to claim 1 or 2, R ₁ is a methyl group or an ethyl group. The method of claim 1, Compound represented by Formula 1 is a compound represented by the following formula (4): [Formula 4]

(Wherein A represents a group selected from a hydrocarbon group, -CN, and -NO ₂ , G represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, which may be the same or different from each other, The C3-C20 cycloalkyl group, -OR <_2> , -NR <_3> R <_4> shows any 1 type of group chosen from the group, and m is an integer of 0-5. R ₂ represents an alkyl group having 1 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms) or a cycloalkyl group having 3 to 20 carbon atoms (some of the carbon atoms may be substituted with heteroatoms), R <_3> , R <_4> may represent the same or different C1-C20 alkyl group, C2-C20 alkoxycarbonyl group, or R <_3> and R <_4> may be integrated and may form a C3-C20 ring, When a ring is formed, part of the carbon atoms may be substituted with hetero atoms). The method of claim 1, The photopolymerization initiator is a photosensitive composition which is a mixture of a compound represented by Formula 1 and a compound represented by Formula 5 below: [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 is a resin having a cardo structure in the molecule. The method of claim 1, The colorant comprises a carbon black photosensitive composition. The method of claim 1, The photosensitive composition used as a black resist which comprises the black matrix which comprises a liquid crystal display.