JP2008242089A - Photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition having higher sensitivity. <P>SOLUTION: The photosensitive composition comprises a photopolymerizable compound and a photopolymerization initiator, wherein a photopolymerization initiator represented by formula (1) is used. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive composition containing a photopolymerization initiator, and more particularly to a photosensitive composition used for forming a color filter, a black matrix, a spacer and the like in a liquid crystal display.

The photosensitive composition contains a photopolymerizable compound and a photopolymerization initiator, and is cured by irradiation with light such as ultraviolet rays. This photosensitive composition has been used in various applications such as printing plates and photoresists because a pattern having a desired shape can be obtained by curing a portion irradiated with light.
In particular, a black matrix in a liquid crystal display device is formed from a photosensitive composition containing a light-shielding agent. The photocuring of the photosensitive composition may be insufficient.
In the photosensitive composition, the performance of the photopolymerization initiator is an important factor for improving the sensitivity of the photosensitive composition. As such a photopolymerization initiator, an oxime photopolymerization initiator has been developed. (For example, see Patent Documents 1 to 6)
JP-T-2004-534797 Japanese Patent Laid-Open No. 2004-359639 Japanese Patent Laid-Open No. 2005-220097 JP 2006-160634 A JP-T-2006-516246 International Publication No. 2006/018405 Pamphlet

  However, higher sensitivity is also required in the photosensitive composition.

  This invention is made | formed in view of the said subject, and is providing the photosensitive composition with higher sensitivity.

（式（１）中、Ａ、Ｂ、Ｇは一価の有機基であり、Ｅは置換基を有していてもよい共役二重結合性環状基である。） The photosensitive composition of the present invention comprises a photopolymerizable compound and a photopolymerization initiator,
The photopolymerization initiator contains a compound having a skeleton represented by the formula (1).

(In Formula (1), A, B, and G are monovalent organic groups, and E is a conjugated double bond cyclic group that may have a substituent.)

  As described above, the sensitivity of the photosensitive composition can be improved by using a photopolymerization initiator having a specific structure and an absorbance at 365 nm of 0.3 or more.

  According to the present invention, since a highly sensitive photopolymerization initiator is used, a more sensitive photosensitive composition can be provided.

（式（１）中、Ａ、Ｂ、Ｇは一価の有機基であり、Ｅは置換基を有していてもよい共役二重結合性環状基である。）
なお、この吸光度は、島津製作所株式会社製 吸光光度計 UV3100を用い、有機溶剤PGMEで対象の開始剤を0.0017％に希釈してスリット幅2.0、サンプリングピッチ0.5で測定したものである。 The photosensitive composition of the present invention contains a photopolymerizable compound and a photopolymerization initiator.
The photopolymerization initiator contains a compound having a skeleton represented by the formula (1) and an absorbance at 365 nm of 0.3 or more.

(In Formula (1), A, B, and G are monovalent organic groups, and E is a conjugated double bond cyclic group that may have a substituent.)
This absorbance was measured using a UV3100 absorptiometer manufactured by Shimadzu Corporation with the target initiator diluted to 0.0017% with an organic solvent PGME and a slit width of 2.0 and a sampling pitch of 0.5.

  In the said photosensitive composition, the sensitivity with respect to the light of the specific wavelength irradiated is calculated | required. In general, light including a wavelength of 365 nm is used, and in particular, high sensitivity to 365 nm light is required. Among the compounds represented by the formula (1), the sensitivity of the photosensitive composition can be improved by using a compound having an absorbance at 365 nm of 0.3 or more. In particular, in the oxime compound having a carbazole group represented by the above formula (1), the effect of improving the sensitivity is remarkable. Further, the absorbance at 365 nm is preferably 0.4 or more, and more preferably 0.5 or more.

Wherein ^{A, G are, -R 1, -OR 1, -COR} 1, -SR 1, or preferably a group represented by ^-NR 1 ^{R 2.} Further, B is preferably —R ¹ , —OR ¹ , —COR ¹ , —SR ¹ , —CONR ¹ R ^2, or —CN. R ¹ and R ² each independently represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, The alkylene part of the group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond, and R ¹ and R ² may be combined to form a ring.
The alkyl group represented by R ¹ and R ² preferably has 1 to 20 carbon atoms, and more preferably has 1 to 5 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tertiary butyl group, amyl group, isoamyl group, tertiary amyl group, hexyl group, heptyl group, octyl Group, isooctyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, isononyl group, decyl group, isodecyl group and other linear or branched saturated hydrocarbon groups, vinyl group, allyl group, butenyl group, Examples thereof include linear or branched unsaturated hydrocarbon groups such as ethynyl group and propynyl group. Moreover, you may have a substituent. Examples thereof include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group, and a 2- (benzoxazol-2′-yl) ethenyl group. Above all, A is preferably a methyl group.

The aryl group represented by R ¹ and R ² preferably has 6 to 20 carbon atoms, and more preferably has 6 to 10 carbon atoms. Moreover, the unsaturated bond may be contained. Examples thereof include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

The aralkyl group represented by R ¹ and R ² preferably has 7 to 20 carbon atoms, and more preferably has 7 to 12 carbon atoms. Moreover, the unsaturated bond may be contained. Examples include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

The heterocyclic group represented by R ¹ and R ² is a 5-membered ring or more, preferably 5 to 7 members, containing at least one atom of nitrogen atom (N), sulfur atom (S) and oxygen atom (O). A heterocyclic group of a ring. The heterocyclic group may contain a condensed ring, and examples thereof include a pyridyl group, a pyrimidyl group, a furyl group, and a thiophenyl group.

These R ¹ and R ² may be substituted with a halogen atom. Examples thereof include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, a chlorophenyl group, and a chlorobenzyl group.

Furthermore, among these R ¹ and R ² , the alkyl group and the alkylene part of the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.

As the ring which R ¹ and R ² may form together, and a heterocyclic. Examples of the heterocyclic ring include 5-membered or more, preferably 5- to 7-membered heterocyclic groups containing at least one atom of nitrogen atom (N), sulfur atom (S) and oxygen atom (O). The heterocyclic group may contain a condensed ring, and examples thereof include a piperidine ring, a piperazine ring, a morpholine ring, and a thiomorpholine ring.

  E is a conjugated double bond cyclic group which may have a substituent. Examples of the conjugated double bond cyclic group include an aromatic ring or a heterocyclic ring having an N atom, an S atom, and an O atom in the ring. Examples of this aromatic ring include a phenyl group, a naphthyl group, and an anthryl group. Examples of the heterocyclic ring include nitrogen-containing 5-membered ring groups such as a pyrrole group, imidazolyl group, and pyrazolyl group; nitrogen-containing 6-membered ring groups such as pyridyl group, pyrazinyl group, pyrimidyl group, and pyridazinyl group; thiazolyl group, isothiazolyl group, and the like Nitrogen-containing groups of oxazolyl groups, isoxazolyl groups, nitrogen-oxygen-containing groups; oxygen-containing groups such as furyl groups and pyranyl groups; and sulfur-containing groups such as thienyl groups and thiopyranyl groups.

Examples of the substituent for E include —NO ₂ , —CN, —SO ₂ R ³ , —COR ³ , —NR ⁴ R ⁵ , —R ^{6, and the} like.
R ³ independently represents an alkyl group, which may be substituted with a halogen atom, and among these, the alkylene part of the alkyl group is interrupted by an ether bond, a thioether bond, or an ester bond. Also good. The alkyl group in R ³ preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, which may be substituted with a halogen atom, and among these, the alkyl group and the alkylene portion of the alkoxy group are ethers. It may be interrupted by a bond, a thioether bond or an ester bond, and R ⁴ and R ⁵ may be combined to form a ring. The alkyl group or alkoxy group in R ⁴ and R ⁵ preferably has 1 to 5 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a methoxy group, An ethoxy group, a propoxy group, etc. are mentioned.
R ⁶ is an alkyl group partially or entirely substituted with a halogen atom. The alkyl group for R ⁶ preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.

In the compound represented by the formula (1), the bond length between the N atom represented by α and the O atom represented by β (bond length between α-β) is 1.360 mm or more. Preferably, it is 1.365 or more. When the bond length between α and β is 1.360 mm or more, the sensitivity of the photosensitive composition of the present invention can be improved.
Furthermore, in the compound represented by the formula (1), the bond order between the N atom represented by α and the O atom represented by β (bond order between α-β) is 0.965 or less. Preferably, it is 0.960 or less. When the bond order between α and β is 0.965 or less, the sensitivity of the photosensitive composition of the present invention can be improved.
The bond length and bond order are calculated using the molecular modeling software “CAChe WorkSystem Pro
"Version 6.1.12.33" (Fujitsu Ltd.), and calculated by MOPAC using PM5 parameter.

Surprisingly, the bond length and bond order between α and β greatly change depending on the type of E, which is far from the α and β atoms. In other words, it is presumed that the bond length and bond order between α and β change depending on the type of E, which in turn improves the sensitivity of the photosensitive composition of the present invention.
The conjugated double bond cyclic group in E is preferably a heterocyclic ring, and more preferably a cyclic group having an N atom in the ring. As the cyclic group having an N atom in the ring, a nitrogen-containing 5-membered cyclic group and a nitrogen-containing 6-membered cyclic group are preferable, and a nitrogen-containing 5-membered cyclic group is particularly preferable. The nitrogen-containing 5-membered ring group is preferably a pyrrole group.
Moreover, as a substituent in said E, what has N atom is preferable and the substituent directly couple | bonded with the ring of a conjugated double bond cyclic group is more preferable. Examples of the substituent directly bonded to the ring of the conjugated double bond cyclic group include the above-mentioned —NR ⁴ R ⁵ , and an amino group, a morpholino group and the like are particularly preferable.

  Moreover, you may use a photoinitiator combining several types of compounds shown by the said Formula (1), and another photoinitiator. Examples of such other photopolymerization initiators include acetophenone such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone. Benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl Sulfur compounds such as ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene Products, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, and organic peroxidation such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide Thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer Imidazolyl compounds such as isomers, 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) etheni L] -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-dimethoxyphenyl) ethenyl] -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl)- Triazine compounds having a halomethyl group such as s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-benzyl-2- Methylamino-1- (4-morpholinophenyl) - aminoketone compound butane -1 one, and the like.

It is preferable that the said photoinitiator is 0.1-50 mass parts with respect to a total of 100 mass parts of solid content, and it is more preferable that it is 1-45 mass parts.
In addition, the said solid content is all the components except the solvent in the photosensitive composition of this invention.

As the photopolymerizable compound, a compound having 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, methacrylic acid 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 dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylo Rupropanetetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate (PTA), pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate (DPHA), di Monomers and oligomers such as pentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxy diacrylate; condensation of polyhydric alcohols with monobasic acid or polybasic acid Polyester (meth) polymer obtained by reacting the resulting polyester prepolymer with (meth) acrylic acid Polyurethane (meth) acrylate obtained by reacting acrylate, polyol group and two isocyanate group and then reacting with (meth) acrylic acid; 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, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, dihydroxy Examples thereof include an epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a benzene type epoxy resin with (meth) acrylic acid. Further, a resin obtained by reacting the epoxy (meth) acrylate resin with a polybasic acid anhydride can also be suitably used.
The photopolymerizable compound is preferably a combination of a resin having an ethylenic double bond and the monomer. These monomers include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol. Diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol Tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol Polyfunctional monomers such as dimethacrylate and cardoepoxy diacrylate are preferred.

  The photopolymerizable compound preferably includes a resin obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid with a polybasic acid anhydride. Among these, a compound represented by the following formula (a1) is preferable. The compound represented by the formula (a1) itself is a preferable compound in terms of high photocurability.

ここで、式（ａ１）で示される化合物のＸは、式（ａ２）で示される基である。

で表される基、Ｒ^１ａはそれぞれ独立して水素原子、炭素数１〜６の炭化水素基、ハロゲン原子を表し、Ｒ^２ａはそれぞれ独立して水素原子またはメチル基を表し、Ｗは単結合、または下記式（ａ３）で表される基を表し、

Ｙはジカルボン酸無水物の酸無水物基を除いた残基、Ｚはテトラカルボン酸二無水物の酸無水物基を除いた残基であり、ｍは０〜２０の整数である。）

Here, X of the compound represented by the formula (a1) is a group represented by the formula (a2).

R ^1a each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^2a each independently represents a hydrogen atom or a methyl group, and W is a single bond. Or a group represented by the following formula (a3),

Y is a residue excluding the acid anhydride group of the dicarboxylic anhydride, Z is a residue excluding the acid anhydride group of the tetracarboxylic dianhydride, and m is an integer of 0-20. )

Examples of Y include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, and methyltetrahydroanhydride. Examples thereof include a residue obtained by removing a carboxylic anhydride group (—CO—O—CO—) from a dicarboxylic anhydride such as phthalic acid or glutaric anhydride.
Examples of Z include two carboxylic acids from tetracarboxylic dianhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like. Examples thereof include a residue excluding an acid anhydride group.
The acid value of the resin having an ethylenic double bond is preferably 10 mgKOH / g or more and 150 mgKOH / g or less, and more preferably 70 mgKOH / g or more and 110 mgKOH / g or less in terms of resin solid content. Sufficient solubility in the developer can be obtained by setting the acid value of the resin to 10 mgKOH / g or more, and sufficient curability can be obtained by setting the acid value to 150 mgKOH / g or less. Can be good.

  Moreover, it is preferable that the weight average molecular weights of resin which has an ethylenic double bond are 1000 or more and 40000 or less, More preferably, they are 2000 or more and 30000 or less. By making the weight average molecular weight 1000 or more, heat resistance and film strength can be improved. Moreover, sufficient solubility with respect to a developing solution can be acquired by setting it as 40000 or less.

  It is preferable that the said photopolymerizable compound is contained in the range of 50-99.9 mass parts with respect to a total of 100 mass parts of solid content. Sufficient heat resistance and chemical resistance can be expected by setting the content to 50 parts by mass or more.

  The photopolymerizable compound may contain a colorant. Examples of the colorant include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the color index (C .. I.) Numbers can be mentioned. This colorant may be used alone or in combination of two or more in order to adjust the color tone.

  C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same and only the numbers are described), 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 the number is described) 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, 79, 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, “CI Pigment Blue” is the same and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment Black 1 and Pigment Black 7.

  Further, when forming a black matrix, a light shielding material is used as a colorant. The light shielding material is not particularly limited as long as it has a sufficient light shielding rate when used as a light shielding layer, and examples thereof include black pigments. Examples of the black pigment include carbon black, titanium black, and perylene black.

  As the light shielding material, it is preferable to use carbon black or titanium black. In addition, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, and Al Inorganic pigments such as various metal oxides, composite oxides, metal sulfides, metal lead sulfates, metal carbonates, and the like can also be used.

  As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. In particular, channel black is preferably used because of its excellent light shielding properties. Resin-coated carbon black can also be used. Specifically, carbon black and a resin-coated carbon black obtained by mixing a resin having reactivity with a carboxyl group, a hydroxyl group, and a carbonyl group present on the surface of carbon black and heating at 50 to 380 degrees, water Examples thereof include resin-coated carbon black obtained by dispersing an ethylenic monomer in an organic solvent mixed system or water-surfactant mixed system and performing radical polymerization or radical copolymerization in the presence of a polymerization initiator. This resin-coated carbon black has lower conductivity than carbon black without resin coating, so there is less current leakage when used as a color filter for liquid crystal displays, etc., forming a highly reliable display with low power consumption. it can.

Moreover, you may add an organic pigment as an auxiliary pigment to said inorganic pigment as a light shielding material. The following effects can be obtained by appropriately selecting and adding organic pigments that exhibit complementary colors of inorganic pigments. For example, carbon black exhibits a reddish black color. Therefore, by adding an organic pigment having a blue color which is a complementary color of red as an auxiliary pigment to the carbon black, the redness of the carbon black disappears, and a more preferable black color as a whole is exhibited.
The organic pigment in the light-shielding material is preferably used in the range of 10 to 80 parts by mass, more preferably 20 to 60 parts by mass of the organic pigment with respect to 100 parts by mass of the sum of the inorganic pigment and the organic pigment. Most preferably, the organic pigment is 20 to 40 parts by mass.

As the inorganic pigment and the organic pigment, a solution in which a pigment is dispersed at an appropriate concentration using a dispersant can be used. For example, as an inorganic pigment, carbon dispersion CF black (containing 20% carbon concentration) made by Gokoku Dye, carbon dispersion CF black made by Gokoku Dye (containing 24% high resistance carbon), titanium black dispersion made by Gokoku Dye CF black (containing 20% black titanium pigment) can be mentioned. Examples of organic pigments include blue pigment dispersion CF blue (containing 20% blue pigment) made by Gokoku Dye, violet dispersion made by Gokoku dye (containing 10% violet pigment), and the like.
As the dispersant, a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant is preferably used.

  When the coloring material is included, the photosensitive composition according to the present invention preferably contains the coloring material in a range of 1 to 70 parts by mass in a solid content of 100 parts by mass, and is contained in a range of 20 to 60 parts by mass. More preferably.

The coloring performance of the colored pattern formed by making a coloring material into 1 mass part or more in said 100 mass of said sum total can be improved.
On the other hand, by setting the composition ratio of the colorant to 70 parts by mass or less, it is possible to suppress poor curing when irradiated with light having a predetermined wavelength.
In particular, when a light-shielding material is used as the coloring material, the OD (Optical Density) value per 1 μm film thickness of the formed film can be adjusted to 3.5 or more, preferably 4.0 or more. preferable. If the OD value per film thickness of 1 μm is 3.5 or more, sufficient display contrast can be obtained when used in a black matrix of a liquid crystal display, and necessary performance can be obtained. As this light shielding agent, carbon black is preferable.
In particular, in the photosensitive composition of the present invention, even when a light-shielding agent is used, since the compound represented by the above (1) is used as a photopolymerization initiator, higher sensitivity can be obtained compared to the conventional one.

Furthermore, the photosensitive composition of the present invention may contain a polymer binder as a binder. The polymer binder may be appropriately selected according to the purpose of improving compatibility, film-forming property, developability, adhesiveness, and the like.
Specific examples of the polymer binder include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate , Isobornyl methacrylate, glycidylme Those obtained by copolymerizing monomers selected from acrylate, styrene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, etc., modified with acidic cellulose having a carboxyl group in the side chain, polyethylene oxide, polyvinylpyrrolidone , Acrylonitrile, vinyl chloride, copolymer of vinylidene chloride, vinylidene chloride, chlorinated polyolefin, or copolymer of vinyl chloride and vinyl acetate, polyvinyl acetate, copolymer of acrylonitrile and styrene, acrylonitrile and styrene, Copolymers with butadiene, polyvinyl alkyl ether, polyvinyl alkyl ketone, polystyrene, polyamide, polyurethane, polyethylene terephthalate isophthalate, acetyl cellulose and poly Or the like can be mentioned butyral. In particular, a monomer having a carboxyl group such as acrylic acid or methacrylic acid is preferably used as a copolymerization component in order to improve developability in an alkaline aqueous solution. The acrylic acid, methacrylic acid and the like are preferably in the range of 5 to 40% by mass in the copolymer component. Moreover, the cellulose resin which made the polybasic acid anhydride react with the hydroxyl group of carboxymethylcellulose, carboxyethylcellulose, carboxypropylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose can also be used preferably.

Moreover, the photosensitive composition which concerns on this invention is good also as adding the solvent for dilution, a thermal-polymerization inhibitor, an antifoamer, surfactant, etc.
Here, as a solvent that can be added to the photosensitive composition, benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate (MA), 3- Methyl-3-methoxybutyl Seteto, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether propionate, methyl carbonate, ethyl carbonate, propyl carbonate and carbonate butyl. Among these, 3-methoxybutyl acetate is preferable because it exhibits excellent solubility in a photopolymerizable compound and a photopolymerization initiator and improves dispersibility of insoluble components such as a coloring material. The amount of the solvent is preferably adjusted so that the solid content is 1 to 50% by mass, and more preferably 5 to 30% by mass.

  Further, hydroquinone, hydroquinone monoethyl ether, etc. as thermal polymerization inhibitors, silicone-based, fluorine-based compounds, etc. as antifoaming agents, anionic, cationic, nonionic, etc. as surfactants are conventionally known. Things can be added.

  Moreover, when forming a pattern using the photosensitive resin composition according to the present invention, a film is formed by applying and drying the photosensitive resin composition according to the present invention on a substrate, as will be described later. . In order to improve the coating property and the physical properties after photocuring, a polymer binder may be further contained as a binder in addition to the above components. What is necessary is just to select a binder suitably according to the improvement objectives, such as compatibility, film formation property, developability, and adhesiveness.

  As a manufacturing method of the photosensitive resin composition which concerns on this invention, it obtains by mixing each above-mentioned component with a stirrer. In addition, you may filter using a filter so that the obtained mixture may become uniform.

[Pattern formation method]
Hereinafter, a method for forming a pattern using the photosensitive resin composition according to the present invention will be described.

  First, the photosensitive resin composition is applied onto a substrate using a contact transfer type coating device such as a roll coater, reverse coater, or bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. .

  After applying this photosensitive resin composition, it is dried to remove the solvent. The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at a temperature of 80 ° C. to 120 ° C., preferably 90 ° C. to 100 ° C. for 60 seconds to 120 seconds, (2) several hours at room temperature Any of the following methods may be used: (3) a method of removing the solvent by placing it in a warm air heater or an infrared heater for several tens of minutes to several hours.

Next, partial exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. Energy dose to be irradiated may differ depending on the composition of the photosensitive resin composition, for example, about 2000 mJ / cm ² from 30 mJ / cm ² is preferred.

  Next, the exposed film is developed into a desired shape by developing with a developer. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

Next, a pattern is formed by post-baking patterning after development at about 200 ° C. Further, it is preferable to expose the entire surface of the formed pattern.
This formed pattern can also be used as a spacer, a black matrix, a color filter, and an inkjet partition.

Next, examples of the photosensitive composition according to the present invention will be described.
<Photopolymerizable compound>
(Resin synthesis example 1)
Resin 1 was synthesized as a photopolymerizable compound having an ethylenically unsaturated bond.
First, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tertbutyl-4-methylphenol and 72.0 g of acrylic acid are charged into a 500 ml four-necked flask. The solution was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. for complete dissolution. Here, although the solution gradually became transparent and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the colorless and transparent solid formula (a4).

Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain Resin 1. The disappearance of the acid anhydride group was confirmed by IR spectrum.
This resin 1 corresponds to a compound represented by the formula (a1). The resin 1 was adjusted to a solid content concentration of 50% by mass with 3-methoxybutyl acetate.

(Resin synthesis example 2)
400 g Epicoy YX4000H (manufactured by Japan Epoxy Resin, epoxy equivalent 192), 4 g of triphenylphosphine, 153 g of acrylic acid, and 600 g of 3-methoxybutyl acetate were mixed and reacted at 90 to 100 ° C. Thereafter, 40 g of 1,2,3,6-tetrahydrophthalic anhydride and 360 g of biphenyltetracarboxylic dianhydride were added as polybasic acid anhydrides, and further reacted to obtain Resin 2. This resin 2 had a mass average molecular weight of 7000 measured by GPC and an acid value of 90 mgKOH / g.
This resin 2 corresponds to the compound represented by the formula (a1). The resin 2 was adjusted to a solid content concentration of 50% by mass with 3-methoxybutyl acetate.

(Resin synthesis example 3)
Resin 3 was synthesized in the same manner except that 500 g of a dicyclopentadiene type epoxy resin (epoxy equivalent 283) represented by the following formula (a5) was used in place of Epicoat YX4000H in Resin Synthesis Example 2. The molecular weight of this resin 3 was 4500. The resin 3 was adjusted to a solid content concentration of 50% by mass with 3-methoxybutyl acetate.

<Photopolymerization initiator>
In the formula (1), the groups A, B, G and E shown in Table 1 were used.

(Examples and comparative examples)
About the photosensitive composition which concerns on a present Example and a comparative example, it prepared with the composition shown in Table 2. The solvent was adjusted such that 3-methoxybutyl acetate: cyclohexanone = 70: 30 (mass ratio) and the solid content concentration of the photosensitive composition was 18% by mass. The mixture having this composition was mixed for 2 hours with a stirrer and filtered through a 5 μm membrane filter to obtain a photosensitive composition.

The obtained photosensitive composition was applied on a glass substrate having a clean surface with a thickness of 1 mm using a spin coater (TR25000: manufactured by Tokyo Ohka Kogyo Co., Ltd.) so that the dry film thickness was 1.2 μm. The film was dried at 90 ° C. for 2 minutes to form a film (photosensitive layer) of the photosensitive composition. Subsequently, the film was selectively irradiated with ultraviolet rays through a negative mask. After that, a black matrix pattern including a line having a line width of 20 μm was formed by spray development with a 0.5 mass% sodium carbonate aqueous solution at 25 ° C. for 60 seconds. Thereafter, post-baking was performed in a circulation oven at 220 ° C. for 30 minutes. The thickness of each prepared black matrix was 1.0 μm.
Moreover, when each created black matrix was measured with an OD measuring apparatus D-200II (manufactured by Gretag Macbeth Co., Ltd.), the OD value was 4.0.

Table 3 shows the results of the evaluation of the black matrix patterns of the respective examples and comparative examples (pattern straightness, peeling, residue) obtained as described above.
For sensitivity evaluation, the exposure amount was increased in steps of 5 mJ from 10 to 180 mJ / cm ² and developed under the above conditions. In addition, as “Bias + 1.0 μm”, the exposure amount at which the line width of the black mask pattern formed on the 20 μm mask was 20 μm + 1 μm was evaluated. Since the photosensitive composition in the present invention is a negative type resist, the larger the exposure amount, the thicker the CD (Critical Dimension). Usually, the target line width for mass production is mask line width + 1 to 2 μm. If patterning can be performed with a lower exposure amount, the exposure time can be shortened and the throughput of the line can be improved.

As a result of the determination, the pattern obtained in the example has an OD value of 4.0, and has high light shielding properties. However, even when the exposure amount is 65 mJ / cm ² , the pattern has excellent linearity, and the residue and the substrate. No peeling was confirmed. On the other hand, in each comparative example, pattern peeling was large and the straightness was not good at a low exposure amount. Further, the value of Bias + 1 μm was not preferable in the comparative example, when the exposure amount was smaller than 95 mJ / cm ² , the line width became thinner than the target value.

Claims (10)

In a photosensitive composition containing a photopolymerizable compound and a photopolymerization initiator,
The said photoinitiator contains the skeleton shown by Formula (1), and contains the compound whose absorbance in 365 nm are 0.3 or more, The photosensitive composition characterized by the above-mentioned.

(In Formula (1), A, B, and G are monovalent organic groups, and E is a conjugated double bond cyclic group that may have a substituent.)   2. The photosensitive composition according to claim 1, wherein the bond length between the N atom represented by α and the O atom represented by β in the formula (1) is 1.360 Å or more.   The photosensitive composition according to claim 1, wherein the conjugated double bond cyclic group is a heterocyclic group.   The photosensitive composition according to claim 3, wherein the conjugated double bond cyclic group has an N atom in the ring.   The tourist composition according to claim 4, wherein the conjugated double bond cyclic group is a 5-membered ring group.   The photosensitive composition according to claim 1, wherein E has an N atom as a substituent of a conjugated double bond cyclic group.   The photosensitive composition according to claim 6, wherein the substituent has an N atom directly bonded to a conjugated double bond cyclic group. The substituent is —NR ⁴ R ⁵ (wherein R ⁴ and R ⁵ each independently represents an alkyl group or an alkoxy group, and these may be substituted with a halogen atom. And the alkylene part of the alkoxy group may be interrupted by an ether bond, a thioether bond or an ester bond, and R ⁴ and R ⁵ may be combined to form a ring). The photosensitive composition according to claim 7.   The photosensitive composition as described in any one of Claims 1-8 characterized by including a coloring material.   The photosensitive composition according to claim 9, wherein the colorant is a light shielding material.