TWI334514B - - Google Patents

Description

1334514 IX. Description of the Invention: TECHNICAL FIELD The present invention relates to a photosensitive composition for forming a black matrix of a panel of a liquid crystal display device. [Prior Art]

A display system such as a liquid crystal display device sandwiches a liquid crystal layer between two substrates, and a pair of electrodes are disposed on the two substrates, and then a liquid crystal layer is disposed on the inner side of one of the substrates to be red (R). A color filter layer composed of pixels of green (G), blue (B), and black. Among them, the black pixel has a function of preventing color mixing of different colors or covering the electrode pattern, and is generally arranged in a matrix shape by dividing pixels of respective colors of R, G, and B. Therefore, it is generally referred to as a "black matrix". In general, color filters are formed by lithography. Specifically, it is coated by coating a composition on a substrate by uniformly dispersing or dissolving a coloring agent such as an organic pigment, dye, or carbon black in a photosensitive resin component. After the cloth is dried and dried, exposure is performed in accordance with a pattern of colors for constituting the color filter. Then, the pixel pattern obtained by developing the organic developing solution or the like is subjected to heat treatment to impart mechanical strength as a permanent film. The steps as described above are repeated in accordance with the respective colors of R, G, and B to form a color filter layer. The black matrix of the color filter has traditionally been patterned using lithography of the vapor deposited chrome 1334514 film. The black matrix composed of the chrome film has high dimensional accuracy and high reliability. However, in order to form a chromium thin film, a vacuum film forming process such as the above-described vapor deposition method or sputtering method is required. Therefore, as the size of the substrate increases, it is necessary to increase the size of the machine, and as a result, there is a problem in the correspondence of the enlargement of the substrate.

In addition, due to environmental problems, like the color filters of other colors, the chromium film has evolved into a resin film formed by using a photocurable composition in which a black coloring agent is dispersed (refer to the patent document of the invention) 1 ). As the black colorant used as the material of the black matrix, carbon black, titanium black or the like is generally used. Among them, carbon black is the most commonly used. Patent Document 1 discloses a photopolymerizable composition comprising a compound containing at least one ethylenically unsaturated double bond capable of undergoing addition polymerization, a photopolymerization initiator, a metal oxide, and the like, and substantially does not contain Halogen atom. This composition can provide a color filter having superior heat resistance and high electrical insulation resistance value because the element atoms are substantially removed.

(Patent Document 1) Japanese Laid-Open Patent Publication No. Hei No. Hei. No. 1 -84 1 25 [Invention] [Technical Problem to be Solved] However, if high blackout resistance is to be imparted to the black matrix, the shading is not improved. The content of the material is not acceptable. Therefore, the optical density is increased, and as a result, when the exposure is performed, the light cannot reach the deep portion of the film, making it impossible to charge -6-1334514

The case of photocuring (photosensitive reaction) is carried out in different places. As a result, the margin of development is narrowed, and there is a problem that the linearity of the pattern is lowered, the pattern is peeled off from the substrate, or a residue is generated on the substrate. Further, in the case of producing a color filter, depending on the coloring photosensitive resin to be used, if heat is applied in a baking oven after exposure and development, there is a possibility that volatile matter is generated by the colored pattern. If the volatile matter enters the colored pattern and becomes a foreign matter, the product may be defective. In view of the above problems, an object of the present invention is to provide a photo-resistance material in which a black matrix pattern having good linearity, not easily peeled off, and few residues can be formed in a color filter of a liquid crystal display device. Further, another object thereof is to provide a photosensitive resist which can form a black matrix pattern having less volatile matter generated upon heating after shadowing. [Means for Solving the Problem] The inventors of the present invention have found that a photopolymerization initiator which is a photosensitive product having a fluorene skeleton and a benzoyl group-based compound can be used as a photopolymerization initiator. The photosensitive composition can be a black matrix case which has a good linearity, is not easily peeled off, and has few residues. Further, the inventors of the present invention have found that when the benzamidine benzoyl moiety is a bulky group, The generation of volatiles upon heat after development can be suppressed. More specifically, the present invention provides a composition as described below. (1) A photosensitive composition comprising a photopolymerizable compound and a topping tree mixed with an emotion profile) (adding 1334514 photopolymerization initiator, and a coloring agent, and as the photopolymerization initiator And a compound represented by the formula (1) shown below:

[wherein A represents a Ri, an O R1 '-CO R1 ' _ SRi B represents a Ri, a 0 R1 '-C 0 R1 ' — SRi, —CONRiRz or a CN; the G system represents a hydrogen atom, a Ri, an ORi, a CORi, a SRi or a NRiR2;

Wherein Ri and R2 each independently represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, and these may also be substituted with at least one of a dentate atom or a heterocyclic group, such as an alkyl group And the alkyl moiety of the aralkyl group may also be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond. Further, the Ri and R2 groups may be combined to form a ring; D may be the same or Different from each other, it may represent a dentate atom or a hydrocarbon group having a carbon number of 1 or more and 20 or less and containing a hetero atom; E may be the same or different and represent an alkyl group having a carbon number of 1 to 20 and a carbon number of Alkoxy group of 1 to 20, cycloalkyl group having 3 to 20 carbon atoms, OR_3 or NR4R5 ' wherein R3 represents an alkyl group having 1 to 20 carbon atoms (a portion of 1334514 carbon atoms may also be used) a hetero atom is substituted), or a cycloalkyl group having a carbon number of 3 to 20 (a part of a carbon atom may also be substituted with a hetero atom); the R4 and R5 may be the same or different and represent a carbon number of 1 to 20 An alkyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, or R4 and R5 systems may be combined to form a ring having a carbon number of 3 to 20; When forming a ring, one part of the carbon atom may be substituted with a hetero atom; further, at least one of E represents a group having a molecular weight of 30 or more; m is an integer of 0 to 5, and η is an integer of 0 to 3, and is in accordance with m +

η > 1 condition. ].

According to the invention as recited in the item (1), the photopolymerization initiator can be made sensitive to light by forming the structure as described above. Therefore, the photosensitive composition can be efficiently activated by a small amount of irradiation of light to cure the photosensitive composition. As a result, it is possible to provide a black matrix pattern having a high linearity without causing peeling or residue. Further, by setting at least one of the ruthenium to a base having a molecular weight of 30 or more, the phenomenon of reducing the amount of the film is less, and the sensitivity to light is not impaired, and the generation of volatile matter can be further suppressed. (2) The photosensitive composition according to Item (1), wherein the oxime is selected from the group consisting of an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an OR3 or a NR4R5. Any of the ethnic groups. According to the invention as recited in the item (2), by setting E to a group having a carbon number of 3 to 20, a cycloalkyl group having 3 to 20 carbon atoms, _OR3 or a NR4R5, It is possible to provide a photosensitive composition which forms a black matrix pattern which generates less volatile matter upon heating after development. (13) The photosensitive composition according to Item (1) or (2), wherein m is 1 or more and η is 0. According to the invention as recited in the item (3), by setting the value of η to 〇, the sensitivity to light can be further improved. (4) The photosensitive composition according to the item (1), wherein the lanthanoid carbon number is 7 or more and 12 or less alkyl groups.

According to the invention as recited in the item (4), the ruthenium is an alkyl group having a carbon number of 7 or more and 12 or less, whereby the ruthenium has a bulky structure. Thereby, the sensitivity to light is not impaired, and the generation of the volatiles can be further suppressed. (5) The photosensitive composition according to the item (1), wherein the compound represented by the formula (1) is a compound represented by the formula (2) shown below:

(2) According to the invention as set forth in the item (5), by adding a pyranyl group to the phenyl hydrazone moiety of the compound represented by the formula (1), the system can be prevented from being damaged. And the sensitivity to light makes the phenylhydrazine moiety a bulky structure. Therefore, a photosensitive compound capable of further suppressing the generation of -10- 1334514 volatile matter can be provided. (6) The photosensitive composition according to the item (1), wherein the compound represented by the formula (1) is a compound represented by the formula (3) shown below:

(3)

According to the invention as described in the item (6), if a specific group is added to the phenylhydrazine group of the compound represented by the formula (1) as shown in the formula (3), The invention described in the item (5) is the same, and the benzoquinone moiety becomes a bulky structure without impairing the sensitivity to light. Therefore, it is possible to provide a photosensitive compound capable of further suppressing the generation of volatile matter, and it is possible to suppress a decrease in the amount of the film formed. (7) The photosensitive composition according to the item (1), wherein the photopolymerization initiator further contains a compound represented by the formula (4) shown below as -11 - 1334514

According to the invention as recited in the item (7), if the photopolymerization initiator contains the compound as described above, it can be efficiently activated by a very small amount of irradiation light. This is because the φ compound having a different electron band spectrum exists simultaneously, and the substantial wavelength region of the high-sensitivity light which the photopolymerization initiator has, or at least two compounds interact with each other. Therefore, by combining and using the photopolymerization initiator of the invention as described above and the compound represented by the formula (4), the sensitivity and development allowable range of the photosensitive composition are further improved, making it possible to further The black matrix pattern is easily made into a good form having high linearity without peeling or residue. (8) The photosensitive composition according to the item (1), wherein the photopolymerization initiator further contains a compound represented by the formula (5) shown below

(5) -12- 1334514 According to the invention as recited in the item (8), in the same manner as the invention described in the item (7), by combining and using the photopolymerization initiator of the invention as described above and The compound represented by the formula (5) is a black matrix pattern which is more linear and free from flaking or residue. (9) The photosensitive composition according to item (1), wherein the photopolymerization initiator further contains a thiocaptobenzimidazole (mercaptobenzimidazole)

According to the invention as set forth in the item (9), as in the inventions of the items (7) and (8), by combining them, it is possible to provide a high linearity without peeling or residue. Black matrix pattern. Further, since the thiosulfenylbenzimidazole also acts as an antioxidant, by further adding it as a photopolymerization initiator, it is possible to more reliably prevent the occurrence of flaking or residue. (10) The photosensitive composition according to the item (1), wherein the photopolymerizable compound is a compound having at least one ethylenic double bond in the molecule.

According to the invention as recited in the item (10), by using a photopolymerizable compound having an ethylenic double bond in the molecule as a photopolymerizable compound, it is possible to improve photosensitivity in a wide wavelength region. The absorbance concentration of the composition can be activated even with a very small amount of irradiation light. As a result, it is possible to easily form a high black light-shielding property while having a high linearity and a good black matrix pattern without peeling or residue. Further, the "compound having at least one ethylenic double bond in the molecule" also includes a monomer, an oligomer, a prepolymer, etc., and at least one of them is preferably selected from among them. To use. The photosensitive composition according to the item (1), wherein the photopolymerizable compound is an acryl resin. According to the invention as set forth in the item (11), the photopolymerizable compound is an acryl resin, which improves the weather resistance and chemical resistance of the photosensitive composition. Here, as the "acrylic resin", acrylic acid, mercaptoacrylic acid, and derivatives thereof, for example, acrylamide (a c r y 1 a m i d e ), acrylonitrile or the like can be used.

(12) The photosensitive composition according to the item (1), wherein the photopolymerizable compound contains a resin having a cardo structure in the molecule and having at least one ethylenic double bond in the molecule. . According to the invention as set forth in the item (12), the photopolymerizable compound is a resin having a structure of Carraux in the molecule, whereby the heat resistance and chemical resistance of the photosensitive composition can be improved. (13) The photosensitive composition according to Item (1), wherein the coloring agent contains carbon black.

According to the invention as recited in the item (13), by setting the coloring agent to carbon black, it is possible to provide a black matrix pattern of a film having high light shielding properties. [Effect of the Invention] According to the present invention, by using a photopolymerization initiator having excellent sensitivity to light, it is easy to form a superior linearity on a substrate without causing peeling or residue, and A black matrix pattern with superior display contrast. Further, even in the case of a high light-shielding photoresist, a -14-1334514 black matrix pattern having high sensitivity and excellent development allowable range and high resolution can be provided. Further, by using the polymerization initiator of the present invention, it is possible to provide a photosensitive composition which can form a black matrix pattern in which a small amount of volatile matter is generated upon heating after development. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be specifically described.

The photosensitive composition of the present invention contains a photopolymerizable compound, a photopolymerization initiator, and a color former. [Photopolymerization Initiator] The term "photopolymerization initiator" is a compound which is a component of a photocurable composition and which is polymerized and polymerized by irradiation of ultraviolet rays or electron beams. In the present invention, the photopolymerization initiator may be a compound represented by the formula (1) shown below:

(1) [wherein A represents _ Ri, a 0 R1 ' _ C 0 R1 ' _ SRi or _ NR1R2 B represents a R1, a 0R1, a _C0R1, a _SRi, a _CONIU2 or a CN; -15- 1334514 G is a nitrogen atom, _R!, _ 0 R1 ' - C 0 R1 ' - SRi or -NRiR2; wherein Rt and R2 each independently represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, and These may also be substituted with at least one of a dentate atom or a heterocyclic group, and the alkylene moiety of the alkyl group and the aralkyl group may also be an unsaturated bond, a crypto bond, or a sulfur. The _ key and the S key are interrupted. In addition, the Ri and R2 systems can also be combined to form a ring;

D may be the same or different and may represent a halogen atom, or may be a hydrocarbon group having a carbon number of 1 or more and 20 or less and containing a hetero atom; E may be the same or different and represent 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, an OR 3 or an NR 4 R 5 wherein the R 3 represents an alkyl group having 1 to 20 carbon atoms (one part of a carbon atom) Alternatively, a hetero atom may be substituted or an ester bond may be substituted. A cycloalkyl group having a carbon number of 3 to 20 (a part of a carbon atom may be substituted by a hetero atom or may be substituted by an ester bond);

The R4 and R5 may be the same or different and represent an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, or R4 and R5 may be combined to form a carbon number of 3 to a ring of 20; if a ring is formed, one part of the carbon atom may be substituted with a hetero atom; further, at least one of E represents a group having a molecular weight of 30 or more; m is an integer of 0 to 5, and η is 0 to 3 An integer that meets the conditions of m + η > 1. Where the Α represents a Ri, an ORi, a CORi, a SRi, or -16-1334514

- NR1R2, and more preferably a Ri° B system represents a Ri, a CORi, a SRi, a CONRiRz, or a CN, and more preferably a Ri is used identically. Further, the G system represents a nitrogen atom, a Ri, _CΟR1 '-SRi, or a NR1R2, and more preferably a Ri is used with A and ground. In the above-mentioned A, B, and G, the substituent j is represented by Ri and R 2 , preferably, the carbon number is 1 to 20, and more preferably the carbon number is 1 j, including, for example, mercapto, ethyl, and c. Base, isopropyl, n-butyl; i group, secondary butyl, tert-butyl, fluorenyl, isodecyl, tertiary; fluorenyl, heptyl 'octyl, isooctyl, 2-ethylhexyl A linear or branched food such as a tertiary octyl group, an isodecyl group, a fluorenyl group or an isoindolyl group. Among them, a methyl group having a carbon number of 1 is preferably used. The "aryl group" represented by R! and R2 preferably has a carbon number of 20 and more preferably has a carbon number of 6 to 10. The structure includes, for example, phenylene, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthryl, etc., "aralkyl" represented by the ruthenium and R2, preferably carbon porphyrin 20, and More preferably, the carbon number is from 7 to 1 2 » which includes, for example, a-mercaptophenylphenyl, α,α-dimercaptophenyl, phenylethylvinyl and the like. The "heterocyclic group" represented by the ruthenium and R2 includes a heterocyclic ring containing at least one member ring of (N), a sulfur atom (S) and an oxygen atom (0), preferably a 5- to 7-membered ring. base. The heterocyclic ring contains a condensed ring, such as a bite group, a mouth bite group, a 11 fluorenyl group, and a benzene-ORi ' is the same as A and a 0 R 1 B: "alkane I 5 .", isobutylene, and :, 壬基i and smoke base are 6 to: base, armor, etc. : 7 to : methyl, phenyl nitrogen atom: 5 I group of the group can also be L group, etc. -17- 1334514

Further, these R丨 and R2 may be substituted by a halogen atom. These include, for example, monofluoromethyl, difluoromethyl, trifluoromethyl, perfluoroethylphenyl, benzyl, and the like. Further, the alkyl group and the alkyl group of the aralkyl group among the above 1 and R2 may be interrupted by an unsaturated bond, a crypto bond, a thioether bond or a S bond. The body has a linear or branched unsaturated hydrocarbon group such as a vinyl group, an allyl group, a butenyl group or an ethynylpropynyl group, or may have a substituent. As such a group, a group represented by A or B may, for example, be methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl or methoxypropyl. 2-(benzoxazole-2'-yl)vinyl and the like ' In addition, a ring which R1 and R_2 can combine together to form a heterocyclic ring which includes at least a nitrogen atom (N) 'sulfur atom (S) and a 5-membered ring or more of one atom in the atom (0), preferably a 5- to 7-membered ring heterocyclic group. The heterocyclic group may also contain a "condensed ring" which includes, for example, a piteridine ring. Piperazine ring, morpholine ring, thiomorpholine ring, etc. Further, D may be the same or different and represents a halogen atom or a hydrocarbon group having a carbon number of 1 or more and 20 or less and containing a hetero atom. The base system includes a hydrocarbon group having, for example, an oxygen group, a thio group, a disulfide group, an imido group, a nitrilo group, a hydrazo group, an azo group and the like and having a number of from 1 to 20. In addition, it may contain an unsaturated bond or may form a ring. At least one of the groups of E, preferably having a molecular weight of 30 parts and having a ruthenium-oxygen group (which may have an iso-base carbon form of from -18 to 1334514, more preferably a molecular weight of 50 or more) Further, the upper limit of the base is preferably 250 or less, and more preferably 150 or less, from the viewpoints of sensitivity and solubility to a solvent, etc. Among them, it is more preferable to use a hydroxyl group. Hydropyranyl) 〇

Further, E may be the same or different and represents 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, a 0R3, or a NR4R5. Among them, it is preferable to use _ 〇 R3. Further, the term "alkyl group having 1 to 20 carbon atoms" includes, for example, methyl group, ethyl group, propyl group, isopropyl 'n-butyl group, isobutyl group, secondary butyl group, and tertiary butyl group. Pentyl, isopentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, etc. A linear or branched saturated hydrocarbon group. Further, the "alkoxy group having a carbon number of 1 to 20" includes, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, an isopropoxy group, and an isobutoxy group. and many more. Further, the "cycloalkyl group having a carbon number of 3 to 20" includes, for example, φ: cyclopropyl group, cyclohexyl group, cyclohexyl group or the like. Further, R3 of a 0R3 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a heterocyclic group. The "alkyl group" includes, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tert-butyl group, and pentyl group as described above. , isoamyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, fluorenyl, isodecyl, etc. Saturated or branched saturated hydrocarbon group. The alkyl groups may also contain, for example, an oxy group, a thio group, and a -19-1334514

Sulfur, imido, nitrogen, thiol, azo, and the like. Further, examples of the "cycloalkyl group" include a cyclopropylhexyl group, a cyclohexyl group and the like. As the above, the cycloalkyl group also has, for example, an oxy group, a thio group, a dithio group, an imido group, a nitrogen group, an exoazo group, and the like. The system includes, for example, a tetrahydrofuranyl ring, a tetrahy dropyrany 1 ring, and the like. Further, the groups may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or the like. From the viewpoint of solubility in a solvent, one of the alkyl group and the naphthene carbon atom is particularly preferably substituted by an ether bond or an ester bond. It is contained in the alkyl group or the cycloalkyl group in an amount of 1 to 6, more preferably 2 or more of the ether bond or the ester bond. Further, as the "solvent" at this time, it is preferred to use a mercapto diol-alkyl radical, an alkyl diol, a ketone, an ether, a ketone, an ester, and particularly preferably Propylene glycol monomethyl ester, 3-methoxybutyl acetate was used. The "heterocyclic ring" includes a heterocyclic group having a 5-membered ring or more and a 5- to 7-membered ring containing at least one of a nitrogen atom (N) and a sulfur atom S) and an oxygen atom (0). The heterocyclic group may also contain a condensed ring. Further, R>4 and R5 of a NR4R5 may be the same or different, an alkyl group of 1 to 20, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a combination of R4 and R5 to form a carbon number of 3 To the ring of 20. The alkyl group includes, for example, the same as described above: mercapto, ethyl, isopropyl, n-butyl, isobutyl, dibutyl, tert-butyl, isopentyl, tertiary a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a hexyl group, a trioctyl group, a decyl group, an isodecyl group, a fluorenyl group, an isodecyl group, etc., a ring-containing group, and a fluorenyl group as a further group Good to 4 for the ester ether vinegar (preferably carbon or "propyl propyl pentyl 2- bis straight -20- 1334514

A chain or branched saturated hydrocarbon group. Further, the "alkoxycarbonyl group" includes, for example, an anthracenyloxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, a tertiary butoxycarbonyl group, or a cyclohexane. a linear, branched or cyclic group such as an oxycarbonyl group. When "R4 and R5 are combined to form a ring", the tether is, for example, a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring or the like. Further, the rings may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or the like. Further, in the general formula (1), a compound having an m system of 1 or more and η-based 0 is preferably used. As the compound having such a structure, a compound represented by the formula (2) shown below is preferred. By making yttrium and lanthanum methyl, G being a base, and η being 0, the sensitivity to light can be improved. Further, when a piperyl group having a large volume is added to the ruthenium, the volatile matter can be reduced at the time of exposure. (2) When the above compound is used as a photopolymerization initiator, the content is 1 in a total amount of 100 parts by weight of the photopolymerizable compound. The basis of weight basis is divided into 6 and

To -21 - 1334514

The range of 150 parts by weight is preferably from 5 parts by weight to 100 parts by weight, and more preferably from 10 parts by weight to 50 parts by weight. When the content is 150 parts by weight or less, sufficient heat resistance chemical properties can be obtained. Further, when the content is 1 part by weight or more, the film formation ability is high and the photocuring is prevented from being caused. . Further, in addition to the β-pyranyl group, Ri may have a bulky skeleton base. It is also possible to use, for example, a compound represented by the following (3): (3) When the above compound is used as a photopolymerization initiator, it is contained in an amount of 1 part by weight to 100 parts by weight of the photopolymerizable compound. The range of parts is preferably from 5 parts by weight to 100 parts by weight, more preferably from 10 parts by weight to 50 parts by weight. When the content is at most the parts by weight, sufficient heat resistance and chemical resistance can be obtained. When the content is 1 part by weight or more, the coating film can be improved to prevent photocuring failure. Further, the "photopolymerization initiator" may be combined and used as described above, and the resistance is 150% of the formula phase 150, which is represented by the formula -22-1334514 represented by the formula (1) Compounds and several other compounds (photopolymerization initiated enthalpy). Such compounds include, for example, acetophenone (ie, acetophenone) '2,2-diethoxyethyl benzene, p-dimercapto benzene, p-dimethylamino group. "Acetophenone", such as acetophenone, diacetophenone, triethylene acetophenone, p-tertiary butyl tris, or benzophenone (ie, diphenyl ketone) Benzophenone), 2-benzophenone, P, P'-bisdimethylammonylbenzophenone, etc.; or benzozene, benzoin (benzoin), benzoin A

"Benzene ketone" such as phenyl ether, benzoin isopropyl ether, benzoin isobutyl ether, or phenyl fluorenyl thiol, thioxanthene, 2-sulfur "Sulfur compound" such as Mt. Yamaguchi, 2,4-diethyl sulphate, Yamaguchi, 2-methylthio sulphate, 2 isopropyl sulphate, or 2-ethyl scallions, gossip "anthraquinone" such as guanidine, 1,2-benzopyrene, 2,3-diphenylanthracene; or azobisisobutylonitorile, alum-based peroxidation (benz〇yi peroxide), cumene peroxide, etc.

Machine peroxide": or 2-hydrothiobenzimidazole, 2·hydrosulfanyl stupid. a "thiol compound" such as caesium, 2-hydrothiobenzothiazole; or 2_(o-phenyl)-4,5-di(m-methoxyphenyl)-imidazolyl "Imidazolyl" compound of a polymer or the like; or "triazine compound" of a p-methoxytriazine well or the like: or 2,4,6-paran (trioxanyl)- Spiral-trinitrogen well, 2-methyl-4,6-bis(trimethylmethyl)-spiro-trinitrogen well, 2-[2-(5-methylfuran-2yl)vinyl] _4,6 double (tri-gas methyl)-spiro-diaza well, 2-[2-(<folly-2-yl)ethyl bake]·4 6 -23- 1334514 bis (tri-gas methyl) )-Spiro-trinitrogen well, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trimethylsulfonyl)-spiro-trinitrogen Well, 2-[

2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trimethylsulfonyl)-spiro-trinitrogen well, 2-(4-methoxyphenyl)-4 ,6-bis(trimethylsulfonyl)-spiro-trinitrogen well, 2-(4-ethoxystyryl)-4,6-bis(trimethylmethyl)-spiro-trinitrogen well, 2-(4-n-butoxyphenyl)-4,6-bis(trichloroindenyl)-spiro-trinitrogen well, etc. "a triazine well compound having a halogen group"; 2-benzyl group -2 - "Aminoketone compound" such as diammonium-1-(4-morpholinylphenyl)-butan-1-one. Among these compounds, a thiosulfonylbenzimidazole or a triazine well compound is preferably used, but a compound represented by the formula (4) shown below is more preferably used. By combining and using these compounds, the sensitivity to light can be further improved.

Further, by using a compound represented by the general formula (5) shown below, the sensitivity to light can be further improved: -24 - 1334514

When the compound as described above is used in combination with the compound represented by the formula (1) and used as a photopolymerization initiator, the content thereof is in the range of 1 part by weight to 150 parts by weight based on the total mass parts of the photopolymerizable compound. It is preferably in the range of 5 parts by weight to 100 parts by weight, more preferably 10 parts by weight to 50 parts by weight. When the content is 150 parts by weight, sufficient heat resistance and chemical resistance can be obtained. Further, when the content is 1 part by weight or more, the film formation ability can be improved and the photocuring failure can be prevented. Further, in combination with a compound represented by the formula (1), a compound other than the compound represented by the formula (1) (special formula (4), formula (5), and thiothiobenzimidazole, etc.) In the case of ratio, it is preferably 10:90 to 90:10, and particularly preferably 50:50 to 30. The mixing ratio of the compound represented by the formula (1) and the compound other than the compound of the formula (1), if it is within the range, allows the two compounds to effectively interact with each other, and the system is The sensitivity and development tolerance of the photosensitive composition can be further improved. The method for producing a photopolymerization initiator of the present invention, the examples of which include 100 parts of the compound in the case of the termination and the removal of the weight 70: which are as described in the following -25 - 1334514 Synthesis process. A synthesis example in which the synthesis process is in which η is 0

In the formula, Ri corresponds to B in the present invention, and R2 corresponds to a phenyl group containing E in the present invention. Further, R3 corresponds to A in the present invention, and R corresponds to G in the present invention. [Photopolymerizable compound] The term "photopolymerizable compound" means a substance which is polymerized and solidified when exposed to light such as ultraviolet rays. As the "photopolymerization -26-1334514

The compound is preferably a compound having an ethylenic double bond, and specifically includes, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, monodecyl fumarate. , monoethyl fumarate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol monodecyl ether acrylate, ethylene glycol monodecyl ether decyl acrylate, ethylene Alcohol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylic acid g glycerol methacrylic acid, acrylamide, mercapto propylene Methacrylamide, acrylonitrile, mercapto acrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, acrylic acid 2 - Ethylhexyl ester, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimercapto acrylate, diethylene glycol diacrylate , triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate Ester, tetraethylene glycol dimethacrylate, butanediol dimethacrylate, propylene glycol diacrylate, propylene glycol dimercapto acrylate, trihydroxymethyl propane triacrylate, trimethylolpropane tridecyl acrylate Ester 'tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tridecyl acrylate, neopentyl alcohol tetraacrylate, neopentyl Tetracohol tetradecyl acrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentadecyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethylene acrylate, 1, 6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxy diacrylate, etc. monomers, oligomers; condensed polyols (polyhydric alcohol) class-27-

Γ334514 and a polyester prepolymer obtained from a unit acid or a polybasic acid, and a polyester (meth) acrylate obtained by reacting a methyl olefinic acid; a compound having a polybasic group and a compound having two isocyanato groups; After the reaction, the polyamine phthalate-methacrylate obtained by the reaction with (methacrylic acid); the type A epoxy resin, the bisphenol F type epoxy resin, the bisphenol S type epoxy resin, or the like A phenol or cresol Novolac type epoxy, a resol type epoxy resin, a trisphenol decane type ring grease, a polyglycolic acid polyglycidyl group, a polyol polyglycidyl group, a fat or a fat An epoxy resin, an amine epoxy resin, an epoxy resin of a dihydroxybenzene type epoxy resin, an epoxy (meth)acrylate resin obtained by reacting with (meth)acrylic acid, etc. A resin obtained by reacting a meta-anhydride with an epoxy (meth) acrylate resin as described above may be used. Among them, an acryl resin or a resin having a caldo structure in the sub-group is preferably used. Caldo structural grease due to heat resistance or resistance High, for use in photopolymerizable compound [Phi], whereby the heat resistance can be improved and the chemical resistance of the photosensitive composition, it is preferably a resin having the structure shown as follows:

C00H I HOOC-Y-CO-O+X-O-CO-Z-CO-O-

C00H (6); wherein, the compound represented by the general formula (6) is represented by the group represented by the formula: () propyl alcohol group) bisphenolic fat, resin oxygen tree fat, etc. Specific when dividing trees

X-0-C0-Y-C00H -28- 1334514

In the formula, γ is derived from, for example, maleic anhydride, succinic anhydride, creatinine, fumaric anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endonalidene tetrahydroortylene A residue obtained by removing a carboxylic acid φ (-C0-0-C0-) from a dicarboxylic anhydride such as dicarboxylic anhydride, gas anhydride, methyl hydrogen o-diphthalic anhydride or glutaric anhydride. Further, in the formula, the oxime is obtained by removing four carboxylic anhydride groups from tetracarboxylic anhydride such as pyromellitic anhydride, benzophenone tetra phthalic anhydride, biphenyltetracarboxylic dianhydride, and diphenyl ether tetracarboxylic dianhydride. Subsequent residues. The content of the "photopolymerizable compound" as described above is in the range of 60 parts by weight to 99.9 parts based on 100 parts by weight of the photosensitive composition. When the content is 99.9 parts by weight or less, heat resistance and chemical resistance can be obtained, and when the content is 60 parts by weight Φ, the film formation ability can be improved and photocuring failure can be prevented. [Colorant] The term "colorant j" means a component which is used as a photosensitive resin and which is colored on a substrate, and includes, for example, a color index (CI; Dye and Colorist Society ( In the Society of Dyers and Colourists, published, the compound of the Pigment, in particular, the one comprising the dye oxime (CI) number attached. The weight of the carboxylic acid is two parts, and the weight of the carboxylic acid is equal to the weight of the material. The photo is like -29-1334514.

Factory CI Pigment Yellow j 1 (hereinafter, "CI Pigment Yellow J is the same as this only lists its number), 3 ' 1 1 ' 1 2, 1 3 , 14 15 , 16, 20 '24 , 3 1 , 53, 55 , 60, 61 '65 7 1 73 % 74 , 8 ] 86 , 93 , 95 ' 97 ' 98 , 99 ' 100 10 1 , 1 04 , 106 , 109 , 1 10 > 113 ' 1 14 , 116 , 117 11 9 , 1 20 > 125 127, 1 28 , 129 ' 1 : 37 , 138 > 139 , 147 · , 1 48 > 150 , 152 , 1 53 , 1 54 ' 1 55 156 , 166 , 167 · • 1 68 175 185 ; Factory CI Pigment Orange J 1 (hereinafter, "C. I · Pigment Orange j is the same, this only lists its number" > 5 ' 1 3, 1 4 ' 16 , 17 % 24 34, 38 , 40 > 43 , 4 6 , 49 5 1 '55 , 59 61 , 63 64 , 7 ] Factory CI Yan Yan 14 Purple " 1 (hereinafter, "C.1. Pigment Violet" is the same, only its number is listed), 19, 23, 29, 30 ' 32 36, 37, 39 40, 50 ; Factory C. I. Pigment Red 1 (The following, "CI·Pigment Red" is the same.玛), 2 ' 3, 4, 5, 6 ' , Ί, 8, 9 ' 10, 12, 14 15 , 1 6 , 1 7 , 18 , 19 , 21 , 22 ' 23 , 30 '3 1 37 &gt 38 40 41, 42 , 48 : 1, 48 : 2, 48 : 3 ' .48 : 49 1 , 49 : 2 , 50 : 1 ' 52 : 1 '53 : 1, 57 , 57 : 1 ' 2 , 58 : 2, 58 4, 60 : 1, 63 : 1, 63 : 2 , 64 : 1 ' { , 83 % 88 90 丨 : 1 ' 97 , 101 , 102 104 , 1 05 , 106 , 11 2 , 1 13 % 1 1 4, 122, 123, 144, 146, 1 49 '150, 155, 1 66, 168, 170, 171, 172, 174, 1 75 ' 176 , because 17, l ' 83 , 108 , 126 ' 15 1 , 180, because 36, [' 73, because 38 ', because 11' [, 32:4, 57: 5 1: 1, 108, 151, 177 -30- 1334514

, 178, 179, 180, 185, 187, 188, 190, 192, 193, 202, 206, 207, 208' 209, 215 > 216, 217, 220, 224, 226, 227 '228, 240, 242, 243, 245, 254, 264, 265; "CI Pigment Blue" 1 (hereinafter, "CI Pigment Blue 1" is therefore only listed), 2, 15, 15: 3, 15: 4, 15: ( ' 22' 60' 64, 66; C. I. Pigment Green 7, C. I. Pigment Green 3 6 , C. I. Pigment Green 3 7 ; CI Pigment Brown 23, CI Pigment 椋 25, CI Pigment 椋 26' Pigment brown 28; C. I. Pigment black 1, Pigment black 7. In addition, carbon black is also suitable as a black pigment. The photosensitive composition of the present invention is particularly suitable for forming a black matrix because of its high sensitivity. The coloring agent is suitably used as a light-shielding agent such as carbon black as described above. Specifically, carbon black or a carbon black dispersion liquid dispersed by an acid-based dispersion liquid can be used. Further, titanium black, copper, and fission are used. Metal oxides, complexes, metal sulfides, metal lead sulfate or metal carbonates such as Ming, Luo, Lu, Zinc, Hexa, and Silver can also be used. It is more preferable to use a light-shielding carbon black among the coloring agents. Although "carbon black" is used, it is possible to use cha η ne 1 b 1 ack , (furnace black), thermal black (thermal black). A conventional carbon black such as a lamp lamp Mack), but it is particularly preferable to use a grooved black having a light-shielding property. Further, carbon black coated with a resin can also be used. , 194 ' 223 , 255 with , ; , 1 6 > CI is the upper propylene , iron oxygen machine furnace black ( superior -31 - 1334514 ) resin coated carbon black , due to its conductivity When it is used as a color filter (black matrix) such as a liquid crystal display device, it can form a display device with low leakage current and high reliability and low power consumption.

Further, an organic pigment may be further added to be used as an auxiliary pigment for carbon black. Since the organic pigment added as a complementary color of the inorganic pigment is appropriately selected, the red color of the carbon black can be eliminated. The system includes, for example, phthalocy anine pigments, azo pigments, and salt-based dye lake pigments, and the like. The amount of the organic pigment to be used is preferably in the range of 10 parts by weight to 80 parts by weight, more preferably 20 parts by weight to 40 parts by weight, based on 100 parts by total of the total of the inorganic pigment and the organic pigment. The inorganic pigment and the organic pigment may be a solution obtained by dispersing into a proper concentration by a dispersing agent. Further, as the "dispersing agent", a polyethylene imine or urethane resin is preferably used. A polymer dispersant such as φ acrylic resin. [Composition of photosensitive composition] The photosensitive composition of the present invention preferably contains 20 parts by weight to 60 parts by mass based on 100 parts by mass of the total amount of the photopolymerizable compound, the photopolymerization initiator and the colorant. The photopolymerizable compound in the range of parts by weight, the photopolymerization initiator in the range of 0.5 part by weight to 30 parts by weight, and the coloring agent in the range of 10 parts by weight to 70 parts by weight. By setting the content of the colorant to 1 part by weight or more, the light-shielding property of the formed black case -32-1334514 can be sufficiently obtained. Further, when the content of the coloring agent is 70 parts by weight or less, the curing property can be improved when light of a specific wavelength is irradiated. Further, in the composition ratio as described above, the coloring agent may be an inorganic pigment such as carbon black or titanium black, but may contain an auxiliary pigment.

Further, when the concentration of the colorant is used to form a phosphine black matrix by using the photosensitive composition of the present invention as described below, it is preferable to adjust the OD (Optical Density) value of the photosensitive composition per lym film thickness. Can be 3.5 or more. When the 0D value of the photosensitive composition per 1/zm film thickness is 3.5 or more, when it is used as a black matrix of a liquid crystal display device, sufficient display contrast can be obtained.

Further, when the photosensitive composition of the present invention is used to form a black matrix pattern, the photosensitive composition of the present invention is applied onto a substrate as described below, and dried to form a film. In order to improve the coatability at this time and the physical properties after photocuring, in addition to the components described above, a binder of a high molecular weight may be further contained as a binder. The binder can be appropriately selected depending on the purpose of improvement in compatibility, film formability, developability, and adhesion. The thickness of the black matrix pattern formed on the substrate is usually set at O.lym to 10.0/zm, preferably in the range of 0.2#m to 5.0#m, more preferably 0.2/zm to 3.0; tzm. Further, a solvent for dilution, a thermal polymerization inhibitor, an antifoaming agent, a surfactant, or the like may be added to the photosensitive composition of the present invention. Among these, "solvent j" which can be added to the photosensitive composition includes, for example, ethylene glycol monodecyl ether, ethylene glycol monoethyl ether, ethylene glycol -33-1334514

Mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether alcohol monoethyl ether, diethylene glycol mono-n-propyl ether 'diethylene glycol mono-n-butyl glycol monodecyl ether , triethylene glycol monoethyl ether, propylene glycol monodecyl ether alcohol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl propylene glycol monodecyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoether, "(poly)alkylene glycol monoalkyl ether", such as dipropylene glycol mono-n-butyl ether, tri-propylene glycol monodecyl ether, glycol monoethyl ether, etc., glycol monomethyl ether acetate, ethylene glycol "(poly)alkylene monoalkyl ether acetate, such as monoethyl ether acetate, dimercapto ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether acetate, etc. Other alcohols such as diethylene glycol dimethyl ether, diethylene glycol oxime ether, diethylene glycol diethyl ether, tetrahydrofuran, etc., ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone "ketones"; "methyl lactate acid alkyl esters" such as methyl propionate or ethyl 2-hydroxypropionate; 2 - thioglycolic acid acid Ester, ethyl 3-methoxyoxypropionate, ethyl 3-ethoxypropionate ethoxylate, ethyl ethoxyacetate, hydroxyethyl acetate 2-hydroxy-3-methyl decyl ester, 3-methyl-3-methoxybutyl acetate, methyl-3-methoxybutyl ester, ethyl acetate, n-propyl acetate, acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate Ester, acetic acid, n-butyl propionate, ethyl butyrate, n-propyl butyrate, n-butyl isopropylate, methyl pyruvate, ethyl pyruvate, methyl n-propyl pyruvate, B Ethyl acetate, ethyl 2-oxobutyrate, etc.; "aromatic hydrocarbons" such as benzene, xylene, etc.; N-anthracene, diethylene glycol, tris, propylene diether, di-n-propyl乙三丙丙类; ethylene glycol monomethyl ether diol ethyl: methyl 2- thiol (lactic 3-methoxy ester, 3-, butyric acid and acid 3-acid isoamyl ester Butyl butyl ketone and other "deuteramines" such as kebyl-34-1334514 ketone, hydrazine, hydrazine dimethyl decylamine, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

Among these, preferred are: propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol didecyl ether, two Glycol methyl ethyl ether, cyclohexanone, and 3-methoxy butyl acetate, because these solvents exhibit superior solubility to photopolymerizable compounds and photopolymerization initiators, and at the same time, insoluble in black pigments and the like. The dispersibility of the components tends to be good, and among them, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferred. The solvent may be used in an amount of from 50 parts by weight to 500 parts by weight based on 100 parts by weight of the total of the photopolymerizable compound, the photopolymerization initiator and the light-shielding material. Further, as the "thermal polymerization inhibitor", hydroquinone, hydroquinone-ethyl group or the like can be used. Further, as the "antifoaming agent", a polysilicon-based or fluorine-based compound can be used, and as the "surfactant", various conventional thermal polymerization inhibitors such as an anionic, cationic or nonionic surfactant can be used. .

The method for producing a photosensitive composition of the present invention can be prepared by mixing all of the photopolymerizable compound, the photopolymerization initiator, and the coloring agent as described above with a stirrer. Further, the obtained mixture may be filtered to make it uniform using a filter. (Method of Forming Color Filters) A specific example of a method of forming a "color filter" using the photosensitive composition of the present invention is as follows. [Formation of a black matrix (black colored layer)] First, a roll is used. Coating machine, reverse coating machine, bar coater, etc. -35-1334514

The contact transfer type coating device or the non-contact type coating device such as a spin coater (rotary type) or a curtain coater is a substrate optical composition (including a black colorant). A substrate is used for the substrate. Further, in the present embodiment, a glass substrate having a thickness of 1.1 mm is used. In order to improve the adhesion between the glass substrate and the photosensitive composition, a decane coupling agent may be applied to the glass substrate, or a stagnation coupling agent may be added in advance when the composition is adjusted. After the photosensitive composition is applied, the method of drying it to remove the drying method is not particularly limited, and for example, any of the following may be used: (1) on a hot plate at 80 ° C to 120 ° C, Preferably, the method is dried at a temperature of 90 ° C for 60 seconds to 120 seconds; (2) for several hours to several days; (3) for tens of minutes to several hours for being placed in a warm air infrared heater After the removal is performed, the active energy ray such as ultraviolet laser light is irradiated through the negative hood to perform local exposure. The amount of irradiation varies depending on the composition of the photosensitive composition, but is, for example, from about 30 mJ/cm 2 to 2000 mJ/cm2. Next, the exposed film is developed with a developing solution to form a specific shape. The developing method is not particularly limited, and a filming method, a spraying method, or the like can be used. : an organic system such as monoethanolamine or triethanolamine; or an aqueous solution of sodium hydroxide _, sodium chlorate, gas water, and quaternary salt. The coating device has a light transmission of 0.5 mm and can be prefabricated. Photosensitive solvent. Dry one method to 100 ° c At room temperature, the method of the heater or the agent, the energy of the excimer shot is preferably patterned, for example, by dipping ethanolamine, and hydrating -36-1334514

Next, the developed pattern is post-baked at about 2 Ο 0 ° C. Further, it is preferred to expose the formed pattern to a full extent. [Formation of Other Colored Layers] The photosensitive composition is coated, dried, lighted, and developed in the same manner as described above on the glass substrate on which the black matrix formed by the above method is formed, so that the colored layer having a specific color is The special position (opening) of the black matrix forms a pattern (stripes, dots, etc.). For example, in the case of producing RGB color filters, the photosensitive composition of each of R, G, and B is used, and the above-described steps are repeated to form a layer of three colors and form a color filter. EXAMPLES <Example 1> [Synthesis of photopolymerizable compound] A copolymer of methacrylic acid/benzyl methacrylate/1-hydroxyethyl methacrylate was synthesized (hereinafter referred to as "compound 1" ” φ is a photopolymerizable compound having an ethylenically unsaturated bond. First, 400 grams of propylene glycol monodecyl ether acetate (PGMEA), 75 grams of acrylic acid, 210 grams of alum, methacrylate, 15 grams of 2-hydroxyethyl methacrylate, and 5 grams of azobisisobutyronitrile It was fed into a 500-neck four-necked flask and purged with nitrogen while maintaining the temperature at . (: The reaction is carried out by stirring for 3 hours at 70 ° C. [Photopolymerization initiator] The "photopolymerization initiator" is obtained by using a general-purpose coloring acid 5 as shown below to raise the terpene. Compound of the structure represented by 65 (2 -37- 1334514). This compound is produced according to the synthetic scheme as described above: (2)

When the compound is synthesized, the compound of the formula (8) shown below is produced according to the following scheme:

R2 A

Cl (8) wherein R2 corresponds to R2 in the above-described scheme and corresponds to a phenyl group containing E in the present invention. 〕

The "polymer 1" shown above and the pentaerythritol tetraacrylate (PETTA) as a monomer were used as photopolymerizable compounds, and the photosensitive composition of the present invention was prepared at a mixing ratio of Table 1. In this case, the pigment is a carbon dispersion (CF black EX-1 455, containing 24% by mass of high-electricity -38-1334514 carbon, manufactured by Royal Chinese Co., Ltd.), and the solvent is 3-methoxyl acetate. Butyl ester. These were all mixed in a blender for 2 hours, and then passed through a 5 &quot;m membrane filter to prepare a photosensitive composition of the present invention. <Example 2> The photosensitive composition was adjusted in the same manner as in Example 1 except that the photopolymerizable compound was changed to a compound (compound 2) having a structure represented by the following formula. (See Table 1).

[Synthesis of photopolymerizable compound] A cardo resin having a structure represented by the formula (6) shown below is synthesized:

COOH I hooc-y-co-o--x-o-co-z-co-o--x-o-co-y-cooh

I

C00H (6) wherein X is a group having a structure represented by the general formula (7):

23 5 g (epoxy equivalent of 23 5 ) of bisphenol fluorene type epoxy resin with 110 mg of tetramethyl gas, 100 mg of 2,6-di-tertiary butyl-4 -Methylphenol' and 72.0 g of acrylic acid, fed into a 500 ml four-necked flask, while blowing air at a rate of -25 to 1334514 at 25 ml/min, at a temperature of 90 ° C to 100 ° C Heat to dissolve it. Next, in a state where the solution was still cloudy, the temperature was slowly raised to 120 ° C to completely dissolve it. At this point, the solution will gradually become transparent and viscous, but stirring will continue in this state. During this period, the acid value was measured until it reached less than 1.0 mg KOH/g and heating was continued for about 12 hours. Then, it was cooled to room temperature to obtain a colorless transparent and solid bisphenol oxime type epoxy acrylate represented by the following formula (9):

Next, in the 307.0 g of the bisphenol type epoxy acrylate obtained thereby, 600 g of propylene glycol monomethyl ether acetate (PGMEA) was added and dissolved, and 80.5 g of dibenzophenone tetracarboxylate was mixed. Acid dianhydride, and 1 gram of tetraethylammonium bromide, and reacting at 110 ° C to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 3 8.0 g of 1, 2, 3, 6 - tetrahydroortylene is mixed. The dicarboxylic anhydride was reacted at 90 ° C for 6 hours to obtain a cardo resin represented by the above formula (7). Further, the disappearance of the acid anhydride group was confirmed by an IR (infrared) spectrum. Then, the "cardo resin" is referred to as "compound 2" hereinafter. The "Compound 2" is a compound represented by the formula (6): -4034514, X is a group represented by the formula (7), and Y is a 1,2,3,6-tetrahydroortylene group. The residue after removal of the anhydride group (C0-0-C0_) by diacetyl dianhydride, and the residue of Z after removal of the anhydride by 3,3',4,4'-dibenzophenone tetracarboxylic acid tetrahydride Base, and the Y/Z molar ratio is 50.0/50.0. <Example 3> In addition to the photopolymerization initiator of Example 2, a compound represented by the formula (4) shown below was further added:

(4) 2-(Didecylamino)-1-[4-(4-morpholinyl)phenyl]-2-(phenylindenyl)-1-butan (Photopolymerization Initiator 2: Trade Name The photosensitive composition of the present invention was prepared in the same mixing ratio and method as in Example 2 except for Irgacure 369 (manufactured by Ciba-Geigy Co., Ltd.) (Refer to Table 1 <Example 4 &gt; In addition to the light in Example 2) The polymerization initiator of the present invention was prepared in the same manner as in Example 2 except that the polymerization initiator was further added with a thiothiobenzimidazole (photopolymerization initiator 3) (see Table 1). &gt; In addition to changing the photopolymerization initiator to a compound represented by the general formula (5) -41 - 1334514 as shown below:

(5) (Photopolymerization Initiator 4: Ciba Specialty Chemicals, CGI242) The remainder of the procedure was the same as in Example 1 to prepare the optical composition of the present invention (see Table 1). Sense

-42- 1334514 Table 1 Photopolymerizable Compound Photopolymerization Initiator Carbon Dispersion Solvent Resin Monomer Example 1 Compound 1: 150 parts by mass of hydrazine: 30 parts by mass of photopolymerization initiator 1: 12 parts by mass of 700 parts by mass of acetic acid 3- Methoxybutyl ester: 300 parts by mass of Example 2 Compound 2: 150 parts by mass of PETTA: 30 parts by mass of photopolymerization initiator 1: 12 parts by mass of 700 parts by mass of 3-methoxybutyl acetate: 300 parts by mass of Example 3 Compound 2: 150 parts by mass of PETTA: 30 parts by mass of photopolymerization initiator 1: 12 parts by mass of photopolymerization initiator 2: 6 parts by mass of 700 parts by mass of 3-methoxybutyl acetate: 300 parts by mass of Example 4 Compound 2: 150 parts by mass of PETTA: 30 parts by mass of photopolymerization initiator 1: 12 parts by mass of photopolymerization initiator 3: 6 parts by mass of 700 parts by mass of 3-methoxybutyl acetate: 300 parts by mass of Comparative Example 1 Compound 2: 150 parts by mass PETTA: 30 parts by mass of photopolymerization initiator 4: 12 parts by mass of 700 parts by mass of 3-methoxybutyl acetate: 300 parts by mass

<Evaluation> The photosensitive compositions as described above were respectively applied to a dry film on a glass substrate having a clean surface having a thickness of 1 mm by a spin coater (TR2500, manufactured by Tokyo Ohka Kogyo Co., Ltd.). The thickness was 1.2 μm, and then dried at 90 ° C for 2 minutes to form a film (photosensitive layer) of the photosensitive composition. Next, the film is selectively irradiated with ultraviolet rays through a negative pattern mask. The exposure amount is set to four stages of 40, 45, 50, and 60 mJ.

Then, it was spray-developed at 0 5 ° C in a 0.5% by mass aqueous sodium carbonate solution for 60 seconds to form a black matrix pattern having a line width of 10 / / m. Then, a 30-minute "post baking" treatment was applied to the circulating oven at 220 °C. The obtained black matrix had a mold thickness of 1.0 lm, and the 0D value was measured by an 0D measuring device (D-200II, manufactured by GretagMacbeth Co., Ltd.). The results of these are shown in Table 2. -43- 1334514 Table 2 Exposure Amount (mJ/cm2) Pattern Linear Disintegration Residue 0D Value 40 45 50 60 40 45 50 60 Example 1 Poor Good Good Good with or without None 4.0 Example 2 Good Good Good Good No. No. No. No. 4.0 Example 3 Good, good, good, good, good, no, no, no, no, no. 4.0 Example 4 Good, good, good, good, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no, no (straight forward) is judged by the presence or absence of shaking (jumping) at the edge of the visual 1 〇 micron line (width of lOjwm). Further, "pattern peeling" is judged by whether or not peeling or chipping occurs on a 5-micron line (line of 5/zm width). "Residue" is visually judged whether there is any residue on the glass.

Pigment residue. As a result, the patterns obtained by Examples 2 to 4 had superior linearity, and no pigment residue or peeling from the substrate was confirmed. On the other hand, in Comparative Example 1, when the amount of exposure was low, the pattern peeling was large, and the linearity was also poor.

Further, with respect to Example 2 and Comparative Example 1, the results of comparing the residual film ratios at the "post-baking" temperatures of 200 °C and 220 °C are shown in Table 3. The "residual film rate" means the ratio of the film thickness after post-baking to the film thickness before exposure and post-baking. As a result, the residual film ratio of the photosensitive composition of the present invention was about 2% higher, so that it was confirmed that it was possible to suppress the generation of volatiles after post-baking. Table 3 Example 2 Comparative Example 1 200 ° C 86.80% 84.20% 220 〇 C 85.10% 82.90% Further, regarding Example 2 and Comparative Example 1, the generation of volatile matter at the time of exposure was also examined. After 70 exposures of 100 (mJ/cm2), a specific amount of tetrahydrofuran (THF) was used to wash the hood. Next, the amount of the hood attachment was measured by a gel permeation chromatography (manufactured by Shimadzu Corporation) at -44-1334514. The comparison of the amount of volatile matter produced is judged by the peak area near the 16 minutes of the graph. The results are shown in Table 4. From this, it was confirmed that the result of using the photosensitive composition of the present invention was that the generation of volatiles was suppressed. Table 4 Example 2 Comparative Example 1 Area% 36 41 Peak height % 41.1 47.9

-45-

Claims (1)

1334514 X. Patent application scope: 1. A photosensitive composition containing a photopolymerizable compound, a photopolymerization initiator, and a coloring agent, and containing the following formula (1) as the photopolymerization initiator ) the compound represented by: [wherein A represents a Ri, _ 0R1 ' — C0R1 ' — SRi or an NR1 R2 ; the B system represents a Ri, _ 0R1 ' — C0R1 ' _ SR1 ' a C0NIU 2 or a CN; the G system represents a hydrogen atom, _Ri, _ORi, a CORi, a SRi or a Νΐυ2; Wherein R! and R2 each independently represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, and these may also be substituted with at least one of a dentate atom or a heterocyclic group, such as an alkane The alkyl group of the aryl group and the aralkyl group may also be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond. Further, the Ri and R2 groups may be combined to form a ring; the E system represents a OR3 or _NR4R5, R3 represents a heterocyclic group of 5 or more rings containing at least one of a gas atom, a sulfur atom and an oxygen atom, and R4 and R5 represent an alkoxycarbonyl group having 2 to 20 carbon atoms; At least one of E represents a group having a molecular weight of 30 or more; m - 46 - Γ 334514 is an integer of 1 to 5, and η is Ο]. 2. The photosensitive composition according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the formula (2) shown below: (2) The photosensitive composition according to the first aspect of the invention, wherein the compound represented by the formula (1) is a compound represented by the formula (3) shown below: (3) The photosensitive composition according to claim 1, wherein the photopolymerization initiator further contains a compound represented by the following formula (4): -47- 1334514 5. The photosensitive composition according to claim 1, wherein the photopolymerization initiator further contains a compound represented by the following formula (5): 6. The photosensitive composition according to claim 1, wherein the photopolymerization initiator further contains a thiol benzopyrene 11 sitting ( 7. The photosensitive composition according to claim 1, wherein the photopolymerizable compound is a compound having at least one ethylenic double bond in the molecule. 8. The photosensitive composition according to claim 1, wherein the photopolymerizable compound is an acrylic acid (a c r y 1 ) resin. 9. The photosensitive composition according to claim 1, wherein the photopolymerizable compound comprises a cardo-bond-48-Γ334514 structure in the molecule and at least one ethylenic bond in the molecule. Double-bonded resin. 10. The photosensitive composition according to claim 1, wherein the coloring agent contains carbon black. -49-