TWI343930B - - Google Patents

Description

1343930 (1) EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to a photopolymerizable composition for a color filter used in the manufacture of an optical color filter used for a color television, a liquid crystal display element, a solid-state imaging device, a camera, or the like. And a color filter obtained from the composition, in particular, the present invention relates to a black matrix (Black Matrix, hereinafter abbreviated as BM) which is excellent in high light-shielding property and excellent in resolution. A photopolymerizable composition for a color filter and a color filter of a resin B having high precision and high light-shielding property. [Prior Art] A color filter is usually formed on a surface of a transparent substrate such as glass or a plastic sheet to form a ochre substrate, and then three or more different hue such as red, green, and blue are sequentially arranged in a stripe shape or a mosaic form. The color sample is formed. The color sample size varies depending on the color filter application and various colors, and is about 5 to 700 μηι. Further, the positional accuracy of superposition is several to several tens of μm, and can be manufactured by a microfabrication technique with high dimensional accuracy. Representative production methods of the color filter include a dyeing method, a printing method, a pigment dispersion method, and an electrolytic deposition method. Among these, in particular, a photopolymerizable composition containing a color material is applied onto a transparent substrate, and the image is exposed, developed, and repeatedly hardened as needed to form a pigment dispersion of the color filter image. The method is excellent in durability such as high-resolution color filter position and film thickness, and excellent in durability such as light resistance and heat resistance, and thus has many defects such as pin holes. -4- (2) (2) 1343930 BM is arranged in a grid, stripe or mosaic in the red, green and blue samples, and the contrast is improved or the light is leaked due to the suppression of color mixing between the colors. The prevention of malfunction of the thin film transistor (TFT) has its effect. Therefore, BM is required to have a high degree of opacity. The conventional BM is formed by a metal film such as chromium. In this method, a metal such as chromium is vapor-deposited on a transparent substrate, and the chromium layer is etched by a lithographic step. Therefore, high light-shielding properties can be obtained with high precision at a thin film thickness. On the contrary, because of the long manufacturing process and low productivity, high cost, environmental problems due to etching treatment, and the like are required. Therefore, a method of forming a low-cost, pollution-free resin BM by using a photosensitive resin in which a light-shielding pigment or a dye is dispersed is fully studied. However, since the resin BM has problems such as those described later, it is currently not practical. In the resin BM, in order to exhibit a light-shielding property (optical density) similar to that of BM in order to develop a metal film such as chromium, the content of a light-shielding pigment or a dye may be increased, or the film thickness may be increased. In the method of increasing the film thickness, it is affected by the BM unevenness, and the flatness of the RGB coloring pixels formed thereon is damaged. Therefore, the unevenness of the cell gap or the disorder of the liquid crystal orientation may be caused, resulting in a decrease in display ability. Further, there is a problem that the transparent electrode ITO (indium tin oxide) film provided on the color filter is broken (damage of the planar film). In addition, in the method of increasing the amount of the light-shielding pigment or the dye, the photosensitive resin (black resist) sensitivity, developability, resolution, and adhesion - 5 - 3343330 bondability The problem, not only the decrease in productivity, but also the accuracy and reliability required for the color filter is not available. That is to say, the photosensitive material which can exhibit sensitivity and resolution under the condition of film and high light-shielding property cannot be realized, and thus the practical use of the resin BM is hindered. A known method of improving the sensitivity and the resolution performance of a photosensitive resin such as a general photosensitive resin or a photosensitive photosensitive composition for a color filter having a certain light transmittance is known. For example, as a coloring composition for a color filter for dispersing a pigment, a photosensitive resin having a binder resin, a polyfunctional propylene monomer, and an initiator containing a triterpenoid compound is known (refer to Patent Documents 1 to 4). Further, in the homofluorene composition, the initiator is known as bisimidazole (see Patent Documents 5 to 6), and in the case of the disclosed compositions, exposure to air is inhibited by polymerization due to oxygen. Sensitivity is not available in practice. As in the case of the resin BM, there is a case where the light-shielding ability is required in the entire wavelength range of light, and (1) it is extremely difficult to make the difference in the crosslinking density in the exposed portion and the unexposed portion, and (2) even in the portion to be exposed, The crosslink density in the film thickness direction is different, that is, even if it is sufficiently hardened on the light-irradiated surface, it does not harden on the base surface, and (3) a large amount of indigo color material is blended in the developing solution, causing significant When the image quality is remarkably lowered, the photosensitive property is impaired. In particular, the development of (1) and (2) above is reversed, and if the exposure is thick, the film is exposed, and the method is unsuccessful. group. The density is reduced, the hard and hard force is reduced to the image part, and the light is divided into the exposed part. The difference is the large degree of liquid density, and the difference between the hard part and the hard part is not dissolved. (4) (4) 1343930 It is also difficult to use, and it is difficult to improve the imaging performance. A photosensitive composition for forming ruthenium ruthenium (for example, refer to Japanese Patent Laid-Open No. Hei 7-8), which can avoid such a situation, but does not form a light-shielding resin of the same degree as the metal ruthenium, but to some extent Light passes through to obtain photosensitivity, but its light-shielding ability is significantly reduced and cannot be practically used. Therefore, since the resin having a high film thickness and a low light-shielding property is formed by shrinking the film in the cure step after the formation, a resin BM having a high light-shielding property in the film is proposed (refer to Patent Document 9). However, since the step is re-examined, the problem of the decrease in the adhesion due to the accumulation of the strain at the time of film shrinkage is difficult to put into practical use. In this case, the so-called shading causes a photoreaction under the condition that the original reaction with the light is reversed, so that it is quite contradictory in view of this, and therefore it is difficult to realize the practical use of the resin BM. Further, as a photopolymerization initiator, a technique using a specific oxime ester compound is known (refer to Patent Document 〇), an initiator used in a conventional resin (for example, a diimidazole or a triazine initiator), if only In place of the compound, the image characteristics required for the resin β Μ cannot be improved, that is, the sensitivity or the resolution cannot be improved. [Patent Document 1] Japanese Unexamined Patent Application Publication No. JP-A No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei 6-75373 (Patent Document 7) Japanese Laid-Open Patent Publication No. Hei 6-75373 (Patent Document 7) Japanese Patent Laid-Open No. Hei 6-5 (499) (5) 1343930 [Patent Document 8] [Patent Document 9] Japanese Laid-Open Patent Publication No. Hei. No. 2000-80068 (Patent Document 10) [Problems to be Solved by the Invention] The present invention has been made to solve the above problems. Provided is a resist material which is more easily formed by photolithography with a film and a high light-shielding pattern, and which has sufficient sensitivity and resolution, so that the resin BM of the color filter can be high precision and low. Manufactured under cost. Further, a liquid crystal display device using a color filter manufactured in such a manner is excellent in display capability such as contrast. Moreover, the resin of BM can measure the high image quality and pollution-free color of the color filter. [Means for Solving the Problem] The present inventors have found that a specific oxime ester compound as a photopolymerization initiator is used as a photopolymerization initiator, and an epoxy acrylate resin having a carboxyl group is combined as an organic binder. The above object can be attained by using a photopolymerizable composition contained therein, and thus the present invention has been completed. That is, the gist of the present invention is in a photopolymerizable composition containing (a) a ochre color material, (b) an organic binder, and (c) a photopolymerization initiator. (b) is an epoxy acrylate having a carboxyl group. The ester resin and (c) are oxime ester-based compounds, and the above-mentioned photopolymerizable composition is particularly preferred. Further, the photopolymerizable composition of the present invention further contains (d) -8 - (6) 1343930 photopolymerizable monomer, which is a photopolymerizable composition. Further, in the present invention, the photopolymerizable composition further contains (e) a polymer dispersing agent having a basic functional group as a photopolymerizable composition. Further, the present invention relates to a BM formed of the photopolymerizable composition on a substrate, a color filter characterized by the same, and a liquid crystal display device manufactured by using the color filter manufactured in this manner. [Effects of the Invention] The photopolymerizable composition of the present invention has high light-shielding property in a film, and is excellent in sensitivity and resolution, so that a high-quality resin can be formed at a low cost, B Μ. The color filter of the resin B of the present invention is excellent in accuracy, flatness, and durability, so that the display quality of the liquid crystal element can be improved. Moreover, the manufacturing steps and the color filter itself do not contain harmful substances, so the danger to the human body can be reduced and the environmental safety can be improved. [Best Mode for Carrying Out the Invention] (a) Twilight Color Material The green color material of the present invention may be a single color material or a red color material obtained by mixing red, green, blue or the like. These ochre color materials may be selected from inorganic 'or organic pigments and dyes, and may be used singly or in combination. Separate color materials, such as carbon black, acetylene black, lamP black, bone black, erroneous, sputum 'aniline black, flower -9 · (7) 1343930 black (cyanin black )Wait. Among these, in particular, carbon black is preferred in terms of light blocking rate and image characteristics. Examples of commercial products related to carbon black, such as the following brands. Mitsubishi Chemical Corporation: MA7, MA8, MA 11, MA 100, MA 220, MA 23 0, #52, well 50, well 47, well 45, well 2700, well 2650, well 2200 'well 1 000, well 990, #900等.

D egu ssa company: P rint ex 95, Printex 90, Printex 85, Printex 75, Printex 55, Printex 45, Printex 40, Printex 30, Printex 3, Printex A, Printex G, Special Black 550, Special Black 3 50, Special Black 250, Special Black 1 00, etc.

Cabot company: Monarch 460, Monarch 430, Monarch 2 8 0, Monarch 120, Monarch 8 0 0, Monarch 4 6 3 0, REGAL 99, REGAL 99R, REGAL 415 ' REGAL 415R,

REGAL 2 50, REGAL 2 50R, REGAL 3 3 0, BLACK PEARLS 480, P EARLS 130

Columbian Carbon Company: RAVEN II, RAVEN 15, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 7 80, RAVEN 8 5 0, RAVEN 8 90H, RAVEN 1 000, RAVEN 1020, RAVEN 1 040, etc. Next, the description will be made on the color of the ochre material. Specific examples of the color material of the mixed base include Victoria Pure Blue (42595), auramine Ο (4 1 000 ), and Kachiron Gorgeo Yellow -10- (8) 1343930 (briliant flavin) (primary color) 13), rhodamine 6GCP ( 45160 ), rhodamine B ( 4 5 1 7 0 ), safranine OK70: 100 ( 50240), wool erythroid ( erioglaucine ) ( 4208 0 ) , NO, 120 / Li Ao Huang (rionol

Yellow) ( 21090), Li Ao Huang - GRO ( 21090), Shimla fast yellow -8GF ( 21105 ) , Benzidine Yellow - 4T-564D ( 2 1 095 ), Shimla Fast Red 4015 (12355), Li Aohong 7B440 1 (1 5 8 5 0 ), Fastgen Blue-TGR-L (74 1 60 ), Leo Blue-SM (26150), Leo Blue-ES (Pigment Blue-15:6 ), Ri〇no gen red GD (pigment red 168), Leo green 2YS (pigment green 36), etc. (again, the number in the above () refers to the colorimetric index (CI)). Further, other pigments which can be used in combination, if expressed by C.I., are, for example, C.I. yellow pigments 20, 24, 86, 93, 109, ; 10

,117, 125, 137, 138, 147, 148, 153, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, (: 1. red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217 '220 ' 223,224,226,227,22 8,240, CI violet pigment 19,23,29,30,37,40,50,CI blue Color pigments 15, 15:1, 15:4, 22, 60, 64, Cl·green pigment 7, brown pigment 23, 25 > 26, etc. Further, the above carbon black can be combined with other tantalum or colored inorganic, The organic pigments are used in combination. Other pigments have a lower ratio of light-shielding properties or image characteristics than carbon black. Therefore, the mixing ratio of the pigments is limited. -11 - 1343930 (9) (b) Organic binders (b) Organic bonding in the present invention An epoxy acrylate resin having a carboxyl group is used as the material, and the above epoxy acrylate resin is an α,β-unsaturated monocarboxylic acid or an a' β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety. It is synthesized by reacting with an epoxy resin and further with a polybasic acid anhydride. These reaction products are chemically and substantially not The epoxy group is not limited to the "acrylate", but the epoxy resin is a raw material, and the "acrylate" is a representative example. Therefore, the epoxy resin which is a raw material can be suitably used. , (o-, inter-, p-) cresol novolac type epoxy resin, phenolic aldehyde varnish type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy The resin, the epoxy resin shown in the following [Chemical Formula 4], etc. (refer to Patent No. 28*7 8 48 6). The molecular weight of the epoxy resin and the weight average molecular weight measured by GPC are usually 200 to 200,000. Preferably, it is in the range of 300 to 100000. When the molecular weight is less than the above range, there are many problems in film formability, and the opposite, the resin exceeding the above range is in the addition reaction of the α,β-unsaturated monocarboxylic acid. It is easy to cause gelation, but it is difficult to manufacture. -12- 1343930 do) 【化4】

The α,β-unsaturated monocarboxylic acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, etc., preferably acrylic acid, methacrylic acid, and especially acrylic acid are preferred because of their good reactivity. a, β-un.saturated monocarboxylate having a carboxyl group in the ester moiety, 2-nonylsulfonyloxyethyl acrylate, 2-ondanyloxyethyl acrylate, 2-nonyloxy acrylate Ethyl ester, -2-hexahydroacetic acid ethyl acrylate, 2-succinyloxyethyl methacrylate, methacrylic acid 2- 2 maleic acid ethyl ester, methacrylic acid 2-mercaptooxy oxygen Ethyl ester, • -2-hexahydroindenyloxyethyl methacrylate, octadecyl-2-bromodecyloxy acetoacetate, etc., preferably, _2_maleyl oxyethyl acrylate and acrylic acid - 2_Mercaptooxyethyl ester, especially 2-malonyloxyethyl acrylate is preferred. a' β-addition reaction of an unsaturated monocarboxylic acid or an ester thereof with an epoxy resin, and a known method, for example, in the presence of an esterification catalyst, at a temperature of 5 〇 to 1 50 ° C . The esterification catalyst may be a tertiary amine such as triethylamine, trimethylamine, benzyl dimethylamine or benzyldiethylamine, tetramethylammonium chloride, tetraethyl chlorinated or decyl chloride. A grade 4 ammonium salt such as methylammonium or the like. The amount of the a'p-unsaturated monocarboxylic acid or its ester is preferably in the range of from 0.5 to 1.2 equivalents per 1 equivalent of the epoxy group of the starting epoxy resin, and more preferably -13 (11) (11 ) 1343930 is in the range of 0.7 to 1. I equivalent of ' a' β - the amount of unsaturated monocarboxylic acid or its vinegar is small, the amount of introduction of the unsaturated group is insufficient, and then the reaction with the multi-anhydride is not It is also not advantageous to have a sufficient amount of residual epoxy groups. On the other hand, if the amount used is large, the α,β-unsaturated monocarboxylic acid or its ester remains as an unreacted product. In either case, it is considered that the hardening property tends to be deuterated. An epoxy resin to which an a, β-unsaturated carboxylic acid or an ester thereof is added, and further a basic acid anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Pyromellitic anhydride, trimellitic anhydride, diphenyl ketone tetracarboxylic dianhydride, methyl hexahydrophthalic anhydride, terminal methylene tetraphthalic anhydride, chlorendic anhydride, methyl tetragas anhydride anhydride Phenyltetracarboxylic dianhydride or the like, preferably, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, biphenyltetracarboxylic acid The acid dianhydride, the most preferred compound, is tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. The additional reaction with a polybasic acid anhydride can also be obtained by continuing the reaction under the same conditions as the additional reaction of the a'β-unsaturated carboxylic acid or its ester by a known method. The amount of the polybasic acid anhydride to be added is preferably in the range of from 1 to 150 mg KOH/g, more preferably from 20 to 140 mg KOH/g, based on the acid cerium of the produced epoxy acrylate resin. When the resin strontium silicate is less than the above range, it lacks alkali developability, and when it exceeds the above range, it is considered that the hardenability is degraded. (c) Photopolymerization initiator C S ) -14- (12) (12) 1343930 The photopolymerizable composition of the present invention contains a moon vinegar-based compound as a photopolymerization initiator. A preferred oxime ester compound is a compound represented by the general formula (2). 【化5】

(wherein R1 is a phenyl group which may be substituted, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, a benzamidine group, a carbon number 2 to 12 alkoxycarbonyl, phenoxycarbonyl, decylamino or nitro, R 2 , an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, and benzene each independently substituted A mercapto group having a carbon number of 2 to 6 alkoxycarbonyl or a phenoxy alkane group, R 3 , R 4 , R 5 , R 6 and R 7 are mutually independent hydrogen atoms 'halogen atom, each of which may be substituted with a carbon number of 1 to 12 Alkoxy group having a carbon number of 1 to 12, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, a benzyl group, a benzamyl group, an alkyl 2 group having 2 to 12 carbon atoms, and an alkyl group having 2 to 12 carbon atoms At least one of oxycarbonyl, phenoxycarbonyl or -OR8, -SR9, -SOR9, -S02R9 or -NRMR11, and R3, R4, R5, R6 and R7, representing _〇R8, -Sr9 or _NR^ R11. However, R8 is an alkyl group having 1 to 12 carbon atoms which may be substituted by a hydrogen atom, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, and an olefin having a carbon number of 3 to 6. Base, phenyl or -(CH2CH2〇) nH (n is a -15-(13) (13) 1343930 number) of 1 to 20, R9 is a hydrogen atom, Self-substituted alkyl group having 1 to 12 carbon atoms, alkenyl group having 3 to 12 carbon atoms or phenyl group, R1Q and R11 being independently hydrogen atoms, and alkyl groups each having 1 to 12 carbon atoms; a hydroxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or a phenyl group, and R 3 , R 4 , R 5 ' R 6 and R 7 may be bonded to each other to form a ring structure). The oxime ester compound itself is A known compound, for example, one of the series of compounds described in JP-A-2000-80068, and the above-mentioned oxime ester-based compound, the preferred substituent of the compound is as follows. R1: a carbon number of 1 to 10 which may be substituted, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and the like. It is preferably an alkyl group having 2 to 8 carbon atoms, more preferably 5 to 7 carbon atoms, particularly preferably a hexyl group. R2·· has an ethyl fluorenyl 'benzoyl' 4-methylphenyl fluorenyl group, a 4-chlorophenyl fluorenyl group, a 2'4'6-trichlorophenyl fluorenyl group or a 3-methylphenyl fluorenyl group. It is preferably an ethyl fluorenyl group, a benzoinyl group, and particularly preferably a benzoquinone group. R3 ' R6, R7: hydrogen atom R4: hydrogen atom or methoxy group R5: methyl thio group, phenyl thio group or 1,4-oxaza group R3, R4, R5, R6 and R7 may be bonded to each other The junction forming ring structure means that two or more of R3 to R7 are bonded to form a ring structure. Further, a specific compound, a combination of the substituents R1, R2, R4 and R5 is shown in Table 1 as shown in Table 1. Further, R3' R6 and R7 which are not described in Table 1 are all hydrogen atoms. Among the compounds in Table 1, 21 and 22 -16- (14) 1343930

Preferably, the compound of the number No., especially the compound of No. 2 is more preferred. [Table 1] Compound number R1- R2- R4- R5, 1 C2H5-CH3CO-H CHgS- 2 c2h5- C6H5C0-H CH3S- 3 c2h5- ch3co- H 1,4-oxaza- 4 c2h5- C6H5CO- H 1,4-oxaza5C2He-CHgCO-CH3O-CHaO-6 C2He-CbH5CO-CH3O-CH30- 7 c6h5- ch3co- H CHgS- 8 c2h5— ch3co- H CH3O- 9 c2h5— c6h5co- H CH3O- 10 C2Hs — ch3co— H c6h5s- 11 c2h5- CeHsCO- H c6h5s- 12 c2h5— 2.4,6-(CH3)3C6H2CO- H CH3S- 13 ch3- c6h5co- H ch3s- 14 n_C6H13 — CH3C0- .H ch3s- 15 n— C6H13 — c6h6co- H ch3s- 16 (CHa)3CCH2CH(CH3)- c6hbco- H ch3s- 17 (CHa) 3CCHzCH (CHa)-CH3CO- H ch3s— 18 n —C6Hi3—4CH3C6H4CO- H c6h5s- 19 n— C6H13 — 4 CIC6H4CO—H c6h5s- 20 n — C6H13 — 3-CH3C6H4CO- H c6h5s- 21 n—CeHl3 — C6H5C0-- H c6h5s- 22 n—C3H7 — ch3co- H ch3s- 23 η —〇3Η7 — ch3co- H C6HsS- 24 n —C3H7—CsH5C0- H CHgS- Other oxime ester compounds, the following general formulas (3), (4)

(.S -17- (15) 1343930 and (5) compounds.

(wherein R1, R2, R3, R4, R5, r6 and R7 are the same definitions in (2), and R4 to R6 are mutually bonded: Further, lanthanide, (^丨-C丨2 olefinic group) , cycloalkenyl group, (CO) o-(c2-c12 alkenyl)-O(CO)-, .ch2ch2o), -(CO)- or -(CO)-(c2-c12 form a ring structure with the above general formula Phenylene group, --(CO ) 0-(alkenyl)-( -18-(16) (16)1343930 CO ). Among the above-mentioned vinegar-based compounds, preferably the general formula (4) The mercaptoester-based compound, more preferably the substituent group of the oxime ester compound represented by the general formula (4), is as follows. R: an alkyl group having a carbon number of 1 to ί, which may be substituted, for example, a methyl group or an ethyl group. And propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, etc. Preferably, the carbon number is from 1 to 6, more preferably from 1 to 3, particularly preferably methyl. R2: an alkanoyl group or a benzamidine group having a carbon number of 2 to 10, an alkano group having a carbon number of 2 to 10, and, for example, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a amyl fluorenyl group, and a fluorene group Brewing base, octyl base, decanoic acid group, broth base, etc., preferably having a carbon number of 2 to 5, more preferably a carbon number of 2 to 3, especially Ethyl fluorenyl is preferred. R3 to R7: a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted, a fluorenyl group having 2 to 12 carbon atoms, a phenyl group, a benzyl group, a benzamidine group, or _NRMr11, R4 The R6 groups may be bonded to each other to form a ring structure, and r7 is preferably a hydrogen atom. Further, R3 and R7 are each a hydrogen atom, and at least one of R4, R5 and r6 is preferably -N R1QRH. Further, R3 and R7 are each a hydrogen atom, and at least one of R4, R5 and R6 is -NRMr11, and at least one of them is a substitutable phenyl group. In this case, it may be substituted with a phenyl group. a substituent, a phenyl group which may be substituted, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl fluorenyl group having 2 to 20 carbon atoms, a benzamidine group, and a carbon number of 2 to 12 Alkenyloxycarbonyl 'phenoxycarbonyl, decylamino or nitro. Preferred substituted benzamidine, more preferably toluene, especially o-toluene, preferably R4 to R6 are mutually bondable The ring structure formed by the knot and any one of 2 or more of R4 to R6 may be bonded to each other. Further, the ring structure may be an aromatic ring, a lipid (S) -19 - (17) 1343930, a aliphatic ring, or a heterocyclic ring. Any of the rings, preferably miscellaneous More preferably, it is preferably a heterocyclic atom of a 5-membered ring or a δ-membered ring, especially a heterocyclic 5-membered ring. Among the above-mentioned vinegar-based compounds, the following general formula (the vinegar-based compound which is indefinite) is preferred. 7)

(6) (wherein R1 is a substitutable carbon number of 1 to 1 alkyl group R2 is a substitutable carbon number of 2 to 10 alkyl fluorenyl group, benzamyl group, RlQ is a separate hydrogen atom, and each An alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or a phenyl group, and R1Q being an aromatic ring bonded to a bonded gas atom. One or one of the substituents or one of the carbon atoms of the aromatic ring may be bonded to form a ring structure, R12, R13, RM and R15, which may be mutually independent 'each substituted with a carbon number of 1 to 10, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl fluorenyl group having 2 carbon atoms, a benzhydryl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxy group, a decylamino group or a nitro group.) " In the compound, a preferred substituent of the compound is not Λ R1: an alkyl group having a carbon number of 1 to 10, for example, a methyl group, an ethyl group, each, and a carbon number may be further substituted with a phenyl group of -20 carbonyl groups. , C - 20 - 08) 1343930 pentyl, hexyl, heptyl, octyl, decyl, decyl and the like. More than -6, more preferably carbon number 〜3, particularly preferably methyl. 2 · "^τ •nj replaces alkane groups with a carbon number of 2 to 10, such as ethyl fluorenyl, propyl aryl, butyl ketone, pentylene, hexyl, decyl, decyl, fluorenyl, fluorene Stuffed base. It is preferably a carbon number of 2 to 5, more preferably a carbon number of 2 to 3, and particularly preferably an ethylene group.

Base, butyl, preferably carbon number 1

Rl〇: an alkyl group having 1 to 12 carbon atoms which may be substituted, for example, methyl, ethyl, propyl, butyl 'pentyl, hexyl, heptyl, octyl' fluorenyl, fluorenyl, eleven, ten Second base and so on. It is preferably a carbon number of 2 to 8, more preferably a carbon number of 2 to 6, and particularly preferably an ethyl group.

Rl2 R14 and R15: hydrogen atom

Rl3: a substituted benzamidine group, preferably a toluene group, and particularly preferably an ortho-methyl group. The compounds of the above general formulas (3), (4), (5) and (6) are also the same as the ones which are known per se, for example, in the publication of the Japanese Patent Publication No. 2 000-8 006 8 a compound of one kind. Further, the photopolymerization initiator of the present invention can be used alone or in combination with other photopolymerization initiators, and can be expected to have high sensitivity due to use. For example, the following compounds are mentioned. 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-s-three tillage, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethane) -s-triterpene, 2-(4-ethoxynaphthyl)6-bis(trichloromethyl)-s-trin, 2-(4-ethoxycarbonylnaphthyl)-4,6 - Halomethylated triterpene derivative of bis(trichloromethyl)-s-three tillage, 2-trichloromethyl-5-(2'-benzofuranyl)-1,3, -21 - (19) (19) 1343930 4-oxadiazepine, 2-trichloromethyl·5·[ P-( 2,-benzofuranyl)vinyl]-1,3,4-oxadiazepine, 2-trichloromethyl-5-[β-(2,-(6-benzofuranyl)vinyl)]-1 '3' 4 oxadiazepine, 2-trichloromethyl-5-furan Halomethylated oxydiazepine derivatives of the group -1 '3,4-oxadiazepine, 2-(2·-chlorophenyl)-4' 5-diphenylimidazole dimer, 2- (2·-Chlorophenyl)-4,5-bis(3,-methoxyphenyl)imidazole dimer, 2-(2·-fluorophenyl)-4,5·diphenylimidazole dimerization , 2·(2'-methoxyphenyl)-4' 5-diphenylimidate dimer, (4^methoxyphenyl)-4,5-diphenylimidazole dimer, etc. Imidazole derivative, rest Benzoyl methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, etc., benzoin acid, 2-methyl bacterium '2-ethyl bacterium' 2 - Diterpenoids such as dibutyl onion, 1-chloro onion, etc., benzanthrone derivatives, diphenyl hydrazine, rice egg '嗣 (Michlers ketone), 2-methyldiphenyl Diphenyl ketone derivatives such as ketone, 3-methyl-benzyl fluorene, 4-methyl-phenyl ketone, 2-chlorodiphenyl ketone, 4-bromodiphenyl ketone, 2-carboxydiphenyl ketone , 2,2-dimethoxy-2-phenylethyl benzene, 2' 2 -dimethoxy acetophenone, 1-hydroxycyclohexyl phenyl ketone, a-hydroxy-2-methyl phenyl ketone, 1-hydroxy-1-methylethyl-(P-isopropylphenyl)one, hydroxy-indole-(P-dodecyl)one, 2-methyl-(4'•(methylsulfide) Generation) phenyl)-2 - morpholino -I - propyl hydrazine, 1 ' 1 ' 丨 _ dichloromethyl-(P-butylphenyl) ketone, etc. Ketone (thioxanth〇ne), 2-ethylthioxanthene, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2.4-dimethylthioxanthone, 2, 4_2 Thioxanthone derivatives such as thioxanthone, 2,4-isopropylthiathione, P-dimethylaminobenzoic acid, E-22-(20) (20)1343930 vinegar, P-diethyl a benzoate derivative such as ethyl benzoate or an acridine derivative of 9-phenyl acridine '9-(p-methoxyphenyl) acridine or the like, 9,10-dimethyl A phenanthrene derivative such as benzphenazine, bis-cyclopentadiene-Ti-dichloride, bis-cyclopentadiene_Ti-bis-phenyl, bis-cyclopentadiene_Ti • bis-(2,3,4,5,6-pentafluorophenyl), bis-cyclopentadiene-Ti-bis-(2,3,5,6-tetrafluorobenzene-U-based), double -cyclopentadiene-Ti-bis-(2,4,6-trifluorophenyl-1-yl), bis-cyclopentadiene-Ti-2' 6-di-fluorophenyl-1-yl, bis- Cyclopentadiene-Ti-2,4-di-fluorophenyl-1·yl, bis-methylcyclopentadiene-Ti_bis-(2' 3,4,5,6-pentafluorobenzene-1- , bis-methylcyclopentadiene-Ti·bis-(^^di-fluorophenyl), bis-cyclopentadiene-Ti-2,6-di-fluoro-3-(pyrryl)丨 基 基 基 ti ti 基 基 -1- -1- -1- -1- -1- -1- -1- -1- -1- -1- ti -1- -1- ti 。. In addition to the above-described initiator component, the photopolymerizable composition of the present invention may further contain a sensitizing dye. It is preferred to add a sensitizing dye to the photopolymerization reaction under high light shielding. For example, the coumarin compound having a heterocyclic ring described in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. The benzoic acid ketocoumarin compound described in the Japanese Patent Publication No. Hei. ), a pyrromethene dye described in Japanese Patent Laid-Open Publication No. Hei 6-19240, Japanese Laid-Open Patent Publication No. SHO-47-252 No., No. Sho. 56- 1 6 6 1 54 and JP-A-59-56403 (p-dialkyl-23-(21)(21)1343930 benzylidene) ketone, benzene A base dye, a bismuth dye having a duralidyl group, and a diaminobenzene compound described in JP-A No. Hei 1-326624. Among these sensitizing dyes, an amine group-containing sensitizing dye and a diphenyl sulfonium pigment are particularly preferred. (d) Photopolymerizable monomer The photopolymerizable monomer of the present invention is one or more compounds having an ethylenically unsaturated group (hereinafter referred to as an ethylenic compound). Specifically, there are esters of aliphatic (poly)hydroxy compounds and unsaturated carboxylic acids, esters of aromatic (poly)hydroxy compounds and unsaturated carboxylic acids, unsaturated carboxylic acids and polyvalent carboxylic acids, and aliphatic polyhydroxy compounds. The obtained ester, an ethylene oxide of an aromatic polyhydroxy compound, an esterification reaction of a propylene oxide adduct with an unsaturated carboxylic acid, an ethylene oxide or a propylene oxide adduct of an aliphatic polyhydroxy compound, Esterification reactant of unsaturated carboxylic acid, ester of decarboxylated polyvalent alcohol and unsaturated carboxylic acid, reaction of polyvalent alcohol with polyvalent isocyanate and unsaturated carboxylic acid, styryl terminal compound, phosphoric acid a saturated compound, an adduct of a polyepoxy group and an unsaturated carboxylic acid, or the like, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, specifically, ethylene glycol diacrylate, triethylene glycol Alcohol diacrylate 'nepentanediol diacrylate, hexanediol diacrylate, trimethylolpropane tripropylene sulphuric acid vinegar, three methyl ketone triacetic acid vinegar, neopentyl alcohol dipropylene Acid ester, neopentyl alcohol triacrylate, neopentyl alcohol Acrylate, new < S > -24- (22) (22) 1343930 Acrylates such as pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerin acrylate, etc. The acrylate of the exemplified compound is substituted with a methacrylate of methacrylate, the same itaconate substituted with itaconate, a butenoate substituted with a butenoate or replaced by a horse. The acid maleate and the like. An ester of an aromatic polyhydroxy compound with an unsaturated carboxylic acid, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, isophthalic dimethyl propylene vinegar, caramel Discretion (pyrogallol) and so on. The ester obtained by esterification of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not a single substance, and specific examples thereof include a condensate of methacrylic acid, citric acid and ethylene glycol, and methacrylic acid. a condensate of maleic acid and diethylene glycol, a condensate of methacrylic acid, p-citric acid and neopentyl alcohol, a condensate of methacrylic acid, adipic acid, butanediol and glycerin, and the like. Other examples of the ethylenic compound used in the present invention, acrylamides such as ethylene bis acrylamide; allyl esters such as diallyl citrate; propylene-containing compounds such as dipropylene phthalate; Also useful. Preferred among the above-mentioned ethylenic compounds are (meth) acrylonitrile groups, and more preferably those having acryl fluorenyl groups. These compounds are trimethylolpropane triacrylate, trimethylolethane triacrylate, neopentyl alcohol diacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol Alcohol tetraacrylate, dipentaerythritol pentenoate, dipentaerythritol hexenoate, and the like. The amount of the photopolymerizable composition of the present invention is (b) is usually -25-(23) (23) 1343930 0. 1~50 with respect to 100 parts by weight of the organic binder (C) photopolymerization initiator. The photopolymerizable monomer is usually 0 to 200 parts by weight, preferably 3 to 180 parts by weight, based on parts by weight, preferably 1 to 45 parts by weight. Further, (the ochre color material is usually 30 to 70% by weight in the total solid content except for the solvent, preferably 3 to 65 % by weight. Further, the sensitizing dye, relative to (b) the organic binder 1 〇 The amount by weight of the ruthenium is usually from 30 to 30 parts by weight, preferably from 10,000 to 10 parts by weight. When the photopolymerization initiator is less than the above range, it is low in sensitivity, and it is defective in terms of work efficiency, and if it exceeds the above In the range, when the photopolymerizable monomer (ethylenic compound) is less than the above, the crosslinking density is lowered, and problems such as durability and heat resistance are likely to occur, and when it exceeds the above range, When the coloring material is less than the above range, the light-shielding property is lowered, so that it is difficult to form the resin BM having a sufficient optical density. Conversely, if it exceeds the above range, sensitivity, resolution, and development are required. The reduction in the properties and the like is severe, and the formation of the image is difficult. The photopolymerizable composition of the present invention is usually composed of (a) a ochre color material, (b) an organic binder (a carboxyl group-containing epoxy acrylate resin), c) a photopolymerization initiator (an oxime ester compound), and if necessary, (d) a photopolymerizable monomer (ethylenic compound) is dissolved in a solvent. The solvent can be used as a component of the composition. It is preferred to dissolve or disperse, and it is preferred to select a boiling point of from 1 〇〇 to 200 ° C. More preferably, it has a boiling point of from 120 to 170 ° C. These solvents are, for example, ethylene glycol monomethyl ether, ethylene Alcohol monoethyl-26- (24) (24) 1343930 ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol third Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3 - ethylene glycol monoalkyl ethers such as methyl-3-methoxybutanol and tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, two Ethylene glycol dialkyl ethers such as ethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc.; ethylene glycol monomethyl ether acetate, ethylene Monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, dipropylene glycol Ethylene glycol acetate, 3-methyl-3-methoxybutyl acetate, etc.; ethylene glycol alkyl ether acetate; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentane An ether such as an alkyl ether, ethyl isobutyl ether or dihexyl ether; acetone, methyl ethyl ketone, methyl pentanone, methyl isopropyl ketone, methyl isoamyl ketone, and Ketones such as isobutyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl pentanone, methyl butyl ketone, methyl hexyl ketone, methyl decyl ketone; ethanol, propanol a monovalent or polyvalent alcohol such as an alcohol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol or glycerin; n-pentane, n-octane, diisobutylene, n-hexane, hexane Aliphatic hydrocarbons such as isoprene, dipentene, dodecane, etc.: Cyclohexane, methylcyclohexane, methylcyclohexene, dicyclohexyl, etc. -27- (25) (25 ) 1343930 Cyclic hydrocarbons: benzene Aromatic hydrocarbons such as toluene, xylene, cumene, etc. amyl formate, ethyl formate, ethyl acetate butyl acetate, propyl acetate, amyl acetate, ethylene glycol acetate Ester, ethyl propionate, propyl propionate, butyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl octanoate, propyl stearate, ethyl benzoate , methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate , chain or cyclic esters such as ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; 3-methoxy Alkoxycarboxylic acids such as propylpropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and pentyl chloride: ether ketones such as methoxymethylpentanone: acetonitrile, benzonitrile, etc. Nitriles; should be in the above solvents, mineral spirit, Barsol #2, APCO #1 8 Solvent, APCO thinner (thinner), Solcal dissolve No.l and N0.2, Solbeso #150 , Shell TS28 solvent, carbiol, ethyl carbitol, butyl carb (Carbital), methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, as Diglyme the trade names of commercially available products. These solvents may be used singly or in combination of several. Further, the photopolymerizable composition of the present invention is preferably a solvent which has a solid content concentration of 5 to 50% by weight, preferably 1 to 30% by weight, based on the solvent. -28- (26) (26) 1343930 In the present invention, these essential components (a), (b), and (c), can be added to the optional component (d), and a pigment dispersant can be appropriately added. , adhesion improver, coating improver, development improver, and the like. In particular, in the composition of the present invention, the ochre color material is finely dispersed and stabilized in a dispersed state, and it is important in quality stability. Therefore, it is desirable to blend a pigment dispersant. a pigment dispersant, a (a) ochre color material, and (b) an organic binder, both having affinity, a nonionic, cationic, anionic surfactant, a polymer dispersant, etc., wherein the polymer is dispersed Preferably, the polymer dispersant having a basic functional group, such as a primary, secondary or tertiary amine group, a pyridine, a pyrimidine, a pyrazine or the like, may be advantageously used. use. (e) As a polymer dispersing agent having a basic functional group, a preferred chemical structure, for example, a polyisofluoric acid ester compound, a compound having one or two hydroxyl groups in the molecule, and an active molecule in the same molecule are specifically exemplified. A dispersion resin obtained by reacting hydrogen with a compound of a tertiary amino group. Examples of the above polyisocyanate compound include p-phenylene diisocyanate, 2'4-benzylidene isocyanate, 2,6-benzylidene diisocyanate, 4,4^diphenylmethane diisocyanate, naphthyl-1, An aromatic diisocyanate such as 5-diisocyanate or tolidine diisocyanate, hexylene diisocyanate, lysine methyl diisocyanate, 2,4,4-trimethylhexylene diisocyanate, Aliphatic diisocyanate such as dimer acid diisocyanate, isophorone diisocyanate _, 4,4·-methylene bis(cyclohexyl isocyanate), ω, diisocyanate dimethyl ring-29 - (27) 1343930 alicyclic diisocyanate such as hexane, phenyldimethyl diisocyanate, α,, α,-tetramethyl benzene diisocyanate, etc. having an aromatic diisocyanate, lysine Acid ester triisocyanate, 1 '6 alkyl triisocyanate, 1,8-diisocyanate-4·isocyanate methyl: 3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate isocyanate phenylmethane), tris(isocyanate) Phenyl) thio ( ) phosphate, etc. Isopropyl ester atmosphere, and terpolymers of such 'adducts of such polyhydric alcohols, and water (polyol). Polyisocyanate A terpolymer of an organic diisocyanate, preferably a trimer of a benzylidene diisocyanate and an isophorone diisocyanate, which may be used alone. A method for producing an isocyanate trimer, wherein the polyisocyanate is subjected to isocyanic acid using an appropriate trimerization catalyst, for example, a tertiary amine, a phosphine metal, a metal oxide, a carboxylate or the like. Trimerization, a method of removing a polyisocyanate after the trimerization is stopped by solvent extraction and thin film distillation to remove the isocyanurate cyanate ester of the target product by the addition of a catalytic poison. a compound having one or two hydroxyl groups in the same molecule, ethylene glycol, polyester glycol, polycarbonate ethylene glycol, polyolefin, and one of the compounds having a terminal hydroxyl group of 1 to 25 carbon atoms A base material and a mixture of the two or more types. Polyether glycols, polyether diols, polyether ester diols, and mixtures of the above. The polyether diol is a single vinegar, α,α: alicyclic grease, 11-fluorene-based octane, 1 ester, and tris(phosphate. adduct, ester, preferably ester) Separately used, cyanate esters, alkoxy ester groups, and vice versa, and obtained polyisomeric, polyether glycol or the like, such as two kinds of mono- or copolymerization -30- (28 (28) 1343930 The obtained product, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyethylene diol, polyoxyoctanediol, and the like a mixture of a polyether ester diol, a mixture of an ether group-containing diol or another ethylene glycol, and a dicarboxylic acid or an anhydrate thereof, or a reaction of the epoxide in a polyester glycol. Such as poly(polyoxytetraethylene) adipate, etc. Polyether glycol, preferably polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or one of the compounds The hydroxyl group is a compound which is alkoxylated with an alkyl group having 1 to 25 carbon atoms. Polyethylene glycol has a dicarboxylic acid (succinic acid, glutaric acid, adipic acid, Diacid, fumaric acid, maleic acid, citric acid, etc.) or such anhydrates and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, Tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1, 5-pentanediol, neopentyl Glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5- Pentyl glycol, 1 '6-hexanediol, 2-methyl-2,4-pentanediol, 2' 2,4-trimethyl-1,3-pentanediol, 2-ethyl-1, 3-pentanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octanediol, 2-methyl-, 8-octanediol, hydrazine, 9-decanediol An aliphatic diol such as an aliphatic ethylene glycol or a bishydroxymethylcyclohexane, an aromatic diol such as benzodimethyl glycol or bishydroxyethoxybenzene, or N-methyldiethanolamine The N-alkyl dialkanolamine or the like obtained by condensation polymerization, for example, polyethylene adipate, polybutylene adipate, polyhexene adipate, polyethylene/propylene adipate Etc. or the aforementioned diol Or a polyvalent lactone diol or a polylactone monool, such as polycaprolactone diol or polymethyl pentene, having a carbon number of 1 -31 - (29) (29) 1343930 to 25 valent alcohol as an initiator. a lactone (valerolactone) and a mixture of two or more of them. The polyester diol is preferably a polycaprolactone diol or a polycaprolactone having a carbon number of 1 to 25 as an initiator. Poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate, etc., polyolefin diol having polybutadiene diol, hydrogen addition type polybutadiene A diol, a hydrogen-added polyisoprene (isoprene) diol, or the like. The number average molecular weight of one or two hydroxyl compounds in the same molecule is from 300 to 10,000, preferably from 500 to 6,000, more preferably from 1,000 to 4,000. The compound having active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. An active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, a hydrogen atom in a functional group having a hydroxyl group, an amine group, a thiol group, or the like, wherein an amine group, especially The hydrogen atom of the amine group of the first order is preferred. The tertiary metal group is not particularly limited. Further, the tertiary amino group is an amine group having an alkyl group having 1 to 4 carbon atoms or a heterocyclic ring structure, more specifically, an imidazole ring or a triazole ring. Examples of the compound having an active hydrogen and a tertiary amino group in the same molecule are as follows, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, Ν ' N -Dipropyl-1,3-propanediamine, N,N-dibutyl-1 '3-propanediamine, Ν' Ν-dimethylethylenediamine, hydrazine, hydrazine-diethyl Ethylenediamine, hydrazine, hydrazine-dipropylethylenediamine, Ν' Ν-dibutylethylenediamine, hydrazine, hydrazine-dimethyl-1,4-butanediamine, hydrazine, hydrazine-diethyl- 1,4-butanediamine, hydrazine, hydrazine-dipropyl-1,4-butanediamine, Ν' Ν-dibutyl hydrazine, 4-butanediamine, and the like. -32- (30) (30) 1343930 Further, the tertiary amine group is a nitrogen-containing heterocyclic ring, and then has a pyrazole (pyraz〇ie) ring, an imidazole ring, a triazole ring, a tetrazole ring, an anthracene ring, and a carbazole. (carbazole) ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzosoxadiazole ring, etc. Steep ring, pyridazine ring, mute steep ring, Sanxiao ring 'quinoline ring' acridine ring, isoquine ring, etc. containing N hetero 6 ring. The nitrogen-containing heterocyclic ring is preferably an imidazole ring or a triazole ring. Such compounds having an imidazole ring and an amine group, specifically exemplified by 1-(3-aminopropyl)imidazole, histizine, 2-aminoimidazole, 1·(2-aminoethyl) Base) imidazole and the like. Further, a compound having a triazole ring and an amine group, and specifically exemplified is 3-amino-1,2,4-triazole, 5-(2-amino-5-arylphenyl)-3-phenyl -1Η-1,2,4-diindole, 4-amino-4Η-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1Η-1,3 , 4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1Η-2,4-triazole, and the like. Wherein, hydrazine, hydrazine-dimethyl-1,3-propanediamine, hydrazine, hydrazine-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino group -1,2,4-triazole is preferred. The preferred blending ratio of the dispersant raw material is 100 parts by weight of the polyisocyanate compound, and the average molecular weight of the compound having 1 or 2 hydroxyl groups in the same molecule is 300 to 1 Å, and the compound of hydrazine is 1 〇 2 〇〇. The compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 18 parts by weight. Share. (e) The GPC conversion weight of the polymer dispersing agent having a base functional group is -33-(31)1343930. The average molecular weight is 〇〇〇~200,000, preferably 2,000~, more preferably 3,000~50,000. . The molecular weight of 1,000 is poor and the dispersion stability is poor, the solubility is lowered at 200,000 or more, and the control of the reaction is difficult, and the production of the polymer dispersant is carried out by a known method for producing a polyurethane resin. A solvent is usually produced, and a ketone such as acetone, methyl ethyl ketone, methyl isobutyl pentanone, cyclohexanone or isophorone, or an ester such as ethyl acetate, ethyl acetate or cellosolve acetate is used. Benzene, toluene 'xylene, hexane, diacetone alcohol, isopropanol, second butanol, third butanol, etc., methylene chloride, chloroform, etc., tetrahydrofuran, two An aprotic polar solvent such as an ether such as ethyl ether, an aprotic polar solvent such as dimethylformamide pyrrolidone or dimethyl sulfoxide, or the like, is usually a urethane catalyst. For example, dibutyltin dilaurate, dioctyltin divalent, dibutyltin octoate, stannous octoate, etc., tin, iron ethoxide, iron chloride, etc., triethylamine, triacetate The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably in the range of 1 to 100 mg KOH/g of the amine after the reaction. More preferably, it is in the range of 5 to 9 5 mg KOH/g. The amine valence is neutralized by titration with the acid, and is shown by the mg corresponding to the acid oxime. When the amine value is less than the above range, the dispersibility tends to decrease, and if it exceeds the above range, the developability tends to decrease. In the case where the isocyanate group remains in the polymer dispersant as described above, the chlorination and N-methylation reaction of the alcohol in the hydrocarbon portion such as ketone or butyl ketone are dispersed and dispersed in accordance with 100,000. The third-order introduction control of citrate-based acetic acid is lower than that of the basic amine, and the reaction is stabilized by the reaction of the isocyanate group with an alcohol or -34-(32)1343930 amine compound. Gao is good. Further, in the case of using a polymer dispersant, the use ratio thereof is preferably 0.1 to 30% by weight, particularly preferably 0.5 to 5% by weight, based on (a) the ochre color material. Next, a method for producing the photopolymerizable composition of the present invention will be described. In the invention, it is preferred that the ochre color material is previously subjected to dispersion treatment using a brush conditioner, a sand filter, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. By dispersing the color material to be finely divided, the light-shielding ability of the resist can be improved and the coating property can be improved. In the dispersion treatment, the coloring material has a binder with a solvent or a dispersing function, or the pigment dispersing agent is further In the system to be used, it is better to handle it. In particular, when a polymer dispersant is used, it is preferred because it has excellent stability over time. Further, when the entire composition of the resist liquid is blended, the dispersion treatment under the mixed liquid and the heat generated during the dispersion cause degeneration of the reactive component, which is not preferable. In the case of dispersing in a sand grinder, glass beads (bead) or zirconia having a diameter of 0.1 to 8 mm can be suitably used. The conditions for dispersion, usually, the temperature is in the range of 〇 ° C to 100 ° C, preferably from room temperature to 80 ° C. The dispersion time can be adjusted according to the composition of the ink (color, solvent, dispersant) and the size of the sander, etc., and the gloss of the ink can be adjusted to make the 20 degree of the resist in the 100~ The scope of 200, the goal of dispersion. When the resist gloss is lowered, the dispersion treatment is not enough to have the residual of the coarse pigment particles, and the image is changed to 25. The int 黒 U U Uik 怀 散 同 的 的 的 的 - - - - - - - - - - - - - - - - - - - - - - - 33) 1343930, adhesion, resolution, etc. are not sufficient. Further, when the dispersing treatment is carried out, the gloss 値 exceeds the above range, and most of the ultrafine particles are generated, which in turn tends to impair the dispersion stability. Next, the ochre ink and the resist component obtained by the above dispersion treatment can be added and mixed with the above-mentioned other components to form a homogeneous solution. In the manufacturing step, fine dust is often mixed in the photosensitive liquid, so that the resulting resist photosensitive liquid is subjected to filtration treatment by a filter or the like. Next, a method of producing a color filter using the photopolymerizable composition of the present invention will be described. First, the photopolymerization of the present invention is carried out on a transparent substrate by a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, a sprayer or the like. After the composition is applied and dried, a photomask is placed on the sample, and the image is exposed and developed by the mask, and a BM image for shading is formed by heat hardening or light hardening as needed. This operation is repeated for each of the RGB 3 colors to form a color filter image. Further, in the case where the photopolymerizable composition of the present invention is used to form a color filter pixel, since it has a very high sensitivity and a high resolution, exposure and development can be performed without forming an oxygen barrier layer such as polyvinyl alcohol. portrait. The transparent substrate and the transparent substrate for a color filter used herein are not particularly limited, and examples thereof include polyester such as polyethylene terephthalate or polyolefin such as polypropylene or polyethylene, and polycarbonate. , Thermoplastic plastic sheets such as polymethyl methacrylate, poly-rolling, thermosetting plastic sheets such as epoxy resin 'polyester resin, polymethacrylate resin, or various glass plates. In particular, in terms of heat resistance, it is preferable to use a glass plate or a heat-resistant plastic -36- 1343930, a pre-acid, a non-acid, a 0.1, a base method, or a thick coating agent. . After the symmetry of the condensate, the color of the surface, the membrane 黒 薄 薄 薄 之 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改 改The coating is equal to the smear, and the electricity is determined to be in the range of 2, η, preferably 0, 1 to 1 , 5 μηη, more preferably 0.1 to Ι μηι. Further, the color filter of the present invention is preferably one having a light-shielding property of 1 μm and an optical density of 3.0 or more. Further, it is advantageous to use a dispersion state of a solid component such as a pigment as an index, and a 度20 degree gloss 値 of 1 〇〇 to 200. A hot plate, an IR oven, a convection oven, or the like may be used for drying, preferably in a drying condition of 40 to 150 ° C and a drying time of 10 to 00 minutes. And light source for exposure, for example, gas lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, etc. or argon ion laser, YAG laser, excited state A laser source such as an excimer laser or a nitrogen laser. An optical pulverizer can be utilized where only a particular illumination light wavelength is used. The developing treatment is not particularly limited as long as it is a solvent for dissolving the resist film in the unexposed portion. For example, an organic solvent such as acetone, dichloroethylene, tricholene or cyclohexanone can be used. However, it is preferred that the organic solvent is environmentally polluting, harmful to humans, fire hazard, etc., and it is preferable to use such a non-hazardous alkaline developing solution. Such basic imaging liquids, for example, inorganic alkaline agents such as sodium carbonate, potassium carbonate, sodium citrate, potassium citrate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethanolamine, hydroxylated-37- (35) (35)! 343930 A tetraalkylammonium salt or the like containing an aqueous solution of an organic alkaline agent. In the alkaline developing solution, it may be necessary, including a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxyl group, and the like. In particular, the surfactant has an improved effect with respect to development, resolution, texture contamination, etc., so that it is preferably added. For example, a surfactant for a developing solution, an anionic surfactant having a naphthylsulfonate-based sodium group, a sodium phenylsulfonate group, a polyalkyloxy group-containing nonionic surfactant, and a tetraalkyl group. An ammonium-based cationic surfactant or the like. There is no particular limitation on the development processing method, and usually, at a temperature of 10 to 50 ° C, preferably at a temperature of 15 to 45 ° C, clarification, spray imaging, and brush imaging. , ultrasonic imaging and other methods to carry out. Next, a liquid crystal display device (panel) of the present invention will be described. The liquid crystal display device of the present invention is characterized by the use of the above-described color filter. Therefore, it can be manufactured in the following manner. First, an alignment film is formed on a color filter, and a spacer is placed on the alignment film, and then bonded to the opposite substrate to form a liquid crystal cell. Next, liquid crystal cells are injected into the formed liquid crystal cell, and the alignment is completed with the counter electrode. The alignment film and the resin film such as polyamine are suitable. The formation of the alignment film is usually carried out by a gravure printing method or an flexography printing method, and usually, the thickness of the alignment film is 〜1 〇〇 nm. After the orientation film hardening treatment by the thermal calcination, the surface treatment by the ultraviolet irradiation or the lapping coating treatment is performed on the surface state in which the liquid crystal is tilted. The spacer is preferably used in accordance with the interval (cap) of the counter substrate (gap -38-(36) (36) 1343930), usually 2 to 8 μm. On the substrate of the color filter, a photo spacer (PS) of a transparent resin film is formed by a photolithography method, and the spacer can be used instead. It is appropriate to use an (array) substrate, in particular, a TFT (thin film transistor) substrate for a counter substrate. The interval to be bonded to the counter substrate is different depending on the use of the liquid crystal display device, and a range of 2 to 8 μm is usually selected. After bonding to the counter substrate, the portion other than the liquid crystal injection D is sealed with a sealing material such as an epoxy resin. The sealing material is hardened by UV irradiation and/or heating and sealed around the liquid crystal cell. After the liquid crystal cell sealed in the periphery is cut by the panel, decompressed in the vacuum reaction chamber, and the liquid crystal injection port is immersed in the liquid crystal, "the liquid crystal is injected into the liquid crystal cell by leakage in the reaction chamber." The degree of decompression in the liquid crystal cell is usually lxl (Γ2 to lxlO'7Pa, preferably lxl0.3~lxl〇-6Pa. Further, when the pressure is reduced, the liquid crystal cell is preferably heated, the heating temperature is It is usually 30 to 10 ° C, preferably 50 to 90 ° C, and is heated at a reduced pressure, usually in the range of 10 to 60 minutes, and thereafter immersed in a liquid crystal. The liquid crystal display device (panel) can be completed by curing the UV-curable resin, and the liquid crystal injection port can be sealed. The liquid crystal type is not particularly limited, and may be an aromatic system, an aliphatic system, a polycyclic compound, or the like. Any known liquid crystal, lyotropic liquid crystal, or thermal liquid crystal, etc. In a thermaltropic liquid crystal, nematic liquid crystal, smectic The liquid crystal, the cholesterol phase (ch〇resteric) liquid crystal, etc. are known as -39-(37)1343930, and one of these may be selected. [Embodiment] [Examples] Hereinafter, the details will be described in more detail with reference to examples and comparative examples. In the scope of not exceeding the gist of the present, it is not limited to Synthesis Example-1 (polymer Preparation of powder solution) Terpolymer of benzylidene diisocyanate (Mitsubishi Mytec GP75 0A, resin solid content 50% by weight 'B 3 2 g and dibutyl tin dilaurate as catalyst 〇. 〇 2g ether acetate (PGMEA) Diluted and dissolved at 47g. The number of methoxy groups at the end of the stirrer is 1,000, and the average molecular weight is 1,000. UNIOXM-1000) 1 4.4 g with Huo, propylene glycol (Sanyo Chemical Industry Co., Ltd. 1 000) After the titration of 9.6 g of the mixture was carried out at 70 ° C. Then, N,N-dimethylamino-1,3 - ί 4 〇 ° C was added to further react for 1 hour. The thus obtained high-liquid fraction was obtained. The amine valence was determined by neutralization titration to obtain 14 mg. The resin content was determined by a dry up method (clock, the solvent was removed on a hot plate, and the weight change was 40% by weight. Synthesis Example-2 (Synthesis of Organic Bonding Material) Invention, but the example of the present invention. 匕 公司 公司 酸 酸 酸 在 在 在 在 在 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙 丙SUNIKSPP - in turn, the reaction 3 is diamine, 1 g, dissolved in the dispersant KOH/g. Further, 1 50 〇C, 30 points of resin concentration) -40 - (38) (38) 1343930 Ethylene phenol varnish ring with epoxy equivalent of 200g/eq and softening point of 65 °C 200 g of oxyresin, 72 g of acrylic acid, 0.2 g of p-methoxyphenol, 0.2 g of dodecyltrimethylammonium chloride, and 272 g of PGMEA were placed in a flask, and reacted at a temperature of 1 Torr for 8 hours (relative to epoxy group 1). Equivalent, 1 equivalent of acrylic acid is reacted). Further, 42 g of tetrahydrophthalic anhydride was added and reacted at 80 ° C for 3 hours. The reaction solution was again poured into water and vacuum dried to obtain a powdery aldehyde varnish epoxy acrylate resin. Neutralization titration by KOH The acid hydrazine of the resin was 50 mg KOH/g. Synthesis Example-3 (Synthesis of Organic Binding Material) The reaction was carried out in the same manner as in Synthesis Example 2 except that the amount of tetrahydrophthalic anhydride added was 63 g. The obtained resin strontium was 70 mg KOH/g. (Dispersion of carbon black) 50 parts by weight of the carbon black (manufactured by Mitsubishi Chemical Corporation, MA-220), and the polymer dispersant represented by Synthesis Example-1 is a ratio of 5 parts by weight of the solid component, and the solid content concentration is Carbon black, a polymer dispersant solution, and PGMEA were added in an amount of 50% by weight. The total weight of the dispersion was 50 g. Premixing is carried out by stirring it with a mixer. Then, dispersion treatment was carried out for 6 hours in a range of 25 to 45 ° C by a Paint shaker. The beads were made of 55 mm 0 鍩 oxygen beads, and the same weight as the dispersion was added. After the dispersion is completed, the beads are separated from the dispersion by a filter. -41 - (39) 1343930 . Examples 1 to 3 and Comparative Examples 1 to 3 ' (1) Preparation of resist liquid * Using the carbon black dispersion ink described above, each component (a), (b), ( c), (d), (e), an organic solvent, and a surfactant adjust the black resist photosensitive liquid by setting the solid content to the blending ratio described below, stirring and dissolving by a stirrer. (a) Green color material 50g ® carbon black (Mitsubishi Chemical Co., Ltd. 'MA-220) 30g (b) Organic binder (described in Table 2) ^ (d) Photopolymerizable monomer: ethylenic compound l〇g Dipentaerythritol hexaacrylate (c) Photopolymerization initiator (described in Table 2) Organic solvent ^ Propylene glycol monomethyl ether acetate 3 00 g (e) Polymer dispersant (Synthesis Example-1) 5 g Interface activity Agent (manufactured by Sumitomo 3M Co., Ltd., FC-430) lOOppm (2) Evaluation of resist The black resist photosensitive liquid was applied to a glass substrate (manufactured by Corning, Inc., 7059) in a spin coater, and dried on a hot plate. 80 ° C, 1 minute. The thickness of the resist film after drying was 1 μm by a stylus film thickness meter (manufactured by Tencor Co., Ltd., α-step). Next, the sample was exposed to light by a mask using a high pressure -42-(40) (40) 1343930 mercury lamp to change the exposure. A resist pattern was obtained by spray development using a sodium carbonate aqueous solution having a temperature of 25 ° C and a concentration of 0.8%. The sensitivity, the resolution, and the light-shielding property were evaluated by the following criteria, and the results of Table 2 were obtained. 1. Sensitivity The mask pattern of 20μηι is expressed by a suitable amount of exposure (mj/cm2) formed by size. In other words, since the resist having a small exposure amount can form an image at a low exposure amount, it is displayed as high sensitivity. 2. Resolution The 顕 micromirror was observed at a magnification of 200 times in the minimum pattern size of the solvable resist in the exposure amount which faithfully reproduced the 20 μm mask pattern. The minimum pattern size is ΙΟμπι or less, and the resolution is more than 〇, 1〇μηι is indicated by X. 3. Light-shielding The optical density (OD) of the line portion was measured by a Macbeth reflection densitometer (Gretag Macbeth (formerly Komolgun), TR 9 2 7). Further, the OD system indicates that the number of light-shielding capabilities is high, and the higher the light-shielding property. (S > -43- (41) (41) Ϊ 343930 [Table 2] (b) Organic binder (C) Photopolymerization initiator sensitivity resolution light-shielding property mj/cm2 Example 1 Synthesis Example 2 C-1 40 〇3.5 Example 2 Synthesis Example 3 C-1 50 〇 3.5 Example 3 Synthesis Example 3 C-4 30 〇 3.5 Comparative Example 1 Synthesis Example 2 C-2 100 〇 3.5 Comparative Example 2 a-1 C-1 150 X 3.5 Comparative Example 3 Synthesis Example 2 c-3 200 〇3.5 Further, the meanings of the symbols in Table 2 are as follows: a-1: propylene polymer (manufactured by Daicel Chemical Industry Co., Ltd., ACA-200M) c-1: photopolymerization initiator ( Chiba Special Chemicals Co., Ltd., CGI-124).........(5g) -44- (42)1343930

【化8】

C-2: 4-(m-bromo-p-methoxyphenyl)-2,6-di(trichloromethyl)-s-triazine... (5 g ) c-3 :2,2'-bis(o-chlorophenyl)-4,4' 5,5'-s tetraphenyldiimidazole (2g) deca 4,4'-bis(diethylamine)diphenyl ketone ( Lg) Dec-2-thiothiabenzothiazole (1 g )

C-4: Photopolymerization initiator (manufactured by Chiba Special Chemicals Co., Ltd., CGI-242) ... (5 g ) [Chem. 9]

(S) -45- (43) (43) 1343930

Industrial Applicability The photopolymerizable composition of the present invention and a color filter using the same can be used for a color television, a liquid crystal display element, a solid-state imaging device, a camera, and the like. -46 -

Claims (1)

V * Patent Application No. 095M6906, Revision of Chinese Patent Application Scope; • Amendment of the Republic of China on February 1st, 100. Patent Application No. 1. A photopolymerizable composition containing (a) a twilight color material, (b) an organic binder and (c) a photopolymerizable composition of a photopolymerization initiator, characterized in that (b) the organic binder is an epoxy acrylate resin having a carboxyl group' (c) a photopolymerization initiator The compound of the oxime ester compound represented by the formula (6) (wherein R1 is an alkyl group having 1 to 10 carbon atoms which may be substituted, R2 is an alkanoyl group having 2 to 10 carbon atoms which may be substituted, and a benzhydryl group, and rIQ independently represents a hydrogen atom, each of which is replaceable The alkyl group having a carbon number of 1 to 12, the base group having a carbon number of 2 to 4, the susceptor having a carbon number of 3 to 5 or a phenyl group, and the r 1Q system may also be a nitrogen atom bonded via R 1 〇. It is bonded to one of the bonded aromatic rings or one of the further substituents or one carbon atom of the aromatic ring to form a ring structure. R12, R14 and R15 are hydrogen atoms, and R13 represents a replaceable benzene.醯基). 2. The photopolymerizable composition according to claim 1, wherein the photopolymerizable composition further contains (d) a photopolymerizable monomer. 3. The photopolymerizable composition of claim 1 or 2 wherein the photopolymerizable composition further comprises (e) a 1343930 polymer dispersant having a basic functional group. . 4. The photopolymerizable composition of claim 2 or 2, wherein (b) the organic binder is a reaction product of a novolac type epoxy resin and (meth)propionic acid; Epoxy acrylate obtained by the reaction of hydrogen) phthalic anhydride. A color filter comprising a black matrix formed of the photopolymerizable composition according to any one of claims 1 to 4, which is a transparent substrate. 6 - A liquid crystal display device which is formed by using a color filter of the fifth application of the patent application. [S] -2-