JP4442710B2 - Photopolymerizable composition, color filter and liquid crystal display device - Google Patents

Description

  The present invention relates to a photopolymerizable composition for a color filter used in the production of an optical color filter used for a color television, a liquid crystal display element, a solid-state imaging device, a camera, and the like, and a color filter obtained from the composition, Specifically, the photopolymerizable composition for a color filter suitable for the production of a black matrix (hereinafter abbreviated as BM) that has high light-shielding properties but high sensitivity and excellent resolution, and high accuracy and high light-shielding properties. The present invention relates to a color filter having a functional resin BM.

  A color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic sheet, and then sequentially applies three or more different hues such as red, green and blue in a striped or mosaic shape. It is formed with a color pattern. The pattern size varies depending on the use of the color filter and each color, but is about 5 to 700 μm. Further, the positional accuracy of superposition is several to several tens of μm, and is manufactured by a fine processing technique with high dimensional accuracy.

  Typical methods for producing a color filter include a dyeing method, a printing method, a pigment dispersion method, and an electrodeposition method. Among these, in particular, a pigment dispersion method for forming a color filter image by coating a photopolymerizable composition containing a color material on a transparent substrate and repeating image exposure, development, and curing as necessary is a color filter. It is widely used because it has high accuracy such as pixel position and film thickness, excellent durability such as light resistance and heat resistance, and few defects such as pinholes.

  BMs are generally arranged in a grid, stripe, or mosaic between red, green, and blue color patterns, and thin film transistors (Thin Film Transistors) that improve contrast by suppressing color mixture between colors or leak light. : TFT) to prevent malfunction. For this reason, the BM is required to have high light shielding properties. Conventionally, BM is generally 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 through a photolithography process. Therefore, a high light-shielding property can be obtained with high accuracy with a thin film thickness. On the other hand, it has a long manufacturing process, low productivity and high cost, and has problems such as environmental problems caused by waste liquid of etching treatment.

  For this reason, a method for forming a low-cost, pollution-free resin BM with a photosensitive resin in which a light-shielding pigment or dye is dispersed has been energetically studied. However, since the resin BM has problems as described later, it has not been put into practical use yet. In the resin BM, in order to develop a light-shielding property (optical density) equivalent to that of a BM made of a metal film such as chromium, it is necessary to increase the content of light-shielding pigments and dyes or to increase the film thickness. There is.

  In the method of increasing the film thickness, the flatness of the RGB colored pixels formed thereon is impaired due to the influence of the unevenness of the BM. For this reason, non-uniformity of the liquid crystal cell gap or disorder of the alignment of the liquid crystal occurs to cause a reduction in display capability. In addition, problems such as disconnection of the transparent electrode ITO (indium tin oxide) film provided on the color filter (breakage of the planar film) occur.

  In addition, in the method of increasing the content of light-shielding pigments and dyes, there is a problem that the sensitivity, developability, resolution, adhesion, etc. of the photosensitive resin (black resist) deteriorate, and only a decrease in productivity. Therefore, the accuracy and reliability required for the color filter cannot be obtained. That is, since a photosensitive material that can exhibit sensitivity and resolution under conditions of a thin film and high light-shielding properties has not been realized, the practical use of the resin BM is hindered.

  Conventionally, a technique for improving sensitivity and resolution performance is known for a general photosensitive resin or a photosensitive resin having a certain light transmittance such as a colored photosensitive composition for a color filter. For example, a photosensitive composition containing an initiator composed of a binder resin, a polyfunctional acrylic monomer, and a triazine compound is known as a coloring composition for a color filter in which a pigment is dispersed (see Patent Documents 1 to 4). In addition, it is also known that the initiator is bisimidazole in the same composition (see Patent Documents 5 to 6). However, in the case of the compositions disclosed therein, the polymerization inhibition by oxygen occurs when exposed in air. Therefore, practical sensitivity could not be obtained.

  When light blocking capability is required in the entire wavelength region of light as in the case of resin BM, (1) it is extremely difficult to make a difference in crosslink density between the exposed portion and the unexposed portion, and (2) the exposed portion. However, there is a difference in crosslink density with respect to the film thickness direction. That is, even when sufficiently cured on the light-irradiated surface, it does not cure on the base surface. (3) To blend a large amount of black color material insoluble in the developer. This is a hindrance in imparting significant photosensitivity such as a significant decrease in developability.

  In particular, the above phenomena (1) and (2) are contradictory, and as the exposed portion is more cured, the difference in the curing density in the film thickness direction becomes larger, leading to lower resolution. Further, if the difference in cross-linking density between the exposed area / unexposed area and the cured density of the exposed area cannot be made uniform, it becomes difficult to use a developing solution having a strong dissolving power, so that it is difficult to improve developability. Conventionally known photosensitive compositions for forming a resin BM (see, for example, Patent Documents 7 to 8) avoid such a situation, and form a resin BM that can shield light at the same level as a metal BM. Instead, the light was transmitted to some extent to give a photosensitive ability, and the light shielding ability was remarkably low, which was not practical. For this reason, a resin BM having a high light-shielding degree with a thin film has also been proposed due to film shrinkage in the curing process after once forming a resin BM having a high film thickness and low light-shielding properties (see Patent Document 9). However, it is difficult to put it into practical use due to problems such as the complexity of adhesion and the decrease in adhesion due to strain accumulation during film shrinkage. Thus, due to the seemingly contradictory problem of causing a photoreaction under the condition of light shielding, which is inherently opposite to the photoreaction, it has been difficult to realize a practical resin BM.

  Moreover, although the technique which uses a specific oxime ester compound as a photoinitiator is known (refer patent document 10), the initiator (for example, bisimidazole and a triazine type | system | group initiator) currently used by resin BM is known. ) Was simply replaced with the oxime compound, the image characteristics required for the resin BM, that is, sensitivity and resolution could not be improved.

Japanese Patent Laid-Open No. 1-152449 JP-A-1-254918 JP-A-2-153353 JP-A-2-804 JP-A-6-75372 JP-A-6-75373 JP-A-6-51499 JP-A-6-3518 JP-A-8-44050 JP 2000-80068 A

  The present invention solves the above-mentioned problems and provides a resist material that can easily form a thin film and a highly light-shielding pattern by a photolithography method and has sufficient sensitivity and resolution. BM can be manufactured with high accuracy and low cost. In addition, a liquid crystal display device using the color filter manufactured in this way is excellent in display capability such as contrast. Further, by making BM resin, the color filter can be improved in image quality and non-polluted.

  As a result of diligent research, the inventor has used a photopolymerizable composition containing a specific oxime ester compound as a photopolymerization initiator and an epoxy acrylate resin having a carboxyl group as an organic binder in combination. The inventors have found that such an object can be achieved and have completed the present invention.

That is, the gist of the present invention is a photopolymerizable composition containing (a) a black color material, (b) an organic binder, (c) a photopolymerization initiator, and (e) a polymer dispersant having a basic functional group. (B) the organic binder is an epoxy acrylate resin having a carboxyl group, and (c) the photopolymerization initiator is an oxime ester compound represented by the following general formula : Present in the composition.

  The present invention also resides in a photopolymerizable composition, wherein the photopolymerizable composition further contains (d) a photopolymerizable monomer.

  The present invention also resides in a color filter having a BM formed of the photopolymerizable composition on a substrate, and a liquid crystal display device manufactured using the color filter thus manufactured. .

  Since the photopolymerizable composition of the present invention is highly light-shielding in a thin film and excellent in sensitivity and resolution, a high-quality resin BM can be formed at low cost. Since the color filter using the resin BM of the present invention is excellent in accuracy, flatness and durability, the display quality of the liquid crystal element can be improved. In addition, since the manufacturing process and the color filter itself do not contain harmful substances, the danger to the human body is reduced and the environmental safety is improved.

(A) Black color material As the black color material of the present invention, a single black color material or a black color material obtained by mixing red, green, blue and the like can be used. These black color materials can be appropriately selected from inorganic or organic pigments and dyes, and can be used alone or in combination.

  Examples of the single black color material include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black. Among these, carbon black and titanium black are particularly preferable from the viewpoints of light shielding rate and image characteristics. Examples of commercially available carbon black include the following brands.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.

  Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, Special BlackS, 350c, p

  Manufactured by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARLS480, PEARLS480.

  Made by Colombian Carbon: Raven11, Raven15, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040 and the like.

  Next, the black color material by mixing is demonstrated. Specific examples of the color material used as a base for mixing include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Erioglaucine X (42080), no. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  Further, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  The above carbon black may be used in combination with other black or colored inorganic or organic pigments. Other pigments naturally have a light shielding property or image characteristic lower than that of carbon black, so the mixing ratio is naturally limited.

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. Sho 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. is not.

  Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.

(B) Organic Binder In the present invention, an epoxy acrylate resin having a carboxyl group is used as the (b) organic binder.

  In the epoxy acrylate resin, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to the epoxy resin, and a polybasic acid anhydride is further reacted. Is synthesized. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As an epoxy resin used as a raw material, (o, m, p-) cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, ] Can be suitably used (see Japanese Patent No. 2878486). The molecular weight of an epoxy resin is 200-200000 normally as a weight average molecular weight measured by GPC, Preferably it is the range of 300-100000. If the molecular weight is less than the above range, there are many cases where problems occur in the film-forming property. Conversely, resins exceeding the above range are prone to gelation during the addition reaction of α, β-unsaturated monocarboxylic acid, and are difficult to produce. There is a risk of becoming.

  Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is highly reactive. Therefore, it is preferable. The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred.

  A known method can be used for the addition reaction of α, β-unsaturated monocarboxylic acid or an ester thereof with an epoxy resin, for example, the reaction can be performed at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. . As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

  The amount of α, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. Equivalent range. If the amount of α, β-unsaturated monocarboxylic acid or ester thereof used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with the polybasic acid anhydride becomes insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, α, β-unsaturated monocarboxylic acid or ester thereof remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  The polybasic acid anhydride to be further added to the epoxy resin to which the α, β-unsaturated carboxylic acid or ester thereof is added includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetra Carboxylic acid dianhydride and the like, preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Biphenyltetracarboxylic dianhydride Particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride.

  A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be obtained by continuing the reaction under the same conditions as in the addition reaction of α, β-unsaturated carboxylic acid or ester thereof. The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mgKOH / g, more preferably 20 to 140 mgKOH / g. When the resin acid value is below the above range, the alkali developability is poor, and when the resin acid value exceeds the above range, the curing performance tends to be inferior.

(C) Photopolymerization initiator The photopolymerizable composition of the present invention contains an oxime ester compound represented by the general formula (4) as a photopolymerization initiator.

(In the formula, R ¹ is an optionally substituted phenyl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkanoyl having 2 to 20 carbon atoms. show group, a benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, phenoxycarbonyl group having 7 to 20 carbon atoms, an amide group or a nitro group having 1 to 20 carbon atoms, R ² are each An optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a phenoxy group having 7 to 20 carbon atoms indicates a carbonyl ^{group, R 3, R 4, R} 5, R 6 and R ^7, independently of one another, a hydrogen atom, a halogen atom, each optionally substituted alkyl group having 1 to 12 carbon atoms, carbon atoms -12 alkoxy group, cycloalkyl group having 5 to 8 carbon atoms, phenyl group having 6 to 20 carbon atoms, benzyl group having 7 to 20 carbon atoms, benzoyl group having 7 to 20 carbon atoms, alkanoyl having 2 to 12 carbon atoms group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or phenoxycarbonyl group having 7 to 20 carbon ^{atoms, -OR 8, -SR 9, -SOR} 9, shows a -SO ₂ R ⁹ or -NR ¹⁰ R ^11, and , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent —OR ⁸ , —SR ⁹ or —NR ¹⁰ R ¹¹ , provided that R ⁸ is a hydrogen atom, each substituted. An alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, a phenyl group having 6 to 20 carbon atoms, or-( _{CH 2 CH 2 O) n H} (n is from 1 to 20 R ⁹ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, or a phenyl group having 6 to 20 carbon atoms, and R ¹⁰ And R ¹¹ are each independently a hydrogen atom, an optionally substituted 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 carbon number. 6 to 20 phenyl groups, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring structure.)

  Among the oxime ester compounds, preferred substituents of the oxime ester compound represented by the general formula (4) are shown below.

R ^{1 is an} optionally substituted alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group Etc. Preferably it is C1-C6, More preferably, it is C1-C3, and especially a methyl group is preferable.

R ² : an optionally substituted alkanoyl group having 2 to 10 carbon atoms or a benzoyl group having 7 to 20 carbon atoms (preferably an upper limit of 12 carbon atoms). Examples of the alkanoyl group having 2 to 10 carbon atoms include ethanoyl Group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group and the like. The number of carbon atoms is preferably 2 to 5, more preferably 2 to 3, and particularly preferably an ethanoyl group.

R ^{3 to} R ⁷ : a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenoyl group having 2 to 12 carbon atoms, a phenyl group, a benzyl group, a benzoyl group, or —NR ¹⁰ R ¹¹ And R ^{4 to} R ⁶ may be bonded to each other to form a ring structure. R ³ and R ⁷ are preferably both hydrogen atoms. More preferably, R ³ and R ⁷ are both hydrogen atoms, and at least one of R ⁴ , R ⁵ and R ⁶ is —NR ¹⁰ R ¹¹ . R ³ and R ⁷ are both hydrogen atoms, and at least one of R ⁴ , R ⁵ and R ⁶ is —NR ¹⁰ R ¹¹ and at least one is substituted. Particularly preferred is a phenyl group having 6 to 20 carbon atoms (preferably an upper limit of 12 carbon atoms). In this case, the substituent which may be substituted with the phenyl group may be a phenyl group having 6 to 20 carbon atoms (preferably an upper limit of 12 carbon atoms), an alkyl group having 1 to 10 carbon atoms, or carbon. A cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group having 7 to 20 carbon atoms (preferably an upper limit of 12 carbon atoms), an alkoxycarbonyl group having 2 to 12 carbon atoms, and 7 to 20 carbon atoms. Examples thereof include a phenoxycarbonyl group (preferably having an upper limit of 12 carbon atoms), an amide group having 1 to 20 carbon atoms (preferably an upper limit of 12 carbon atoms), and a nitro group. A benzoyl group having 7 to 20 carbon atoms (preferably an upper limit of 12 carbon atoms) which may be substituted is preferable, but a toluoyl group is more preferable, and an o-toluoyl group is particularly preferable. R ⁴ to R ⁶ ring structure which may be formed bond to each other, two or more any themselves may be bonded among R ⁴ to R ^6. The ring structure may be an aromatic ring, an aliphatic ring or a heterocyclic ring, but is preferably a heterocyclic ring, more preferably a hetero 5-membered ring or 6-membered ring in which the hetero atom is a nitrogen atom, A hetero 5-membered ring is preferred.

  Among the oxime ester compounds, more preferred are oxime ester compounds represented by the following general formula (6).

(In the formula, R ¹ is an optionally substituted alkyl group having 1 to 10 carbon atoms, and R ² is an optionally substituted alkanoyl group having 2 to 10 carbon atoms and 7 to 20 carbon atoms. A benzoyl group (preferably having an upper limit of 12 carbon atoms), and R ¹⁰ are independently of each other a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or a hydroxyalkyl having 2 to 4 carbon atoms. Group, an alkenyl group having 3 to 5 carbon atoms, or a phenyl group having 6 to 20 carbon atoms (preferably upper limit carbon number 12), and R ¹⁰ is an aromatic ring bonded via a nitrogen atom to which R ¹⁰ is bonded. It may combine with one or both additional substituents or one of the aromatic ring carbon atoms to form a ring structure, wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently substituted Carbon number of 6 to 20 (preferably upper limit) A prime 12) phenyl group, 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, and a benzoyl group having 7 to 20 carbon atoms (preferably an upper limit of 12 carbon atoms). Group, an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms (preferably upper limit carbon number 12), an amide group or a nitro group having 1 to 20 carbon atoms (preferably upper limit carbon number 12). Show.)

  Of the oxime ester compounds, preferred substituents of the compounds are shown below.

R ^{1 is an} optionally substituted alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group Etc. Preferably it is C1-C6, More preferably, it is C1-C3, and especially a methyl group is preferable.

R ² : an optionally substituted alkanoyl group having 2 to 10 carbon atoms, such as ethanoyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, etc. It is done. The number of carbon atoms is preferably 2 to 5, more preferably 2 to 3, and particularly preferably an ethanoyl group.

R ¹⁰ is an optionally substituted alkyl group having 1 to 12 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group , Undecyl group, dodecyl group and the like. Preferably, it has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably an ethyl group.

R ¹² , R ¹⁴ and R ¹⁵ : hydrogen atom R ¹³ : a benzoyl group which may be substituted is exemplified, and a toluoyl group is preferable, and an o-toluoyl group is particularly preferable.

  The compounds represented by the general formulas (4) and (6) are similarly known per se, and are, for example, one of a series of compounds described in JP-A No. 2000-80068.

  Moreover, although the said oxime ester type compound can be used independently as a photoinitiator of this invention, it can also use together with another photoinitiator and can anticipate the high sensitivity by combined use. For example, the following compounds can be mentioned.

  2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, -Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-[[beta]-(2'-benzofuryl) vinyl] -1,3,4-oxadi Azole, 2-trichloromethyl-5- [β- (2 '-(6 "benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl Halomethylated oxadiazole derivatives such as ru-1,3,4-oxadiazole, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4, 5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenyl Imidazole dimers, imidazole derivatives such as (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2 -Methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl Anthraquinone derivatives such as luanthraquinone and 1-chloroanthraquinone, benzanthrone derivatives, benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, etc. Benzophenone derivatives, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (P-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2, Thioxanthone derivatives such as 4-diethylthioxanthone and 2,4-diisopropylthioxanthone, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, 9-phenylacridine, 9- (p-methoxyphenyl) Acridine derivatives such as acridine, phenazine derivatives such as 9,10-dimethylbenzphenazine, bis-cyclopentadienyl-Ti-dichloride, bis-cyclopentadienyl-Ti-bis-phenyl, bis-cycl Pentadienyl-Ti-bis- (2,3,4,5,6-pentafluorophen-1-yl), bis-cyclopentadienyl-Ti-bis- (2,3,5,6-tetrafluoropheny- 1-yl), bis-cyclopentadienyl-Ti-bis- (2,4,6-trifluorophen-1-yl), bis-cyclopentadienyl-Ti-2,6-difluorophenyl- 1-yl, bis-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl, bis-methylcyclopentadienyl-Ti-bis- (2,3,4,5,6-penta Fluorophen-1-yl), bis-methylcyclopentadienyl-Ti-bis- (2,6-di-fluorophen-1-yl), bis-cyclopentadienyl-Ti-2,6-di- Fluoro-3- (pill- - yl) - titanocene derivatives of 1-yl and the like, and the like.

  In addition to the initiator component, a sensitizing dye can be further added to the photopolymerizable composition of the present invention. In order to cause a photopolymerization reaction under high light shielding, it is preferable to add a sensitizing dye. Examples of such a sensitizing dye include a coumarin compound having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and a 3-ketocoumarin compound described in JP-A 63-221110. Xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, pyromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292 (P-dialkylaminobenzylidene) ketone and styryl dye described in JP-A-56-166154 and JP-A-59-56403, and a julolidyl group described in JP-A-6-295061. Examples thereof include sensitizing dyes and diaminobenzene compounds described in JP-A No. 11-326624.

  Of these sensitizing dyes, amino group-containing sensitizing dyes and xanthene dyes are particularly preferable.

(D) Photopolymerizable monomer As the photopolymerizable monomer of the present invention, a compound having one or more ethylenically unsaturated groups (hereinafter referred to as an ethylenic compound) is used. Specifically, ester of aliphatic (poly) hydroxy compound and unsaturated carboxylic acid, ester of aromatic (poly) hydroxy compound and unsaturated carboxylic acid, unsaturated carboxylic acid, polyvalent carboxylic acid and aliphatic poly Ester obtained from hydroxy compound, ethylene oxide of aromatic polyhydroxy compound, esterification reaction product of propylene oxide adduct and unsaturated carboxylic acid, ethylene oxide of aliphatic polyhydroxy compound, propylene oxide adduct and unsaturated carboxylic acid Esterification reaction product, ester of caprolactone-modified polyhydric alcohol and unsaturated carboxylic acid, reaction product of polyhydric alcohol, polyisocyanate and unsaturated carboxylic acid, styryl-terminated compound, phosphoric acid unsaturated compound, polyepoxy And an adduct of unsaturated carboxylic acid.

  Among these, specific examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylol propane tri Acrylate esters such as acrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Methacrylic acid with the acrylate of the exemplified compound replaced with methacrylate Ether, similarly itaconic acid ester instead itaconate, maleic acid esters, and the like was replaced with crotonic acid ester or maleate was replaced crotonate.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but typical examples include (meth) acrylic acid, phthalic acid and ethylene. Condensate of glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol, condensate of (meth) acrylic acid, terephthalic acid and pentaerythritol, condensate of (meth) acrylic acid, adipic acid, butanediol and glycerin Etc.

  Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.

  Among the ethylenic compounds listed above, preferred are those having a (meth) acryloyl group, more preferably an acryloyl group. Such compounds include trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. Is mentioned.

  The blending amount of the photopolymerizable composition of the present invention described above is usually 0.1 to 50 parts by weight, preferably 1 to 45 parts of (c) photopolymerization initiator with respect to 100 parts by weight of (b) organic binder. Part by weight, (d) the photopolymerizable monomer is usually 0 to 200 parts by weight, preferably 3 to 180 parts by weight. Moreover, (a) black color material is 30 to 70 weight% normally in the total solid content except a solvent, Preferably it is 35 to 65 weight%. Further, the sensitizing dye is usually 0 to 30 parts by weight, preferably 0 to 10 parts by weight with respect to 100 parts by weight of the (b) organic binder.

  If the photopolymerization initiator is less than the above range, the sensitivity becomes low and the working efficiency is poor, and if it exceeds the above range, the coating film forming function is liable to be adversely affected. If the photopolymerizable monomer (ethylenic compound) is less than the above, problems such as durability and heat resistance due to a decrease in crosslink density are likely to occur, and if the above range is exceeded, developability may be degraded. There is. If the black color material is less than the above range, the light shielding property is lowered, and it becomes difficult to form a resin BM having a sufficient optical density. On the other hand, if the above range is exceeded, the sensitivity, resolution, developability and the like are drastically lowered, making it difficult to form an image.

  The photopolymerizable composition of the present invention usually requires (a) a black color material, (b) an organic binder (epoxy acrylate resin having a carboxyl group), (c) a photopolymerization initiator (oxime ester compound), and further necessary. Depending on (d), it is used in the state which melt | dissolved the photopolymerizable monomer (ethylenic compound) in the solvent.

  As the solvent, it is preferable to select a solvent that can dissolve or disperse each component constituting the composition and has a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120-170 ° C.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl. Glycol mono, such as ether, diethylene glycol monoethyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether Alkyl ethers;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, dipropylene glycol monomethyl ether acetate, 3- Glycol alkyl ether acetates such as methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate Rate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy Linear or cyclic esters such as propyl propionate, butyl 3-methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile;
Solvents corresponding to the above include mineral spirit, Valsol # 2, Apco # 18 Solvent, Apco Thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, diglyme and other commercial products.

  These solvents can be used alone or in combination. The photopolymerizable composition of the present invention is desirably prepared using these solvents so that the solid content concentration is in the range of 5 to 50% by weight, preferably 10 to 30% by weight.

  In the present invention, an optional component (d) is added to these essential components (a), (b) and (c) as necessary, but in addition to these, a pigment dispersant, an adhesion improver, a coatability improver, a development An improver or the like can be suitably added. In particular, in the composition of the present invention, since it is important for quality stability to finely disperse the black color material and stabilize the dispersion state, it is desirable to incorporate a pigment dispersant.

  The pigment dispersant has affinity for both (a) the black color material and (b) the organic binder, and examples thereof include surfactants such as nonions, cations and anions, and polymer dispersants. Among these, a polymer dispersant is preferable, and in particular, a polymer dispersant having a basic functional group (e) such as a primary, secondary, or tertiary amino group, a nitrogen-containing heterocycle such as pyridine, pyrimidine, and pyrazine. Advantageously used.

  (E) If the chemical structure preferable as a polymer dispersant having a basic functional group is specifically exemplified, for example, a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule, and an activity in the same molecule Examples thereof include a dispersion resin obtained by reacting hydrogen with a compound having a tertiary amino group.

  Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

  Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms. And mixtures of two or more of these.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and the like. The mixture of 2 or more types of these is mentioned.

  Polyether ester diols include those obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or an anhydride thereof, or reacting a polyester glycol with an alkylene oxide, such as poly ( And polyoxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides 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-pentanediol, 1,6-hexanediol, 2-methyl-2,4 Pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diols or carbon number 1-25 Polylactone diol or polylactone monool obtained by using a monovalent alcohol as an initiator, for example, polycaprolactone glycol, poly methyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms.

  Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned. The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

  A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of an amino group is preferred. The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is an N-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, N-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. Preferred as these N-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.

  Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Is preferred. A preferable blending ratio of the dispersant raw material is 10 to 200 parts by weight, preferably 20 to 200 parts by weight of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 190 parts by weight, more preferably 30 to 180 parts by weight, and 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.

  (E) The weight average molecular weight in terms of GPC of the polymer dispersant having a basic functional group is 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. It is. When the molecular weight is 1,000 or less, the dispersibility and dispersion stability are poor, and when it is 200,000 or more, the solubility is lowered and the dispersibility is poor, and at the same time, the reaction is difficult to control. The polymer dispersant is produced according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

  In the above production, a urethanization reaction catalyst is usually used. For example, tin such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate, iron such as iron acetylacetonate and ferric chloride, tertiary amine such as triethylamine and triethylenediamine, etc. Can be mentioned.

  The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease. In addition, when an isocyanate group remains in a polymer dispersing agent by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time increases. In addition, when using a polymer dispersing agent, 0.1 to 30 weight% is preferable with respect to (a) black color material, and 0.5 to 25 weight% is especially preferable.

  Next, the manufacturing method of the photopolymerizable composition of this invention is demonstrated. In the present invention, it is preferable that the black color material is usually subjected to a dispersion treatment in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the black color material is finely divided by the dispersion treatment, the light shielding ability of the resist and the coating characteristics are improved.

  In the dispersion treatment, the treatment is preferably carried out in a system in which a black color material and a solvent or an organic binder having a dispersion function or the above-described pigment dispersant are further used in combination. In particular, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time. Dispersion treatment with a solution in which all components to be blended as a resist solution are mixed at the same time is not preferable because a highly reactive component may be denatured due to heat generated during dispersion.

  In the case of dispersing with a sand grinder, glass beads or zirconia beads having a diameter of 0.1 to 8 mm are preferably used. The conditions for the dispersion are usually that the temperature is from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the ink (black color material, solvent, dispersant) and the size of the sand grinder. The standard of dispersion is to control the gloss of the ink so that the 20-degree gloss value of the resist is in the range of 100 to 200. When the resist gloss is low, the dispersion treatment is not sufficient and rough pigment particles often remain, which is insufficient in terms of developability, adhesion, resolution, and the like. In addition, when the dispersion treatment is performed until the gloss value exceeds the above range, a large number of ultrafine particles are generated, and the dispersion stability tends to be impaired.

  Next, the black ink obtained by the dispersion treatment and the other components necessary as a resist component are added and mixed to obtain a uniform solution. In the manufacturing process, fine dust is often mixed with the photosensitive solution. Therefore, the obtained resist photosensitive solution is preferably filtered through a filter or the like. Then, the manufacturing method of the color filter using the photopolymerizable composition of this invention is demonstrated.

  First, the photopolymerizable composition of the present invention is coated on a transparent substrate with a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray and dried, and then a photomask is formed on the sample. Then, a light-shielding BM image is formed by image exposure through the photomask, development, and heat curing or photocuring as necessary, and this operation is repeated for each of the three RGB colors to form a color filter image.

  In addition, when forming a pixel of a color filter using the photopolymerizable composition of the present invention, since it has very high sensitivity and high resolution, exposure and development can be performed without providing an oxygen blocking layer such as polyvinyl alcohol. Thus, an image can be formed. The transparent substrate used here is a transparent substrate for a color filter, and its material is not particularly limited. For example, polyester such as polyethylene terephthalate, polypropylene, polyolefin such as polyethylene, polycarbonate, polymethyl methacrylate, A thermoplastic plastic sheet such as polysulfone, an epoxy resin, a polyester resin, a thermosetting plastic sheet such as poly (meth) acrylic resin, or various glass plates can be used. In particular, a glass plate and a heat resistant plastic are preferably used from the viewpoint of heat resistance.

  In order to improve physical properties such as surface adhesion, such a transparent substrate can be previously subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as silane coupling agents and urethane polymers, and the like. . The coating method is not particularly limited, but the thickness of the resin black matrix after coating and drying is 0.1 to 2 μm, preferably 0.1 to 1.5 μm, more preferably 0.1 to 1 μm. good. The color filter of the present invention preferably has an optical density of 3.0 or more at a film thickness of 1 μm from the viewpoint of light shielding properties. Further, it is advantageous that the 20 degree gloss value of BM is 100 to 200 as an indicator of the dispersion state of solid components such as pigments.

  In drying, a hot plate, IR oven, convection oven or the like can be used, and preferable drying conditions are 40 to 150 ° C., and drying time is in the range of 10 seconds to 60 minutes. The light source used for exposure is, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, or the like, an argon ion laser, a YAG laser, an excimer laser, A laser light source such as a nitrogen laser may be used. In the case where only the wavelength of specific irradiation light is used, an optical filter can also be used.

  The development treatment is not particularly limited as long as it is a solvent capable of dissolving the resist film in the unexposed area. For example, organic solvents such as acetone, methylene chloride, trichlene, and cyclohexanone can be used. However, since many organic solvents have environmental pollution, harmfulness to human body, fire risk, etc., it is preferable to use an alkaline developer without such danger. Examples of such an alkali developer include inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethanolamine, tetraalkylammonium hydroxide salt, etc. And an aqueous solution containing an organic alkali agent. If necessary, the alkaline developer may contain a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxyl group, and the like. In particular, it is preferable to add a surfactant since many surfactants have an improving effect on developability, resolution, and background stains.

  For example, as a surfactant for a developer, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group Can be mentioned. Although there is no restriction | limiting in particular about the image development processing method, Usually, it is carried out by methods, such as immersion image development, spray image development, brush image development, ultrasonic wave development, at 10-50 degreeC, Preferably it is 15-45 degreeC.

  Next, the liquid crystal display device (panel) of the present invention will be described. The liquid crystal display device of the present invention is characterized by using the color filter. And it can manufacture as follows.

  First, an alignment film is formed on a color filter, a spacer is disposed on the alignment film, and then a liquid crystal cell is formed by being attached to a counter substrate. Next, liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode to complete.

  The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method or a flexographic printing method is usually employed, and the thickness of the alignment film is usually 10 to 100 nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

  A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film is formed on the color filter substrate by photolithography, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.

The liquid crystal cell whose periphery is sealed is cut into panel units, then the pressure is reduced in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. To do. The degree of vacuum in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, Preferably it is 50-90 degreeC. The warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. In the liquid crystal cell into which the liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of the liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of a lyotropic liquid crystal, a thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of these may be used.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated still in detail, this invention is not limited to a following example, unless the summary is exceeded.

Synthesis Example 1 (Preparation of polymer dispersant solution)
32 g of tolylene diisocyanate trimer (Mitsubishi Chemical Corporation, Mytec GP750A, resin solid content 50 wt%, butyl acetate solution) and 0.02 g of dibutyltin dilaurate as a catalyst were diluted with 47 g of propylene glycol monomethyl ether acetate (PGMEA) Dissolved. While stirring, 14.4 g of polyethylene glycol (manufactured by NOF Corporation, UNIOX M-1000) having a methoxy group at one end and polypropylene glycol having a number average molecular weight of 1,000. A mixture of 9.6 g (Sanix PP-1000, manufactured by Sanyo Chemical Industries, Ltd.) was dropped, and the mixture was further reacted at 70 ° C. for 3 hours. Next, 1 g of N, N-dimethylamino-1,3-propanediamine was added, and the mixture was further reacted at 40 ° C. for 1 hour. The amine value of the solution containing the polymer dispersant thus obtained was determined by neutralization titration to be 14 mg KOH / g. The resin content was 40% by weight as determined by the dry-up method (at 150 ° C. for 30 minutes, the solvent was removed on a hot plate and the resin concentration was calculated from the weight change).

Synthesis Example 2 (Synthesis of organic binder)
200 g / eq of epoxy equivalent, 200 g of o-cresol novolac epoxy resin having a softening point of 65 ° C., 72 g of acrylic acid, 0.2 g of p-methoxyphenol, 0.2 g of dodecyltrimethylammonium chloride, and 272 g of PGMEA were charged in a flask at a temperature of 100 ° C. The reaction was continued for 1 hour (1 equivalent of acrylic acid reacted with 1 equivalent of epoxy group). Further, 42 g of tetrahydrophthalic anhydride was added and reacted at 80 ° C. for 3 hours. This reaction solution was re-precipitated in water and vacuum-dried to obtain a novolak epoxy acrylate resin having a carboxyl group. When neutralization titration with KOH was performed, the acid value of the resin was 50 mgKOH / g.

Synthesis Example 3 (Synthesis of organic binder)
The reaction was performed in the same manner as in Synthesis Example-2 except that the amount of tetrahydrophthalic anhydride added was 63 g. The resin acid value obtained was 70 mg KOH / g.
(Dispersion of carbon black)
Carbon black for color (Mitsubishi Chemical Co., Ltd., MA-220) 50 parts by weight, the polymer dispersant shown in Synthesis Example-1 as a solid content at a ratio of 5 parts by weight, and the solid content concentration becomes 50% by weight Carbon black, polymer dispersant solution and PGMEA were added as described above. The total weight of the dispersion was 50 g. This was thoroughly stirred with a stirrer and premixed.

  Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the completion of dispersion, the beads and the dispersion were separated by a filter.

[Example 1 and Comparative Examples 1 to 3]
(1) Preparation of resist solution Each component (a), (b), (c), (d), (e), organic so as to have the following mixing ratio as a solid content using the carbon black dispersion ink described above A solvent and a surfactant were added, and the mixture was stirred and dissolved with a stirrer to prepare a black resist photosensitive solution.

(A) Black color material
Carbon black (Mitsubishi Chemical Corporation MA-220) 50g
(B) Organic binder
(Listed in Table 1) 30 g
(D) Photopolymerizable monomer: ethylenic compound
Dipentaerythritol hexaacrylate 10g
(C) Photopolymerization initiator
(Listed in Table 1)
Organic solvent
Propylene glycol monomethyl ether acetate 300g
(E) Polymer dispersant (Synthesis Example 1) 5 g
Surfactant (Sumitomo 3M, FC-430) 100ppm

(2) Evaluation of resist A black resist photosensitive solution was applied to a glass substrate (Corning Corp., 7059) with a spin coater and dried on a hot plate at 80 ° C. for 1 minute. The film thickness of the resist after drying was measured with a stylus type film thickness meter (manufactured by Tencor, α-step) and found to be 1 μm. Next, this sample was image-exposed through a mask while changing the exposure amount with a high-pressure mercury lamp. 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, resolution, and light shielding properties were evaluated according to the following criteria, and the results shown in Table 1 were obtained.
1. Sensitivity A 20 μm mask pattern was displayed with an appropriate exposure amount (mj / cm ² ) that can be formed according to dimensions. That is, a resist with a small exposure amount has high sensitivity because an image can be formed with a low exposure amount.
2. Resolution The minimum resist pattern size that can be resolved at an exposure amount that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 200 times. The minimum pattern dimension was 10 μm or less, and the resolution power was over 10 μm.
3. Light-shielding property The optical density (OD) of the image area was measured with a Macbeth reflection densitometer (TR927, manufactured by Kolmorgun). The OD value is a numerical value indicating the light shielding ability, and the larger the numerical value, the higher the light shielding property.

尚、表１中、記号の意味は次の通りである。
ａ−１：アクリルポリマー（ダイセル化学工業社製、ＡＣＡ−２００Ｍ）

In Table 1, the meanings of the symbols are as follows.
a-1: Acrylic polymer (manufactured by Daicel Chemical Industries, ACA-200M)

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′-tetraphenylbiimidazole (2 g) + 4,4′-bis (diethylamino) benzophenone (1 g) + 2-mercapto Benzothiazole (1 g)
c-4: Photopolymerization initiator (manufactured by Ciba Specialty Chemical Co., CGI-242) (5 g)

[Example 2]
In Example 1, it replaced with carbon black (Mitsubishi Chemical Corporation make, MA-220) used as a black color material, and was the same as Example 1 except having used titanium black (Mitsubishi Materials company make, 13M-C). Processing was performed to obtain a black matrix pattern. The results are shown in Table 1.

[Comparative Example 4]
Comparative Example 3 was the same as Comparative Example 3 except that titanium black (Mitsubishi Materials Corporation, 13M-C) was used instead of carbon black (Mitsubishi Chemical Corporation, MA-220) used as a black color material. Processing was performed to obtain a black matrix pattern. The results are shown in Table 1.

  The photopolymerizable composition of the present invention and a color filter using the same can be used for color televisions, liquid crystal display elements, solid-state image sensors, cameras, and the like.

Claims (6)

A photopolymerizable composition comprising (a) a black color material, (b) an organic binder, (c) a photopolymerization initiator, and (e) a polymer dispersant having a basic functional group, wherein (b) The organic binder is an epoxy acrylate resin having a carboxyl group, and (e) a photopolymerization initiator combined with a polymer dispersant having a basic functional group is an oxime ester compound represented by the following general formula A photopolymerizable composition comprising:

  The photopolymerizable composition according to claim 1, wherein the photopolymerizable composition further contains (d) a photopolymerizable monomer.   (B) The organic binder adds an α, β-unsaturated monocarboxylic acid to the epoxy resin or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group at the ester moiety, and further adds a polybasic acid anhydride. The photopolymerizable composition according to claim 1, which is a resin synthesized by reacting.   (B) The organic binder is an epoxy acrylate obtained by reacting a reaction product of a novolac type epoxy resin and (meth) acrylic acid with (hydro) phthalic anhydride. Item 4. A photopolymerizable composition according to item.   A color filter comprising a black matrix formed of the photopolymerizable composition according to claim 1 on a transparent substrate.   A liquid crystal display device formed using the color filter according to claim 5.