JP2011141413A - Blue photosensitive resin composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a blue photosensitive resin composition to form a blue pixel whose surface peeling problem is solved by a laser scan exposure method. <P>SOLUTION: The blue photosensitive resin composition contains a blue coloring material, a resin, a polymerizable monomer, a photoinitiator and a solvent. The photoinitiator is an oxime ester compound having a structure shown by formula (1) (wherein X<SB>1</SB>-X<SB>3</SB>are each independently a 1-20C alkyl group or aryl group, wherein the alkyl group may have a linear, branched or cyclic structure; X<SB>4</SB>is a hydrogen atom, an alkanoyl group or an aryloyl group; X<SB>1</SB>-X<SB>4</SB>can have no substituent or a substituent). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a blue photosensitive resin composition and a color filter used for producing a color filter necessary for colorization of a television receiver, a computer, a mobile phone terminal and the like.

  A color filter is an indispensable component for colorization of a liquid crystal display device that has been applied in various fields in recent years. The color filter is provided with colored pixels such as red (R), green (G), and blue (B) on a transparent substrate such as glass. By using a backlight that emits white light and controlling the orientation of the liquid crystal molecules to adjust the amount of light that passes through the filters of each color, it becomes possible to display any color. In order to improve the contrast between the colored pixels and the outer periphery of the display region, a black matrix is generally provided to prevent malfunction of the TFT (thin film transistor) element due to light.

  As a method for producing a color filter, there are various methods such as a photolithography method, a printing method, an electrodeposition method, and an ink jet method, and a photolithography method that is excellent in quality is widely used.

  The production of a color filter by photolithography is performed as follows. A black matrix is formed by applying a photosensitive resin composition containing a black color material to a substrate, and performing exposure, development, and baking treatment through a photomask having a predetermined pattern. Subsequently, for example, a photosensitive resin composition containing a red color material is applied, and exposure, development, and baking are performed through a photomask corresponding to the black matrix opening in the display region, thereby red pixels are formed. Form. By performing the same operation using the photosensitive resin composition containing green and blue color materials, a color filter having colored pixels of red, green and blue can be produced.

  In recent years, large substrates exceeding 1 m □ have been used as the application of liquid crystal display devices to television receivers has progressed. As the size of the substrate increases, it is necessary to increase the size of the photomask as well in the conventional method of exposing the entire surface of the substrate at once. Increasing the size of the photomask increases the cost and makes it difficult to ensure quality. Therefore, a method of dividing a substrate into a plurality of regions and performing a plurality of exposures using a photomask smaller than the substrate corresponding to the divided regions (so-called step exposure method) has come to be used. However, since the division method needs to be exposed a plurality of times, there is a problem that productivity is lowered as compared with the batch method. In addition, as the introduction of ultra-large substrates ranging from 2m to 3m □ is realized, in order to maintain productivity, even when the division method is used, an increase in the size of the mask and the accompanying dramatic increase in cost can be avoided. There is no situation. The demand for lower prices for liquid crystal display devices is only increasing, and there is an urgent need to develop a method for reducing mask costs.

  In order to solve such a problem, for example, Patent Documents 1 and 2 propose to expose a wide area without enlarging the mask by performing scan exposure using a small mask. . In this method, since the color pixels are aligned by acquiring the position information of the black matrix of the color filter with the image sensor, alignment marks necessary for forming the color pixels by the collective exposure and the step exposure method are unnecessary. For this reason, for example, by using a plurality of inexpensive small masks smaller than the screen size and scanning with an exposure head corresponding to each mask, the mask cost can be greatly reduced and high productivity can be maintained.

  In this method, when a continuous light source such as an ultra-high pressure mercury lamp that has been used in the manufacture of conventional color filters is used, only a simple stripe pattern can be formed, which greatly restricts the design of the color filter. Arise. However, by using pulsed light as a light source and performing pulse irradiation to substrate movement repeatedly, it becomes possible to form an isolated pattern such as an island pattern or a dot pattern, and the above-described restrictions can be removed.

  There are various light sources such as xenon flash, solid state laser, excimer laser, and semiconductor laser as pulse light source, but it has high output required for the above method and is excellent in terms of cost including utilities, solid state laser, In particular, a YAG laser having a wavelength of 343 nm and 355 nm is preferably used.

  In manufacturing a color filter, so-called multi-sided processing is generally performed in which a plurality of color filters corresponding to a predetermined screen size are formed on a single glass substrate. FIG. 1 is a schematic diagram showing multi-cavity of a color filter. 1A to 1D are regions where color filters having the same pattern arrangement (A) are formed. In the conventional step exposure method, for example, a photomask corresponding to the pattern arrangement (A) is arranged on the area (a) and exposed to form a color filter pattern in the area (a). Subsequently, the substrate is moved so that the photomask is disposed on the region (b), and exposure is performed again to form a color filter pattern in the region (b). By repeating the same operation for (c) and (d), a color filter pattern can be formed on the entire surface of the substrate.

  On the other hand, in the above-described small mask scan exposure method, a small photomask corresponding to the pattern array (A ′) which is a part of the pattern array (A) is used, and scanning is performed while moving the substrate along the long axis direction of the pattern. By performing exposure, a color filter pattern is formed in the regions (a1) and (b1) which are part of the regions (a) and (b). By repeating the same operation in (a2) to (b2), (a3) to (b3), (c1) to (d1), (c2) to (d2), and (c3) to (d3), the substrate is obtained. A color filter pattern can be formed on the entire surface. Although a decrease in productivity becomes a problem by repeating scanning exposure, it is possible to reduce the number of scans and improve productivity by using a plurality of small masks corresponding to a plurality of exposure heads.

  In the small mask scan exposure system, scan exposure is performed by moving the substrate while irradiating the small mask with pulsed light oscillating at a constant frequency. In this case, for example, there is a problem that a repeated pattern similar to the display areas (a) to (d) is also formed in the area (e) where no pattern originally exists in FIG. In order to solve such a problem, Patent Documents 3 and 4 propose an exposure apparatus including a shutter that operates in synchronization with a region where no pattern exists under a small mask. In this exposure apparatus, for example, when the region (e) in which the pattern does not exist after exposure of the region (a1) in FIG. 1 reaches the light irradiation section, that is, under the small mask, the shutter installed in the exposure optical system is closed. To prevent the pattern from being formed in the region (e). Subsequently, when the region (b1) reaches under the small mask, the shutter opens and scanning exposure continues. In this way, by using the shutter, it is possible to prevent a pattern from being formed in an area where no pattern originally exists, for example, between the black matrixes on the outer periphery of the display area of the color filter in multi-sided layout. .

JP 2006-292955 A JP 2006-323188 A JP 2007-121344 A JP 2007-281317 A

  In the method of controlling the pattern forming part / non-forming part using the shutter as described above, the shutter opening / closing operation is performed on the black matrix at the boundary between the pattern forming part and the non-forming part, that is, the outer peripheral part of the display area of the color filter. . When the operation time for opening and closing the shutter is sufficiently shorter than the pulse width of the laser, it is possible to precisely control the presence or absence of the colored pixel pattern on the black matrix. However, since it is difficult to increase the speed of opening and closing the shutter, there is an area on the black matrix where light leaks when the shutter is opened and closed. That is, the exposure amount on the black matrix in the outer peripheral portion of the display region is not zero, and weak light that is lower than the exposure amount necessary for curing the colored photosensitive resin composition is irradiated. In this case, in particular, in the blue photosensitive resin composition having a low transmittance with respect to the light source wavelength of the YAG laser, there is a problem that the surface of the pattern is turned up and a protrusion is formed after the development process. When protrusions are formed on the black matrix, the transparent electrode film such as ITO formed on the color filter film surface in a general liquid crystal display device is damaged, and the signal processing for controlling the liquid crystal alignment, that is, the transmittance is performed. May cause trouble. In addition, the cell gap uniformity in the vicinity of the protrusion is impaired, and there is a concern that the display quality is remarkably lowered. Therefore, there is a strong demand for eliminating surface peeling problems of blue pixels on the black matrix in the outer periphery of the display area.

  The present invention has been made in view of such a situation, and it is an object of the present invention to solve the above-described problems and enable formation of blue pixels by a scan exposure method using a small mask. As a result of intensive studies, the present inventors have found that the occurrence of surface peeling of the blue photosensitive resin composition in the method of controlling the pattern forming portion / non-forming portion using a shutter causes the photoinitiator in the composition to We found that the characteristics have a big influence. Then, various photoinitiators were examined and it came to invention of the blue photosensitive resin composition without surface peeling.

  The invention according to claim 1 of the present invention uses a laser light source that oscillates at a constant frequency as an exposure light source, forms a pattern of a display region by scanning exposure through a photomask having a predetermined pattern, A blue photosensitive resin composition containing at least a blue colorant, a resin, a polymerizable monomer, a photopolymerization initiator, and a solvent used in a method for producing a color filter by shielding a non-display area using a shutter. The photopolymerization initiator is an oxime ester-based compound having a structure represented by the following formula (1).

式（１）においてＸ_１〜Ｘ_３はそれぞれ独立に炭素数１〜２０のアルキル基またはアリール基を表す。アルキル基は直鎖状であっても分岐構造を有していてもよい。また、環状構造を有していてもよい。Ｘ_４は水素原子、アルカノイル基、更にはアリーロイル基を表す。Ｘ_１〜Ｘ_４は無置換であっても置換基を有していてもよい。

In the formula (1), X _{1 to} X ₃ each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms. The alkyl group may be linear or have a branched structure. Moreover, you may have a cyclic structure. X ₄ represents a hydrogen atom, an alkanoyl group, or an aryloyl group. X _{1 to} X ₄ may be unsubstituted or may have a substituent.

  The invention according to claim 2 of the present invention is characterized in that the content of the photopolymerization initiator in the solid content of the blue photosensitive resin composition is 5 to 20 mass percent. It is a blue photosensitive resin composition to be described.

  The invention according to claim 3 of the present invention is the blue photosensitive resin composition according to claim 1, wherein the light source of the laser beam is a solid (YAG) laser having a wavelength of 343 nm or 355 nm. .

  The invention according to claim 4 of the present invention is the blue photosensitive resin composition according to claim 1 or 3, wherein the laser beam has a frequency of 20 to 100 Hz.

Further, in the invention according to claim 5 of the present invention, the energy amount per pulse of the laser beam is in the range of 0.5 to 2.0 mJ / cm ² , or 4 is a blue photosensitive resin composition.

  The invention according to claim 6 of the present invention is a color filter comprising a blue pixel formed using the blue photosensitive resin composition according to any one of claims 1 to 5. is there.

  According to the present invention, even in a small mask scan exposure method in which the presence / absence of pattern formation is controlled by opening / closing a shutter using a pulsed light source, surface peeling of blue pixels does not occur on the black matrix of the color filter. Therefore, a color filter and further a liquid crystal display device having the same quality as that of the current proximity exposure method can be manufactured even in the method in which a significant reduction in mask cost can be expected.

Schematic representation of multi-faceted color filter FIG. 1A is a schematic diagram showing a pattern arrangement in the area (a). The schematic diagram showing the exposure area in color filter manufacture of this invention The schematic diagram showing the board | substrate which formed the black matrix of the color filter of this invention

  The blue photosensitive resin composition for color filters of the present invention will be described in detail below.

[Blue colorant]
As the blue colorant, organic or inorganic blue pigments can be used alone or in admixture of two or more. As the pigment, a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance is preferable, and an organic pigment is usually used. Specific examples of organic pigments that can be used in the blue photosensitive resin composition of the present invention are represented by color index numbers. I. And blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64. The blue photosensitive resin composition includes C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination. Examples of inorganic pigments include ultramarine blue and bitumen. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

  Moreover, the blue photosensitive resin composition of the present invention can contain a dye within a range that does not decrease the heat resistance for color matching.

  As content of the said blue coloring material, it is preferable that it is the range of 15 mass% to 45 mass% in solid content of a blue photosensitive resin composition. When the content is 15% by mass or less, the color reproducibility is insufficient in the liquid crystal display device. Moreover, when content is 45 mass% or more, the sensitivity fall of the photosensitive resin composition will be caused, and pattern shape defect will occur easily.

[resin]
As the resin, a transparent resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region is used. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone or in combination of two or more. Among these, a thermoplastic resin capable of obtaining a good pattern shape is preferably used, and an acrylic resin is most preferably used.

  As the thermoplastic resin, in addition to the acrylic resin, for example, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins. These thermosetting resins have the effect of improving the crosslink density and reducing the elution of impurities, and can be appropriately used within a range that does not impair the pattern shape.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used. By using these photosensitive resin compositions, it is possible to improve the sensitivity of the blue photosensitive resin composition, and it can be used appropriately within a range that does not impair the pattern shape.

[Polymerizable monomer]
Examples of polymerizable monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and propylene oxide-modified trimethylolpropane. Representative examples include various acrylic esters and methacrylic esters such as tri (meth) acrylate.

  As the polymerizable monomer, a polyfunctional urethane acrylate having a (meth) acryloyl group obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group may be used. Examples of the polyfunctional urethane acrylate include a compound represented by the following formula (2) and a compound represented by the following formula (3).

上記重合性モノマーは、例えば現像速度、パターン形状の調整といった目的に応じて単独または２種以上を混合して用いることができる。

The polymerizable monomers can be used alone or in admixture of two or more according to the purpose of adjusting the development speed and pattern shape, for example.

[Photopolymerization initiator]
The blue photosensitive resin composition of the present invention is characterized in that the photopolymerization initiator is an oxime ester-based compound including a structure represented by the following formula (1).

式（１）においてＸ_１〜Ｘ_３はそれぞれ独立に炭素数１〜２０のアルキル基またはアリール基を表す。アルキル基は直鎖状であっても分岐構造を有していてもよい。また、環状構造を有していてもよい。直鎖状のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等が挙げられる。分岐構造を有するアルキル基としては、１−メチルエチル基、１−メチルプロピル基、２−メチルプロピル基、１−メチルブチル基、１−エチルブチル基、２−メチルブチル基、２−エチルブチル基、３−メチルブチル基、３−エチルブチル基等が挙げられる。環状構造を有するアルキル基としては、シクロペンチル基、シクロヘキシル基等が挙げられる。アリール基は単環構造であっても縮環構造を有していてもよい。縮環構造を有するアリール基としては、ナフタレン、アントラセン、テトラセン等が挙げられる。

In the formula (1), X _{1 to} X ₃ each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms. The alkyl group may be linear or have a branched structure. Moreover, you may have a cyclic structure. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the alkyl group having a branched structure include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 1-ethylbutyl group, 2-methylbutyl group, 2-ethylbutyl group, and 3-methylbutyl. Group, 3-ethylbutyl group and the like. Examples of the alkyl group having a cyclic structure include a cyclopentyl group and a cyclohexyl group. The aryl group may have a monocyclic structure or a condensed ring structure. Examples of the aryl group having a condensed ring structure include naphthalene, anthracene, and tetracene.

In Formula (1), X _{1 to} X ₃ may be unsubstituted or may have a substituent. The substituent may be in the alkyl chain or terminal. As the substituent, aryl group, alkenyl group, alkynyl group, alkoxy group, thioalkoxy group, alkanoyl group, alkenoyl group, aryloyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthiocarbonyl group, arylthiocarbonyl group, alcohol group Amino group, cyano group, nitroso group and various halogen atoms.

In the formula (1), X ₄ represents a hydrogen atom, an alkanoyl group, or an aryloyl group. The alkanoyl group and aryloyl group may be unsubstituted or have a substituent. The substituent may be in the alkyl chain or terminal. As the substituent, aryl group, alkenyl group, alkynyl group, alkoxy group, thioalkoxy group, alkanoyl group, alkenoyl group, aryloyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthiocarbonyl group, arylthiocarbonyl group, alcohol group Amino group, cyano group, nitroso group and various halogen atoms.

X ₁ is preferably a linear alkyl group, more preferably a methyl group or an ethyl group. X ₂ is preferably a linear alkyl group or an aryl group, and particularly preferably a methyl group or a phenyl group. X ₃ is preferably a linear alkyl group, particularly preferably a methyl group or an ethyl group. X ₄ is preferably an alkanoyl group or an aryloyl group, and more preferably a benzoyl group.

  In addition, the present invention is characterized in that the content of the photopolymerization initiator in the solid content of the blue photosensitive resin composition is 5 to 20 mass percent. The content of the photopolymerization initiator is more preferably in the range of 8 to 18% by mass, particularly preferably in the range of 10 to 15% by mass. When the content of the polymerization initiator is less than 5 mass percent, the exposure sensitivity of the blue photosensitive resin composition is insufficient and the productivity of the color filter is lowered. When the content of the photopolymerization initiator exceeds 20 mass percent, the content of the alkali-soluble resin in the blue photosensitive resin composition is lowered, the alkali development solubility is insufficient, the productivity is lowered, and the development stain is generated. This causes problems.

In the blue photosensitive resin composition of the present invention, other photopolymerization initiators can be used in combination with the photopolymerization initiator represented by the above formula (1). Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Acetophenone compounds such as butan-1-one, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzoate Benzophenone compounds such as zophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2- Thioxanthone compounds such as chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2-pi Peronyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine , 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine and other triazine compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and other oxime ester systems Compounds, phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, etc. Quinone compounds, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like are used. These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

[solvent]
Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,5,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butylal N-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic esters, and the like, used these alone or in mixtures.

[Blue photosensitive resin composition]
The blue photosensitive resin composition of the present invention is obtained by finely dispersing the blue colorant in the photosensitive resin composition using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, an attritor, and a paint conditioner. It can be dispersed and manufactured. When a pigment is used as the colorant, a dispersion aid such as a resin-type pigment dispersant, a dye derivative, or a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersing the pigment and has a great effect of preventing reaggregation of the pigment after dispersion, a blue photosensitive resin composition obtained by dispersing the pigment in the photosensitive resin composition using the dispersion aid. When an object is used, a color filter excellent in transparency can be obtained. The dispersion aid can be used in an amount of preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the colorant.

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the photosensitive transparent resin and the non-photosensitive transparent resin. It functions to stabilize dispersion in the resin composition. Resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polycarboxylic acid esters Siloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and the like Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are also used. These can be used alone or in admixture of two or more.

Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Te
SOLPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, manufactured by Abyssia, etc. 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, manufactured by Fuka Chemicals LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503 and the like.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used singly or in combination of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as laurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline These can be used alone or in admixture of two or more.

[Exposure method]
The blue photosensitive resin composition of the present invention uses a laser beam pulsating at a constant frequency as an exposure light source, forms a pattern of a display area by scanning exposure through a photomask having a predetermined pattern, and a shutter. It is used for a method of manufacturing a color filter by shielding a non-display area. Arbitrary repetitive patterns can be formed by synchronizing the movement of the substrate with the pulse interval. In addition, for example, when scanning a region where a pattern is not formed, such as between screens in the case of manufacturing a color filter with multiple impositions, light is shielded by a shutter to prevent unnecessary patterns from being formed in the region. Can do.

  The blue photosensitive resin composition of the present invention is characterized in that the laser light source is a solid (YAG) laser having a wavelength of 343 nm or 355 nm. Various other laser light sources such as excimer lasers and semiconductor lasers can be cited as pulsed laser light sources, but they each have problems such as high utility costs and insufficient output. Therefore, a solid (YAG) laser having high performance in both cost and output is preferably used.

In the blue photosensitive resin composition of the present invention, the laser beam frequency is 20 to 100 Hz.
It is characterized by being. The frequency of the laser beam is preferably in the range of 30 to 80 Hz, and particularly preferably in the range of 50 to 70 Hz. When the frequency is less than 20 Hz, it is necessary to lower the scanning speed in order to obtain an integrated exposure amount sufficient to cure the blue photosensitive resin composition of the present invention by multiple exposure, and productivity is lowered. When the frequency exceeds 100 Hz, it is necessary to move the stage at a high speed, and the load on the apparatus increases.

In addition, the blue photosensitive resin composition of the present invention is characterized in that the amount of energy per pulse of the laser beam is in the range of 0.5 to 2.0 mJ / cm ² . Energy per pulse is preferably in the range Of these the 0.6~1.5mJ / cm ^2, particularly preferably from 0.7~1.3mJ / cm ^2. When the energy amount per pulse is less than 0.5 mJ / cm ^2, it is necessary to reduce the scanning speed in order to obtain an integrated exposure amount sufficient to cure the blue photosensitive resin composition of the present invention by multiple exposure. There is a decrease in productivity. Increasing the amount of energy per pulse makes it possible to increase the scan speed and improve productivity, but it is technically difficult to exceed the current amount of energy per pulse exceeding 2.0 mJ / cm ^2. Is the situation.

[Color filter]
Moreover, this invention is a color filter which comprises the blue pixel formed using the above-mentioned blue photosensitive resin composition of this invention. In this color filter, the surface peeling of the pixel on the black matrix at the outer peripheral portion of the screen, which occurs when a blue pixel is formed by the above-described exposure method using the conventional blue photosensitive resin composition, does not occur. Although the mechanism of action that can prevent the occurrence of surface peeling is not clear, because of the problem of shutter opening and closing speed, internal curing is promoted to some extent by the weak light irradiated to the blue pixels on the black matrix. It is presumed that only the surface can be cured and the occurrence of peeling can be prevented. In the color filter of the present invention, since there is no surface peeling of the blue pixels on the outer peripheral black matrix, the transparent electrode layer is damaged when the color filter substrate and the drive circuit substrate are bonded in the cell process of manufacturing the liquid crystal display device. No abnormality occurs in the cell gap in the vicinity of the black matrix on the outer periphery. Therefore, high-quality image display is possible in the liquid crystal display device.

  As a substrate used for manufacturing the color filter of the present invention, a glass plate having a high transmittance with respect to visible light, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like is used.

  The blue pixel of the color filter of the present invention is formed by the following method. That is, the blue photosensitive resin composition of the present invention is applied on a substrate by a coating method such as spray coating, spin coating, slit coating, roll coating or the like. After drying, the pattern forming portion is cured under the conditions described in the above-described exposure method, and the uncured portion is removed by dipping in a solvent or an alkaline developer, or spraying the developer with a spray or the like. After washing with pure water, a blue pixel of the color filter of the present invention can be formed by performing a baking treatment.

  Each normal color pixel of the color filter of the present invention is formed by performing application, exposure, development, and hardening process in the same manner as the blue pixel. As the exposure process for each color pixel, for example, either normal ultraviolet light irradiation such as a high-pressure mercury lamp or laser light irradiation may be used. Thereby, the color filter of this invention which has a red, green, and blue coloring pixel can be manufactured.

  Each colored pixel other than the blue color can be formed using a normal color photosensitive resin composition containing each color coloring material, the transparent resin, and the polymerizable monomer.

  Examples of the red photosensitive resin composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, 185 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279, etc. are used. The red photosensitive resin composition includes C.I. I. Orange pigments such as Pigment Orange 43, 71, 73 can be used in combination.

  Examples of the green photosensitive resin composition include C.I. I. Pigment Green 7, 10, 36, 37, 58 or the like is used. The green photosensitive resin composition includes C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 , 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214 and the like can be used in combination.

  Specific examples of the present invention will be described below.

<Example 1>
[Method for producing pigment dispersion]
After uniformly stirring and mixing a mixture having the following composition, the mixture was dispersed for 2 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and filtered through a 5 μm filter. A blue pigment dispersion was prepared.
Ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6)
("Heliogen Blue L-6700F" manufactured by BASF) 11.0 parts-Phthalocyanine pigment derivative (following formula (4)) 1.0 part

・アクリルワニス溶液（固形分２０質量％） ４０．０部
・シクロヘキサノン ４８．０部
［青色感光性樹脂組成物（１）の製造］
下記組成の混合物を均一になるように攪拌混合した後、１μｍのフィルタで濾過し、青色感光性樹脂組成物（１）を得た。
・前記で調整した青色顔料分散体 ４５．０部
・アクリルワニス溶液（固形分２０質量％） ２３．０部
・重合性モノマー ４．０部
カプロラクトン変性ジペンタエリスリトールペンタ／ヘキサアクリレート（「日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＣＡ３０」）
・光重合開始剤 ２．４部
（チバガイギー社製「ＩｒｇａｃｕｒｅＯＸＥ０２」下記式（５））

Acrylic varnish solution (solid content 20% by mass) 40.0 parts Cyclohexanone 48.0 parts [Production of blue photosensitive resin composition (1)]
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a blue photosensitive resin composition (1).
-Blue pigment dispersion prepared as described above 45.0 parts-Acrylic varnish solution (solid content 20% by mass) 23.0 parts-Polymerizable monomer 4.0 parts Caprolactone-modified dipentaerythritol penta / hexaacrylate ("Nippon Kayaku "KAYARAD DPCA30")
Photopolymerization initiator 2.4 parts (“Irgacure OXE02” below formula (5) manufactured by Ciba Geigy)

・シクロヘキサノン ２５．６部
＜実施例２＞
[青色感光性樹脂組成物（２）の製造]
下記組成の混合物を均一になるように攪拌混合した後、１μｍのフィルタで濾過し、青色感光性樹脂組成物（２）を得た。
・前記で調整した青色顔料分散体 ４５．０部
・アクリルワニス溶液（固形分２０質量％） ２０．０部
・重合性モノマー ５．０部
カプロラクトン変性ジペンタエリスリトールペンタ／ヘキサアクリレート（「日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＣＡ３０」）
・光重合開始剤 １．８部
（チバガイギー社製「ＩｒｇａｃｕｒｅＯＸＥ０２」）
・増感剤（保土ヶ谷化学社製「ＥＡＢ−Ｆ」） ０．２部
・シクロヘキサノン ２８．０部
＜実施例３＞
[青色感光性樹脂組成物（３）の製造]
下記組成の混合物を均一になるように攪拌混合した後、１μｍのフィルタで濾過し、青色感光性樹脂組成物（３）を得た。
・前記で調整した青色顔料分散体 ４５．０部
・アクリルワニス溶液（固形分２０質量％） １７．０部
・重合性モノマー ４．２部
カプロラクトン変性ジペンタエリスリトールペンタ／ヘキサアクリレート（「日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＣＡ３０」）
・重合性モノマー １．８部
トリメチロールプロパントリアクリレート（「日本化薬社製「ＫＡＹＡＲＡＤ ＴＭＰＴＡ」）
・光重合開始剤 １．６部
（チバガイギー社製「ＩｒｇａｃｕｒｅＯＸＥ０２」）
・シクロヘキサノン ３０．４部
＜実施例４＞
[青色感光性樹脂組成物（４）の製造]
下記組成の混合物を均一になるように攪拌混合した後、１μｍのフィルタで濾過し、青色感光性樹脂組成物（４）を得た。
・前記で調整した青色顔料分散体 ３０．０部
・アクリルワニス溶液（固形分２０質量％） ３８．０部
・重合性モノマー ４．０部
カプロラクトン変性ジペンタエリスリトールペンタ／ヘキサアクリレート（「日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＣＡ３０」）
・光重合開始剤 ２．４部
（チバガイギー社製「ＩｒｇａｃｕｒｅＯＸＥ０２」）
・シクロヘキサノン ２５．６部
＜実施例５＞
[青色感光性樹脂組成物（５）の製造]
下記組成の混合物を均一になるように攪拌混合した後、１μｍのフィルタで濾過し、青色感光性樹脂組成物（５）を得た。
・前記で調整した青色顔料分散体 ４５．０部
・アクリルワニス溶液（固形分２０質量％） １９．０部
・重合性モノマー ４．０部
カプロラクトン変性ジペンタエリスリトールペンタ／ヘキサアクリレート（「日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＣＡ３０」）
・光重合開始剤 ３．２部
（ＡＤＥＫＡ社製「Ｎ１９１９」下記式（６））

-Cyclohexanone 25.6 parts <Example 2>
[Production of blue photosensitive resin composition (2)]
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a blue photosensitive resin composition (2).
・ Blue pigment dispersion prepared as above 45.0 parts ・ Acrylic varnish solution (solid content 20% by mass) 20.0 parts ・ Polymerizable monomer 5.0 parts Caprolactone-modified dipentaerythritol penta / hexaacrylate (“Nippon Kayaku "KAYARAD DPCA30")
-Photopolymerization initiator 1.8 parts ("Irgacure OXE02" manufactured by Ciba Geigy)
-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part-Cyclohexanone 28.0 parts <Example 3>
[Production of blue photosensitive resin composition (3)]
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a blue photosensitive resin composition (3).
-Blue pigment dispersion prepared as above 45.0 parts-Acrylic varnish solution (solid content 20% by weight) 17.0 parts-Polymerizable monomer 4.2 parts Caprolactone-modified dipentaerythritol penta / hexaacrylate ("Nippon Kayaku "KAYARAD DPCA30")
・ Polymerizable monomer 1.8 parts Trimethylolpropane triacrylate (“KAYARAD TMPTA” manufactured by Nippon Kayaku Co., Ltd.)
-Photopolymerization initiator 1.6 parts (“Irgacure OXE02” manufactured by Ciba Geigy)
Cyclohexanone 30.4 parts <Example 4>
[Production of blue photosensitive resin composition (4)]
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue photosensitive resin composition (4).
-30.0 parts of the blue pigment dispersion prepared as described above-38.0 parts of acrylic varnish solution (solid content 20% by mass)-4.0 parts of polymerizable monomer caprolactone-modified dipentaerythritol penta / hexaacrylate ("Nippon Kayaku "KAYARAD DPCA30")
Photopolymerization initiator 2.4 parts (“Irgacure OXE02” manufactured by Ciba Geigy)
Cyclohexanone 25.6 parts <Example 5>
[Production of blue photosensitive resin composition (5)]
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a blue photosensitive resin composition (5).
-Blue pigment dispersion prepared as above 45.0 parts-Acrylic varnish solution (solid content 20% by mass) 19.0 parts-Polymerizable monomer 4.0 parts Caprolactone-modified dipentaerythritol penta / hexaacrylate ("Nippon Kayaku "KAYARAD DPCA30")
-Photopolymerization initiator 3.2 parts ("N1919" following formula (6) manufactured by ADEKA)

・シクロヘキサノン ２８．８部
＜比較例１＞
［青色感光性樹脂組成物（６）の製造］
下記組成の混合物を均一になるように攪拌混合した後、１μｍのフィルタで濾過し、青色感光性樹脂組成物（６）を得た。
・前記で調整した青色顔料分散体 ４５．０部
・重合性モノマー ６．８部
カプロラクトン変性ジペンタエリスリトールペンタ／ヘキサアクリレート（「日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＣＡ３０」）
・光重合開始剤 ３．８部
（チバガイギー社製「Ｉｒｇａｃｕｒｅ３７９」）
・増感剤（保土ヶ谷化学社製「ＥＡＢ−Ｆ」） ０．４部
・シクロヘキサノン ４４．０部
＜比較例２＞
［青色感光性樹脂組成物（７）の製造］
下記組成の混合物を均一になるように攪拌混合した後、１μｍのフィルタで濾過し、青色感光性樹脂組成物（７）を得た。
・前記で調整した青色顔料分散体 ４５．０部
・重合性モノマー ６．８部
カプロラクトン変性ジペンタエリスリトールペンタ／ヘキサアクリレート（「日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＣＡ３０」）
・光重合開始剤 ３．８部
（チバガイギー社製「Ｉｒｇａｃｕｒｅ９０７」）
・増感剤（保土ヶ谷化学社製「ＥＡＢ−Ｆ」） ０．４部
・シクロヘキサノン ４４．０部
＜比較例３＞
［青色感光性樹脂組成物（８）の製造］
下記組成の混合物を均一になるように攪拌混合した後、１μｍのフィルタで濾過し、青色感光性樹脂組成物（８）を得た。
・前記で調整した青色顔料分散体 ４５．０部
・重合性モノマー ６．８部
カプロラクトン変性ジペンタエリスリトールペンタ／ヘキサアクリレート（「日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＣＡ３０」）
・光重合開始剤 ３．８部
（チバガイギー社製「ＩｒｇａｃｕｒｅＯＸＥ０１」）
・増感剤（保土ヶ谷化学社製「ＥＡＢ−Ｆ」） ０．４部
・シクロヘキサノン ４４．０部
＜比較例４＞
［青色感光性樹脂組成物（９）の製造］
下記組成の混合物を均一になるように攪拌混合した後、１μｍのフィルタで濾過し、青色感光性樹脂組成物（９）を得た。
・前記で調整した青色顔料分散体 ４５．０部
・アクリルワニス溶液（固形分２０質量％） １７．０部
・重合性モノマー ６．８部
カプロラクトン変性ジペンタエリスリトールペンタ／ヘキサアクリレート（「日本化薬社製「ＫＡＹＡＲＡＤ ＤＰＣＡ３０」）
・光重合開始剤（チバガイギー社製「ＩｒｇａｃｕｒｅＯＸＥ０２」） ０．８部
・シクロヘキサノン ３０．４部
［ブラックマトリックスの形成］
板厚０．７ｍｍの無アルカリガラス（コーニング社製「イーグル２０００」）基板に、図４の模式図に示すブラックマトリックスパターンを一般的なフォトリソグラフィー法により形成した。ブラックマトリックスのパターン線幅は２０μｍ、ピッチは１００μm、外周部のパターン線幅は５ｍｍとした。

Cyclohexanone 28.8 parts <Comparative example 1>
[Production of blue photosensitive resin composition (6)]
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a blue photosensitive resin composition (6).
-Blue pigment dispersion prepared as above 45.0 parts-Polymerizable monomer 6.8 parts Caprolactone-modified dipentaerythritol penta / hexaacrylate ("KAYARAD DPCA30" manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator 3.8 parts (“Irgacure 379” manufactured by Ciba Geigy)
-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part-cyclohexanone 44.0 parts <Comparative Example 2>
[Production of blue photosensitive resin composition (7)]
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue photosensitive resin composition (7).
-Blue pigment dispersion prepared as above 45.0 parts-Polymerizable monomer 6.8 parts Caprolactone-modified dipentaerythritol penta / hexaacrylate ("KAYARAD DPCA30" manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator 3.8 parts (“Irgacure 907” manufactured by Ciba Geigy)
・ Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part ・ Cyclohexanone 44.0 parts <Comparative Example 3>
[Production of blue photosensitive resin composition (8)]
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a blue photosensitive resin composition (8).
-Blue pigment dispersion prepared as above 45.0 parts-Polymerizable monomer 6.8 parts Caprolactone-modified dipentaerythritol penta / hexaacrylate ("KAYARAD DPCA30" manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator 3.8 parts (“Irgacure OXE01” manufactured by Ciba Geigy)
-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part-Cyclohexanone 44.0 parts <Comparative Example 4>
[Production of blue photosensitive resin composition (9)]
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a blue photosensitive resin composition (9).
-Blue pigment dispersion prepared as above 45.0 parts-Acrylic varnish solution (solid content 20% by mass) 17.0 parts-Polymerizable monomer 6.8 parts Caprolactone-modified dipentaerythritol penta / hexaacrylate ("Nippon Kayaku "KAYARAD DPCA30")
-Photopolymerization initiator ("Irgacure OXE02" manufactured by Ciba Geigy) 0.8 part-30.4 parts cyclohexanone [Formation of black matrix]
A black matrix pattern shown in the schematic diagram of FIG. 4 was formed on a non-alkali glass (Corning “Eagle 2000”) substrate having a thickness of 0.7 mm by a general photolithography method. The pattern line width of the black matrix was 20 μm, the pitch was 100 μm, and the pattern line width of the outer peripheral portion was 5 mm.

[Evaluation of blue photosensitive resin composition]
About the blue photosensitive resin compositions (1) to (5) of Examples 1 to 5 and the blue photosensitive resin compositions (6) to (9) of Comparative Examples 1 to 4 obtained above, the above black The substrate on which the matrix was formed was spin-coated so that the film thickness after coating was 2.4 μm. Next, a YAG laser with a wavelength of 355 nm is oscillated at an energy density of 1 mJ / cm ² per pulse, a frequency of 50 Hz, and a pulse width of 7 nsec, and the integrated exposure amount is obtained through a photomask having a stripe pattern corresponding to the opening of the black matrix Scan exposure was carried out while moving the substrate so that the value was 30 mJ / cm ² . At this time, light was shielded by opening and closing the shutter in synchronization with the movement of the substrate so that a pattern was not formed in the non-display area (the part not surrounded by the black matrix) of FIG. Further, spray development was performed with a developer comprising a 0.2% sodium carbonate aqueous solution to remove an unexposed portion, and then washed with ion-exchanged water to form a blue stripe pattern at the opening of the black matrix. About this board | substrate, the black matrix outer peripheral part was observed with the optical microscope. The evaluation was made with x indicating that the phenomenon that the surface of the blue pixel was turned up was observed, and ○ indicating that the phenomenon was not observed. The results are shown in Table 1.

本発明の青色感光性樹脂組成物（１）〜（５）を用いた場合においては、ブラックマトリックス外周部における青色画素の表面ハガレが認められなかった。一方、比較例の青色感光性樹脂組成物（６）〜（９）を用いた場合においては、いずれの組成物においてもブラックマトリックス外周部において青色画素の表面ハガレが認められた。

In the case of using the blue photosensitive resin compositions (1) to (5) of the present invention, no surface peeling of the blue pixels at the outer periphery of the black matrix was observed. On the other hand, in the case where the blue photosensitive resin compositions (6) to (9) of the comparative example were used, surface peeling of blue pixels was observed at the outer periphery of the black matrix in any composition.

  According to the blue photosensitive resin composition of the present invention, a color filter is manufactured by forming a pattern of a display area by scanning exposure using a laser beam as an exposure light source and shielding a non-display area by using a shutter. Even in this method, surface peeling of the blue pixels does not occur on the black matrix around the color filter that is the boundary between the display area and the non-display area. Therefore, the transparent electrode layer is not damaged when the color filter substrate and the drive circuit substrate are bonded in the cell process of manufacturing the liquid crystal display device, and no abnormality occurs in the cell gap near the black matrix in the outer peripheral portion. For this reason, a liquid crystal display device with good display quality can be obtained.

Claims (6)

Using a laser light source that oscillates at a constant frequency as an exposure light source, scan exposure is performed through a photomask having a predetermined pattern, and a non-display area is shielded by using a shutter. A blue photosensitive resin composition containing at least a blue colorant, a resin, a polymerizable monomer, a photopolymerization initiator, and a solvent used in a method for producing a color filter, wherein the photopolymerization initiator is represented by the following formula (1) It is an oxime ester-type compound containing the structure represented by this. It is a blue photosensitive resin composition characterized by the above-mentioned.

In the formula (1), X _{1 to} X ₃ each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms. The alkyl group may be linear or have a branched structure. Moreover, you may have a cyclic structure. X ₄ represents a hydrogen atom, an alkanoyl group, or an aryloyl group. X _{1 to} X ₄ may be unsubstituted or may have a substituent.   2. The blue photosensitive resin composition according to claim 1, wherein the content of the photopolymerization initiator in the solid content of the blue photosensitive resin composition is 5 to 20 mass percent.   The blue photosensitive resin composition according to claim 1, wherein the light source of the laser light is a solid (YAG) laser having a wavelength of 343 nm or 355 nm.   The blue photosensitive resin composition according to claim 1 or 3, wherein the laser beam has a frequency of 20 to 100 Hz. 5. The blue photosensitive resin composition according to claim 1, wherein the laser beam has an energy amount per pulse of 0.5 to 2.0 mJ / cm ² .   A color filter comprising a blue pixel formed using the blue photosensitive resin composition according to any one of claims 1 to 5.

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