JP6413320B2 - Column spacer for color filter for liquid crystal display device, color filter for liquid crystal display device, and liquid crystal display device - Google Patents

Description

  The present invention relates to a columnar spacer for a color filter for a liquid crystal display device, a color filter for a liquid crystal display device in which the columnar spacer is formed, and a liquid crystal display device manufactured using the color filter for a liquid crystal display device.

  Conventionally, in the liquid crystal display device technology, in order to maintain the thickness of the liquid crystal layer between the color filter side substrate and the thin film transistor (TFT) side substrate for liquid crystal display devices, glass or resin transparent spherical particles called spacers are used. (Beads) were sprayed inside the cell. However, since these spacers are transparent particles, if there is a liquid crystal and a spacer in the pixel, light leaks through the spacer particles during black display, and the liquid crystal is sealed. The presence of the spacer particles between the substrates disturbs the alignment of the liquid crystal molecules in the vicinity of the spacer particles, causing light leakage at this portion, and lowering the contrast of the liquid crystal display device, which adversely affects the display quality. It was. In addition, in a liquid crystal display device in which the distance between the two substrates (the thickness of the liquid crystal layer) is narrow, such as a ferroelectric liquid crystal, it is difficult to maintain a uniform and accurate distance between the two substrates using the spacer particles. there were.

  As a technique for solving such a problem, for example, a columnar resin spacer is formed on a black matrix having a lattice pattern located at a desired position, for example, between pixels by a photolithography method such as partial pattern exposure and development using a photosensitive resin. There has been proposed a method for forming the. Since such a spacer can be formed at a position avoiding the pixels, the display quality is not adversely affected as described above, and the display quality can be improved.

  Columnar spacers formed with conventional materials and methods are a method for obtaining a high-quality image without display unevenness, so that the thickness of the liquid crystal layer can be set as desired, and the thickness of the liquid crystal layer is kept uniform. In order to make this possible, it has been common to increase the hardness of the columnar spacers.

  However, as a problem caused by the high hardness of the columnar spacer, the liquid crystal display device is cooled at an extremely low temperature in Patent Document 1, so that even if the liquid crystal is contracted, the columnar spacer is too hard and the gap of the liquid crystal layer contracts. Therefore, the problem that voids are generated in the liquid crystal layer is described.

  Further, since the hardness of the columnar spacer is large, there is a concern that the columnar spacer may damage the alignment film on the TFT side when an external pressure or impact is applied.

  By the way, as shown in Patent Document 2, the shape of the columnar spacer when the columnar spacer is formed by a photolithography method is preferably a forward tapered shape. This is because the contact area between the color filter for a liquid crystal display device and the columnar spacer portion is wide, and thus there is an advantage that the adhesion is improved. However, the color filters for liquid crystal display devices are now becoming higher in definition, and it is necessary to reduce the contact area of columnar spacers on the color filters for liquid crystal display devices. If the surface area of the columnar spacer is small, there is a concern about a reduction in the restoration rate when a load is applied, and thus it is necessary to make the shape close to vertical.

JP 2007-148372 A Japanese Patent No. 5002936

  The present invention has been made in consideration of such circumstances, and the columnar spacer in the color filter for the liquid crystal display device does not cause damage to the alignment film on the TFT side due to external pressure or impact after the liquid crystal panel is formed. It is an object of the present invention to provide a color filter for a liquid crystal display device that enables easy image display.

In order to solve the above-mentioned problems in the present invention, first, in the invention of claim 1, a photosensitive material comprising at least a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and an organic solvent (D). A columnar spacer that is formed by a photolithography method using a conductive resin composition, and that makes a gap between a color filter for a liquid crystal display device and a TFT substrate constant,
When the columnar spacer is pushed with a load of 2 mN over 5 seconds with an indenter (Vickers indenter) having a quadrangular pyramid-shaped minute tip, the measured Vickers hardness (HV) is 33 or more and 36 or less, and ratio d / e of the upper base 90% linewidth d and the lower base 0% line width e of the columnar spacers Ri der 0.65 or more,
When the initial height of the columnar spacer is A, the height when a load is applied to the columnar spacer with a flat indenter of 50 μm × 50 μm is B, and the height after removing the load is C, A columnar spacer for a color filter for a liquid crystal display device, characterized in that the elastic recovery rate represented by [(C−B) / (A−B)] × 100 (%) is 90 or more and 92 or less. is there.

  In the invention of claim 2, in the photosensitive resin composition, the mass ratio of the solid content of the photopolymerizable compound (B) to the solid content of the binder resin (A) is 0.8 or more and 1.2 or less. A columnar spacer for a color filter for a liquid crystal display device according to claim 1.

  Moreover, in invention of Claim 3, the said photosensitive resin composition contains 1 or more types of components in which the photoinitiator (C) has a maximum absorption wavelength in 230-330 nm, It is characterized by the above-mentioned. Or it is set as the columnar spacer for color filters for liquid crystal display devices of 2.

  According to a fourth aspect of the present invention, there is provided a color filter for a liquid crystal display device, wherein the columnar spacer for a color filter for a liquid crystal display device according to any one of the first to third aspects is formed. is there.

  According to a fifth aspect of the present invention, there is provided a liquid crystal display device using the color filter for a liquid crystal display device according to the fourth aspect.

  Columnar spacers on color filters for liquid crystal display devices by adjusting the content of the photopolymerizable compound to the binder resin contained in the photosensitive resin composition to an appropriate range and setting the Vickers hardness of the surface after curing of the columnar spacers to 36 or less Can prevent the alignment film of the TFT side substrate after being made into a liquid crystal panel from being damaged. In addition, with regard to the decrease in the recovery rate, which is a concern due to a decrease in Vickers hardness, the shape of the columnar spacer is made closer to the vertical from the forward tapered shape by increasing the type of photopolymerization initiator, and the surface area of the upper base is increased. The restoration rate can be increased.

  Therefore, the present invention is for a liquid crystal display device that enables good image display without causing columnar spacers in the color filter for the liquid crystal display device to damage the alignment film on the TFT side due to external pressure or impact after the liquid crystal panel is formed. There is an effect that a color filter can be provided.

The figure which shows the definition regarding the shape of a columnar spacer. (A) is initial, (b) is load addition, (c) is a figure which shows the shape of the columnar spacer in load unloading about the measurement of the elastic restoring rate performed in order of initial stage, load addition, and load unloading.

  Hereinafter, an embodiment of the present invention will be described.

  The photosensitive resin composition used for the columnar spacer for a color filter for a liquid crystal display device of the present invention comprises at least a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), an organic solvent (D Vickers hardness (HV) measured when a columnar spacer formed by photolithography is pushed with a load of 2 mN over 5 seconds with an indenter (Vickers indenter) having a quadrangular pyramid tip. It is 30 or more and 36 or less.

  If the Vickers hardness of the columnar spacer is larger than 36, there is a concern that the alignment film on the TFT side may be damaged by external pressure or impact after the liquid crystal panel is formed. This concern can be eliminated by reducing the hardness of the columnar spacer.

  On the other hand, if the hardness of the columnar spacer is small, the restoration rate when a load is applied is lowered, which may lead to display failure of the liquid crystal display device. Therefore, by reducing the shape of the columnar spacer from the forward tapered shape to the vertical shape and increasing the surface area of the upper bottom portion of the columnar spacer, it is possible to suppress a reduction in the restoration rate. If the ratio d / e between the upper base 90% line width d and the lower base 0% line width e of the columnar spacer is smaller than 0.65, the reduction of the restoration rate cannot be suppressed, leading to display failure of the liquid crystal display device. .

  If the Vickers hardness of the columnar spacer is less than 30, the restoration rate is lowered even when the columnar spacer is made nearly vertical, leading to a display failure of the color filter for a liquid crystal display device.

  The binder resin (A) according to the present invention will be described. The binder resin includes non-photosensitive resins such as thermoplastic resins and thermosetting resins and photosensitive resins. If necessary, the binder resin can be used alone or in admixture of two or more monomers or oligomers that are precursors thereof that are cured by irradiation with radiation to form a binder resin.

  Examples of thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic 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 an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

  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 carboxy group, and 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.

  Next, the photopolymerizable compound (B) will be described. Examples of photopolymerizable compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, tri Various acrylic esters and methacrylic esters such as methylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, (meth ) Acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile and the like.

  Moreover, you may use the polyfunctional (meth) acrylate containing a carboxy group as a photopolymerizable compound. The polyfunctional (meth) acrylate containing a carboxy group is more preferable because the linearity and cross-sectional shape of the filter segment are further improved as compared with the polyfunctional acrylate not containing a carboxy group. Examples of polyfunctional (meth) acrylates containing a carboxy group include trihydric or higher polyhydric alcohols, (meth) acrylates, and esterified products of polyvalent carboxylic acids. The polyfunctional (meth) acrylate containing a carboxy group may have a urethane bond in the structure. As a commercial item of the polyfunctional (meth) acrylate containing a carboxy group, for example, TO-1382 containing a dibasic acid anhydride adduct of dipentaerythritol penta (meth) acrylate manufactured by Toagosei Co., Ltd. may be mentioned. .

  Next, the photopolymerization initiator (C) will be described. Examples of the photopolymerization initiator 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) -butane- Acetophenone photopolymerization initiators such as 1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 − Benzophenone photopolymerization initiators such as phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Thioxanthone photopolymerization initiators such as 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-piperonyl-4,6-bis (trichloromethyl) -s- Triazine, 2,4-bis (trick (Romethyl) -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, etc. Examples thereof include a polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, and an imidazole photopolymerization initiator. A photoinitiator can be used individually by 1 type or in mixture of 2 or more types. Moreover, it is preferable that the photoinitiator contains 1 or more types of components which have a maximum absorption wavelength in 230-330 nm.

  The amount of the photopolymerization initiator used is preferably 0.05 to 50% by mass, more preferably 0.5 to 30% by mass based on the total solid content of the photosensitive resin composition.

  Moreover, a thermal crosslinking agent can also be added as needed. Examples of the thermal crosslinking agent include melamine resin and epoxy resin.

  Examples of the melamine resin include alkylated melamine resins (methylated melamine resin, butylated melamine resin, etc.), mixed etherified melamine resins, and the like, which may be a high condensation type or a low condensation type. Any of these may be used alone or in admixture of two or more. Moreover, an epoxy resin can also be mixed and used as needed.

  Examples of the epoxy resin include glycerol / polyglycidyl ether, trimethylolpropane / polyglycidyl ether, resorcin / diglycidyl ether, neopentyl glycol / diglycidyl ether, 1,6-hexanediol / diglycidyl ether, ethylene glycol (polyethylene). Glycol) and diglycidyl ether. Also about these, it can use individually or in mixture of 2 or more types.

  Next, the organic solvent (D) will be described. Suitable organic solvents to be used include, for example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol. Examples thereof include monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, etc., and these are used alone or in combination.

  Next, the photosensitive resin composition used for the black matrix formation of the color filter for liquid crystal display devices in this invention is demonstrated.

  In order to form a lattice-like black matrix (hereinafter referred to as BM) on a transparent substrate, a black photosensitive colored resin composition is used. The black photosensitive colored resin composition is not particularly limited as long as it can achieve the required light shielding properties. In the present invention, at least a photopolymerization initiator and a photopolymerizable compound are added to a dispersion in which a black pigment such as a carbon black pigment is dispersed in a resin from the viewpoint that pattern formation is easy and uniformity is obtained. The resulting black photosensitive colored resin composition is used.

  The pigments that can be used in the black photosensitive coloring resin composition include carbon black pigments and titanium carbon black pigments, and there is a problem even if a red pigment, a green pigment, and a blue pigment are mixed as necessary. Absent. As carbon black used as a light-shielding agent, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850 manufactured by Mitsubishi Chemical Corporation, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44 , # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234 , Diamond black I, diamond black LI, diamond black II, diamond Rack 339, diamond black SH, diamond black SHA, diamond black LH, diamond black H, diamond black HA, diamond black SF, diamond black N550M, diamond black E, diamond black G, diamond black R, diamond black N760M, diamond black LR . Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb. Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw1, ColorBlack Fw1, ColorBlack F170, BlackBlack 170, BlackBlack 170 , SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140V And the like.

  Resins that can be used in the black photosensitive colored resin composition include thermoplastic resins, thermosetting resins, and photosensitive resins.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, 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.

  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.

  A polymerizable monomer or oligomer is used as the photopolymerizable compound. Polymerizable monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meta ) Acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate Neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, Various acrylic esters and methacrylic esters such as caprolactone-modified dipentaerythritol hexaacrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

  The amount added is preferably as long as it does not impair applicability and development suitability, and is about 20% by mass to 80% by mass, more preferably 50% by mass to 70%, based on the total solid content of the black photosensitive colored resin composition. It is about mass%. If the addition amount is less than this range, the crosslinkability is insufficient and the liquid crystal resistance deteriorates. If the addition amount is larger than this range, unevenness and pinholes are likely to occur when the black photosensitive colored resin composition is applied, and the applicability is remarkably deteriorated, or the solubility in the developer is remarkably lowered, resulting in poor development suitability. End up.

  As photopolymerization initiators contained in the black photosensitive colored resin composition, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2 -Acetophenone compounds such as methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether Benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated Benzophenone compounds such as nzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone Thioxanthone compounds such as 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- Piperonyl-4,6-bis (trichloromethyl)- -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)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl) Oxime ester compounds such as 2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) fe Phosphine compounds such as nylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone, borate compounds, carbazole compounds, imidazole Compounds, titanocene compounds and the like are used. These photopolymerization initiators can be used alone or in combination.

  The amount of the photopolymerization initiator used is preferably 0.5 to 50% by mass, more preferably 3 to 30% by mass based on the total solid content of the black photosensitive colored resin composition.

Further, as sensitizers, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-Ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethyl) Amine-based compounds such as amino) benzophenone can also be used in combination. These sensitizers can be used alone or in combination.

  The amount of the sensitizer used is preferably 0.5 to 60% by mass, more preferably 3 to 40% by mass based on the total amount of the photopolymerization initiator and the sensitizer.

  Furthermore, the black photosensitive coloring resin composition can contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination.

  The amount of the polyfunctional thiol used is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the total solid content of the black photosensitive colored resin composition. If it is less than 0.1% by mass, the effect of adding a polyfunctional thiol is insufficient, and if it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

  Moreover, a thermal crosslinking agent can also be added as needed. Examples of the thermal crosslinking agent include melamine resin and epoxy resin.

  Examples of the melamine resin include alkylated melamine resins (methylated melamine resin, butylated melamine resin, etc.), mixed etherified melamine resins, and the like, which may be a high condensation type or a low condensation type. Any of these may be used alone or in admixture of two or more. Moreover, an epoxy resin can also be mixed and used as needed.

  Examples of the epoxy resin include glycerol / polyglycidyl ether, trimethylolpropane / polyglycidyl ether, resorcin / diglycidyl ether, neopentyl glycol / diglycidyl ether, 1,6-hexanediol / diglycidyl ether, ethylene glycol (polyethylene). Glycol) diglycidyl ether. Also about these, it can use individually or in mixture of 2 or more types.

  Examples of organic solvents that can be used in the black photosensitive colored resin composition include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, and ethyl cellosolve. , Methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination.

  Next, the photosensitive colored resin composition necessary for forming the color layer of the color filter for a liquid crystal display device in the present invention will be described. The photosensitive colored resin composition includes at least a pigment dispersion in which a pigment is dispersed in a binder resin.

  The specific example of the organic pigment which can be used for the photosensitive coloring resin composition which forms the coloring pixel of the color filter of this invention is shown with a color index number.

  Examples of the red photosensitive coloring resin composition for forming a red pixel include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, Red pigments such as H.264, 272, and 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red photosensitive colored resin composition.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 144, 146, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 1 73, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 and the like.

  Examples of orange pigments include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 and the like.

  Examples of the green photosensitive coloring resin composition for forming a green pixel include C.I. I. Pigment Green 7, 10, 36, 37, 58, or other green pigments can be used. The green photosensitive colored resin composition can be used in combination with the same yellow pigment as the red photosensitive colored resin composition.

Examples of the blue photosensitive coloring resin composition for forming a blue pixel include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 80, etc., preferably C.I. I. Pigment Blue
15: 6 can be used. The blue photosensitive colored resin composition includes C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like, preferably C.I. I. Pigment Violet 23 can be used in combination.

  In combination with the organic pigment, an inorganic pigment may be used in combination in order to ensure good coatability, sensitivity, developability and the like while balancing saturation and lightness. Inorganic pigments include yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green and other metal oxide powders, metal sulfide powders, metal powders, etc. Can be mentioned. Furthermore, for color matching, a dye can be contained within a range that does not lower the heat resistance.

  The transparent resin that can be used for the photosensitive colored resin composition is a 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. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin. If necessary, the transparent resin can be used alone or in admixture of two or more monomers or oligomers that are precursors thereof that are cured by irradiation with radiation to produce a transparent resin.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, 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.

  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.

  A polymerizable monomer or oligomer is used as the photopolymerizable compound. Polymerizable monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meta ) Acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate Neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, Various acrylic esters and methacrylic esters such as caprolactone-modified dipentaerythritol hexaacrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

  The amount added is preferably as long as it does not impair the applicability and development suitability, and is based on the total solid content of the photosensitive colored resin composition, about 20% by mass to 80% by mass, more preferably 50% by mass to 70% by mass. %. If the addition amount is less than this range, the crosslinkability is insufficient and the liquid crystal resistance deteriorates. If the added amount is larger than this range, unevenness and pinholes are likely to occur when the photosensitive colored resin composition is applied, and the applicability is remarkably deteriorated, or the solubility in the developer is remarkably reduced, resulting in poor development suitability. End up.

  When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the photosensitive colored resin composition. Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone compounds such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin compounds such as dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 Benzophenone-based compounds such as methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4- Thioxanthone compounds such as diisopropylthioxanthone and 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-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (tri (Loromethyl) -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 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 ′ -Methoxy-naphthyl) ethylidene) oxime ester compounds such as hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4, Phosphine compounds such as 6-trimethylbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, etc. Used. These photopolymerization initiators can be used alone or in combination.

  The amount of the photopolymerization initiator used is preferably 0.5 to 50% by mass, more preferably 3 to 30% by mass based on the total solid content of the photosensitive colored resin composition.

  Further, as sensitizers, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-Ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethyl) Amine-based compounds such as amino) benzophenone can also be used in combination. These sensitizers can be used alone or in combination.

  The amount of the sensitizer used is preferably 0.5 to 60% by mass, more preferably 3 to 40% by mass based on the total amount of the photopolymerization initiator and the sensitizer.

  Furthermore, the multifunctional thiol which functions as a chain transfer agent can be contained in the photosensitive colored resin composition. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination.

  The amount of the polyfunctional thiol used is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, based on the total solid content of the photosensitive colored resin composition. If it is less than 0.1% by mass, the effect of adding a polyfunctional thiol is insufficient, and if it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

  Moreover, a thermal crosslinking agent can also be added as needed. Examples of the thermal crosslinking agent include melamine resin and epoxy resin.

  Examples of the melamine resin include alkylated melamine resins (methylated melamine resin, butylated melamine resin, etc.), mixed etherified melamine resins, and the like, which may be a high condensation type or a low condensation type. Any of these may be used alone or in admixture of two or more. Moreover, an epoxy resin can also be mixed and used as needed.

  Examples of the epoxy resin include glycerol / polyglycidyl ether, trimethylolpropane / polyglycidyl ether, resorcin / diglycidyl ether, neopentyl glycol / diglycidyl ether, 1,6-hexanediol / diglycidyl ether, ethylene glycol (polyethylene). Glycol) diglycidyl ether. Also about these, it can use individually or in mixture of 2 or more types.

  The photosensitive colored resin composition can contain an organic solvent as necessary. Examples of the organic solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination.

Finally, the material of the overcoat layer may be any material that can be formed on the color filter and is transparent in the visible range and applicable to the alignment film forming process and the liquid crystal panel forming process, and commercially available organic materials can be applied . This overcoat layer is smooth and tough, has transparency, high heat resistance and light resistance, does not cause deterioration such as yellowing and whitening over a long period of time, water resistance, solvent resistance, acid resistance In addition, it is necessary to have excellent alkali resistance. Examples of such resins include epoxy resins, acrylic resins, acrylic epoxy resins, phenol resins, polyimide resins, silicon-containing polyimides, polyimide siloxane films, and the like. Among these, polyimide resins such as polyimide resin, silicon-containing polyimide, and polyimidesiloxane are preferable from the viewpoint of chemical resistance. On the other hand, epoxy resins and acrylic resins are preferable from the viewpoints of flatness and photocurability. The material constituting the overcoat layer may be photosensitive or non-photosensitive.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this Example. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. The pigment symbol indicates a color index number. For example, “PR254” represents “CI PigmentRed 254”. A color filter for a liquid crystal display device using the photosensitive resin composition for columnar spacers shown in Examples and Comparative Examples was produced by the following method.

  The manufacturing method of the black photosensitive coloring resin composition used for the BM layer formed on a transparent substrate below and the BM layer forming method are shown.

<Production Method of Black Photosensitive Colored Resin Composition>
As a black photosensitive colored resin composition, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to obtain a black photosensitive colored resin composition.

-Carbon black dispersion: 21.0% by weight (manufactured by Mikuni Color Co., Ltd. (TPBK-2016)
Resin: V259-ME (manufactured by Nippon Steel Chemical Co., Ltd.) (solid content 56.1% by weight) 7.6% by weight
Photopolymerizable compound: DPHA (manufactured by Nippon Kayaku Co., Ltd.) 1.9% by weight
Photopolymerization initiator: OXE-02 (Ciba Specialty Chemicals)
0.6% by weight
Solvent: Propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, or a mixture thereof 67.9% by weight
・ Leveling agent: BYK-330 / Bic Chemie 1.0% by weight

<Formation of resin BM layer>
The black photosensitive colored resin composition was applied on the transparent substrate by spin coating so as to have a film thickness of 1.5 μm. After drying under reduced pressure, the film was dried at 100 ° C. for 3 minutes, and then exposed in a lattice pattern with a photomask using an exposure machine. The exposure amount was 50 mJ / cm ² and the distance (exposure gap) between the photomask and the substrate was 70 μm. Thereafter, development was carried out for a time necessary to completely wash away unexposed portions with an alkali developer, followed by heat treatment at 230 ° C. for 60 minutes to fix and form a lattice-like resin BM layer on the transparent substrate. The alkaline developer has the following composition. Similarly, in the step of forming the color layer, the overcoat layer, and the columnar spacer, development is performed using the following alkaline developer.

・ 1.5% by weight sodium carbonate
・ Sodium bicarbonate 0.5% by weight
・ Anionic surfactants ("Perirex NBL" manufactured by Kao Corporation)
8.0% by weight
・ Water 90% by weight

  A method for producing a photosensitive colored resin composition used for a color layer in a color filter for a liquid crystal display device and a method for forming a color layer are described below.

<Preparation of red pigment dispersion>
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a red pigment dispersion.

-Red pigment: C.I. I. Pigment Red254 18 parts by weight Red pigment: C.I. I. Pigment Red 177 2 parts by weight Dispersant: (Ajinomoto Fine Techno Co., Ltd. “Ajisper PB821”) 2 parts by weight Acrylic varnish (solid content 20%) 50 parts by weight Cyclohexanone 28 parts by weight

<Preparation of transparent acrylic resin solution>
Next, 370 parts by weight of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator is added dropwise over the course of 1 hour at the same temperature. Went.

・ 32 parts by weight of methacrylic acid 10 parts by weight of methyl methacrylate 44 parts by weight of n-butyl methacrylate 14 parts by weight of 2-hydroxyethyl methacrylate 4 parts by weight of 2,2′-azobisisobutyronitrile

  After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part by weight of azobisisobutyronitrile dissolved in 50 parts by weight of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A solution of a non-photosensitive transparent resin was obtained. After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and the previously synthesized transparent acrylic resin solution had a nonvolatile content of 20% by weight. Cyclohexanone was added so that a transparent acrylic resin solution was prepared.

<Preparation of red photosensitive colored resin composition>
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 5 μm filter to obtain a red photosensitive colored resin composition.

・ 55.3% by weight of the above dispersion
-13.2% by weight of the above transparent acrylic resin solution
Photopolymerizable compound: Dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) 4.5% by weight
Photopolymerization initiator: (Irgacure 379, manufactured by Ciba Specialty Chemicals)
1.0% by weight
Surfactant: 1: 1 solution of BYK-323 and BYK-348 (manufactured by Big Chemie Japan) 1.6% by weight
・ Solvent: 24.4% by weight of cyclohexanone

<Preparation of green pigment dispersion>
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a green pigment dispersion.

Green pigment: C.I. I. Pigment Green 36 (“Rionol Green 6YK” manufactured by Toyo Ink Co., Ltd.) 7 parts by weight / yellow pigment: C.I. I. Pigment Yellow 150 ("Funcheon First Yellow Y-5688" manufactured by Bayer) 5 parts by weight Dispersant ("Disperbyk-163" manufactured by Big Chemie) 2 parts by weight Acrylic varnish (solid content 20%) 48 parts by weight Cyclohexanone 38 Parts by weight

<Preparation of green photosensitive colored resin composition>
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to obtain a green photosensitive colored resin composition.

-56.6% by weight of the above dispersion
-11.0% by weight of the above transparent acrylic resin solution
Photopolymerizable compound: Dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) 4.0% by weight
Photopolymerization initiator: Irgacure 907 manufactured by Ciba Specialty Chemicals
1.7% by weight
Surfactant: FZ-2122 (manufactured by Toray Dow Corning)
1.2% by weight
・ Solvent: 25.5% by weight of cyclohexanone

<Preparation of blue pigment dispersion>
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a blue pigment dispersion.

Blue pigment: C.I. I. Pigment Blue 15: 6 (“Lionol Blue ES” manufactured by Toyo Ink Co., Ltd.) 4 parts by weight, dispersant (“Solce Birds 20000” manufactured by Zeneca) 1 part by weight, acrylic varnish (solid content 20%) 45 parts by weight, cyclohexanone 50 Parts by weight

<Preparation of blue photosensitive colored resin composition>
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to obtain a blue photosensitive colored resin composition 1.
-38.0% by weight of the above dispersion
・ The above transparent acrylic resin solution 18.3% by weight
Photopolymerizable compound: dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) 4.7% by weight
Photopolymerization initiator: Irgacure 907 manufactured by Ciba Specialty Chemicals
2.3% by weight
Surfactant: FZ-2122 (manufactured by Toray Dow Corning) 1.3% by weight
・ Solvent: 35.4% by weight of cyclohexanone

<Formation of color layer>
On the transparent substrate on which the resin BM layer was formed, the red photosensitive colored resin composition was applied by spin coating so that the film thickness became 2.0 μm. After drying under reduced pressure, ultraviolet light was exposed at an exposure amount of 100 mJ / cm ² through a photomask for forming a predetermined pattern. The exposure gap was 150 μm. Development is performed for a time necessary to completely wash away the unexposed portion of the red photosensitive colored resin composition film with the alkali developer, and the pattern of the resin BM is formed on the striped red layer by heating at 230 ° C. for 20 minutes. It formed on the formed transparent substrate.

Next, the green photosensitive colored resin composition was applied on a transparent substrate on which a red layer was formed by spin coating so that the film thickness was 2.0 μm. After drying under reduced pressure, the red photosensitive colored resin composition is exposed to the same location as the red photosensitive colored resin composition, with the same exposure amount and exposure gap, and the green photosensitive colored resin composition film is not yet formed with an alkaline developer. Development was performed for a time necessary to completely wash away the exposed portion, and heating was performed at 230 ° C. for 20 minutes to form a striped green layer adjacent to the red layer.

  Further, with respect to the blue photosensitive colored resin composition, a striped blue layer adjacent to the red layer and the green layer was formed by the same method so as to have a film thickness of 2.0 μm.

<Preparation of photosensitive resin composition for overcoat layer formation>
The photosensitive resin composition for overcoat layer formation was produced with the following method.

<Resin synthesis>
In a five-necked reaction vessel with an internal volume of 2 liters, 800 g of propylene glycol monomethyl ether acetate (PGMAc), 30 g of benzyl methacrylate (BzMA), 78 g of butyl methacrylate (BMA), 44 g of methacrylic acid (MAA), hydroxyethyl methacrylate (HEMA) 48 g and azobisisobutyronitrile (AIBN) 4 g were added and heated at 80 ° C. for 6 hours while blowing nitrogen to obtain a resin solution.

<Synthesis of photosensitive resin composition for overcoat layer formation>
The photosensitive resin composition was produced by mixing the compound shown below.

-Binder resin: 34% by weight of the above resin
Photopolymerizable compound: dipentaerythritol hexaacrylate 13.5% by weight
Photopolymerization initiator: 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one 1.2% by weight
Surfactant: 1% polyether-modified silicone oil SH8400 (trade name: manufactured by Tore Silicone Co., Ltd.) 0.55% by weight
Silane coupling agent: KBM-403 Shin-Etsu Chemical Co., Ltd. 1.1% by weight
Organic solvent: Propylene glycol monomethyl ether acetate 49.65% by weight

<Formation of overcoat layer>
The above-described photosensitive resin composition for forming an overcoat layer is applied on a substrate on which a resin BM layer and a color layer are formed using a spin coat method so as to have a film thickness of 1.5 μm, and dried at 90 ° C. for 5 minutes. did. 150 mJ / cm ^{2 was} irradiated with light from a high-pressure mercury lamp through a photomask for overcoat formation. The distance (exposure gap) between the photomask and the substrate was 100 μm. Thereafter, development was performed for a time necessary to completely wash away the unexposed portion using the developer used for the production of the resin BM layer and the colored layer. After washing with water, baking was performed at 230 ° C. for 60 minutes to form an overcoat layer on the transparent substrate on which the color layer was formed.

  Columnar spacers were formed on the substrate on which the overcoat was formed using the photosensitive resin composition for columnar spacers.

(Preparation of photosensitive resin composition for columnar spacer)
The photosensitive resin composition for columnar spacers was produced by the method shown below.

・ Synthesis of binder resin In a five-necked reaction vessel with an internal volume of 2 liters, 486 g of propylene glycol monomethyl ether acetate (PGMAc), phenol novolac epoxy resin (“EPPN-201” manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 190)) 264 g, 84 g of acetic acid, and 1.8 g of triphenylphosphine (TPP) were added and heated at 80 ° C. for 6 hours while blowing nitrogen. Furthermore, 136 g of tetrahydrophthalic anhydride was added to the acetic acid adduct solution of the novolak resin thus obtained, and heated at 70 ° C. for 10 hours to synthesize a binder resin. Thereafter, cyclohexanone was added so that the nonvolatile content was 20% by weight to obtain a resin solution a.

Synthesis of photosensitive resin composition The binder resin (resin solution a), photopolymerizable compound, photopolymerization initiator, and surfactant component shown in the following examples and comparative examples are mixed in the photosensitive resin composition. It diluted with cyclohexanone so that a part might be 30 weight%, and the photosensitive resin composition for columnar spacers was prepared.

<Example 1>
Photopolymerizable compound “PET3A” manufactured by Osaka Organic Chemical Industry Co., Ltd. 18.2% by weight
-Binder resin resin solution a 75.8% by weight
Photopolymerization initiator “Irgacure 907” manufactured by Ciba Specialty Chemicals 4.4% by weight
(Maximum absorption wavelength 307 nm)
Nippon Kayaku Co., Ltd. “Kayacure DETX” 1.5% by weight
・ Surfactant DIC "Megafac F445" 0.1% by weight

<Example 2>
Photopolymerizable compound “PET3A” manufactured by Osaka Organic Chemical Industry Co., Ltd. 13.0% by weight
・ Binder resin
Resin solution a 81.0% by weight
Photopolymerization initiator “Irgacure 907” manufactured by Ciba Specialty Chemicals 4.4% by weight
Nippon Kayaku Co., Ltd. “Kayacure DETX” 1.5% by weight
・ Surfactant DIC "Megafac F445" 0.1% by weight

<Comparative Example 1>
Photopolymerizable compound “PET3A” manufactured by Osaka Organic Chemical Industry Co., Ltd. 21.7% by weight
・ Binder resin
Resin solution a 72.3 wt%
Photopolymerization initiator “Irgacure 907” manufactured by Ciba Specialty Chemicals 4.4% by weight
Nippon Kayaku Co., Ltd. “Kayacure DETX” 1.5% by weight
・ Surfactant DIC "Megafac F445" 0.1% by weight

<Comparative example 2>
Photopolymerizable compound “PET3A” manufactured by Osaka Organic Chemical Industry Co., Ltd. 18.2% by weight
・ Binder resin
Resin solution a 75.8% by weight
Photopolymerization initiator TRG278 (maximum absorption wavelength 357 nm) 5.9% by weight
・ Surfactant DIC "Megafac F445" 0.1% by weight

<Comparative Example 3>
Photopolymerizable compound “PET3A” manufactured by Osaka Organic Chemical Industry Co., Ltd. 13.0% by weight
-Binder resin resin solution a 81.0% by weight
Photopolymerization initiator TRG278 (maximum absorption wavelength 357 nm) 5.9% by weight
・ Surfactant DIC "Megafac F445" 0.1% by weight

<Comparative example 4>
-Photopolymerizable compound "PET3A" manufactured by Osaka Organic Chemical Industry Co., Ltd. 8.5% by weight
-Binder resin resin solution a 85.5% by weight
Photopolymerization initiator “Irgacure 907” manufactured by Ciba Specialty Chemicals 4.4% by weight
Nippon Kayaku Co., Ltd. “Kayacure DETX” 1.5% by weight
・ Surfactant DIC "Megafac F445" 0.1% by weight

<Comparative Example 5>
Photopolymerizable compound “PET3A” manufactured by Osaka Organic Chemical Industry Co., Ltd. 10.1% by weight
-Binder resin resin solution a 83.9% by weight
Photopolymerization initiator “Irgacure 907” manufactured by Ciba Specialty Chemicals 4.4% by weight
Nippon Kayaku Co., Ltd. “Kayacure DETX” 1.5% by weight
・ Surfactant DIC "Megafac F445" 0.1% by weight

<Formation of columnar spacer>
Columnar spacers were formed using the columnar spacer-forming photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1 to 5. On the transparent substrate on which the resin BM layer, the color layer, and the overcoat layer described above are formed, the columnar spacer forming photosensitive resin composition is spin-coated so that the finished film thickness is 3.5 μm. Dried for minutes. Next, light from a high-pressure mercury lamp was irradiated at a dose of 100 mJ / cm ² through a photomask for forming a circular columnar spacer having a mask opening diameter of 8 μmφ. The exposure was performed with the distance (exposure gap) between the photomask and the substrate being 100 μm. Thereafter, development is performed using an alkali developer similar to the formation of the resin BM layer and the color layer, and after washing with water, heating is performed at 230 ° C. for 30 minutes to form a columnar spacer, and a color filter for a liquid crystal display device is formed. Obtained.

(Vickers hardness evaluation)
The Vickers hardness of the columnar spacer on the color filter for a liquid crystal display device produced using the photosensitive resin composition for columnar spacers of Examples and Comparative Examples was measured using a microfilm hardness meter HM2000 manufactured by Fischer Instruments. A numerical value (HV) when a square pyramid indenter (Vickers indenter) was pushed in with a load of 2 mN over 5 seconds was used as a measured value.

(Shape evaluation)
With respect to the line width of the columnar spacer as shown in FIG. 1, the ratio d / e of the line width d of the upper base 90% and the line width e of the lower base 0% was evaluated using a scanning electron microscope (SEM). S-4800 manufactured by Hitachi High-Technologies Corporation was used for the scanning electron microscope. Here, the upper base 90% is a portion indicated by a columnar spacer x% height b in the case of x = 90 in FIG. 1, and a portion having a height 90% of the columnar spacer height a. That is. In addition, the lower base 0% is a portion indicated by a columnar spacer y% height c in the case of y = 0 in FIG. 1 and is a portion having a height of 0% of the columnar spacer height a. That is, it is the bottom of the columnar spacer.

(Elasticity measurement)
The elastic properties of columnar spacers of color filters for liquid crystal display devices produced using the photosensitive resin compositions for columnar spacers of Examples and Comparative Examples were evaluated by a microfilm hardness meter HM2000 manufactured by Fisher Instruments. For the elastic characteristics, a flat indenter of 50 μm × 50 μm was used and pushed in with a load of 20 mN over 10 seconds, and the elastic recovery rate was evaluated. The elastic recovery rate was calculated according to the following formula. (See Figure 2)
A: Initial height of the columnar spacer B: Height when a predetermined load is applied C: Height after a predetermined load is applied and then the load is removed Elastic recovery rate: [(CB) / ( A-B)] × 100 (%) deformation rate.

(Alignment film damage test)
A color filter for a liquid crystal display device in which columnar spacers were formed using the photosensitive resin compositions for columnar spacers of Examples and Comparative Examples was made into a panel, and a pressing test was carried out by pressing the load 10,000 times from the TFT side with 10N applied. A film in which the TFT-side alignment film after the pressing test was not scratched was rated as ◯, and a film in which the film was scratched was marked as x.

(Pressure test unevenness evaluation)
A color filter for a liquid crystal display device in which columnar spacers are formed using the photosensitive resin composition for columnar spacers of Examples and Comparative Examples is made into a panel, and a steel ball having a diameter of 11 mm is freely dropped from a height of 10 cm, followed by display unevenness. The presence or absence of was investigated. A sample in which no unevenness was observed was marked with ◯, and a sample with unevenness was marked with ×.

  The evaluation results are shown in Table 1 below. In Comparative Example 4, since the sensitivity was insufficient and the columnar spacers could not be formed by the photolithography method, each evaluation was not performed.

  When a photosensitive resin composition having a large Vickers hardness, that is, a hard photosensitive resin composition is used as a columnar spacer, the columnar spacer damages the alignment film due to external pressure when the panel is formed. A reduction in the restoration rate, which is a concern by lowering the Vickers hardness, can be suppressed by bringing the shape of the columnar spacer closer to the vertical. However, if the Vickers hardness is too small, the shape control cannot suppress the reduction of the restoration rate, and when the panel is formed, an external pressure or an impact is applied to cause display unevenness. Further, when the mass of the photopolymerizable compound is reduced with respect to the mass of the binder resin, it is difficult to form a pattern by a photolithography method because of insufficient sensitivity.

1: Columnar spacer 2: TFT
3: Color filter substrate for liquid crystal display device 4: Load application 5: Load unloading A: Initial height B of columnar spacer B: Height when a predetermined load is applied C: A load after a predetermined load is applied Height after removal a: Columnar spacer height b: Columnar spacer x% height (x = b / a × 100)
c: columnar spacer y% height (y = c / a × 100)
d: Upper base x% line width e: Lower base y% line width

Claims (5)

It is formed by a photolithography method using a photosensitive resin composition comprising at least a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and an organic solvent (D). A columnar spacer for making the gap between the color filter and the TFT substrate constant,
When the columnar spacer is pushed with a load of 2 mN over 5 seconds with an indenter (Vickers indenter) having a quadrangular pyramid-shaped minute tip, the measured Vickers hardness (HV) is 33 or more and 36 or less, and ratio d / e of the upper base 90% linewidth d and the lower base 0% line width e of the columnar spacers Ri der 0.65 or more,
When the initial height of the columnar spacer is A, the height when a load is applied to the columnar spacer with a flat indenter of 50 μm × 50 μm is B, and the height after removing the load is C, A columnar spacer for a color filter for a liquid crystal display device, wherein an elastic recovery rate represented by [(C−B) / (A−B)] × 100 (%) is 90 or more and 92 or less .   The mass ratio of the solid content of the photopolymerizable compound (B) to the solid content of the binder resin (A) in the photosensitive resin composition is 0.8 or more and 1.2 or less. Column spacers for color filters for liquid crystal display devices.   3. The liquid crystal display device according to claim 1, wherein the photosensitive resin composition contains at least one component having a maximum absorption wavelength of 230 to 330 nm in the photopolymerization initiator (C). Column spacer for color filter.   A color filter for a liquid crystal display device, wherein the columnar spacer for a color filter for a liquid crystal display device according to any one of claims 1 to 3 is formed.   A liquid crystal display device using the color filter for a liquid crystal display device according to claim 4.