JP5672677B2 - Photosensitive resin composition for color filter, and color filter using the photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition used to form a cured layer having a predetermined pattern such as a pixel, and a color filter using the photosensitive resin composition.

Liquid crystal display devices have been mainly used as monitors for personal computers, but in recent years, not only as monitors for personal computers but also for TV monitors, they have been rapidly developed. Increasing contrast is an important issue.
In general, as shown in FIG. 2, the color liquid crystal display device (101) has a color filter 1 and an electrode substrate 2 such as a TFT substrate facing each other to provide a gap portion 3 of about 1 to 10 μm. The liquid crystal compound L is filled and the periphery thereof is sealed with a sealing material 4. The color filter 1 includes a light shielding layer (black matrix layer) 6 formed in a predetermined pattern on the transparent substrate 5 to shield the boundary between the colored layers, and a plurality of colors (usually normal) to form each pixel. , Red (R), green (G), and blue (B) are arranged in a predetermined order, a protective layer 8 and a transparent electrode film 9 are arranged in this order from the side close to the transparent substrate. It has a laminated structure. An alignment film 10 is provided on the inner surface side of the color filter 1 and the electrode substrate 2 facing the color filter 1. Furthermore, a spacer is provided in the gap portion 3 in order to maintain a constant and uniform cell gap between the color filter 1 and the electrode substrate 2. As the spacer, bead spacers 11 having a constant particle diameter are dispersed, or columnar spacers 12 having a height corresponding to the cell gap as shown in FIG. Or formed in a region overlapping the formed position. A color image can be obtained by controlling the light transmittance of each colored layer colored in each color or the liquid crystal layer behind the color filter.

  Liquid crystal display devices are required to be improved in display performance such as luminance, contrast, and visual field characteristics (display characteristics when viewed from an oblique direction) with the spread of use in television and the like. In recent years, improvement in visual field characteristics has been particularly demanded for television applications, and in the past, the problem has been solved by improving the retardation plate.

  On the other hand, a technique for performing phase difference control by providing a phase difference thin film instead of the phase difference plate has been developed. Patent Document 1 improves the viewing angle characteristics and contrast of a liquid crystal display device, is used in a liquid crystal display device, has optically negative uniaxial anisotropy, and the optical axis is substantially perpendicular to the thin film surface. And a retardation thin film resin composition for forming a retardation thin film having a thickness direction birefringence Δn of 0.01 to 0.3, and a retardation thin film formed from the resin composition, A technique relating to a color filter substrate for a liquid crystal display device, which is formed so as to cover pixels, is disclosed.

JP 2008-107766 A

  The invention of the color filter substrate disclosed in Patent Document 1 is to further provide a retardation film on a pixel. Therefore, the thickness increases by the amount of the thin film, so that the demand for volume saving is met. It is not a thing. Further, the invention of the color filter substrate disclosed in Patent Document 1 has poor manufacturing efficiency because an extra step of providing a retardation film has to be added at the time of production.

Unlike the prior art described above, the present invention omits extra components such as a phase difference plate and a phase difference thin film, with the aim of simplifying the layer configuration and downsizing and increasing the functionality of the entire liquid crystal display device. Even so, an object of the present invention is to exert the effect of phase difference control in other functional layers included in a color filter or the like so that the phase difference can be controlled.
A representative example of the functional layer is a colored layer of a color filter. The inventors have found that the pigment in the colored layer of the color filter is oriented with anisotropy during firing, and as a result, causes retardation. Further, the inventors have found that even when a resin composition not containing a pigment is used, the phase difference can be controlled by adjusting the contraction stress of the film.
The present invention has been achieved in view of the above knowledge obtained by the inventors, and a photosensitive resin composition for a color filter capable of controlling a phase difference generated during the production of a color filter, and the photosensitive resin composition. An object is to provide a color filter using a product.

The photosensitive resin composition for a color filter of the present invention includes at least a photocurable resin component, a photopolymerization initiator, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate. ], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], and n-octadecyl 3- (3,5-di-t-butyl-4 -A photosensitive resin composition for a color filter, comprising at least one hindered phenol compound selected from the group consisting of -hydroxyphenyl) propionate and a mercaptopropionic acid derivative having a molecular weight of 200 to 1000 ( However, those containing a maleimide compound are excluded) .

  Since the photosensitive resin composition for a color filter having such a structure contains a hindered phenol-based compound that plays a role of a phase difference adjusting agent, it is possible to reduce the phase difference that occurs during color filter preparation, particularly during heating. . Moreover, since the photosensitive resin composition for color filters of this invention contains the chain transfer agent containing a thiol group together, it can maintain favorable platemaking property.

  The photosensitive resin composition for a color filter of the present invention is characterized by further containing a color material.

  The photosensitive resin composition for a color filter having such a configuration can adjust a phase difference caused particularly by a color material.

  The photosensitive resin composition for a color filter of the present invention is characterized in that the colorant is a pigment.

  The photosensitive resin composition for a color filter having such a configuration can adjust a phase difference caused particularly by a pigment.

  The photosensitive resin composition for a color filter of the present invention is characterized in that the content ratio of the hindered phenol compound in the solid content of the photosensitive resin composition for a color filter is 0.01 to 20% by mass. To do.

  Since the photosensitive resin composition for a color filter having such a configuration has an appropriate amount of the hindered phenol compound, the effect of reducing the phase difference can be exhibited better without hindering photocuring during the production of the color filter. it can.

The photosensitive resin composition for color filters of the present invention is characterized in that the content ratio of the mercaptopropionic acid derivative in the solid content of the photosensitive resin composition for color filters is 0.01 to 20% by mass. .

Since the photosensitive resin composition for a color filter having such a configuration has an appropriate amount of the mercaptopropionic acid derivative , it is possible to further improve the plate-making property at the time of producing the color filter while maintaining the storage stability.

  The color filter of the present invention is characterized by having a layer obtained by curing the photosensitive resin composition on one side of the substrate.

  According to the present invention, since the hindered phenol-based compound serving as a phase difference adjusting agent is contained, it is possible to reduce the phase difference that occurs at the time of producing a color filter, particularly at the time of heating. Moreover, according to this invention, since the chain transfer agent containing a thiol group is contained together, platemaking property is not impaired.

It is a typical longitudinal section showing an example of a color filter concerning the present invention. It is typical sectional drawing about an example of a liquid crystal panel. It is typical sectional drawing about another example of a liquid crystal panel. It is the schematic diagram which illustrated the prediction mechanism of retardation (Rth) expression.

The photosensitive resin composition for a color filter of the present invention contains at least a photocurable resin component, a photopolymerization initiator, a hindered phenol-based compound, and a chain transfer agent containing a thiol group.
Hereinafter, a hindered phenol type compound, a chain transfer agent containing a thiol group, a photocurable resin component, and a photopolymerization initiator will be described in order.

(Hindered phenolic compounds)
One of the main characteristics of the photosensitive resin composition of the present invention is that it contains a hindered phenol-based compound that plays a role as a phase difference adjusting agent.
As described above, in the conventional liquid crystal display device, the phase difference control is performed by the phase difference plate. However, in order to further improve the image quality, the phase difference control of the entire liquid crystal display device including the color filter is necessary. . In order to reduce the cost, it is necessary to remove the phase difference plate from the constituent elements and perform phase difference control in another functional layer included in the color filter or the like.
As a result of the inventors' diligent efforts, the objective of retardation reduction in a color filter can be achieved by including a hindered phenol-based compound that plays a role as a retardation adjusting agent in the photosensitive resin composition. It became clear.

FIG. 4 is a schematic diagram illustrating a mechanism for estimating the phase difference (retardation) in a conventional color filter. In addition, in this figure, the mechanism at the time of using a pigment as a kind of coloring material is demonstrated. A double wavy line means that the drawing is omitted.
FIG. 4A is a schematic diagram showing the state of the pigment periphery during post-baking, and FIG. 4B is a schematic diagram showing the state of the pigment periphery after post-baking. The pigment 30 is surrounded by a dispersion material adsorption layer 31, and the adsorption layer 31 is further covered with a resin layer 32. In the dispersion material adsorbing layer 31, phase difference main factor molecules 33, which are part of the pigment mainly dissolved from the pigment particles, are randomly mixed.
In FIG. 4A, the direction of stress caused by thermal expansion that occurs during post-baking is indicated by an arrow 34. Thus, the stress due to thermal expansion occurs mainly along the film thickness direction of the color filter. The molecular orientation of the retardation main factor molecule 33 is generated by the stress, and the retardation main factor molecules 33 cause a crosslinking reaction with each other, so that the retardation main factor molecule 33 is the same as shown in FIG. It is considered that a phase difference is developed as a result of crystallization by aligning in the direction, particularly the direction in which the stress due to thermal expansion occurs. In addition, it is considered that shrinkage stress generated mainly along the film thickness direction of the color filter after post-baking is also a cause of the phase difference.

It is considered that inclusion of a hindered phenol compound in the photosensitive resin composition as a phase difference adjusting agent is an effective means for preventing the expression of such phase difference.
The inventors have confirmed that the phase difference principal factor molecule 33 is oriented with crystallization. Although the details of the mechanism are not clear, it is considered that the hindered phenol-based compound suppresses crystallization of the retardation main factor molecule 33 and contributes to the reduction of the retardation.
Hindered phenolic compounds also have a function to relieve the shrinkage stress in the film thickness direction of the color filter that occurs after post-baking, and this stress relieving action also contributes to the reduction of the phase difference. It is thought that there is.

In the case of using a photosensitive resin composition that does not contain a pigment, it is considered that a phase difference is developed mainly due to shrinkage stress generated along the film thickness direction of the color filter after post-baking.
Thus, also when using the photosensitive resin composition which does not contain a pigment, expression of a phase difference can be prevented by adding a hindered phenol-type compound. Although the details of the mechanism for preventing retardation are not clear, hindered phenolic compounds have a function to relieve the shrinkage stress in the film thickness direction of the color filter that occurs after post-baking. Is considered to contribute to the reduction of the phase difference.

The molecular weight of the hindered phenol compound is preferably 300 to 1500. If the molecular weight is less than 300, sublimation during firing or a decrease in the electrical characteristics of the color filter is considered as a demerit, and if the molecular weight is more than 1500, the plate-making performance is reduced and optical properties are reduced. Deterioration of characteristics is considered as a disadvantage.
In addition, it is especially preferable that the molecular weight of a hindered phenol type compound is 400-1400, and it is most preferable that it is 500-1300.

  Specific examples of hindered phenol compounds include 2,6-di-t-butylphenol (molecular weight 206), 2,6-di-t-butyl-p-cresol (molecular weight 220) (trade name: Yoshinox BHT (AP) 4,4'-butylidenebis (6-tert-butyl-3-methylphenol) (molecular weight 383) (trade name: Yoshinox BB (manufactured by API Corporation)), 2,2'-methylenebis (4-Methyl-6-t-butylphenol) (molecular weight 341) (trade name: Yoshinox 2246G (manufactured by API Corporation)), 2,2'-methylenebis (4-ethyl-6-t-butylphenol) (molecular weight 369 ) (Product name: Yoshinox 425 (manufactured by API Corporation)), 2, -Di-t-butyl-4-ethylphenol (molecular weight 234) (trade name: Yoshinox 250 (manufactured by API Corporation)), 1,1,3-tris (2-methyl-4-hydroxy-5-t- Butylphenyl) butane (molecular weight 545) (trade name: Yoshinox 930 (manufactured by API Corporation)), n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (molecular weight 531) (Trade name: Tominox SS (manufactured by API Corporation), trade name: IRGANOX 1076 (manufactured by Ciba Japan)), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate] methane (molecular weight 1178) (trade name: Tominox TT) (Trade name: IRGANOX 1010 (manufactured by Ciba Japan Co., Ltd.)), triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (molecular weight 587) (Product name: Tominox 917 (manufactured by API Corporation), product name: IRGANOX 245 (manufactured by Ciba Japan)), Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (Molecular weight 784) (trade name: Yoshinox 314 (manufactured by API Corporation), trade name: IRGANOX 3114 (manufactured by Ciba Japan)), 3,9-bis [2- [3- (3-t-butyl) -4-hydroxy-5-methylphenyl) propionyloxy] -1,1 Dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] -undecane (molecular weight 741) (trade name: Sumilizer GA-80 (manufactured by Sumitomo Chemical)), 2,2-thio-diethylenebis [ 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (molecular weight 643) (trade name: IRGANOX 1035 (manufactured by Ciba Japan KK)), N, N′-hexamethylenebis (3 , 5-di-t-butyl-4-hydroxy-hydrocinnamamide) (molecular weight 637) (trade name: IRGANOX 1098 (manufactured by Ciba Japan)), isooctyl-3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate (molecular weight 391) (trade name: IRGANOX 1135 (manufactured by Ciba Japan)), 1 , 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (molecular weight 775) (trade name: IRGANOX 1330 (manufactured by Ciba Japan)) 2,4-bis (dodecylthiomethyl) -6-methylphenol (molecular weight 537) (trade name: IRGANOX 1726 (manufactured by Ciba Japan)), bis (3,5-di-t-butyl-4- Ethyl hydroxybenzylphosphonate) Mixture of calcium and polyethylene wax (molecular weight 695) (trade name: IRGANOX 1425 (manufactured by Ciba Japan)), 2,4-bis [(octylthio) methyl] -o-cresol (molecular weight) 425) (trade name: IRGANOX 1520 (manufactured by Ciba Japan KK)), 1,6-hexanedio -Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (molecular weight 639) (trade name: IRGANOX 259 (manufactured by Ciba Japan KK)), 2,4-bis- ( n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (molecular weight 589) (trade name: IRGANOX 565 (manufactured by Ciba Japan KK)), Examples include diethyl ((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) phosphonate (molecular weight 356) (trade name: IRGAMOD 295 (manufactured by Ciba Japan Co., Ltd.)).

It is preferable that the content rate of the said hindered phenol type compound in solid content of the photosensitive resin composition for color filters of this invention is 0.01-20 mass%. In addition, solid content refers to all components other than a solvent, for example, a liquid monomer at normal temperature is also contained in solid content here.
If the content of the hindered phenol compound is more than 20% by mass, the photocuring of the resin may be hindered during the production of the color filter. Moreover, when the content rate of a hindered phenol type compound is less than 0.01 mass%, it will be difficult to acquire the effect of sufficient phase difference reduction.
In addition, it is especially preferable that the content rate of a hindered phenol type compound is 0.02-10 mass% in solid content of the photosensitive resin composition for color filters of this invention, and is 0.03-5 mass%. Most preferably it is.

(Chain transfer agent)
As described above, it is one of the main features of the present invention that a hindered phenol compound is added as a retardation adjusting agent to the photosensitive resin composition for a color filter. However, since the hindered phenolic compound also has a function as a radical scavenger, when only the hindered phenolic compound is added to the photosensitive resin composition, it is sufficiently photosensitive during the exposure process in color filter production. There is a possibility that the resin composition is not cured and the plate making property is impaired.
The photosensitive resin composition for a color filter of the present invention can maintain a good plate-making property at the time of producing a color filter by further containing a hindered phenol compound and a chain transfer agent containing a thiol group. A chain transfer agent containing a thiol group, particularly a polyfunctional thiol compound as described later, has a higher chain transfer constant than a hindered phenol compound. Therefore, the chain transfer agent generates radicals faster than the hindered phenol-based compound captures radicals, thereby promoting photocuring of the photosensitive resin composition.

  The chain transfer agent used in the photosensitive resin composition for a color filter of the present invention is a compound containing a thiol group. As the compound containing such a thiol group, for example, a polyfunctional thiol compound can be used. The polyfunctional thiol compound is a compound having at least 2, preferably 3 or more, more preferably 4 or more mercapto groups (-SH) in the molecule. This is because, as the number of mercapto groups increases, the sensitivity to a low exposure amount is improved, so that the residual film ratio after development can be easily controlled during pattern formation.

The molecular weight of the chain transfer agent containing a thiol group is preferably 200 to 1000. If the molecular weight is less than 200, a decrease in storage stability is considered as a disadvantage, and if the molecular weight is more than 1000, a decrease in reactivity is considered as a disadvantage.
The molecular weight of the chain transfer agent containing a thiol group is particularly preferably 250 to 900, and most preferably 350 to 800.

  Specific examples of the polyfunctional thiol compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate. Nate (PETP), pentaerythritol tetrakis (3-mercaptobutyrate) (molecular weight: 544.8) (trade name: Karenz MT PE1 (manufactured by Showa Denko KK)), 1,3,5-tris (3-mercaptobuty Ryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (molecular weight: 567.7) (trade name: Karenz MT NR1 (manufactured by Showa Denko KK)), 1,4-bis (3-mercaptobutyryloxy) butane (trade name: Karenz MT BD1 (molecular weight: 294.4) (manufactured by Showa Denko KK)), THEIC-BMPA represented by the following formula (1)

Mercaptopropionic acid derivatives such as ethylene glycol bisthioglycolate (EGTG), butanediol bisthioglycolate (BDTG), hexanediol bisthioglycolate (HDTG), trimethylolpropane tristhioglycolate (TMTG), pentaerythritol Thioglycolic acid derivatives such as tetrakisthioglycolate (PETG); 1,2-benzenedithiol, 1,3-benzenedithiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, Thiols such as 2,2 ′-(ethylenedithio) diethanethiol, meso-2,3-dimercaptosuccinic acid, p-xylenedithiol, m-xylenedithiol; mercaptoates such as di (mercaptoethyl) ether Examples of tellurium can be given.

  Among these, pentaerythritol tetrakisthiopropionate (PETP), THEIC-BMPA represented by the above formula (1), pentaerythritol tetrakisthioglycolate (PETG), pentaerythritol tetrakis (3-mercaptobutyrate), 1 , 3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and 1,4-bis (3-mercaptobutyryl) Oxy) butane is preferred, especially pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione and 1,4-bis (3-mercaptobutyryloxy) buta It is preferred.

The content ratio of the chain transfer agent containing a thiol group in the solid content of the photosensitive resin composition for a color filter of the present invention is preferably 0.01 to 20% by mass, more preferably 0.1% by mass. It is preferable to be within the range of -10% by mass. In addition, solid content refers to all components other than a solvent as mentioned above.
When the content ratio of the chain transfer agent containing a thiol group is more than 20% by mass, there are disadvantages in that the storage stability is deteriorated and the odor is increased. Moreover, when the content rate of the chain transfer agent containing a thiol group is less than 0.01% by mass, it is difficult to obtain a sufficient effect of improving the plate-making property.

(Photocurable resin component)
i) Polymer In a binder-forming system containing a photocurable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams, the molecular weight is relatively high for the purpose of providing film formability and adhesion to the surface to be coated. It is preferable to contain a high polymer. Here, the relatively high molecular weight means that the molecular weight is higher than that of so-called monomers and oligomers, and the weight average molecular weight can be 5,000 or more. As a polymer having a relatively high molecular weight, any of a polymer having no polymerization reactivity per se and a polymer having a polymerization reactivity per se may be used, and a combination of two or more types may be used. May be. It is mainly composed of a polymer having a relatively high molecular weight, and if necessary, a polyfunctional monomer or oligomer, a monofunctional monomer or oligomer, a photopolymerization initiator activated by light, and a sensitizer. Thus, a photocurable binder forming system is constituted.

  In the case where a polymer having no polymerization reactivity per se is used as a polymer having a relatively high molecular weight, a polyfunctional polymerizable component such as a bifunctional or higher polyfunctional monomer or oligomer is blended in the binder forming system. In this case, in the binder formation system, the polyfunctional polymerizable component is polymerized spontaneously by light irradiation or polymerized by the action of other components such as a photopolymerization initiator activated by light irradiation. Thus, a network structure is formed in the coating film, and a component such as a resin or a pigment having no polymerization reactivity is wrapped in the network structure and cured.

As such a polymer having no polymerization reactivity, a so-called acrylic polymer, for example, a copolymer composed of two or more of the following monomers can be used: (Meth) acrylic acid (hereinafter, this expression is Acrylic acid and methacrylic acid are collectively referred to.), Methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate macromonomer.
More specifically, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, benzyl methacrylate / styrene copolymer, benzyl methacrylate macromonomer / styrene copolymer, benzyl methacrylate / styrene macromonomer A copolymer etc. can be illustrated.

As a polymer having a polymerization reactivity per se, it is an oligomer obtained by introducing a polymerizable functional group into a polymer molecule having no polymerization reactivity or a polymer having a higher molecular weight than an oligomer, and is subjected to light irradiation. Those that cause a polymerization reaction themselves or that induce a polymerization reaction by the action of other components such as a photopolymerization initiator activated by irradiation with light can be used.
Various ethylenic double bond-containing compounds themselves have polymerization reactivity and can be used as photocurable resins.

ii) Polyfunctional polymerizable component In order to improve the strength of the coating film and the adhesion to the substrate even in the case of using a polymer having a relatively high molecular weight that can be polymerized and cured, a polyfunctional monomer It is preferable to blend a polyfunctional polymerizable component such as olefin or oligomer. Polymer molecules with relatively high molecular weight that are polymerizable not only polymerize with polymers with relatively high molecular weight, but also polymerize with other polymerizable components such as polyfunctional monomers to form a network and cure. To do.
As the polyfunctional polymerizable component forming the network structure of the coating film, a bifunctional or higher functional monomer or oligomer can be used. In order to impart sufficient film strength and adhesion to the photocurable resin, a tetrafunctional or higher functional monomer or oligomer is usually used.

  Examples of the bifunctional to trifunctional monomers include 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, and polyethylene glycol diester. Examples thereof include acrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, and 3-butylene glycol dimethacrylate.

  Examples of tetrafunctional or higher polyfunctional monomers and oligomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

iii) Monofunctional polymerizable component In addition, a monofunctional monomer or oligomer may be blended in the photocurable binder forming system, if necessary.
Examples of monofunctional monomers and oligomers include vinyl monomers such as styrene and vinyl acetate, and monofunctional acrylic monomers such as n-hexyl acrylate and phenoxyethyl acrylate.

iv) Photopolymerization initiator The photocurable binder-forming system is usually blended with a photopolymerization initiator having activity with respect to the wavelength of the light source used. The photopolymerization initiator is appropriately selected in consideration of the difference in the reaction format of the resin or polyfunctional monomer (for example, radical polymerization or cationic polymerization) and the type of each material. For example, 1-hydroxycyclohexyl-phenyl ketone 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-monforinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] 2-hydroxy-2-methyl-1-propan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, bisacyl phosphite Oxide, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone- 9-one mesochloride, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl), p-dimethyl Aminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 1,3,5-triacroylhexahydro-s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4 , 6-Bis (trichloromethyl) ) -S-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, methylbenzoylformate, 2,4,6-trimethylbenzoyldiphenylphos A photopolymerization initiator such as fin oxide can be used. In the present invention, commercially available polymerization initiators can be used. For example, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 907 (all are trade names, manufactured by Ciba Specialty Chemicals), Darocur (trade name). Merck & Co.), Adeka 1717 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) and the like, and 2,2′-bis (o-chlorophenyl) -4,5,4′-tetraphenyl-1,2 Biimidazole compounds such as' biimidazole (manufactured by Kurokin Kasei Co., Ltd.) are preferred.

In addition, it is preferable that content of a photoinitiator is 5-15 mass% with respect to the whole solid content.
In addition, in order to impart sufficient adhesion, strength, and hardness to the cured photosensitive resin composition layer, the binder forming system component occupies the total solid content of the photosensitive resin composition including the pigment and other components. The total proportion is preferably 30% by mass or more.

The photosensitive resin composition for a color filter of the present invention can be configured to further contain a color material. Moreover, the photosensitive resin composition for color filters of this invention can take the structure that a pigment is contained as a coloring material.
Hereinafter, the items will be described in the order of the pigment, and the pigment dispersant and solvent used as necessary.

(Pigment)
As a pigment in the photosensitive resin composition used in the present invention, any pigment selected from known organic colorants and inorganic colorants can be used. As the organic colorant, for example, dyes, organic pigments, natural pigments, and the like can be used. Moreover, as an inorganic coloring agent, an inorganic pigment, an extender pigment, etc. can be used, for example. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. As organic pigments, for example, compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colorists), specifically, the following Color Index (CI) numbers are attached. You can list what you have.

  CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment .... DOO Yellow 155, C.I Pigment Yellow 156, C.I Pigment Yellow 166, C.I Pigment Yellow 168, C.I Pigment Yellow 175;

  CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Buy Olet 32, C.I. pigment violet 36, C.I. pigment violet 38;

  CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58 : 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI pigmentless 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 77, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red . 64, C.I Pigment Red 265;

  CI Pigment Blue 1, CI Pigment Blue 15, CI Pigment Blue 15: 1, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60; CI Pigment Green 7, CI Pigment CI Pigment Green 58; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, Pigment Black 7.

Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, amber, etc. Can be mentioned. In the present invention, other pigments can be used alone or in admixture of two or more.
In the photosensitive resin composition used in the present invention, the pigment is usually 1 to 60 mass based on the total amount of the photocurable resin component, the photopolymerization initiator, the pigment and the pigment dispersant in the photosensitive resin composition. %, Preferably 5 to 40% by mass. When there are too few pigments, there exists a possibility that the permeation | transmission density | concentration at the time of apply | coating the photosensitive resin composition to predetermined | prescribed film thickness (usually 0.5-5.0 micrometers) may not be enough. In addition, if there are too many pigments, the coating properties such as adhesion to the substrate when the photosensitive resin composition is applied and cured on the substrate, surface roughness of the cured film, and coating film hardness are insufficient. There is a risk of becoming.

(Pigment dispersant)
It is preferable that the pigment dispersant is further blended in the pigment dispersion in order to favorably disperse the pigment. Examples of the pigment dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable. A pigment derivative that dissolves in a small amount in a solvent may be used as a pigment dispersant.

  The pigment dispersant is appropriately selected and used in order to favorably disperse the pigment used. As specific examples, one or more selected from the group consisting of polyethyleneimine derivatives and polyallylamine derivatives can be suitably used. Besides, nonanamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecyl Amide compounds such as propioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide, diethylamine, diheptylamine, dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine , Amine compounds such as tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N '-Tri (hydroxy Ethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethylpolyoxyethylene) -1,2-diaminoethane, 1,4-bis (2-hydroxyethyl) piperazine and 1 Examples include amines having a hydroxy group such as-(2-hydroxyethyl) piperazine, and other compounds such as nipecotamide, isonipecotamide, and nicotinamide.

  As a commercial product of the polyallylamine derivative, Azisper Pb821 (trade name; manufactured by Ajinomoto Fine Techno Co., Ltd.), and as a commercial product of the polyethyleneimine derivative, Solsperse 33500 (trade name, manufactured by Nippon Lubrizol Co., Ltd.) can be used.

Furthermore, specific examples of the pigment dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amines of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid Salts, (partially) ammonium salts and (partially) alkylamine salts; hydroxyl group-containing unsaturated carboxylic acid ester (co) polymers such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; Polysiloxanes; long-chain polyaminoamide phosphates; amides obtained by the reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters and salts thereof, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, poly Polyoxyethylene alkyl ethers such as oxyethylene oleyl ether , Polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate, sorbitan fatty acid esters, fatty acid-modified polyesters And tertiary amine-modified polyurethanes.
In the present invention, commercially available dispersants can also be used, for example, various Solsperse dispersants such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 20000, 24000, 26000, and 28000 (all above) A trade name, manufactured by Zeneca Corporation), and Disperbyk111 (trade name, manufactured by Big Chemie Japan Co., Ltd.) are preferable.

(solvent)
In the present invention, the color filter pigment dispersion preferably contains a solvent in order to disperse the pigment.
Examples of the solvent used in the pigment dispersion of the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; Carbitol solvents such as ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone, cyclohexanone, and methyl ethyl ketone; methoxy Ethyl acetate, methoxypropyl acetate, methoxybutyl acetate, ethoxyethyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl celloso Cellosolve acetate solvents such as buacetate; carbitol acetate solvents such as carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate; diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Ether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetrahydrofuran; N, N-dimethyl Formamide, N, N-dimethylacetate Aprotic amide solvents such as amide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; N-heptane, N-hexane and N-octane Organic solvents such as saturated hydrocarbon solvents such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Examples include organic solvents such as dibutyl ether. Among them, the solvent used in the present invention is at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether and 3-methoxybutyl acetate, and the solubility and coating of other components. It is preferable from the point of aptitude.

These solvents may be used alone or in combination of two or more.
In the present invention, the pigment dispersion is prepared by using the above solvent in a proportion of usually 60 to 85% by mass with respect to the total amount of the pigment dispersion containing the solvent. When the amount of the solvent is too small, the viscosity is increased, and the pigment dispersibility and the pigment dispersion stability with time are likely to be lowered. Moreover, when there are too many solvents, applicability | paintability may fall.

(Other ingredients)
The photosensitive resin composition of the present invention may contain one or more other additives as required. Examples of such additives include antioxidants, sensitizers, dispersion aids, fillers, adhesion promoters, ultraviolet absorbers, and aggregation inhibitors.

The photosensitive resin composition of the present invention can be used for a colored layer of a color filter or the like when a coloring material such as a pigment is included.
On the other hand, when a coloring material such as a pigment is not included, the photosensitive resin composition of the present invention can be used for, for example, a protective layer of a color filter.

  The color filter according to the present invention is characterized by having a layer obtained by curing at least the above-described photosensitive resin composition on one side of the substrate. The color filter having such a configuration is provided with a layer obtained by curing the above-described photosensitive resin composition, whereby the phase difference is reduced, and as a result, the visual field characteristics are excellent.

FIG. 1A is a longitudinal sectional view showing an example (color filter 103) of a color filter for a display device belonging to the color filter according to the present invention.
The color filter 103 includes, as necessary, a light shielding layer 6 formed in a predetermined pattern on the transparent substrate 5, and a colored layer 7 (7R, 7G, 7B) formed in a predetermined pattern on the light shielding layer. The protective film 8 formed so that the said colored layer may be covered is provided as needed. A transparent electrode 9 for driving liquid crystal may be formed on the protective film as necessary. An alignment film 10 is formed on the innermost surface of the color filter 103, in this case on the transparent electrode.

  The columnar spacer 12 has a shape of a convex spacer, and is formed at a plurality of predetermined positions on the transparent electrode 9 in accordance with the region (non-display region) where the light shielding layer 6 is formed. The columnar spacer 12 is formed on the transparent electrode 9, the colored layer 7, or the protective film 8. In the color filter 103, columnar spacers are formed in a sea island shape on the protective film 8 via the transparent electrode 9, but the protective film 8 and the columnar spacer 12 are integrally formed and transparent so as to cover it. An electrode layer may be formed.

  As the transparent substrate 5 of the color filter 103, a non-flexible transparent rigid material such as quartz glass, Pyrex (registered trademark) glass, synthetic quartz plate, or a flexible resin material such as a transparent resin film or an optical resin plate. The transparent flexible material which has can be used.

The light shielding layer 6 may be provided so as to surround between the colored layers 7R, 7G, and 7B and the outside of the colored layer forming region in order to improve the contrast of the display image. In the present invention, the light shielding layer 6 is preferably formed using a resin composition containing light shielding particles. For example, when the resin composition for forming a light shielding layer has alkali developability, first, the resin composition for forming a light shielding layer is applied onto the transparent substrate 5 and dried as necessary to form a photosensitive coating film. The light-shielding layer 6 can be formed by forming, exposing and developing the coating film through a photomask for the light-shielding layer, and performing heat treatment as necessary. On the other hand, when the light shielding layer forming resin composition is a thermosetting resin composition or has no alkali developability, the light shielding layer forming resin composition is printed on a predetermined region on the transparent substrate 5, After selectively attaching by thermal transfer or the like, the light shielding layer 6 can be formed by curing by heating or light irradiation.
The thickness of the light shielding layer varies depending on the color filter to be applied, and is about 0.5 to 3.0 μm.

  The colored layer 7 includes a red pattern, a green pattern, and a blue pattern arranged in a desired form such as a mosaic type, a stripe type, a triangle type, and a four colored layer arrangement type, thereby forming a display region. In the present invention, a colored layer is formed using the photosensitive resin composition according to the present invention. Among these, it is preferable to use a resin composition containing a photosensitive binder system because fine patterning is possible. This case will be described below as an example.

The red, green and blue photosensitive resin compositions according to the present invention are prepared. Next, a photosensitive red resin layer is formed by applying a photosensitive resin composition for a certain color, for example, red so as to cover the light shielding layer 6 on the transparent substrate 5 by a known method such as spin coating. The red colored layer 7R is formed by performing exposure through a pattern photomask, alkali development, and heat curing in a clean oven or the like. Thereafter, green and blue photosensitive resin compositions are sequentially used to pattern each color in the same manner to form a green colored layer 7G and a blue colored layer 7B.
The thickness of the colored layer is usually about 0.5 to 5.0 μm.

The protective film 8 is provided to flatten the surface of the color filter and prevent the components contained in the colored layer 7 from eluting into the liquid crystal layer. The protective film 8 covers the light-shielding layer 6 and the colored layer 7 with a known negative photocurable transparent resin composition or thermosetting transparent resin composition by a method such as spin coater, roll coater, spraying, printing, or the like. And can be formed by curing with light or heat.
When the protective film is formed, the thickness of the protective film is set in consideration of the light transmittance of the resin composition, the surface state of the color filter, and the like, for example, about 0.1 to 5.0 μm.

  The transparent electrode film 9 on the protective film is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and alloys thereof, such as sputtering, vacuum deposition, CVD, etc. It is formed by a general method, and is formed into a predetermined pattern by etching using a photoresist or using a jig as necessary. The thickness of the transparent electrode can be about 20 to 300 nm.

  A plurality of convex spacers are provided in a non-display area on the substrate in order to maintain a cell gap when the color filter 103 is bonded to a liquid crystal driving side substrate such as a TFT array substrate. The shape and size of the convex spacer are not particularly limited as long as it can be selectively provided in a non-display region on the substrate and can maintain a predetermined cell gap over the entire substrate. When the columnar spacer 12 as shown in the figure is formed as the convex spacer, it has a certain height in the range of about 2 to 10 μm. Moreover, the thickness of the columnar spacer 12 can be appropriately set within a range of about 5 to 50 μm. The formation density (density) of the columnar spacers 12 can be set as appropriate. For example, a necessary and sufficient spacer function is exhibited at a ratio of one for each colored layer of red, green, and blue. . The shape of such a columnar spacer may be a columnar shape, and may be, for example, a columnar shape, a prismatic shape, a truncated cone shape, or the like.

  The convex spacer can be formed using a curable resin composition. That is, first, the coating liquid of the curable resin composition is applied directly on a transparent substrate by a method such as spin coater, roll coater, spray, printing, or through another layer such as a transparent electrode, and then dried. Then, a photocurable resin layer is formed. Next, this resin layer is exposed through a photomask for convex spacers, and developed with a developer such as an alkaline solution to form a predetermined convex pattern. A convex spacer is formed by heat treatment (post-bake) or the like.

  The alignment film 10 is provided on the inner surface side of the color filter so as to cover the display portion including the colored layer 7 and the non-display portion including the light shielding layer 6 and the columnar spacer 12. The alignment film can be formed by applying a coating solution containing a resin such as a polyimide resin by a known method such as spin coating, drying, curing with heat or light as necessary, and then rubbing.

  The color filter of the present invention is not necessarily limited to the configuration shown in FIG. In addition, a configuration in which the transparent conductive layer 9 does not exist as in the configuration illustrated in FIG. 1B may be used, or the transparent conductive layer 9 is transparent as in the configuration illustrated in FIG. The substrate 5 may be disposed on the opposite side to the colored layer 7.

  When the color filter 103 (display side substrate) thus obtained and the TFT array substrate (liquid crystal drive side substrate) are opposed to each other, and the inner peripheral side peripheral portions of both the substrates are bonded with a sealant, the both substrates are separated by a predetermined distance. Bonding is performed with the cell gap maintained. An active matrix type color liquid crystal display device, which is a typical example of the display device of the present invention belonging to the liquid crystal panel, is obtained by filling and sealing the gap between the substrates with liquid crystal.

[Example 1]
(Preparation of red coloring composition)
First, a curable resin composition for blending with a pigment was prepared by the following method. In a polymerization tank, 63 parts by mass of methyl methacrylate (MMA), 12 parts by mass of acrylic acid (AA), 6 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 88 parts by mass of diethylene glycol dimethyl ether (DMDG) are charged. After stirring and dissolving, 7 parts by mass of 2,2′-azobis (2-methylbutyronitrile) (polymerization initiator) was added and dissolved uniformly. Then, it stirred at 85 degreeC under nitrogen stream for 2 hours, and also was made to react at 100 degreeC for 1 hour. Further, 7 parts by mass of glycidyl methacrylate (GMA), 0.4 parts by mass of triethylamine, and 0.2 parts by mass of hydroquinone were added to the obtained solution, and the mixture was stirred at 100 ° C. for 5 hours to obtain a copolymer resin solution ( A solid content of 50%) was obtained.
Composition of copolymer resin solution (solid content 50%), methyl methacrylate (MMA) (manufactured by Kuraray Co., Ltd.): 63 parts by mass, acrylic acid (AA) (manufactured by Nippon Shokubai): 12 parts by mass, methacrylate-2- Hydroxyethyl (HEMA) (manufactured by Nippon Shokubai): 6 parts by mass Diethylene glycol dimethyl ether (DMDG) (manufactured by Junsei): 88 parts by mass 2,2′-azobis (2-methylbutyronitrile) (polymerization initiator) (Product name: ABN-R, manufactured by Nippon Finechem Co., Ltd.): 7 parts by mass. Glycidyl methacrylate (GMA) (manufactured by NOF Corporation): 7 parts by mass. Triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.): 0.4 Parts by mass / hydroquinone (Seiko Chemical Co., Ltd.): 0.2 parts by mass

Next, the following materials were stirred and mixed at room temperature to obtain a curable resin composition.
Composition of curable resin composition / copolymer resin solution (solid content 50%): 32 parts by mass / dipentaerythritol pentaacrylate (trade name: SR399, manufactured by Sartomer): 24 parts by mass / orthocresol novolac type epoxy resin (Trade name: Epicoat 180S70, manufactured by Yuka Shell Epoxy Co., Ltd.): 4 parts by mass. 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade names: Irgacure 907, Ciba Specialty Chemicals): 3.5 parts by mass Pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Karenz MT PE1, Showa Denko KK): 0.3 parts by mass diethylene glycol dimethyl ether (genuine chemistry) (Made by company): 36 mass parts, phase difference adjusting agent: pentaerythrityl Tetrakis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by Ciba Specialty Chemicals Co.) 0.2 parts by weight

Subsequently, the following materials were mixed using a paint shaker (manufactured by Asada Steel Corporation, bead diameter: 0.3 mm) to obtain a red coloring composition.
Composition of red coloring composition Red pigment: C.I. I. Pigment Red 177 (trade name: Chromofine Red 6605, manufactured by Dainichi Seika) 3.2 parts by mass C.I. I. Pigment Red 254 (trade name: Irgaphor Red BT-CF, manufactured by Ciba Specialty Chemicals) 3.6 parts by mass / yellow pigment: C.I. I. Pigment Yellow 150 (trade name: Byplast Yellow Y-5688, manufactured by Lanxess) 1.2 parts by mass Dispersant: Disperbyk 111 (manufactured by Big Chemie Japan) 2.4 parts by mass The curable resin composition: 16 parts by mass Solvent: 73.6 parts by mass of diethylene glycol dimethyl ether (manufactured by Junsei Co., Ltd.)

(Manufacture of red filter)
The red composition was applied to a 0.7 mm glass substrate (AN material manufactured by Asahi Glass Co., Ltd.) using a spin coater, and then pre-baked at 80 ° C. for 3 minutes to dry the red coating film. Next, the dried coating film was exposed at 200 mJ / cm ² using a high-pressure mercury lamp and then post-baked at 230 ° C. for 30 minutes to produce a red filter having a thickness of 2.0 μm.

[Example 2]
Pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl), which is a kind of hindered phenolic compound used as a phase difference adjusting agent in the stage of adjusting the curable resin composition Propionate] (trade name: IRGANOX 1010, manufactured by Ciba Specialty Chemicals) was added in an amount of 0.06 parts by mass (that is, one third of the amount added in Example 1), and DMDG as a solvent was added in an amount of 0. Except for adding 14 parts by mass, a red colored composition was prepared in the same manner as in Example 1 to produce a red filter.

[Example 3]
Pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl), which is a kind of hindered phenolic compound used as a phase difference adjusting agent in the stage of adjusting the curable resin composition Propionate] (trade name: IRGANOX 1010, manufactured by Ciba Specialty Chemicals) was added in an amount of 0.33 parts by mass (that is, 5/3 times the amount added in Example 1), and DMDG as a solvent was added in an amount of 0.003. A red filter was prepared by adjusting the red coloring composition in the same manner as in Example 1 except that 13 parts by mass was added.

[Example 4]
Instead of pentaerythritol tetrakis (3-mercaptobutyrate) in Example 1 above, 1,3,5-tris (3-mercapto) as a chain transfer agent containing a thiol group at the stage of adjusting the curable resin composition 0.3 parts by mass of butyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name: Karenz MT NR1 (manufactured by Showa Denko KK)) Except that, a red colored composition was prepared in the same manner as in Example 1 to produce a red filter.

[Example 5]
As the hindered phenol-based compound used as the phase difference adjusting agent at the stage of adjusting the curable resin composition, the pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-l) of Example 1 above was used. 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1035 (Ciba Japan Co., Ltd.) instead of [hydroxyphenyl) propionate] The red colored composition was prepared in the same manner as in Example 1 except that 0.2 part by mass of (manufactured)) was added to produce a red filter.

[Example 6]
As the hindered phenol-based compound used as the phase difference adjusting agent at the stage of adjusting the curable resin composition, the pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-l) of Example 1 above was used. N-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name: IRGANOX 1076 (manufactured by Ciba Japan Co., Ltd.)) instead of hydroxyphenyl) propionate] Except for adding 2 parts by mass, a red colored composition was prepared in the same manner as in Example 1 to produce a red filter.

[Example 7]
Except for adding 2.4 parts by mass of Azisper Pb821 (trade name; manufactured by Ajinomoto Fine Techno Co., Ltd.) instead of Disperbyk111 of Example 1 as a pigment dispersant at the stage of adjusting the red coloring composition, A red colored composition was prepared in the same manner as in Example 1 to produce a red filter.

[Comparative Example 1]
At the stage of adjusting the curable resin composition, a hindered phenol compound as a phase difference adjusting agent and a chain transfer agent containing a thiol group are not added, and 0.5 part by mass of DMDG as a solvent is added. Except that, a red colored composition was prepared in the same manner as in Example 1 to produce a red filter.

[Comparative Example 2]
In the same manner as in Example 1, except that a chain transfer agent containing a thiol group was not added and 0.3 parts by mass of DMDG as a solvent was added at the stage of adjusting the curable resin composition. The composition was adjusted to produce a red filter.

[Comparative Example 3]
Pentaerythrityl tetrakis [3- (3, 3, which is a kind of hindered phenol compound used as a phase difference adjusting agent without adding a chain transfer agent containing a thiol group at the stage of adjusting the curable resin composition. 5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010, manufactured by Ciba Specialty Chemicals), 0.06 parts by mass (ie, one-third of the amount added in Example 1) In addition, a red colored composition was prepared in the same manner as in Example 1 except that 0.44 parts by mass of DMDG as a solvent was added in a large amount to produce a red filter.

[Comparative Example 4]
Except that the hindered phenol compound as a phase difference adjusting agent was not added at the stage of adjustment of the curable resin composition, and 0.2 parts by mass of DMDG as a solvent was added in a large amount, the above Example 1 and Similarly, a red colored composition was prepared to produce a red filter.

[Example 8]
(Preparation of blue coloring composition)
The adjustment of the copolymer resin solution (solid content 50%) and the adjustment of the curable resin composition using the solution are the same as in Example 1.
Subsequently, the following materials were mixed using a paint shaker (manufactured by Asada Steel Corporation, bead diameter: 0.3 mm) to obtain a blue colored composition.
Composition of blue coloring composition Blue pigment: C.I. I. Pigment Blue 15: 6 (trade name: Chromfine Blue 5250A, manufactured by Dainichi Seika) 7.2 parts by mass, purple pigment: C.I. I. Pigment Violet 23 (trade name: PV Fast Violet RL, manufactured by Clariant) 0.8 parts by mass Dispersant: Disperbyk 111 (manufactured by Big Chemie Japan) 2.4 parts by mass The above curable resin composition: 16 parts by mass solvent : Diethylene glycol dimethyl ether (manufactured by Junsei Co., Ltd.) 73.6 parts by mass

(Manufacture of blue filter)
The blue composition was applied to a 0.7 mm glass substrate (AN material manufactured by Asahi Glass Co., Ltd.) using a spin coater, and then pre-baked at 80 ° C. for 3 minutes to dry the blue coating film. Next, the dried coating film was exposed to 200 mJ / cm ² using a high-pressure mercury lamp and then post-baked at 230 ° C. for 30 minutes to produce a blue filter having a thickness of 2.0 μm.

[Comparative Example 5]
At the stage of adjusting the curable resin composition, a hindered phenol compound as a phase difference adjusting agent and a chain transfer agent containing a thiol group are not added, and 0.5 part by mass of DMDG as a solvent is added. Except for this, a blue colored composition was prepared in the same manner as in Example 8 to produce a blue filter.

[Example 9]
(Preparation of green coloring composition)
The adjustment of the copolymer resin solution (solid content 50%) and the adjustment of the curable resin composition using the solution are the same as in Example 1.
Subsequently, the following materials were mixed using a paint shaker (manufactured by Asada Steel Corporation, bead diameter: 0.3 mm) to obtain a green coloring composition.
Composition of green coloring composition Green pigment: C.I. I. Pigment Green 36 (trade name: Fastogen Green 2YK, manufactured by DIC) 5.6 parts by mass, yellow pigment: C.I. I. Pigment Yellow 150 (trade name: Byplast Yellow Y-5688, manufactured by Lanxess) 2.4 parts by mass Dispersant: Disperbyk 111 (manufactured by Big Chemie Japan) 2.4 parts by mass The curable resin composition: 16 parts by mass Solvent: 73.6 parts by mass of diethylene glycol dimethyl ether (manufactured by Junsei Co., Ltd.)

(Manufacture of green filter)
The green composition was applied to a 0.7 mm glass substrate (AN material manufactured by Asahi Glass Co., Ltd.) using a spin coater, and then prebaked at 80 ° C. for 3 minutes to dry the green coating film. Next, the dried coating film was exposed to 200 mJ / cm ² using a high-pressure mercury lamp and then post-baked at 230 ° C. for 30 minutes to produce a green filter having a thickness of 2.0 μm.

[Example 10]
In the stage of adjusting the green coloring composition, C.I. I. Instead of Pigment Green 36, C.I. I. Except having added 5.6 mass parts of pigment blue 58, the green coloring composition was adjusted similarly to the said Example 9, and the green filter was manufactured.

[Comparative Example 6]
At the stage of adjusting the curable resin composition, a hindered phenol compound as a phase difference adjusting agent and a chain transfer agent containing a thiol group are not added, and 0.5 part by mass of DMDG as a solvent is added. Except for this, a green coloring composition was prepared in the same manner as in Example 9 to produce a green filter.

[Comparative Example 7]
At the stage of adjusting the curable resin composition, a hindered phenol compound as a phase difference adjusting agent and a chain transfer agent containing a thiol group are not added, and as a green pigment at the stage of adjusting the green coloring composition C. of Example 9 above. I. Instead of Pigment Green 36, C.I. I. Except for adding 5.6 parts by mass of Pigment Blue 58 and adding 0.5 parts by mass of DMDG as a solvent, a green colored composition was prepared in the same manner as in Example 9 to produce a green filter. .

[Example 11]
(Preparation of curable resin composition)
In the same manner as in Example 1, a copolymer resin solution (solid content: 50%) was prepared, and a curable resin composition was prepared using the solution. Unlike Example 1, no pigment and pigment dispersant were added.

(Manufacture of colorless filters)
The curable resin composition was applied to a 0.7 mm glass substrate (AN material manufactured by Asahi Glass Co., Ltd.) using a spin coater, and then pre-baked at 80 ° C. for 3 minutes to dry the colorless coating film. Next, the dried coating film was exposed at 200 mJ / cm ² using a high-pressure mercury lamp and then post-baked at 230 ° C. for 30 minutes to produce a colorless filter having a thickness of 2.0 μm.

[Comparative Example 8]
At the stage of adjusting the curable resin composition, a hindered phenol compound as a phase difference adjusting agent and a chain transfer agent containing a thiol group are not added, and 0.5 part by mass of DMDG as a solvent is added. A curable resin composition was prepared in the same manner as in Example 11 except that a colorless filter was produced.

[Comparative Example 9]
The curability was the same as in Example 11 except that a chain transfer agent containing a thiol group was not added and 0.3 parts by mass of DMDG as a solvent was added at the stage of adjusting the curable resin composition. The resin composition was adjusted to produce a colorless filter.

(Evaluation of retardation effect of color filter and plate making)
Regarding the color filters having the color compositions of Examples 1 to 10 and Comparative Examples 1 to 7 described above, and the filters having the curable resin compositions of Examples 11 and Comparative Examples 8 and 9 described above, the position of the color filter. The effect of suppressing the phase difference and the plate-making property were evaluated. The results are shown in Table 1 below. In Table 1 below, the unit of numerical values related to materials is mass%, and the unit of numerical values related to retardation (Rth) is nm.
The evaluation criteria for each evaluation are as follows. About the evaluation standard of the phase difference suppression effect, the phase difference (Rth) of the colored layer, which was measured using a phase difference measuring device (Axoscan ^™ Mueller Matrix Polarimeter manufactured by AXOMETRICS), was used. In the phase difference measurement, the red wavelength layer has a wavelength of 620 nm, the green color layer has a wavelength of 550 nm, the blue color layer has a wavelength of 450 nm, and the colorless filter has a wavelength of 550 nm. It was. Here, the “phase difference (Rth) of the colored layer” means the refractive index Nx in the fast axis direction (the direction in which the refractive index is the smallest) and the slow axis direction (the refractive index is the largest in the plane of the colored layer). Direction) refractive index Ny, thickness direction refractive index Nz, and colored layer thickness d (nm), which is a value obtained from the equation Rth = {(Nx + Ny) / 2−Nz} × d.
In addition, the plate-making property was evaluated from two viewpoints of film roughness and pixel defect, and evaluated by ○ and ×. The evaluation criteria are as follows.

[Film Roughness Evaluation Criteria]
○: Rough film area less than 5% ×: Rough film area 5% or more
[Pixel missing evaluation criteria]
○: Number of missing pixels 0: × Number of missing pixels 1 or more

First, in order to examine the influence of the presence / absence of a phase difference adjusting agent and the presence / absence of a chain transfer agent containing a thiol group in a color filter having a red coloring composition, Example 1 and Comparative Examples 1 to 4 are compared.
When the addition rate of the phase difference adjusting agent is 0% by mass, that is, the phase difference adjusting agent is not added, and the addition rate of the chain transfer agent containing a thiol group is 0% by mass, that is, the chain transfer agent is not added (comparison) In Example 1), the absolute value of the phase difference was as high as 15.5 nm. Further, it contains pentaerythritol tetrakis (3-mercaptobutyrate), which is a kind of chain transfer agent containing a thiol group (hereinafter sometimes referred to as Karenz MT PE1 from the trade name) at an addition rate of 0.05 mass%. Even when the phase difference adjusting agent was not added (Comparative Example 4), the absolute value of the phase difference was as high as 15.7 nm. This shows that when no phase difference adjusting agent is added, a sufficient phase difference reducing effect that is the effect of the present invention cannot be obtained regardless of the presence or absence of a chain transfer agent containing a thiol group. .
On the other hand, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (hereinafter, sometimes referred to as IRGANOX1010 from the trade name), which is a kind of phase difference adjusting agent, is 0. When the content is 0.03% by mass and 0.01% by mass, respectively, and no chain transfer agent is added (Comparative Examples 2 and 3), the absolute value of the retardation is 8.5 nm, It was a relatively low value of .5 nm. However, when the IRGANOX 1010 is contained in an amount of 0.01% by mass as in the comparative example 3, the evaluation of lack of pixels is x, and when the IRGANOX 1010 is contained in the amount of 0.03% by mass as in the comparative example 2, the pixel is evaluated. The evaluation of chipping and film roughness was both x. This is because, when the chain transfer agent containing a thiol group is not added, the hindered phenolic compound that is the phase difference adjusting agent prevents the photocuring during the color filter preparation as the addition rate of the phase difference adjusting agent increases. As a result, it is considered that pixel missing and film roughness occurred.
When these comparative examples 1 to 4 contain 0.03% by mass of IRGANOX1010 as a phase difference adjusting agent and 0.05% by mass of Karenz MT PE1 as a chain transfer agent containing a thiol group (Example 1), the absolute value of the phase difference was a relatively low value of 8.7 nm, and the evaluations of film roughness and missing pixels were all good. This indicates that by containing a phase difference adjusting agent having an appropriate addition rate and a chain transfer agent containing a thiol group, the effect of reducing the phase difference can be obtained while maintaining good plate-making property.

Next, Examples 1 to 3 and Comparative Example 4 in which the same retardation adjusting agent is used at different addition rates in a color filter having a red coloring composition will be compared.
When the addition rate of IRGANOX 1010, which is a kind of phase difference adjusting agent, is 0% by mass, that is, when no phase difference adjusting agent is added (Comparative Example 4), the absolute value of the phase difference is as high as 15.7 nm. On the other hand, when the addition rate was 0.01% by mass (Example 2), the absolute value of the phase difference was a relatively low value of 10.8 nm. This indicates that when the addition ratio is less than 0.01% by mass, the addition amount of the phase difference adjusting agent is too low to obtain the sufficient retardation reduction effect which is the effect of the present invention. Yes. In addition, in the case where the addition ratio is 0.03% by mass (Example 1) and 0.05% by mass (Example 3), the absolute values of the phase differences are 8.7 nm and 6.6 nm, respectively. The value was less than about half of the absolute value of the phase difference of 4.

Subsequently, Examples 1 and 4 which are cases where chain transfer agents each containing a different thiol group are used at the same addition rate in a color filter having a red coloring composition will be compared.
When Karenz MT PE1 (addition rate: 0.05% by mass) which is a kind of chain transfer agent containing a thiol group is added (Example 1), 1, 3, 5 which is a kind of chain transfer agent containing a thiol group -Tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name: Karenz MT NR1 (manufactured by Showa Denko KK)) (Addition rate: 0.05% by mass) (Example 4) is compared, the absolute value of the phase difference is 8.7 nm (Example 1) and 8.8 nm (Example 4), respectively, and The film roughness and the pixel defect evaluation were all good. This result shows that even when any polyfunctional thiol is used as the chain transfer agent, the effect of reducing the phase difference can be obtained while maintaining good plate-making property.

Subsequently, Examples 1, 5 and 6 which are cases where different retardation adjusting agents are used at the same addition rate in the color filter having the red coloring composition will be compared.
When IRGANOX1010 (addition rate: 0.03% by mass), which is a kind of phase difference adjusting agent, is added (Example 1), 2,2-thio-diethylenebis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1035 (manufactured by Ciba Japan Co., Ltd.)) (addition rate: 0.03 mass%) (Example 5) , N-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name: IRGANOX 1076 (manufactured by Ciba Japan KK)) (addition rate) : 0.03 mass%) (Example 6) is compared, the absolute value of the phase difference is 8.7 nm (Example 1), 9.0 nm (Example 5), and 8.0 nm (implementation), respectively. Example 6 , And the and, film roughness, missing pixels evaluation were both ○. This result shows that no matter what hindered phenolic compound is used as a phase difference adjusting agent, the effect of reducing the phase difference can be obtained while maintaining good plate-making property.

Subsequently, Examples 1 and 7 in which different pigment dispersants are used at the same addition rate in a color filter having a red coloring composition will be compared.
When Disperbyk111 (produced by Big Chemie Japan) (addition rate: 2.4% by mass), which is a kind of pigment dispersant, is added (Example 1), Azisper Pb821 (trade name, Ajinomoto Fine, which is a kind of pigment dispersant). Comparing the case (Example 7) with the addition of (Techno Co., Ltd.) (addition rate: 2.4% by mass), the absolute value of the phase difference was 8.7 nm (Example 1) and 8.2 nm (Example 7), and the evaluations of film roughness and pixel defect were all good. This result shows that, regardless of which pigment dispersant is used, the effect of reducing the retardation can be obtained while maintaining good plate-making properties.

Finally, in a color filter having a blue coloring composition, a color filter having a green coloring composition, and a colorless filter having a curable resin composition containing no pigment, the presence or absence of a phase difference adjusting agent, a chain containing a thiol group In order to examine the effect of the presence or absence of a transfer agent, Examples 8 to 11 and Comparative Examples 5 to 9 are examined. Since the degree of phase difference differs depending on the color, the color filters of the same color are compared.
First, a color filter having a blue coloring composition is examined. When the addition rate of the phase difference adjusting agent is 0% by mass, that is, the phase difference adjusting agent is not added, and the addition rate of the chain transfer agent containing a thiol group is 0% by mass, that is, the chain transfer agent is not added (comparison) In Example 5), the absolute value of the phase difference was as high as 13.8 nm. This indicates that when the phase difference adjusting agent is not added, a sufficient phase difference reduction effect that is the effect of the present invention cannot be obtained. In the case of containing 0.03% by mass of IRGANOX 1010 as a phase difference adjusting agent and 0.05% by mass of Karenz MT PE1 as a chain transfer agent containing a thiol group with respect to Comparative Example 5, (Example 8) The absolute value of the phase difference was a relatively low value of 9.6 nm, and the evaluations of film roughness and pixel defects were all good. This is because, even in a color filter having a blue coloring composition, by containing a retardation adjusting agent having an appropriate addition rate and a chain transfer agent containing a thiol group, the retardation can be reduced while maintaining good plate-making properties. It shows that an effect can be obtained.
Next, a color filter having a green coloring composition will be examined. When the addition rate of the phase difference adjusting agent is 0% by mass, that is, the phase difference adjusting agent is not added, and the addition rate of the chain transfer agent containing a thiol group is 0% by mass, that is, the chain transfer agent is not added (comparison) In Examples 6 and 7), the absolute value of the phase difference was as high as 4.7 nm and 4.5 nm, respectively. This indicates that when the phase difference adjusting agent is not added, a sufficient phase difference reduction effect that is the effect of the present invention cannot be obtained. In the case of containing 0.03% by mass of IRGANOX 1010 as a phase difference adjusting agent and 0.05% by mass of Karenz MT PE1 as a chain transfer agent containing a thiol group with respect to Comparative Examples 6 and 7 (Examples 9 and 10), the absolute value of the phase difference was a relatively low value of 2.9 nm and 3.4 nm, and the evaluations of film roughness and pixel defects were all good. This is because, even in a color filter having a green coloring composition, by containing a retardation adjusting agent having an appropriate addition rate and a chain transfer agent containing a thiol group, the retardation can be reduced while maintaining good plate-making properties. It shows that an effect can be obtained.
Finally, a colorless filter having a curable resin composition containing no pigment is studied. When the addition rate of the phase difference adjusting agent is 0% by mass, that is, the phase difference adjusting agent is not added, and the addition rate of the chain transfer agent containing a thiol group is 0% by mass, that is, the chain transfer agent is not added (comparison) In Example 8), the absolute value of the phase difference was as high as 3.1 nm. This indicates that when the phase difference adjusting agent is not added, a sufficient phase difference reduction effect that is the effect of the present invention cannot be obtained. When IRGANOX 1010, which is a kind of phase difference adjusting agent, is contained at an addition rate of 0.04% by mass and no chain transfer agent is added (Comparative Example 9), the absolute value of the phase difference is 2. It was a relatively low value of 0 nm. However, in the case of Comparative Example 9, the evaluation of the pixel defect and the film roughness was x. This is because when the chain transfer agent containing a thiol group is not added, the added hindered phenol compound which is a retardation adjusting agent prevents photocuring at the time of producing a color filter. It is thought that film roughening occurred. When the comparative examples 8 and 9 contain 0.04% by mass of IRGANOX1010 as a phase difference adjusting agent and 0.05% by mass of Karenz MT PE1 as a chain transfer agent containing a thiol group (Example 11), the absolute value of the phase difference was a relatively low value of 1.9 nm, and the evaluations of film roughness and missing pixels were all good. This is because, even in a colorless filter having a curable resin composition containing no pigment, a good plate-making property is maintained by containing a retardation adjusting agent with an appropriate addition rate and a chain transfer agent containing a thiol group. This shows that the effect of reducing the phase difference can be obtained.

DESCRIPTION OF SYMBOLS 1 Color filter 2 Electrode substrate 3 Gap part 4 Sealing material 5 Transparent substrate 6 Black matrix layer 7 (7R, 7G, 7B) Colored layer 8 Protective film 9 Transparent electrode film 10 Orientation film 11 Bead spacer 12 Columnar spacer 30 Pigment 31 Dispersant Adsorption layer 32 Resin layer 33 Phase difference main factor molecule 34 Arrows indicating the direction of stress generated by thermal expansion or the like 101, 102 Color liquid crystal display device 103 Color filter

Claims (6)

At least a photocurable resin component, a photopolymerization initiator, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and at least selected from the group consisting of n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate A photosensitive resin composition for a color filter, which contains a kind of hindered phenolic compound and a mercaptopropionic acid derivative having a molecular weight of 200 to 1000 (excluding those containing a maleimide compound) .   The photosensitive resin composition for a color filter according to claim 1, further comprising a coloring material.   The photosensitive resin composition for a color filter according to claim 2, wherein the colorant is a pigment.   The content rate of the said hindered phenol type compound in solid content of the photosensitive resin composition for color filters is 0.01-20 mass%, It is any one of Claims 1 thru | or 3 characterized by the above-mentioned. The photosensitive resin composition for color filters as described. 5. The content ratio of the mercaptopropionic acid derivative in the solid content of the photosensitive resin composition for a color filter is 0.01 to 20% by mass, according to claim 1. Photosensitive resin composition for color filters.   A color filter comprising a layer obtained by curing the photosensitive resin composition for a color filter according to any one of claims 1 to 5 on one surface side of a substrate.

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