JP5664299B2 - Photosensitive coloring composition and color filter using the same - Google Patents

Description

  The present invention relates to a photosensitive coloring composition, and in particular, a photosensitive coloring composition used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, etc., particularly a thin film transistor (TFT) type color. A photosensitive coloring composition for use in a color filter of a color filter on array system (hereinafter sometimes abbreviated as COA system), comprising a filter segment having a colored layer formed on a driving substrate of a liquid crystal display device, and The present invention relates to a color filter formed using a photosensitive coloring composition.

In the liquid crystal display device, a liquid crystal material and a pixel are interposed between two polarizing plates, a voltage is applied to each pixel to change the alignment state of the liquid crystal material, and the degree of polarization of light passing through the first polarizing plate is changed. It is a display device that changes and controls the transmitted light passing through the second polarizing plate to display the screen.
By providing a color filter between the two polarizing plates, color display is possible, and it has come to be used for televisions, personal computer monitors and the like. In recent years, color liquid crystal display devices are required to have high image quality and low power consumption, and color filters are also required to be designed to achieve high image quality and low power consumption.

  The color filter is provided with a grid-like light-shielding film black matrix (hereinafter referred to as BM) for the purpose of preventing color mixture of transmitted light and increasing display contrast on a transparent substrate such as a glass plate, and then a plurality of colors (usually red, Green and blue) filter segments are provided. The filter segments are as fine as several microns to several hundreds of microns, and the filter segments are arranged in the form of fine bands (stripes) of two or more different hues (stripe arrangement), or are arranged vertically and horizontally. (Delta arrangement).

  In general, when improving the image quality of a color liquid crystal display device, the resolution of the color filter is increased, that is, the number of pixels is increased. However, as the number of pixels increases, the number of light-shielding parts such as BMs formed so as to surround the pixels and thin-film transistors (TFTs) for driving the liquid crystal also increases, and the ratio of light transmission parts per unit area of the color filter, that is, The aperture ratio is lowered. As a result, the brightness of the color filter decreases and the screen display section becomes dark. In order to compensate for this, the illuminance of the backlight must be increased, leading to an increase in power consumption. For this reason, in order to reduce the image quality and power consumption of a color liquid crystal display device, a conflicting work of increasing the resolution of the color filter and increasing the aperture ratio is necessary, and various methods and structures have been considered.

  In particular, a colored layer is formed directly or via a passivation film such as a silicon nitride film on a driving substrate on which TFTs are arranged in a high aperture ratio structure which has been attracting attention recently, and this substrate and liquid crystal are driven. For example, there is a COA method in which a transparent electrode for bonding is attached to a substrate formed by vapor deposition or sputtering (see Patent Document 1). A normal color filter cannot reduce the width of the light-shielding portion beyond a certain level in order to prevent crosstalk between the gate electrode and the transparent electrode, whereas the COA method has a thickness on the driving substrate on which the TFT is disposed. By forming a colored layer on the film, insulation can be ensured and the width of the light shielding portion can be reduced. As a result, the COA method can greatly increase the aperture ratio and achieve high image quality and low power consumption of a color liquid crystal display device.

  Further, as described above, the COA pixel needs to be thicker than the conventional color filter pixel because it requires insulation, and the contact hole connecting the transparent electrode and the TFT is used as the pixel. Since it is necessary to provide, the photosensitive coloring composition which forms a pixel needs more excellent resolution.

  In addition, the COA system has a problem that it is more susceptible to the electrical characteristics of the color filter due to its mechanism. Liquid crystals used in liquid crystal display devices are easily affected by the electrical characteristics of color filters and other components inherent in the liquid crystal display device, and display defects such as liquid crystal orientation disturbance and switching performance adversely affected by liquid crystal contamination May be a problem. In order to solve such problems, the color filter pixels are required to have insulating properties, and it is necessary to increase the insulating properties by increasing the film thickness or to form pixels having a low dielectric constant. In order to solve such a problem, a method of selecting a dielectric loss tangent of two layers in which green (green) pixel overcoat layers are stacked within a specific range has been studied (see Patent Document 2).

  Moreover, although a method using a specific initiator (see Patent Document 3), a color filter composition using a benzotriazole-based ultraviolet absorber (see Patent Document 4), and the like have been disclosed, in recent years color liquid crystals have been disclosed. Due to the demand for higher image quality and lower power consumption of display devices, higher resolution is required for photosensitive coloring compositions forming pixels. In particular, COA color filter pixels are required to have a thicker film than conventional color filter pixels because insulation is required, and a contact hole must be formed in the thick film portion. In addition, better resolution is required.

  Further, the resolution of the photosensitive coloring composition can be adjusted by the kind and amount of the photopolymerization initiator and the monomer, and can be improved by selecting or reducing the amount of the photopolymerization initiator and the monomer having low sensitivity. In some cases, on the other hand, the adhesiveness between the photosensitive coloring composition and the glass substrate is lowered due to a decrease in sensitivity, and pattern peeling tends to occur. In particular, in the COA method, the pixel thickness of a normal color filter is about 3 to 4 μm as compared to about 1 to 2 μm, and it is a problem to produce a high-resolution pattern without causing pattern peeling. .

JP 2004-94263 A JP 2004-117537 A JP 2001-324611 A JP 2000-214580 A

  The present invention is a photosensitive coloring composition having high resolution that can cope with high image quality and low power consumption of a color liquid crystal display device in recent years, in particular, even with a thick film such as a COA system, high resolution and pattern peeling. It aims at providing the photosensitive coloring composition excellent in the adhesiveness which does not cause, and a color filter using the same.

The photosensitive coloring composition of the present invention is a light containing a colorant (A), a resin (B), a photopolymerizable monomer (C), and an acyl phosphine oxide organic compound or an oxime ester organic compound. the polymerization initiator (D), benzotriazole based organic compound, see contains an ultraviolet absorber (E) is at least one selected from the group consisting of a triazine-based organic compound, and benzophenone-based organic compound,
The resin (B) is copolymerized with the following (b1), (b2) and (b3) to obtain a copolymer (b6). The resulting copolymer (b6) and unsaturated monobasic acid ( a photosensitive resin (B-1) obtained by reacting b4) with a copolymer (b7) and further reacting the obtained copolymer (b7) with a polybasic acid anhydride (b5). ) .

(B1); a compound having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule
(B2); a compound having an epoxy group and an ethylenically unsaturated bond in one molecule
(B3); compounds having an ethylenically unsaturated bond other than (a1) and (a2)

Moreover, this invention relates to the said photosensitive coloring composition characterized by the ultraviolet absorber (E) being a compound represented by General formula (1).
General formula (1)

［一般式（１）中、Ｒ₁、Ｒ₂は互いに独立して、水素原子または、ベンゼン環を含んでも良い炭素数１〜２０のアルキル基、Ｘは、水素原子または、塩素原子を表す。］
また、本発明は、紫外線吸収剤（Ｅ）が、式（２）で表される化合物であることを特徴とする前記感光性着色組成物に関する。
式（２）

[In General Formula (1), R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and X represents a hydrogen atom or a chlorine atom. ]
Moreover, this invention relates to the said photosensitive coloring composition characterized by the ultraviolet absorber (E) being a compound represented by Formula (2).
Formula (2)

また、本発明は、光重合開始剤（Ｄ）が、式（３）で表される化合物を含むことを特徴とする前記感光性着色組成物に関する。
式（３）

Moreover, this invention relates to the said photosensitive coloring composition characterized by the photoinitiator (D) containing the compound represented by Formula (3).
Formula (3)

また、本発明は、樹脂（Ｂ）が、感光性樹脂を含むことを特徴とする前記感光性着色組成物に関する。

Moreover, this invention relates to the said photosensitive coloring composition characterized by resin (B) containing photosensitive resin.

The present invention also relates to a color filter comprising a filter segment formed using a photosensitive coloring composition on a substrate.
The present invention also relates to a color filter, wherein the base material is a driving substrate for a thin film transistor (TFT) type color liquid crystal display device.

  The photosensitive coloring composition of the present invention contains at least a colorant (A), a resin (B), a photopolymerizable monomer (C), and an acyl phosphine oxide organic compound or oxime ester organic compound. A photosensitive coloring composition comprising a photopolymerization initiator (D) and at least one ultraviolet absorber (E) selected from the group consisting of benzotriazole organic compounds, triazine organic compounds, and benzophenone organic compounds Therefore, since the resolution is high and the adhesion to the glass substrate is also high, pattern peeling does not occur.

  This utilizes the difference between the wavelength at which the photopolymerization initiator reacts and the wavelength absorbed by the UV absorber (mainly 400 nm or less). By using these in the above combination, the pixel film thickness is 3 to 4 μm. However, the reaction of the photopolymerization initiator is weakened in the wavelength range absorbed by the UV absorber, resulting in high resolution, and in other wavelength ranges, the sensitivity of the photopolymerization initiator reaction is secured and adhesion of the pattern is formed. This is because the property is also secured.

  Therefore, by forming a filter segment using the photosensitive coloring composition of the present invention, a color filter suitable for a high resolution, high aperture ratio color filter and a COA system can be produced, and using this, high image quality, A liquid crystal display device with low power consumption can be manufactured.

First, the photosensitive coloring composition of this invention is demonstrated.
The photosensitive coloring composition of the present invention comprises a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and an ultraviolet absorber (E). Containing
The photopolymerization initiator (D) contains an acyl phosphine oxide organic compound or an oxime ester organic compound,
Ultraviolet absorber (E) is, Ri least 1 Tanedea selected from the group consisting of benzotriazole organic compounds, triazine-based organic compound, and benzophenone-based organic compound,
The resin (B) is copolymerized with the following (b1), (b2) and (b3) to obtain a copolymer (b6). The obtained copolymer (b6) and the unsaturated monobasic acid (b4) ) To obtain a copolymer (b7), and further, a photosensitive resin (B-1) obtained by reacting the obtained copolymer (b7) with a polybasic acid anhydride (b5). Including

(B1); a compound having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule
(B2); a compound having an epoxy group and an ethylenically unsaturated bond in one molecule
(B3); compounds having an ethylenically unsaturated bond other than (a1) and (a2)

<Colorant (A)>
The photosensitive coloring composition of this invention contains the coloring agent (A), and can form the filter segment of each color which comprises a color filter.
As the colorant (A), organic or inorganic pigments and dyes can be used alone or in admixture of two or more. The colorant preferably has high color developability and high heat resistance, and an organic pigment is usually used.
Further, the organic pigment may be finely divided by salt milling, acid pasting or the like, and is more preferable in terms of the contrast suitability of the color filter.

Below, the specific example of the coloring agent (A) which can be used for the photosensitive coloring composition of this invention is shown.
The colorant (A) used for the red photosensitive coloring composition forming the red filter segment is C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, Red pigments such as 281, 282, 283, 284, 285, 286, or 287 are used. Further, basic dyes exhibiting red color, acidic dyes, and salt-forming compounds of these dyes can also be used.

  The red photosensitive coloring composition includes C.I. I. Pigment orange 43, 71, 73 or the like and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 , 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination. Further, basic dyes exhibiting orange and / or yellow, acid dyes, and salt-forming compounds of these dyes can also be used.

The colorant (A) used in the green photosensitive coloring composition forming the green filter segment is C.I. I. Pigment green 7, 10, 36, 37, 58 and the like.
A yellow pigment can be used in combination with the green photosensitive coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, basic dyes exhibiting yellow, acidic dyes and salt-forming compounds of these dyes can be used in combination.

  The colorant (A) used for the blue photosensitive coloring composition forming the blue filter segment is C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or the like can be used. The blue photosensitive coloring composition includes C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, or 50 can be used in combination. Further, basic dyes exhibiting purple, acidic dyes and salt-forming compounds of these dyes can be used in combination.

  The colorant (A) is preferably contained in the range of 1 to 80% by weight and more preferably in the range of 2 to 70% by weight in 100% by weight of the solid content of the photosensitive coloring composition. If the content of the colorant (A) is less than 1% by weight, the film thickness of the color filter becomes excessively thick, which is not preferable, and if it exceeds 80% by weight, a good dispersion state cannot be obtained.

<Resin (B)>
The resin (B) disperses the colorant (A), and examples thereof include a thermoplastic resin and a thermosetting resin.
The resin (B) is preferably a resin having a spectral 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. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. Moreover, in order to improve photosensitivity, the photosensitive resin which has an ethylenically unsaturated active double bond can also be used.

  The weight average molecular weight (Mw) of the resin (B) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to disperse the colorant (A) preferably. It is. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

Further, from the viewpoint of pigment dispersibility, developability, and heat resistance, a carboxyl group that functions as a pigment adsorbing group and an alkali-soluble group during development, an aliphatic group and an aromatic group that function as an affinity group for a pigment carrier and a solvent. The balance is important for pigment dispersibility, developability, and durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.
The resin (B) is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the colorant (A) because the film-forming property and various resistances are good, and the colorant concentration is high and the color is good. Since the characteristics can be expressed, it is preferably used in an amount of 500 parts by weight or less.

(Thermoplastic resin)
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

(Photosensitive resin)
The photosensitive resin is not limited as long as it is a resin having an ethylenically unsaturated double bond in the side chain, but the main chain is preferably linear, and is alkali-soluble to impart alkali developability. It is more preferable that the resin is applied. In particular, the resin (B-1) having a specific structure has good adhesion to a base material, a base, and the like, and a coating film having good electrical characteristics with a low dielectric constant and dielectric loss tangent can be obtained.

  Photosensitive resins include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxyethyl (meth) acrylate. , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentylglyce Coal diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate Acrylic acid esters and methacrylic acid esters such as styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile Water of a polymer compound obtained by polymerizing a monomer / oligomer such as (meth) acrylic acid or the like (Meth) acryloyl by reacting a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group with a reactive substituent such as an isocyanate group, a carboxyl group, or an amino group, or cinnamate. A resin into which a photocrosslinkable group such as a group or a styryl group is introduced 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. A half-esterified product can also be used.

[Photosensitive resin (B-1)]
Among the photosensitive resins, the following (b1), (b2) and (b3) are copolymerized to obtain a copolymer (b6), and the obtained copolymer (b6) and an unsaturated monobasic acid ( a photosensitive resin (B-1) obtained by reacting b4) with a copolymer (b7) and further reacting the obtained copolymer (b7) with a polybasic acid anhydride (b5). ), The adhesion to the base material or the ground becomes good, and a coating film having a low dielectric constant and dielectric loss tangent and good electrical characteristics can be obtained.

(B1); Compound (b2) having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule; Compound (b3) having an epoxy group and an ethylenically unsaturated bond in one molecule; (a1) and Compounds having an ethylenically unsaturated bond other than (a2)

  (B1); Specifically, as a compound having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl ( (Meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate , Pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, derivatives having substituents pinenyl (meth) acrylate and on the alicyclic ring. Examples of the substituent on the alicyclic ring of these monomers include an alkyl group, a hydroxyl group, and a carboxyl group.

  Among them, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate is preferred, and most preferred are isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. These can be used alone or in combination.

  (B2); As a compound having an epoxy group and an ethylenically unsaturated bond in one molecule, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-propylglycidyl (meth) acrylate, β-methyl Glycidyl-α-ethyl acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) Examples include acrylate and glycidyl vinyl ether, and glycidyl (meth) acrylate is preferred.

Specific examples of compounds having an ethylenically unsaturated bond other than (b3); (a1) and (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl. Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as (meth) acrylates, aminoethyl (meth) acrylates;
Ester compounds containing an aromatic ring of an unsaturated carboxylic acid such as benzyl (meth) acrylate and phenoxy (meth) acrylate;
Aromatic vinyl compounds such as styrene, α-methylstyrene, α-phenylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
And N-substituted maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide. These can be used alone or in combination.

  (B4); As unsaturated monobasic acids, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano Examples thereof include monocarboxylic acids such as substituted products. Of these, (meth) acrylic acid is preferred.

  (B5); dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride: anhydrous Examples thereof include polybasic acid anhydrides such as trimellitic acid, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride or succinic anhydride is preferred.

(Method for producing photosensitive resin (B-1))
The photosensitive resin (B-1) was obtained by copolymerizing (b1), (b2) and (b3) to obtain a copolymer (b6), and the obtained copolymer (b6) and unsaturated one base It is a copolymer obtained by reacting an acid (b4) to obtain a copolymer (b7), and further reacting the obtained copolymer (b7) with a polybasic acid anhydride (b5). .

  First, in order to obtain a copolymer (b6), (b1), (b2) and (b3) are copolymerized. This copolymerization is performed under normal conditions. For example, in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 0.5 to 20 times based on the weight of the total amount of (b1), (b2) and (b3) An amount of solvent is introduced and the atmosphere in the flask is replaced with nitrogen from air. Then, after heating up a solvent to 40-140 degreeC, it is a mass reference | standard with respect to the predetermined amount of (b1), (b2) and (b3), and the total amount of (b1), (b2) and (b3). 0 to 20 times the amount of solvent, and a solution in which 0.1 to 10 parts of the polymerization initiator is added to the weight ratio of (b1), (b2) and (b3) (stirred and dissolved at room temperature or under heating) Is added dropwise from the dropping funnel to the flask over 0.1 to 8 hours, and further stirred at 40 to 140 ° C. for 1 to 10 hours.

  In the above step, a part or the whole amount of the polymerization initiator may be charged to the flask side, and a part or the whole amount of (b1), (b2) and (b3) may be charged to the flask side. Moreover, in order to control molecular weight and molecular weight distribution, you may use (alpha) -methylstyrene dimer and a mercapto compound as a chain transfer agent. The amount of α-methylstyrene dimer or mercapto compound used is 0.005 to 5 parts on a mass basis with respect to the total amount of (b1) to (b3). In addition, the above-described polymerization conditions may be appropriately adjusted in the preparation method and the reaction temperature in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

  The ratio of the constituent components derived from each is a molar fraction with respect to the total number of moles of the constituent components constituting the copolymer (b6), 2 to 40 mol% of the structural units derived from (b1), The structural unit derived from (b2) is preferably 2 to 95 mol% derived from (b2) and 3 to 65 mol% derived from (b3), and derived from (b1) from the balance of flexibility and heat resistance. 5 to 35 mol%, 5 to 80 mol% of structural units derived from (b2), and 15 to 50 mol% of structural units derived from (b3) are more preferable.

  Next, (b4) is added to the copolymer (b6) to impart light and thermosetting properties to the resin (B). The reaction between the copolymers (b6) and (b4) can be performed, for example, under the conditions described in JP-A No. 2001-89533. Specifically, the atmosphere in the flask is replaced from nitrogen to air, and for example, trisdimethylaminomethylphenol is used as a reaction catalyst for carboxyl groups and epoxy groups based on the total amount of (b1) to (b4). In addition, 0.01 to 5%, and as a polymerization inhibitor, for example, hydroquinone is 0.001 to 5% on a mass basis with respect to the total amount of (b1) to (b4), and 60%. The above copolymers (b6) and (b4) can be reacted by reacting at ~ 130 ° C for 1 to 10 hours. Similar to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

  The addition amount of (b4) is 5 to 100 mol%, preferably 10 to 95 mol%, based on the epoxy group in the resin obtained by copolymerizing (b1) to (b3). When the composition ratio of (b2) is within the above range, it is preferable because sufficient photocurability and thermosetting can be obtained and the reliability is excellent.

Next, the copolymer (b7) and (b5) are reacted to impart alkali solubility to the resin (B).
The reaction of the copolymers (b7) and (b5) can be performed, for example, under the conditions described in JP-A-2001-89533. Specifically, as a reaction catalyst, for example, 0.01 to 5% of triethylamine is placed in a flask on a mass basis with respect to the total amount of (b1) to (b4), at 60 to 130 ° C., By reacting for 1 to 10 hours, the above copolymers (b7) and (b5) can be reacted. Similar to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

  The amount of (b5) added is 5 to 100 mol%, preferably 10 to 95 mol%, based on the number of moles of the alcoholic hydroxyl group of the copolymer (b7).

  The weight average molecular weight in terms of polystyrene of the photosensitive resin (B-1) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the photosensitive resin (B-1) is in the above range, the coating property is good, the film is not easily reduced during development, and the developability of the unexposed part is good during development. Some tend to be preferable.

  The molecular weight distribution [weight average molecular weight / number average molecular weight] of the photosensitive resin (B-1) is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. The molecular weight distribution in the above range is preferable because the developability is excellent.

  Content of the photosensitive resin used for the photosensitive coloring composition of this invention is 5-90 weight% normally in 100 weight% of solid content of the photosensitive resin composition, Preferably it is 10-70 weight%. When the content of the photosensitive resin is within the above range, it is preferable because it is excellent in solubility in a developing solution, hardly causes a development residue, and does not easily reduce the film thickness of an exposed portion during development.

  Moreover, the photocuring crosslinking degree becomes high by using photosensitive resin, adhesiveness is favorable, and cross-sectional shape also becomes favorable.

(Thermosetting resin)
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.

<Photopolymerizable monomer (C)>
The photopolymerizable monomer (C) contained in the photosensitive coloring composition of the present invention is a monomer or oligomer that forms a transparent resin by being cured by ultraviolet rays or heat, and these are used alone or in combination of two or more. Can be used.
The content of the photopolymerizable monomer (C) is preferably 10 to 50% by weight in a total of 100% by weight of the solid content of the coloring composition, and 20 to 20% from the viewpoint of photocurability and developability. More preferably, it is 40% by weight.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator (D)>
Since the photosensitive coloring composition of the present invention is cured by ultraviolet irradiation and forms a filter segment by a photolithographic method, a photopolymerization initiator (D) or the like is added to form a solvent developing type or alkali developing type colored resist material. Adjust with.
As a photoinitiator (D), an acyl phosphine oxide type organic compound or an oxime ester type organic compound is included, and it can also be used in mixture of 2 or more types by arbitrary ratios as needed. The content of these photopolymerization initiators (D) is preferably 1 to 16% by weight from the viewpoint of adhesion and resolution, based on the solid content of the photosensitive coloring composition (100% by weight), More preferably, it is 2 to 13% by weight.

Examples of the acylphosphine oxide-based organic compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl 2,4,4-trimethyl-pentylphosphine oxide, represented by the formula (3). And bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
Formula (3)

オキシムエステル系有機化合物としては、１，２−オクタンジオン，１−［４−（フェニルチオ）−，２−（Ｏ−ベンゾイルオキシム）］、エタノン，１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−，１−（Ｏ−アセチルオキシム）、Ｏ−（アセチル）−Ｎ−（１−フェニル−２−オキソ−２−（４’−メトキシ−ナフチル）エチリデン）ヒドロキシルアミン等があげられる。

Examples of the oxime ester organic compounds include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene ) Hydroxylamine and the like.

  Among the photopolymerization initiators (D), acylphosphine oxide organic compounds are preferable from the viewpoint of adhesion and resolution, and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide is the most preferable. preferable. This initiator is less dependent on exposure illuminance and exposure spectrum (particularly 300 to 410 nm), and provides stable sensitivity. Further, since the addition amount is relatively low with a relatively low sensitivity, there is a feature that fine adjustment of the resolution can be easily performed by adjusting the mixing ratio of the initiator and the ultraviolet absorber.

Examples of the photopolymerization initiator that can be used in combination include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-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-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] Phenyl] -2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methyl Ruthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Acetophenone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal, etc. Benzoin compounds, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra ( t-butyl par Benzophenone compounds such as xoxycarbonyl) benzophenone, thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2,4,6- Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl -S-triazine, 2- (naphth-1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl)- Triazine compounds such as 6-triazine and 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetra Phenyl-1,2'-biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl)- Imidazole compounds such as 4,4 ′, 5,5′-tetra (p-methylphenyl) biimidazole, quinones such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone Compounds, borate compounds, carbazole compounds, and the like.
These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

(Sensitizer)
In order to further enhance the reaction of the photopolymerization initiator, a sensitizer may be used in combination with the photosensitive coloring composition of the present invention. Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives and the like.

  Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Among the sensitizers, specific examples of sensitizers that can be used in combination include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole and the like can be mentioned.
These sensitizers can be used individually by 1 type or in mixture of 2 or more types. The content of the sensitizer is preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (D).

<Ultraviolet absorber (E)>
The ultraviolet absorber (E) in the present invention is an organic compound having an ultraviolet absorption function, and is at least one selected from the group consisting of benzotriazole organic compounds, triazine organic compounds, and benzophenone organic compounds. .

The content of the ultraviolet absorber (E) is preferably 5 to 70% by weight in a total of 100% by weight of the photopolymerization initiator (D) and the ultraviolet absorber (E).
When the content of the UV absorber (E) is less than the above, the effect of the UV absorber is small and the resolution cannot be ensured. When the content is higher than the above, the sensitivity is lowered and the pixel peeling and the hole diameter are designed. There may be a problem that it becomes larger than the value.
In particular, when an acylphosphine photopolymerization initiator is included as the photopolymerization initiator (D), the content of the ultraviolet absorber (E) is preferably 5 to 50% by weight, more preferably 10 to 10%. When it is 40% by weight and contains an oxime ester photopolymerization initiator, it is preferably 20 to 70% by weight, more preferably 30 to 60% by weight.

  At this time, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator (D).

The total content of the photopolymerization initiator (D) and the ultraviolet absorber (E) is preferably 1 to 20% by weight in 100% by weight of the solid content of the photosensitive coloring composition.
In particular, when an acylphosphine-based photopolymerization initiator is included as the photopolymerization initiator (D), the total content of the photopolymerization initiator (D) and the ultraviolet absorber (E) is preferably 5 to 20 %, More preferably 8 to 16% by weight, and preferably 1 to 10% by weight and more preferably 2 to 8% by weight when an oxime ester photopolymerization initiator is included.

  When the total content of the photopolymerization initiator (D) and the ultraviolet absorber (E) is less than the above, the adhesion is weakened and the pixels are peeled off. When the total content is more than the above, the sensitivity is too high and the resolution is poor. May be.

  At this time, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator (D).

  Examples of the benzotriazole-based organic compound include 2- (5 methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert-butyl. -4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H) -Benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-tbutyl- 5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2 Hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H— Benzotriazol-2-yl)-(1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazol-2-yl) -4,6 -Bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3) -Tetramethylbutyl) phenol.

  More specifically, “TINUVIN P”, “TINUVIN PS”, “TINUVIN 109”, “TINUVIN 234”, “TINUVIN 326”, “TINUVIN 328”, “TINUVIN 329”, “TINUVIN 384-2” manufactured by BASF , "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130", and the like.

From the viewpoint of adhesion and resolution, a benzotriazole-based organic compound represented by the structural formula of the general formula (1) is preferable, and 2- (2H-benzotriazole-2-) represented by the structure of the formula (2) is preferable. Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol is most preferred.
General formula (1)

［一般式（１）中、Ｒ₁、Ｒ₂は互いに独立して、水素原子または、ベンゼン環を含んでも良い炭素数１〜２０のアルキル基、Ｘは、水素原子または、塩素原子を表す。］
式（２）

[In General Formula (1), R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and X represents a hydrogen atom or a chlorine atom. ]
Formula (2)

トリアジン系有機化合物としては、２−［４，６−ジ（２，４−キシリル）−１，３，５−トリアジン−２−イル］−５−オクチルオキシフェノール、２‐［４，６‐ビス（２，４‐ジメチルフェニル）‐１，３，５‐トリアジン‐２‐イル］‐５‐［３‐（ドデシルオキシ）‐２‐ヒドロキシプロポキシ］フェノール、２−（２，４−ジヒドロキシフェニル）−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジンと（２−エチルヘキシル−グリシド酸エステルの反応生成物、２，４−ビス「２−ヒドロキシ−４−ブトキシフェニル」−６−（２，４−ジブトキシフェニル）−１，３−５−トリアジン等が挙げられる。

Examples of triazine organic compounds include 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol, 2- [4,6-bis. (2,4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl)- Reaction product of 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidic acid ester, 2,4-bis “2-hydroxy-4-butoxyphenyl” And -6- (2,4-dibutoxyphenyl) -1,3-5-triazine.

  More specifically, “KEMISORB 102” manufactured by Chemipro Kasei Co., Ltd., “TINUVIN 400”, “TINUVIN 405”, “TINUVIN 460”, “TINUVIN 477-DW”, “TINUVIN 479” manufactured by BASF, and the like.

  Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Examples include octoxybenzophenone and 2,2-di-hydroxy-4-methoxybenzophenone.

  More specifically, “KEMISORB 10”, “KEMISORB 11”, “KEMISORB 11S”, “KEMISORB 12”, “KEMISORB 111”, and the like manufactured by Chemipro Kasei Co., Ltd., may be mentioned.

<Solvent>
In the photosensitive coloring composition of the present invention, a colorant is sufficiently dispersed and permeated in a colorant carrier, and is applied on a substrate such as a glass substrate so that a dry film thickness is 1 to 5 μm. A solvent can be included to facilitate formation.

  Examples of the solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2 -Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl- 1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m- Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethyl Formamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol mono Propyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, di Lopylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl Ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl Sobuchiruketon, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, from the viewpoint of the storage stability of the photosensitive coloring composition of the present invention, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, benzyl It is preferable to use aromatic alcohols such as alcohol and ketones such as cyclohexanone.

  A solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the photosensitive coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, the amount of the solvent is 800 to 4000 parts by weight with respect to 100 parts by weight of the colorant (A). It is preferable to use in.

<Production method of photosensitive coloring composition>
The photosensitive coloring composition of the present invention comprises a colorant carrier containing a resin (B) and a solvent, and a colorant (A) such as a three-roll mill, a two-roll mill, a sand mill, a kneader, an attritor, and a paint conditioner. A pigment dispersion is produced by finely dispersing using a dispersing means, and a photopolymerizable monomer (C), a photopolymerization initiator (D), and an ultraviolet absorber (E) are mixed with a disper or the like. Can be manufactured.

  The pigment dispersion can also be produced by mixing colorants or the like separately dispersed in a colorant carrier.

  The photosensitive coloring composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust.

(Dispersing aid)
When dispersing the colorant (A) in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the pigment carrier using the dispersion aid is used. If so, a color filter with high spectral transmittance can be obtained.

Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.
Among these, a pigment derivative is preferable, and the structure thereof is a compound represented by the following general formula (4).
P-Ln General formula (4)
(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: an integer of 1 to 4 is there)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. What is currently used can be used, These can be used individually or in mixture of 2 or more types.
The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight or more with respect to 100 parts by weight of the colorant (A) from the viewpoint of improving dispersibility. is there. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40% by weight or less, and most preferably 35% by weight or less with respect to 100 parts by weight of the colorant (A).

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant (A). When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Other additive components>
(Multifunctional thiol)
The photosensitive coloring composition of the present invention can further 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-trimerca DOO -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto--s- triazine.
These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the colorant (A).

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the photosensitive coloring composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the photosensitive coloring composition (100% by weight).

(Storage stabilizer)
The photosensitive coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant (A) contained in the photosensitive coloring composition.

(Adhesion improver)
Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant (A) contained in the photosensitive coloring composition.

<Color filter>
Next, a pixel color filter formed using the photosensitive coloring composition of the present invention and a method for producing the color filter will be described.
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. The said filter segment is formed on a base material by apply | coating the photosensitive coloring composition of this invention by a spin coat system or a die coat system.

  As the base material of the color filter, glass plates such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, etc. with high transmittance for visible light, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. A transparent substrate such as a resin plate or a reflective substrate can be used. These substrates may be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after forming the panel.

  If the BM is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the BM, chromium, a chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. It is also possible to form TFTs on the transparent substrate or the reflective substrate in advance and use it as a driving substrate for a liquid crystal display device, and to form pixels on it. A color filter in which a filter segment is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, so that the aperture ratio can be greatly increased and the image quality and low power consumption of the color liquid crystal display device can be achieved. Can do.

  Here, a method for forming a COA color filter will be described. First, a BM is formed on the surface of the TFT substrate or on the surface of the substrate on which a passivation film such as a silicon nitride film is formed on the surface of the driving substrate, if necessary. On this, after applying a photosensitive coloring composition, it prebakes and a solvent is evaporated and a coating film is formed. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, melt | dissolves and removes the unexposed part of a coating film, and it post-bakes after that. By repeating this for each color photosensitive coloring composition, a pixel array in which pixels are arranged in a predetermined arrangement can be formed. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. An antifoaming agent or a surfactant can also be added to the developer.

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. After forming, UV exposure can also be performed.

The dry thickness of the coating thickness when forming the filter segment on the transparent substrate or the reflective substrate is preferably 1 to 3 μm, more preferably 1 to 2 μm.
In particular, when the photosensitive coloring composition of the present invention is used in the COA system, insulation is required to prevent crosstalk between the gate electrode and the transparent electrode, and a thick film is preferable. It is preferable to use a dry film thickness of 1 to 5 μm, more preferably 3 to 4 μm.

  An overcoat film, a columnar spacer, a transparent electrode, a liquid crystal alignment film, and the like are formed on the pixel as necessary. Therefore, the shape of the photosensitive coloring composition forming the pixel is preferably a forward tapered shape, and if it is a reverse tapered shape, problems such as disconnection of the transparent electrode occur.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  Moreover, the polymerization average molecular weight (Mw) of the resin was measured by using TSKgel column (manufactured by Tosoh Corporation), GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, and using polystyrene as a developing solvent. It is a weight average molecular weight (Mw) in terms of conversion.

  First, the manufacturing method of the resin solution, the refined pigment, and the pigment dispersion used in Examples and Comparative Examples will be described.

<Method for producing resin solution>
(Preparation of resin solution (B1))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to obtain a resin solution (B1).

(Preparation of resin solution (B2))
560 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 45. n-butyl methacrylate from the dropping tube at the same temperature. A mixture of 0 part, 47.0 parts of glycerol monomethacrylate, and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction.
After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 55 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A polymer solution was obtained.
Next, a mixture of 32.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate and 120.0 parts of cyclohexanone was added to 338 parts of the obtained copolymer solution at 70 ° C. over 3 hours. And dripped.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, a resin solution (B2) was obtained. The obtained photosensitive resin had a weight average molecular weight of 12,000.

(Preparation of resin solution (B3))
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel, heat to 120 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, dicyclopenta from the dropping tube. A mixture of 41.0 parts of nyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was purged with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. The reaction was terminated when the value reached 0.8, and a resin solution having a weight average molecular weight of about 12,000 was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours. Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40%, and the resin solution (B3) solution was obtained. Prepared.

<Production method of fine pigment>
(Refinement pigment production example 1)
100 parts of diketopyrrolopyrrole-based red pigment PR254 ("Irgaphore Red B-CF" manufactured by BASF), 1000 parts of crushed salt, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C. For 8 hours. The mixture was poured into 2000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts refined pigment (PR-1).

(Refinement pigment production example 2)
100 parts of anthraquinone red pigment PR177 (“chromophthal red A2B” manufactured by BASF), 800 parts of crushed salt and 180 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. . The mixture was poured into 4000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts refined pigment (PR-2).

(Refinement pigment production example 3)
120 parts of halogenated copper phthalocyanine-based green pigment PG36 (“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd.), 1500 parts of crushed salt, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. And kneading for 15 hours. The mixture was poured into 5000 parts of warm water, stirred at a high-speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts refined pigment (PG-1).

(Fine refined pigment production example 4)
100 parts of a metal complex yellow pigment PY150 (LANCESS "E4GN"), 1500 parts of crushed salt and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. The kneaded product is poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 24 ° C. for 24 hours. After drying for a period of time, 95 parts of a refined pigment (PY-1) was obtained.

(Fine refined pigment production example 5)
100 parts of copper phthalocyanine-based blue pigment PB15: 6 (“Lionol Blue ES” manufactured by Toyo Ink Manufacturing Co., Ltd.), 5 parts of a pigment derivative (Compound 2), 1000 parts of crushed salt, and 100 parts of diethylene glycol were added to a 1 gallon kneader made of stainless steel ( Prepared by Inoue Seisakusho) and kneaded at 50 ° C. for 12 hours. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed with water to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts refined pigment (PB-1).

(Fine refined pigment production example 6)
300 parts of dioxazine-based purple pigment PV23 (“Rionogen Violet RL” manufactured by Toyo Ink Manufacturing Co., Ltd.) was added to 3000 parts of 96% sulfuric acid, stirred for 1 hour, and poured into 5 ° C. water. After stirring for 1 hour, it was filtered, washed with warm water until the washing solution became neutral, and dried at 70 ° C. 120 parts of the obtained acid pasting pigment, 1500 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 20 hours. The mixture was poured into 5000 parts of warm water, stirred at a high-speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts refined pigment (PV-1).

<Method for producing pigment dispersion>
A mixture having the composition (parts by weight) shown in Table 1 was uniformly stirred and mixed, then dispersed with an Eiger mill for 2 hours using zirconia beads having a diameter of 0.5 mm, and filtered through a 5 μm filter to obtain a pigment dispersion (DR- 1, 2, DG-1, DY-1, DB-1, DV-1).

Resin type dispersant: “SOLPERSE-20000” manufactured by Nippon Lubrizol

[Examples 1-20, Comparative Examples 1-9]
<Preparation of photosensitive coloring composition>
The mixture of the composition (parts by weight) shown in Tables 2 to 4 was uniformly stirred and mixed, then filtered through a 1 μm filter, and the red photosensitive coloring compositions of Examples 1-7 and Comparative Examples 1-3, Example 8 To 14 and Comparative Examples 4 to 6, green photosensitive coloring compositions, Examples 15 to 20 and Comparative Examples 7 to 9 were prepared.
However, Examples 2, 3, 9 and 10 are reference examples.

(* 1) Ultraviolet absorber (E) content (%):
Content of UV absorber (E) / Total amount of photopolymerization initiator (D) and UV absorber (E) (* 2) Photopolymerization initiator (D) + UV absorber (E) content (% ):
Total content of photopolymerization initiator (D) and ultraviolet absorber (E) / solid content weight of photosensitive coloring composition When the photosensitive coloring composition contains a sensitizer, the photopolymerization initiator Calculation is made assuming that the content of (D) includes the content of the sensitizer.

Abbreviations in Tables 2 to 4 are shown below.
<Photopolymerizable monomer (C)>
monomer:
Dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toa Gosei Co., Ltd.)
<Photopolymerization initiator>
Photopolymerization initiator a:
(Acylphosphine oxide organic compound) bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide ("IRGACURE 819" manufactured by BASF)
Photopolymerization initiator b:
(Oxime ester organic compound) Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)
("IRGACURE OXE 02" manufactured by BASF)
Photopolymerization initiator c:
(Titanocene-based organic compound) bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (manufactured by BASF “ IRGACURE 784 ")
<Sensitizer>
Sensitizer a: 2,4-diethylthioxanthone ("Kayacure DETX-S" manufactured by Nippon Kayaku Co., Ltd.)

<Ultraviolet absorber>
UV absorber a:
(Benzotriazole-based organic compound) 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (“TINUVIN 900” manufactured by BASF)
UV absorber b:
(Benzotriazole organic compounds)
5% 2-methoxy-1-methylethyl acetate 95% benzenepropanoic acid, 3- (2H-benzotriazol-2-yl)-(1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and straight Chain alkyl ester ("TINUVIN 384-2" manufactured by BASF)
UV absorber c:
(Triazine-based organic compound) 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy ] Phenol ("TINUVIN 400" manufactured by BASF)
UV absorber d:
(Benzophenone-based organic compound) 2-hydroxy-4-n-octoxybenzophenone ("KEMISORB 12" manufactured by Chemipro Kasei Co., Ltd.)
UV absorber e:
(Benzoate organic compound) 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate ("KEMISORB 112" manufactured by Chemipro Kasei Co., Ltd.)

<Solvent>
Solvent: Propylene glycol monomethyl ether acetate

<Evaluation>
[Adhesion evaluation]
The obtained photosensitive coloring composition was applied to a glass substrate (substrate 1) having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm, and a substrate (substrate 2) in which a silicon nitride film was formed on the surface of a TFT liquid crystal driving substrate. Using a spin coater, coating was carried out at a rotational speed such that the film thickness after heating and drying was 3 μm.
After drying under reduced pressure, using an ultrahigh pressure mercury lamp, ultraviolet exposure was performed with a cumulative light quantity of 50 mJ and an illuminance of 30 mW through a photomask containing a regular hexagonal hole with a diameter of 30 μm and a thin wire with a diameter of 50 μm.
Thereafter, a 0.2 wt% sodium carbonate aqueous solution was used as a developing solution, and development was further performed for 15 seconds from the point where the unexposed portion of the coating film disappeared to form a pattern.
Thereafter, red: 60 minutes, green: 40 minutes, blue: 20 minutes were dried by heating at 230 ° C. to prepare an evaluation substrate.
The adhesion of this coating film was visually evaluated in three stages according to the following criteria.
○: No pattern peeling is observed △: Pattern peeling is slightly observed ×: Pattern peeling is recognized

[Resolution evaluation]
About the board | substrate used for preparation evaluation for adhesive evaluation, the hole diameter exposed and formed with the mask hole diameter of 30 micrometers with the analysis software (Image-Pro by Planetron Co., Ltd.) using an optical microscope is measured, and the following reference | standard Three-level evaluation was performed.
○: A hole of 25 μm or more to less than 31 μm can be formed. Δ: A hole of 15 μm or more to less than 25 μm can be formed. ×: A hole of less than 15 μm or 31 μm or more is formed.

[Cross-sectional shape evaluation]
About the board | substrate used for preparation evaluation for adhesive evaluation, the thin line part of the pattern was evaluated 3 steps | paragraphs with the following reference | standard using the scanning electron microscope (SEM).
○: Forward tapered shape (section is trapezoidal and exposure surface is small)
Δ: Non-tapered shape (exposure surface and substrate surface are the same)
X: Inverse taper shape (the cross section is trapezoidal and the exposure surface is large) or the shape is not uniform. The evaluation results are shown in Table 5.

  In terms of adhesion, resolution and shape, the glass substrate (substrate 1) and the driving substrate (substrate 2) of the thin film transistor (TFT) type color liquid crystal display device all showed the same evaluation results.

  As for the photosensitive coloring composition of this invention, the adhesiveness, resolution, and the evaluation result of a shape were all favorable compared with the comparative example. Thus, by combining a specific photopolymerization initiator and a specific ultraviolet absorber, it is possible to achieve both adhesion and resolution even with a 3 μm thick film, and form a COA color filter. As a result, it was confirmed to be excellent.

  Similarly, the evaluation results at a film thickness of 2 μm were all good in adhesion, resolution, and shape.

  In particular, when the ultraviolet absorber (E) is a benzotriazole organic compound 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, adhesion The property was very good.

  In addition, the photosensitive coloring compositions obtained in Examples 7, 8 to 13, and 15 to 20 in which the photopolymerization initiator (D) includes an acylphosphine oxide photopolymerization initiator have an exposure illuminance of 30 mW to 20 mW. Even if it is changed to, even if the exposure spectrum of 300 to 410 nm is changed by interposing a glass plate in the exposure machine, the resolution does not change as before, and the dependence of exposure illuminance and exposure spectrum is small. A more stable sensitivity was confirmed.

  Furthermore, when the resin contains a photosensitive resin, the adhesiveness was good, and the shape was good by using the resin solution (B3) which is the photosensitive resin [B-1] having a specific structure.

  Further, when a sensitizer was used in combination, a better result was obtained in the shape.

Claims (6)

A colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D) containing an acylphosphine oxide organic compound or an oxime ester organic compound, and benzotriazole system organic compound, see contains an ultraviolet absorber (E) is at least one selected from the group consisting of a triazine-based organic compound, and benzophenone-based organic compound,
The resin (B) is copolymerized with the following (b1), (b2) and (b3) to obtain a copolymer (b6). The resulting copolymer (b6) and unsaturated monobasic acid ( a photosensitive resin (B-1) obtained by reacting b4) with a copolymer (b7) and further reacting the obtained copolymer (b7) with a polybasic acid anhydride (b5). The photosensitive coloring composition characterized by including this.

(B1); a compound having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule
(B2); a compound having an epoxy group and an ethylenically unsaturated bond in one molecule
(B3); compounds having an ethylenically unsaturated bond other than (a1) and (a2) The photosensitive coloring composition according to claim 1, wherein the ultraviolet absorber (E) is a compound represented by the general formula (1).
General formula (1)

[In General Formula (1), R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring, and X represents a hydrogen atom or a chlorine atom. ] The photosensitive coloring composition according to claim 2, wherein the ultraviolet absorber (E) is a compound represented by the formula (2).
Formula (2)

The photosensitive coloring composition according to any one of claims 1 to 3, wherein the photopolymerization initiator (D) contains a compound represented by the formula (3).
Formula (3)

A color filter comprising a filter segment formed using the photosensitive coloring composition according to any one of claims 1 to 4 on a substrate. 6. The color filter according to claim 5 , wherein the substrate is a driving substrate for a thin film transistor (TFT) type color liquid crystal display device.