JP4963951B2 - Green photosensitive resin composition, photosensitive resin transfer material, color filter, and display device - Google Patents

Description

  The present invention relates to a green photosensitive resin composition, and a photosensitive resin transfer material, a color filter, and a display device produced using the same.

  In recent years, color filters are frequently used in color liquid crystal displays, sensors, color separation devices, and the like. As a manufacturing method of this color filter, conventionally, a method has been adopted in which a dyeable resin, for example, natural gelatin or casein is patterned and dyed there mainly to obtain a pixel. However, the pixel obtained by this method has a problem that heat resistance and light resistance are low due to restrictions on materials. Thus, recently, a method using a photosensitive material in which a pigment is dispersed for the purpose of improving heat resistance and light resistance has attracted attention and many studies have been conducted. According to this method, the manufacturing method is simplified, and the obtained color filter is known to be stable and have a long lifetime.

However, compared with the case of using a dye, the light transmittance and color purity were insufficient when a pigment was used. Therefore, various combinations of pigments have been conventionally proposed.
For example, in the production of a green color filter, a yellow pigment is often used together for hue correction. A photosensitive composition for a green color filter containing a photopolymerizable compound, a photopolymerization initiator, copper halide phthalocyanine, and a specific yellow pigment is disclosed (for example, see Patent Document 1). Further, a pigment blend and a color filter containing a metal complex of an azobarbitur compound are disclosed (for example, see Patent Document 2).
Japanese Patent No. 3641093 JP 2005-325350 A

  In the methods disclosed in Patent Documents 1 and 2, the viscosity of the pigment dispersion after dispersion may increase during dispersion, and it is difficult to say that the dispersibility is sufficient. Further, when color filters are prepared using these dispersions, there is a problem that contrast is insufficient.

  The present invention has been made in view of the above-described conventional problems, and is a green photosensitive resin composition having a low liquid viscosity and suppressed increase in liquid viscosity after preparation, and a photosensitive resin produced using the same. An object of the present invention is to provide a transfer material, a color filter having good contrast, and a display device including the color filter, and to achieve the object.

Specific means for solving the above problems are as follows.
<1> A pigment, a pigment dispersant, a photopolymerizable compound, and a photopolymerization initiator, wherein the pigment is a ligand of a tautomer of an azo compound represented by the following general formula (I) The metal complex (1) contains a compound having a crystal structure in which a compound different from the metal complex is inserted in the crystal and a halogenated copper phthalocyanine compound , and the pigment dispersant has an amino group Furthermore, it is a green photosensitive resin composition whose contrast coefficient is 3800 or more.

In the general formula (I), the total of the intra-ring and exocyclic double bonds in the rings represented by A and B is 3, respectively.
X, Y, Z and W are independently of each other, a carbonyl group, a thiocarbonyl ^{group, -C (= NR 7) -} , = C (N (R 6) R 7) -, = C (OR 6) - , = C (SR ⁶ )-, = C (CO ₂ R ⁶ )-, = C (CN)-, = C (CON (R ⁶ ) R ⁷ )-, = C (SO ₂ R ⁸ )-or = C (R ⁶ ) —
R ¹ , R ² , R ³ , R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,
R ⁵ represents —OH, —N (R ⁶ ) R ⁷ , an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group,
R ⁷ represents a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group, and R ⁸ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,
R ¹ and Y, R ² and Y, R ³ and W, R ⁴ and W may be bonded to each other to form a 5- or 6-membered ring, and other rings are condensed to this ring. Often,
The substituents R ^{1 to} R ⁸ having a CH bond may be further substituted,
m, n, o, and p each independently represent 1 or 0 when a double bond comes out from a ring nitrogen atom.

<2> A metal complex having a tautomer of the azo compound represented by the general formula (I) as a ligand (1) A compound having a crystal structure in which a compound different from the metal complex is inserted in the crystal Is Yellow Pigment E4GN-GT, The green photosensitive resin composition of Claim 1 characterized by the above-mentioned.
<3> Further, the pigment may be an iron compound (2) different from the metal complex (1) and / or a metal compound (3) different from the metal complex (1) and the iron compound (2). It is contained, It is a green photosensitive resin composition as described in said <1> or <2> .
< 4> A photosensitive resin transfer material in which a photosensitive resin layer is provided on the temporary support using the green photosensitive resin composition according to any one of <1> to <3>.
<5> The photosensitive resin transfer material according to <4>, wherein a thermoplastic resin layer and an intermediate layer are provided between the temporary support and the photosensitive resin layer.
<6> The green photosensitive resin composition according to any one of <1> to <3>, or the photosensitive resin transfer material according to <4> or <5>. It is a color filter.
<7> A display device comprising the color filter according to <6>.

  According to the present invention, a green photosensitive resin composition having a low liquid viscosity and suppressed increase in liquid viscosity after preparation, a photosensitive resin transfer material produced using the same, a color filter having good contrast, and the same A display device including a color filter can be provided.

Hereinafter, the green photosensitive resin composition, photosensitive resin transfer material, color filter, and display device of the present invention will be described in detail.
<Green photosensitive resin composition>
The green photosensitive resin composition of the present invention comprises a pigment, a pigment dispersant, a photopolymerizable compound, and a photopolymerization initiator, wherein the pigment is an azo compound represented by the following general formula (I): Metal complex having tautomer as ligand (1) A compound having a crystal structure in which a compound different from the metal complex is inserted in the crystal and a copper halide phthalocyanine compound , and the pigment dispersant Is a compound having an amino group, and further has a contrast coefficient of 3800 or more.

(Pigment)
The pigment in the present invention contains at least one metal complex having a tautomer of an azo compound represented by the following general formula (I) as a ligand.

In the general formula (I), the total of the intra-ring and exocyclic double bonds in the rings represented by A and B is 3, respectively.
X, Y, Z and W are independently of each other, a carbonyl group, a thiocarbonyl ^{group, -C (= NR 7) -} , = C (N (R 6) R 7) -, = C (OR 6) - , = C (SR ⁶ )-, = C (CO ₂ R ⁶ )-, = C (CN)-, = C (CON (R ⁶ ) R ⁷ )-, = C (SO ₂ R ⁸ )-or = C (R ⁶ ) —
R ¹ , R ² , R ³ , R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,
R ⁵ represents —OH, —NR ⁶ R ⁷ , an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group,
R ⁷ represents a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group,
R ⁸ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,
R ¹ and Y, R ² and Y, R ³ and W, R ⁴ and W may be bonded to each other to form a 5- or 6-membered ring, and other rings are condensed to this ring. Often,
The substituents R ^{1 to} R ⁸ having a CH bond may be further substituted,
m, n, o, and p each independently represent 1 or 0 when a double bond comes out from a ring nitrogen atom.

  The alkyl group in the general formula (I) is particularly preferably an alkyl group having 1 to 6 carbon atoms. Furthermore, the alkyl group may be substituted with a halogen atom (for example, chlorine, bromine or fluorine), a hydroxyl group, a cyano group, an amino group, or an alkoxy group having 1 to 6 carbon atoms.

  As a cycloalkyl group in the said general formula (I), a C3-C7 cycloalkyl group is preferable and a C5-C6 cycloalkyl group is more preferable. Further, the cycloalkyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom (for example, chlorine, bromine or fluorine), a hydroxyl group, a cyano group or an amino group. .

  The aryl group in the general formula (I) is particularly preferably a phenyl group or a naphthyl group. Further, the aryl group is substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom (for example, chlorine, bromine or fluorine), a hydroxyl group, a cyano group, a nitro group or an amino group. Also good.

  As the aralkyl group in the general formula (I), a group in which a phenyl group or a naphthyl group is substituted on an alkyl group having 1 to 4 carbon atoms is particularly preferable. Further, the aralkyl group is substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom (for example, chlorine, bromine or fluorine), a hydroxyl group, a cyano group, a nitro group or an amino group in an aromatic group. May be.

  As the acyl group in the general formula (I), an alkylcarbonyl group having 1 to 6 carbon atoms, a phenylcarbonyl group, an alkylsulfonyl group having 1 to 6 carbon atoms, a phenylsulfonyl group, an alkyl group having 1 to 6 carbon atoms, By a carbamoyl group substituted by a phenyl group or a naphthyl group, an alkyl group having 1 to 6 carbon atoms, a sulfamoyl group substituted by a phenyl group or naphthyl group, or an alkyl group having 1 to 6 carbon atoms, a phenyl group or a naphthyl group A substituted amidino group is preferred. Further, the alkyl moiety in the acyl group may be substituted by an alkoxy group having 1 to 6 carbon atoms, a halogen atom (for example, chlorine, bromine or fluorine), a hydroxyl group, a cyano group or an amino group, and phenyl in the acyl group. Alternatively, the naphthyl moiety may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom (for example, chlorine, bromine or fluorine), a hydroxyl group, a cyano group, a nitro group, or an amino group. .

In the general formula (I), when R ¹ and Y, R ² and Y, R ³ and W, and R ⁴ and W are bonded to each other to form a 5- or 6-membered ring, a triazole ring, an imidazole ring, It is preferable to form a pyrimidine ring or a quinazoline ring. Further, these rings may be condensed with other rings.

  In the general formula (I), the ring represented by A is preferably a compound represented by any one of the following general formulas (II-1) to (II-5).

In formulas (II-1) to (II-5), L ²⁰ and M ²⁰ each independently represent ═O, ═S or ═NR ²⁶ , and L ²¹ represents a hydrogen atom, —OR ²⁶ , —SR ^26. represents ^{-N (R 26) R 27,} -COOR 26, -CON (R 26) R 27, -CN, alkyl group, cycloalkyl group, an aryl group or an aralkyl group,
M ²¹ is ^{-OR 26, -SR 26, -N (} R 26) R 27, -COOR 26, -CON (R 26) R 27, -CN, -SO 2 R 28, an alkyl group, a cycloalkyl group, an aryl Represents a group or an aralkyl group,
R ²⁵ represents —OH, —N (R ²⁶ ) R ²⁷ , an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group,
R ²¹ , R ²² and R ²⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,
R ²⁷ represents a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group,
R ²⁸ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,
M ²¹ and R ²¹ , and M ²¹ and R ²² may be bonded to each other to form a 5- or 6-membered ring.

  Furthermore, the compound represented by the general formula (I) is more preferably a compound represented by the following general formula (III).

In the general formula ^{(III), R 35} represents -OH or -NH ^{_2, M 31} and ^{M 32} represent a hydrogen atom, a hydroxyl group, an amino group, cyanoamino group, an arylamino group or an acylamino group independently of one another.

  Furthermore, the compound represented by the general formula (I) is more preferably a compound represented by the following general formula (IV).

In the general formula (IV), M ⁴¹ and M ⁴² each independently represent a hydroxyl group or a cyanoamino group.

  In particular, the compound represented by the general formula (I) is most preferably a compound represented by the following chemical formula (V).

  The metal complex having the tautomer of the azo compound represented by the general formula (I) as a ligand may be a metal salt of the azo compound. Examples of the metal contained in the metal complex or metal salt include Li, Na, K, Mg, Ca, Ba, Al, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, La, Ce, Pr and Nd are preferable, Na, K, Ca, Ba, Al, Mn, Co, Ni, Cu, Zn, La, and Ce are more preferable, and Ni is still more preferable.

  The constituent ratio of the azo compound and the metal in the metal complex or metal salt is preferably 1: 1 by molar ratio. A particularly preferable metal complex is an azobarbituric acid-nickel 1: 1 complex represented by the chemical formula (VI) or one of tautomers of the complex.

In the metal complex of the present invention, at least one other compound is inserted in the crystal.
“Insertion” in the present invention means a state in which another guest compound is intercalated between a plurality of host compound molecules in the crystal lattice of the host compound (metal complex).
The compound to be inserted (guest compound) may be either an organic compound or an inorganic compound, but in terms of practicality, a compound that is liquid or solid under standard conditions (25 ° C., 101.3 kPa) may be used. preferable.

  Among liquid substances, at 101.3 kPa, the boiling point is more preferably 100 ° C. or more, and further preferably 150 ° C. or more. Preferred compounds include cyclic or acyclic organic compounds such as aliphatic and aromatic hydrocarbons, which may have a substituent. Examples of the substituent include a hydroxyl group, a carboxy group, an amino group, an amide group, a sulfonamide group, a sulfonic acid group, a halogen atom, a nitro group, a cyano group, an alkylsulfone group, an arylsulfone group, an alkyloxy group, an aryloxy group, An acyloxy group etc. can be mentioned, An amino group, an amide group, and a sulfonamide group may have a substituent further.

  Among these, a carboxylic acid amide compound and a sulfonamide compound are preferable, and a heterocyclic compound that is a polycondensate with urea and substituted urea (for example, phenylurea, dodecylurea, etc.) and an aldehyde (particularly formaldehyde) is particularly preferable. Specifically, barbituric acid, benzimidazolone, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquinoxaline, 2,3-dihydroxyquinoxaline-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid 2-hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactam, melamine, 6-phenyl-1,3,5-triazine-2,4-diamine, 6-methyl-1,3,5-triazine-2,4 -Diamine and cyanuric acid are preferably used.

Further, the compound inserted into the metal complex may be a polymer compound, and a water-soluble polymer compound is particularly preferable. Preferable polymer compounds include, for example, ethylene-propylene oxide block polymer, polyvinyl alcohol, poly- (meth) acrylic acid, modified cellulose (for example, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxyethyl cellulose, and ethyl hydroxyethyl cellulose). Can be mentioned. The number average molecular weight M _n of these polymer compounds is preferably 1000 or more, and more preferably 1000 to 10,000.

  As the compound inserted into the metal complex, melamine or a melamine derivative is particularly preferable, and a compound represented by the following general formula (VII) is particularly preferable.

In general formula (VII), ^R71 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be further substituted with a hydroxyl group.
As the compound represented by the general formula (VII), a compound in which R ⁷¹ is a hydrogen atom is particularly preferable.

  The pigment in the present invention further includes an iron compound (2) different from the metal complex (1) having a tautomer of the azo compound represented by the general formula (I) as a ligand, and / or the metal complex. It is preferable that it is a pigment composition containing (1) and a metal compound (3) different from the iron compound (2).

  The pigment in the present invention preferably contains the iron compound (2), for example, as an organic salt or inorganic salt, or as a metal complex. When the iron compound is a metal complex, it is preferably contained as a metal complex of the azo compound represented by the general formula (I), and the same azo compound as the azo compound contained in the metal complex of (1) More preferably, it is contained as an Fe-complex.

  The pigment in the present invention preferably contains the metal compound (3). Examples of the metal contained in the metal compound (3) include Li, Na, K, Ca, Ba, Al, Mn, Co, Ni, Cu, Zn, La, and Ce. Among these, Na, K, Co, and Cu are particularly preferable, and Co and Cu are more preferable.

  The pigment in the present invention contains the metal compound (3) containing a metal different from the metal contained in the metal complex (1), for example, as an inorganic salt or an organic salt, or as an organometallic complex. Is preferred. When the metal compound of (3) is an organometallic complex, it is preferably contained as a complex of the azo compound represented by the general formula (I), and the azo compound contained in the metal complex of (1) It is more preferable to contain it as an organometallic complex of the same azo compound.

  The metal complex (3) preferably has at least one other compound inserted in the crystal, and the other compound is the same as the compound inserted in the metal complex (1). It is particularly preferred that

  The pigment in the present invention can be prepared, for example, by the method described in paragraphs [0012] to [0067] of JP-A-2005-325350. Moreover, you may use a commercially available yellow pigment (For example, Yellow Pigment E4GN-GT, LANXESS Co., Ltd. product).

The green photosensitive resin composition of the present invention preferably contains a green pigment and / or a green dye in addition to the pigment. Thereby, it can be set as the green photosensitive resin composition excellent in chromaticity and light transmittance. As the green pigment and the green dye in the present invention, known ones can be used without particular limitation, but a green pigment is preferable from the viewpoint of weather resistance. Examples of the green pigment suitably used in the present invention include a halogenated copper phthalocyanine compound and a halogenated zinc phthalocyanine. Among these, a halogenated copper phthalocyanine compound is preferable. Thereby, the green photosensitive resin composition with more excellent chromaticity and light transmittance can be prepared.
As a halogenated copper phthalocyanine compound in this invention, the compound represented by the following general formula (VIII) is preferable.

In formula (VIII), X ^{801 to} X ⁸¹⁶ each independently represent a hydrogen atom, a chlorine atom, a bromine atom or a phenyl group.
From the viewpoint of hue, chromaticity and the like, it is preferable to use a compound in which X ^{801 to} X ⁸¹⁶ are a chlorine atom and / or a bromine atom as the halogenated copper phthalocyanine compound. I. More preferably, CI Pigment Green 36 is used.
Thus, when using together a pigment, 50 mass% or more is preferable and, as for content of the copper halide phthalocyanine compound in a pigment, 60 mass% or more is more preferable.

  The green photosensitive resin composition of the present invention preferably contains, as a pigment, the above-described azo compound and a halogenated copper phthalocyanine compound, and the azo compound is a tautomer of the compound represented by the general formula (V). A compound having a crystal structure in which a compound different from the metal complex is inserted in a metal complex crystal having a ligand as a ligand, wherein the halogenated copper phthalocyanine compound is represented by the general formula (VIII), and the halogen atom Is more preferably a compound in which is a chlorine atom and / or a bromine atom, and particularly preferably, a metal complex crystal having an azo compound as a ligand of a tautomer of a compound represented by the above general formula (VI) A compound having a crystal structure in which a compound different from the metal complex is inserted, wherein the halogenated copper phthalocyanine compound is C.I. I. This is the case for Pigment Green 36.

  The pigment used in the present invention preferably has a number average particle size of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm. When the number average particle diameter is 0.001 μm or more, the particle surface energy becomes small and aggregation is difficult, and the dispersion of the pigment becomes easy and the dispersion state can be kept stable. Further, when the number average particle diameter is 0.1 μm or less, the polarization is prevented from being canceled by the pigment, and the contrast is improved. The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, The average value of 100 is said.

The pigment in the present invention is desirably used as a pigment dispersion. This pigment dispersion can be prepared by dispersing a composition obtained by previously mixing the pigment, a pigment dispersant described later and an organic solvent, using a known disperser. At this time, a small amount of resin may be added in order to impart dispersion stability of the pigment. Moreover, it is also possible to prepare by adding and dispersing a composition obtained by mixing the pigment and the pigment dispersant in advance to a photopolymerizable compound (monomer) described later. The disperser used for dispersing the pigment is not particularly limited. For example, a kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, page 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described on page 310 of the document.
Moreover, the pigment dispersion liquid in this invention should just contain the said pigment and the pigment dispersant mentioned later, and can also use it combining the commercial pigment dispersion liquid which satisfy | fills the said requirements suitably. Examples of the commercially available pigment dispersion include “CF Yellow EX3393” manufactured by Mikuni Color Co., Ltd.

(Pigment dispersant)
The photosensitive resin composition of the present invention contains at least one pigment dispersant. By containing the pigment dispersant, the dispersibility and dispersion stability of the pigment are improved. The pigment dispersant in the present invention is a compound having an amino group. By using a compound having an amino group as a pigment dispersant, the dispersion stability of the pigment dispersion is improved, and a photosensitive resin composition having good characteristics can be prepared.
Here, the amino group includes a primary amino group, a secondary amino group, and a tertiary amino group, and the number of amino groups may be one or more. A pigment derivative compound in which a substituent having an amino group is introduced into the pigment skeleton, or a polymer compound having a monomer having an amino group as a polymerization component may be used. Examples thereof include, for example, compounds described in JP-A Nos. 2000-239554, 2003-96329, 2001-31885, JP-A-10-339949, and JP-B-5-72943. However, it is not limited to these.

The pigment dispersant having an amino group used in the present invention is not limited thereto, but at least one selected from compounds represented by the following general formulas (IX), (X) and (XVI) is used. be able to.
[1. Compound represented by general formula (IX)]

  DN = NPQ (IX)

  In general formula (IX), D represents a component capable of forming an azo dye together with PQ. The D can be arbitrarily selected as long as it is a compound capable of forming an azo dye by coupling with a diazonium compound. Specific examples of D are shown below, but the partial structure of the pigment dispersant in the present invention is not limited thereto.

  In general formula (IX), P represents a single bond or a group selected from divalent linking groups represented by structural formulas of the following formulas (i) to (v).

  In general formula (IX), Q represents a group represented by the following general formula (IXa).

In the general formula (IXa), Z ⁹¹ represents a lower alkylene group. Z ⁹¹ is represented as — (CH ₂ ) _b —, and _b represents an integer of 1 to 5, preferably 2 or 3. In General Formula (IXa), —N (R ⁹¹ ) ₂ represents a lower alkylamino group or a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom. When -N (R ⁹¹ ) ₂ represents a lower alkylamino group, it is represented as -N (C _i H _{2i + 1} ) ₂ , i represents an integer of 1 to 4, preferably 1 or 2. When -N (R ⁹¹ ) ₂ represents a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom, any heterocyclic group represented by the following structural formula is preferable.

In the general formula (IXa), Z ⁹¹ and —N (R ⁹¹ ) ₂ may each have a lower alkyl group or an alkoxy group as a substituent. In the general formula (IXa), a represents 1 or 2, preferably 2.

  Specific examples of the compound represented by the general formula (IX) are shown below, but the pigment dispersant in the present invention is not limited to these specific examples.

  The compound represented by the general formula (IX) can be synthesized by, for example, a method described in JP-A No. 2000-239554.

[2. Compound represented by general formula (X)]

In general formula (X), Q ¹⁰¹ is an anthraquinone dye, azo dye, phthalocyanine dye, quinacridone dye, dioxazine dye, anthrapyrimidine dye, anthanthrone dye, indanthrone dye, flavanthrone dye It represents an organic dye residue selected from a dye, a pyranthrone dye, a perinone dye, a perylene dye, and a thioindigo dye, and among them, an azo dye or a dioxazine dye is preferable, and an azo dye is preferable. More preferred.
X ^{101 is, -CO -, - CONH-Y} 102 -, - SO 2 NH-Y 102 -, or ^{_{-CH 2 NHCOCH 2 NH-Y 102}} - represents, -CO-, or ^{-CONH-Y 102} - in Preferably there is.
Y ¹⁰² represents an alkylene group or an arylene group which may have a substituent, and among them, phenylene, toluylene or hexylene is preferable, and phenylene is more preferable.
R ¹⁰¹ and R ¹⁰² each independently represent a substituted or unsubstituted alkyl group, and R ¹⁰¹ and R ¹⁰² may form a heterocyclic group containing at least a nitrogen atom. Of these, a methyl group, an ethyl group, a propyl group, or a pyrrolidinyl group including an N atom is preferable, and an ethyl group is more preferable.
Y ¹⁰¹ represents —NH— or —O—.
Z ¹⁰¹ represents a hydroxyl group or a group represented by the following general formula (Xa), or when n ₁₀₁ is 1, it may be —NH—X ¹⁰¹ —Q ¹⁰¹ . m ₁₀₁ is an integer of 1-6, preferably 2-3. n ₁₀₁ represents an integer of 1 to 4, 1 to 2 is preferred.

_{^{-Y 103 - (CH 2) m}} 101 -N (R 101) R 102 (Xa)

In General Formula (Xa), Y ¹⁰³ represents —NH— or —O—, and m ₁₀₁ , R ¹⁰¹ , and R ¹⁰² have the same meaning as those in General Formula (X).

  More specifically, the compound represented by the general formula (X) is preferably a compound represented by, for example, the following general formulas (X-1) to (X-6).

In general formulas (X-1) to (X-6), Q ¹⁰¹ , m ₁₀₁ , n ₁₀₁ , R ¹⁰¹ , and R ¹⁰² have the same meanings as those in general formula (X). Specific examples of the compound represented by the general formula (X) are shown below, but the pigment dispersant in the present invention is not limited thereto.

The compound represented by the general formula (X) is, for example, an intermediate obtained by reacting an amine compound having R ¹⁰¹ and R ¹⁰² and / or an alcohol compound having R ¹⁰¹ and R ¹⁰² with a halogenated triazine compound. It can be obtained by reacting with a dye compound. The description in Japanese Patent Publication No. 5-72943 can also be referred to.

[3. (Pigment dispersant containing graft copolymer)
The pigment dispersant in the present invention is preferably a dispersant containing a graft copolymer having an amino group and an ether group, and other components appropriately selected as necessary.
The graft copolymer has at least an amino group and an ether group, and may contain other monomers as copolymer units.
The mass average molecular weight (Mw) of the graft copolymer is preferably 3000 to 100,000, more preferably 5000 to 50000. When the mass average molecular weight (Mw) is less than 3000, the aggregation of the pigment cannot be prevented and the viscosity may increase. When the mass average molecular weight (Mw) exceeds 100000, the solubility in an organic solvent is insufficient, and the viscosity May rise. In addition, this mass average molecular weight is a polystyrene conversion mass average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

  The graft copolymer includes (i) a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal, (ii) a monomer having an amino group and an ethylenically unsaturated double bond, and (iii) an ether group. It is preferable that it contains at least a polymerizable monomer having a copolymer unit and, if necessary, (iv) another monomer as a copolymer unit.

  The content of these copolymer units in the graft copolymer is preferably (i) 15 to 98% by mass of the polymerizable oligomer, more preferably 25 to 90% by mass, (Ii) The amino group-containing monomer is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and (iii) the polymerizable monomer having an ether group is 1 to 70% by mass. It is preferably 5 to 60% by mass.

  If the content of the polymerizable oligomer is less than 15% by mass, a steric repulsion effect as a pigment dispersant may not be obtained, and the aggregation of the pigment may not be prevented. In some cases, the proportion of the monomer is reduced, the adsorption ability to the pigment is lowered, and the dispersibility is not sufficient. When the content of the nitrogen-containing monomer is less than 1% by mass, the adsorptive capacity to the pigment is lowered and dispersibility may not be sufficient, and when it exceeds 40% by mass, the ratio of the polymerizable oligomer is decreased. Therefore, the steric repulsion effect as a pigment dispersant cannot be obtained, and the aggregation of the pigment may not be sufficiently prevented. When the content of the polymerizable monomer having an ether group is less than 1% by mass, the development suitability in the production of a color filter or the like may not be sufficient, and when the content exceeds 70% by mass, Capability may be reduced.

(I) Polymerizable oligomer The polymerizable oligomer (hereinafter sometimes referred to as “macromonomer”) is an oligomer having a terminal group having an ethylenically unsaturated double bond at the terminal. In the present invention, among the polymerizable oligomers, it is preferable to have a group having the ethylenically unsaturated double bond only at one of both ends of the oligomer.

  The oligomer is generally a homopolymer formed from at least one monomer selected from, for example, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate, and butadiene. Examples of the copolymer include alkyl (meth) acrylate homopolymers or copolymers, polystyrene, and the like. In the present invention, these oligomers may be substituted with a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom.

  Preferred examples of the group having an ethylenically unsaturated double bond include a (meth) acryloyl group and a vinyl group. Among these, a (meth) acryloyl group is particularly preferred.

  In the present invention, among the polymerizable oligomers, oligomers represented by the following general formula (XI) are preferable.

In the general formula (XI), R ¹¹¹ and R ¹¹³ represent a hydrogen atom or a methyl group. R ¹¹² represents an alkylene group that may be substituted with an alcoholic hydroxyl group having 1 to 8 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms. Y ¹¹¹ is a phenyl group, a phenyl group having an alkyl group having 1 to 4 carbon atoms, or —COOR ¹¹⁴ (where R ¹¹⁴ is an alcoholic hydroxyl group having 1 to 6 carbon atoms, alkyl optionally substituted with halogen). Represents a group, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms.), A phenyl group or —COOR ¹¹⁴ (wherein R ¹¹⁴ may be substituted with an alcoholic hydroxyl group having 1 to 4 carbon atoms). Represents a good alkyl group). q ₁₁₁ represents 20 to 200.

  Specific examples of the polymerizable oligomer include poly-2-hydroxyethyl (meth) acrylate, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate and these. And a polymer having a (meth) acryloyl group bonded to one molecular end.

  The polymerizable oligomer may be a commercially available product or may be appropriately synthesized. Examples of the commercially available products include one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6000, Product name: AA-6, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), one-end methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, product name: AB-6, manufactured by Toa Synthetic Chemical Industry Co., Ltd.) ), One-end methacryloylated polymethyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AA-714, manufactured by Toagosei Co., Ltd.), one-end methacryloylated polybutyl methacrylate / 2-hydroxy Ethyl methacrylate oligomer (Mn = 7000, trade name: 7 7S, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), one-terminal methacryloylated poly-2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade names: AY-707S, AY-714S, Toa Synthetic Chemical Industry) Etc.).

  Preferred specific examples of the polymerizable oligomer in the present invention include at least one oligomer selected from a polymer of alkyl (meth) acrylate and a copolymer of alkyl (meth) acrylate and polystyrene, A number average molecular weight is 1000-20000, and what has a (meth) acryloyl group at the terminal is mentioned.

(Ii) Amino Group-Containing Monomer As the amino group-containing monomer, for example, at least one selected from compounds represented by the following general formula (XII) is preferably exemplified.

In the general formula (XII), R ¹²¹ represents a hydrogen atom or a methyl group. R ¹²² represents an alkylene group having 1 to 8 carbon atoms, and among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is particularly preferable.

X ¹²¹ represents —N (R ¹²³ ) (R ¹²⁴ ), —R ¹²⁵ —N (R ¹²⁶ ) (R ¹²⁷ ). Here, ^R123 and ^R124 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R ¹²⁵ represents an alkylene group having 1 to 6 carbon atoms, and R ¹²⁶ and R ¹²⁷ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

Among the above, R ¹²³ and R ¹²⁴ in —N (R ¹²³ ) (R ¹²⁴ ) are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and —R ¹²⁵ —N (R ¹²⁶ ) (R ^{R 125 127)} is preferably an alkylene group having 2 to 6 carbon ^{atoms, R 126} and ^{R 127} is preferably an alkyl group having 1 to 4 carbon atoms. m ₁₂₁ and n ₁₂₁ represent 1 or 0, and m ₁₂₁ = 1 and n ₁₂₁ = 1, or m ₁₂₁ = 1 and n ₁₂₁ = 0 are preferable (that is, in the following general formulas (XIII) and (XIV)) Corresponding to the compound represented).

  In the present invention, among the compounds represented by the general formula (XII), at least one selected from the compounds represented by any one of the following general formulas (XIII) and (XIV) is preferable.

In the general formula (XIII), R ¹³¹ has the same ^meaning as R ¹²¹ . R ¹³² has the same ^meaning as R ¹²² . X ¹³¹ is synonymous with X ¹²¹ .

In the general formula (XIV), R ¹⁴¹ has the same ^meaning as R ¹²¹ . X ¹⁴¹ has the same meaning as X ¹²¹ , and —N (R ¹⁴³ ) (R ¹⁴⁴ ) (where R ¹⁴³ and R ¹⁴⁴ are the same as R ¹²³ and R ¹²⁴ ), or —R ¹⁴⁵ —. N (R ¹⁴⁶ ) (R ¹⁴⁷ ) (where R ¹⁴⁵ , R ^146, and R ¹⁴⁷ have the same meanings as R ¹²⁵ , R ^126, and R ¹²⁷ , respectively) is preferable.

  Specific examples of the compound represented by the general formula (XII) include dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) acrylamide, and di-i-butyl. (Meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and N, N-methylphenyl (meth) acrylamide (above (meth) acrylamides); (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N -Dimethylamino) propyl (meth) acrylic Amide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide (above aminoalkyl (meth) acrylamides). Preferably mentioned.

(Iii) Polymerizable monomer having an ether group Preferred examples of the polymerizable monomer having an ether group include at least one selected from compounds represented by the following general formula (XV).

In the general formula (XV), R ¹⁵¹ represents a hydrogen atom or a methyl group. R ¹⁵² represents an alkylene group having 1 to 8 carbon atoms, among which an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is more preferable. X ¹⁵¹ represents —OR ¹⁵³ or —OCOR ¹⁵⁴ . Here, R ¹⁵³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms. R ¹⁵⁴ represents an alkyl group having 1 to 18 carbon atoms. _{Further, m 151} represents 2 to 200, preferably 5 to 100, particularly preferably from 10 to 100.

  The polymerizable monomer having an ether group is not particularly limited as long as it has an ether group and is polymerizable, and can be appropriately selected from ordinary ones. For example, polyethylene glycol mono (meth) Examples include acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polytetramethylene glycol monomethacrylate, etc., and these may be commercially available products or may be appropriately synthesized. Good. Examples of the commercially available products include methoxypolyethylene glycol methacrylate (trade names: NK esters M-40G, M-90G, M-230G (manufactured by Toa Gosei Chemical Co., Ltd.); trade names: BLEMMER PME-100, PME. -200, PME-400, PME-1000, PME-2000, PME-4000 (manufactured by Nippon Oil & Fats Co., Ltd.)), polyethylene glycol monomethacrylate (trade names: BLEMMER PE-90, PE-200, PE- 350, manufactured by NOF Corporation), polypropylene glycol monomethacrylate (trade names: BLEMMER PP-500, PP-800, PP-1000, manufactured by NOF Corporation), polyethylene glycol polypropylene glycol monomethacrylate (trade name) : Bremmer 70PEP-370B, Japan Manufactured by Yushi Co., Ltd.), polyethylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer 55PET-800, manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol polytetramethylene glycol monomethacrylate (trade name: Blemmer NHK-5050) , Manufactured by Nippon Oil & Fats Co., Ltd.).

(Iv) Other monomer The graft copolymer may further contain the other monomer as a copolymer unit, and the other monomer is not particularly limited and is appropriately selected depending on the purpose. For example, aromatic vinyl compounds (eg, styrene, α-methylstyrene and vinyltoluene), (meth) acrylic acid alkyl esters (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl) (Meth) acrylate and i-butyl (meth) acrylate), (meth) acrylic acid alkylaryl ester (eg, benzyl (meth) acrylate), glycidyl (meth) acrylate, carboxylic acid vinyl ester (eg, vinyl acetate and propionic acid) Vinyl), vinyl cyanide (eg, (meth) acrylonitrile and And α-chloroacrylonitrile), aliphatic conjugated dienes (eg, 1,3-butadiene and isoprene), (meth) acrylic acid, and the like. Among these, unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid alkyl aryl ester, and carboxylic acid vinyl ester are preferable.

  As content of this other monomer in the said graft copolymer, 5-70 mass% is preferable, for example. When the content is less than 5% by mass, the physical properties of the coating film may not be controlled. When the content exceeds 70% by mass, the ability as a pigment dispersant may not be sufficiently exhibited.

As a preferred specific example of the graft copolymer,
(11) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(12) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polystyrene copolymer,

(13) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / methyl (meth) acrylate-terminated methacryloylated polystyrene copolymer,
(14) a copolymer of a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated methyl (meth) acrylate and 2-hydroxyethyl methacrylate,
(15) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminated methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate copolymer,
(16) a copolymer of a copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate,

(17) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(18) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polypropylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(19) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,
(20) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer, and the like.
Among these, (11), (14), and (18) are preferable, and a compound represented by the following formula (XVI) is more preferable.

  The graft copolymer can be obtained, for example, by radical polymerization of the components to be the copolymer units in a solvent. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used. JP-A-2001-31885 can be referred to for the pigment dispersant containing the graft copolymer.

  The content of the pigment dispersant is preferably small so as not to impair the dispersion stability. Specifically, the content is preferably in the range of 0.1% to 50% by weight of the pigment. It is more preferably 5% by mass to 30% by mass, and particularly preferably 1% by mass to 10% by mass.

(binder)
The photosensitive resin composition of the present invention can contain at least one binder. The binder preferably has an acidic group and may or may not have an alkali-soluble group. As the binder having an alkali-soluble group, a polymer having a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, or a hydroxyalkyl group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers.

  Moreover, in order to improve crosslinking efficiency, you may have a polymeric group in a side chain, UV curable resin, a thermosetting resin, etc. are useful. Although the example of the polymer containing these polymeric groups is shown below, if alkali-soluble groups, such as a COOH group and OH group, and a carbon-carbon unsaturated bond are contained, it will not be limited to the following. Reactive with OH groups in copolymers of OH groups such as 2-hydroxyethyl acrylate, COOH groups such as methacrylic acid, and monomers such as acrylic or vinyl compounds copolymerizable therewith A compound obtained by reacting a compound having an epoxy ring with a carbon-carbon unsaturated bond group, for example, a compound such as glycidyl acrylate, can be used. In the reaction with OH, in addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group, and an acryloyl group can also be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring disclosed in JP-A-6-102669 and JP-A-6-1938 can be used as a saturated or unsaturated polybasic acid anhydride. A reaction product obtained by reacting a product can also be used. Examples of compounds having both an alkali-solubilizing group such as COOH and a carbon-carbon unsaturated group are Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co. Ltd.,). Viscoat R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), etc. Can be mentioned.

Furthermore, as the binder resin, an organic high molecular polymer having a water-soluble atomic group in a part of the side chain can be used. The binder resin is a linear or comb-type organic high molecular polymer that is compatible with the monomer, and is soluble in an organic solvent and an alkali (preferably developable with a weak alkaline aqueous solution). The alkali-soluble resin includes at least (i) at least one acid component monomer selected from maleic anhydride (MAnh), acrylic acid (AA), methacrylic acid (MAA), and fumaric acid (FA), and (ii) It is possible to use a copolymer (hereinafter referred to as “copolymer A”) composed of ()) alkylpolyoxyethylene (meth) acrylate and (iii) benzyl (meth) acrylate.
As a combination of the copolymer A, (i) acid component monomer, (ii) alkylpolyoxyethylene (meth) acrylate (Acr (EO) _n R ′: CH ₂ ═C (R) O (OC ₂ H ₄ ) _N OR ′, (R═H, CH _3, R ′ = alkyl group)), and (iii) benzyl (meth) acrylate (Bz (M) A) is preferably 10 to 25/5 25/50 to 85, more preferably 15 to 20/5 to 20/60 to 80 is preferable. The polystyrene-reduced mass average molecular weight (Mw) by GPC of the copolymer is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.

(I) When the compositional mass ratio of the acid component monomer is within the above range, alkali solubility and solubility in a solvent are unlikely to decrease. Further, (ii) alkylpolyoxyethylene (meth) acrylate _{(Acr (EO) n R '} : CH 2 = C (R) O (OC 2 H 4) n OR', (R = H, CH 3, R ' = Alkyl group)) is within the above range, the composition can easily spread on the substrate, and the dispersibility of the pigment is not easily lowered, so that the effects of the present invention can be effectively achieved. it can. (Iii) When the compositional mass ratio of benzyl (meth) acrylate (Bz (M) A) is within the above range, the dispersion stability of the pigment, the solubility in the composition, and the alkali development suitability of the coating film are unlikely to decrease. .
The above (ii) alkyl polyoxyethylene (meth) acrylate (Acr (EO) _n R ′: CH ₂ ═C (R) O (OC ₂ H ₄ ) _n OR ′, (R = H, CH _3, R The number n of the polyoxyethylene (EO) _{n in} the '= alkyl group)) is preferably 2-15, more preferably 2-10, and particularly preferably 4-10. When the above repeating number n is in the above range, a development residue is less likely to occur after development with an alkaline developer, the fluidity of the composition as a coating solution can be prevented, and coating unevenness can be prevented. It is possible to prevent the thickness uniformity and the liquid-saving property from decreasing.
These binder polymers having a polar group may be used alone or in the form of a composition used in combination with an ordinary film-forming polymer. 200 mass parts is common and 25-100 mass parts is preferable.

  When the alkali-soluble binder having an acidic group is a polymer compound, the number of acidic groups in the polymer compound is not particularly limited, but when the number of repeating units contained in one molecule is 100, the acidic group It is preferable that the repeating unit which has is 5-100, and it is more preferable that it is 10-100. Further, the polymerization ratio of the repeating unit derived from the compound having (1) carboxyl group and the repeating unit derived from the compound having (2) carboxylic acid ester group is the mole of repeating unit (1). % Is preferably 5 to 40, the repeating unit (2) is preferably 40 to 90, and the repeating unit other than the repeating unit (1) or (2) is preferably 25 or less. The molecular weight of the alkali-soluble binder polymer compound having an acidic group is preferably 5000 to 30000, more preferably 7000 to 15000, and particularly preferably 5000 to 80000.

  As the binder in the present invention, when a binder is added at the time of dispersing the pigment, a compound having a structure similar to that of the binder is preferable, and it is most preferable that both are the same. The content of the binder (may be the total content when the binder remains at the time of pigment dispersion) is generally 15 to 50% by mass with respect to the total solid content of the photosensitive resin composition. 20-45 mass% is preferable. If the amount is too large, the viscosity of the composition becomes too high, causing a problem in production suitability. If the amount is too small, there is a problem in forming a coating film.

(Photopolymerizable compound)
The photosensitive resin composition of the present invention contains at least one photopolymerizable compound. The photopolymerizable compound is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Rithritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tris (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, tris (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerin and then (meth) acrylated. Further, as described in JP-A-10-62986, general formulas (1) and (2), a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also suitable. As mentioned.
Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.

Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers (monomers or oligomers having a molecular weight of 200 to 1000 are preferred) may be used alone or in admixture of two or more, and contained in the total solid content of the photosensitive resin composition. The amount is generally 5 to 50% by mass, preferably 10 to 40% by mass. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

(Photopolymerization initiator)
The photosensitive resin composition of the present invention contains at least one photopolymerization initiator. The photopolymerization initiator is a compound having a photopolymerization initiation function alone or a photopolymerization initiator system (in the present invention, a photopolymerization initiator system is a mixture expressing a photopolymerization initiation function by a combination of a plurality of compounds) Any of the above may be used. Examples of the photopolymerization initiator include vicinal polyketaldonyl compounds disclosed in U.S. Pat. No. 2,367,660, acyloin ether compounds described in U.S. Pat. No. 2,448,828, and U.S. Pat. No. 2,722,512. Aromatic α-hydrocarbon compounds substituted with α-hydrocarbons described in US Pat. Nos. 3,046,127 and 2,951,758, triaryls described in US Pat. No. 3,549,367 Combination of imidazole dimer and p-aminoketone, benzothiazole compound and trihalomethyl-s-triazine compound described in JP-B-51-48516, trihalomethyl-triazine compound described in US Pat. No. 4,239,850 U.S. Pat. No. 4,221,976 And the like trihalomethyl oxadiazole compounds described. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.

In addition, “polymerization initiator C” described in JP-A No. 11-133600, oxime ester-based compounds such as 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, -[4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime) and acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide and the like can also be mentioned as suitable ones.
These photopolymerization initiators or photopolymerization initiator systems may be used singly or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low.

(Other additives)
-Organic solvent-
In the photosensitive resin composition of the present invention, an organic solvent may be further used in addition to the above components. Examples of organic solvents include, but are not limited to, esters such as ethyl acetate, butyl acetate, isobutyl formate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methyl Ethyl xylpropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2- Methyl methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-oxobutanoic acid Ethyl, propylene glycol diacetate, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, 1,3-butanediol diacetate, etc .;
Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate (methyl cellosolve acetate), ethylene glycol monoethyl ether acetate (ethyl cellosolve acetate), diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate (ethyl carbitol acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate), propylene glycol monomethyl ether acetate (PGMEA), dipropyle Glycol monomethyl ether acetate, tripropylene glycol methyl ethyl acetate, dipropylene glycol -n- butyl acetate, propylene glycol phenyl ether acetate;
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one and the like;
Aromatic hydrocarbons such as toluene, xyles and the like can be mentioned.
Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate (ethylcarbyl Tall acetate), diethylene glycol monobutyl ether acetate (butyl carbitol acetate), propylene glycol methyl ether acetate and the like are preferably used as the organic solvent in the present invention. These organic solvents may be used alone or in combination of two or more.

Moreover, the organic solvent whose boiling point is 180 to 250 degreeC can be used if needed. Examples of these high-boiling solvents include the following. Diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 3,5,5-trimethyl-2-cyclohexen-1-one, dipropylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene Glycol-n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, tripropylene glycol methyl ethyl acetate, dipropylene glycol-n-butyl acetate, propylene glycol phenyl Ether acetate, 1,3-butanedio Diacetate.
The content of the organic solvent is preferably 10 to 95% by mass with respect to the total amount of the resin composition.

-Surfactant-
It is preferable that the photosensitive resin composition of the present invention further contains a surfactant. Thereby, in the photosensitive resin transfer material of this invention or the color filter of this invention, it can control to a uniform film thickness and can prevent the coating nonuniformity (color nonuniformity by film thickness fluctuation | variation) effectively.
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600. The content of the surfactant is preferably 5% by mass or less with respect to the total amount of the resin composition.

-Thermal polymerization inhibitor-
The photosensitive resin composition of the present invention preferably further contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like. The content of the thermal polymerization inhibitor is preferably 1% by mass or less based on the total amount of the resin composition.

-Supplementary dyes and pigments-
In the photosensitive resin composition of the present invention, other colorants (dyes, pigments) can be added as needed in addition to the pigments (colorants) as long as the effects of the present invention are not impaired. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the photosensitive resin composition. Therefore, the number average particle diameter is preferably 0.1 μm or less, particularly 0.08 μm or less. It is preferable that
Specific examples of the dye or pigment include the colorant described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used. The content of the auxiliary dye or pigment is preferably 5% by mass or less based on the total amount of the resin composition.

-UV absorber-
The photosensitive resin composition of the present invention can contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 2,4-dihydroxy Benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′) -T-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel dibutyldithiocarbamate, bis ( 2,2,6,6-tetramethyl-4-piperidine) -sebacate, 4-hydroxy-2 2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidine) ester, 2- [2-hydroxy-3,5-bis (α, α -Dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -1,3,5-triazin-2-yl] amino} -3-phenylcoumarin and the like. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the resin composition whole quantity.

  Moreover, in the photosensitive resin composition of this invention, the "adhesion adjuvant" described in Unexamined-Japanese-Patent No. 11-133600, other additives, etc. other than the said additive can be contained.

The green photosensitive resin composition of the present invention has a contrast coefficient of 3800 or more. In the present invention, the contrast coefficient can be obtained, for example, as follows.
A photosensitive resin layer made of a photosensitive resin composition to be measured is formed on a glass substrate so as to have a film thickness of 2.0 μm. The photosensitive resin layer may be formed by applying and drying a photosensitive resin composition, or using a photosensitive resin transfer material. Next, a sample glass substrate is prepared by exposing the formed photosensitive resin layer. Using a three-wavelength cold-cathode tube light source with a diffusion plate installed as a backlight unit, the glass substrate prepared above is installed between two polarizing plates, and the light passing through when the polarizing plate is installed in parallel Nicol The contrast can be obtained by dividing the Y value of chromaticity by the Y value of the chromaticity of light that passes through when installed in crossed Nicols. For measurement of chromaticity, a color luminance meter (for example, BM-5 manufactured by Topcon Corporation) can be used. The contrast value of this glass substrate can be used as the contrast coefficient of the photosensitive resin composition.

More specifically, it can be measured as follows.
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., using a spin coater (for example, 1H-DX; manufactured by Mikasa Co., Ltd.), the photosensitive resin composition to be measured is dried to a thickness of 2.0 μm. It was applied and dried at 100 ° C. for 3 minutes.
Further, the substrate was exposed on the entire surface of the substrate with an exposure amount of 1000 mJ / cm ^{2 using} an exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.), and then baked at 240 ° C. for 60 minutes to perform contrast measurement.
The contrast measurement was performed as follows. That is, as a backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) is used, and between two polarizing plates (G1220DUN manufactured by Nitto Denko Corporation). Divide the Y value of the chromaticity of light that passes when the glass substrate prepared above is installed and the polarizing plate is installed in parallel Nicol by the Y value of the chromaticity of light that passes when installed in crossed Nicol. I asked for contrast. A color luminance meter (BM-5 manufactured by Topcon Corporation) was used for the measurement of chromaticity. The contrast value of this glass substrate was used as the contrast coefficient of the photosensitive resin composition.
Two polarizing plates, a glass substrate, and a color luminance meter were installed at a position 13 mm from the backlight, a polarizing plate at a position 40 mm to 60 mm, and a cylinder 11 mm in diameter and 20 mm in length. Light was irradiated to a measurement sample installed at a position of 65 mm, and the transmitted light was measured with a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed.

In the present invention, the contrast coefficient is preferably 3900 or more, and more preferably 4000 or more. Thereby, the contrast of the color filter produced using the green photosensitive composition of this invention can be made higher.
In the present invention, the contrast coefficient within the above range can be realized by appropriately selecting and combining appropriate compounds from the pigment and the pigment dispersant in the present invention described above.

<Photosensitive resin transfer material>
Next, the photosensitive resin transfer material of the present invention will be described.
The photosensitive resin transfer material of the present invention is preferably formed as a photosensitive resin transfer material described in JP-A-5-72724, that is, an integrated film. An example of the structure of the integral film is a structure in which a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film are laminated in this order. Is provided with a photosensitive resin layer by using the green photosensitive resin composition of the present invention described above.
In the photosensitive resin transfer material of the present invention, from the viewpoint of followability to the substrate, the shape of the formed pattern, uniformity in height, and exposure sensitivity control of the photosensitive resin layer, it is between the temporary support and the photosensitive resin layer. It is preferable to provide a thermoplastic resin layer and an intermediate layer.

(Temporary support)
In the photosensitive resin transfer material of the present invention, the temporary support is required to be flexible and not to cause significant deformation, shrinkage or elongation even under pressure or under pressure and heating. is there. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

(Thermoplastic resin layer)
As the component used for the thermoplastic resin layer, organic polymer materials described in JP-A-5-72724 are preferable. It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

(Middle layer)
In the photosensitive resin transfer material of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

(Protective film)
A thin protective film is preferably provided on the photosensitive resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin, or polytetrafluoroethylene sheet is suitable as the protective film material.

(Method for producing photosensitive resin transfer material)
The photosensitive resin transfer material of the present invention is provided with a thermoplastic resin layer by applying a coating solution (a coating solution for a thermoplastic resin layer) in which an additive for a thermoplastic resin layer is dissolved on a temporary support, followed by drying. Then, an intermediate layer material solution comprising a solvent that does not dissolve the thermoplastic resin layer is applied and dried on the thermoplastic resin layer, and then the photosensitive resin layer is applied and dried with a solvent that does not dissolve the intermediate layer. It can produce by providing.
In addition, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer and an intermediate layer on a protective film are also prepared, and a thermoplastic resin layer is prepared. Can also be produced by bonding them so that the intermediate layer is in contact with each other.

  In the photosensitive resin transfer material of the present invention, the thickness of the photosensitive resin layer is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and particularly preferably 1.0 to 3.0 μm. preferable. Further, although not particularly limited, preferred film thicknesses of other layers are 15 to 100 μm for the temporary support, 2 to 30 μm for the thermoplastic resin layer, 0.5 to 3.0 μm for the intermediate layer, and protection. The film is generally preferably 4 to 40 μm.

(Slit nozzle)
The application in the above production method can be formed by applying the photosensitive resin composition of the present invention by a normal application method and drying, but in the present invention, slit-like holes are formed in the portion where the liquid is discharged. It is preferable to apply by a slit-like nozzle having Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

  As a method for applying the photosensitive resin composition to the substrate, spin coating is excellent in that a thin film having a thickness of 1 to 3 μm can be uniformly and highly accurately applied, and it can be widely used for producing color filters. However, in recent years, with the increase in size and mass production of liquid crystal display devices, slit coating suitable for coating a substrate that is wider and larger in area than spin coating has been used in order to increase manufacturing efficiency and manufacturing cost. It has come to be adopted in the production of. From the viewpoint of liquid-saving properties, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid.

  In slit coating, a coating head having a slit (gap) with a width of several tens of microns at the tip and a length corresponding to the coating width of a rectangular substrate is maintained with a clearance (gap) with the substrate of several tens to several hundreds of microns. However, this is a coating method in which the substrate and the coating head have a constant relative speed, and the coating liquid supplied from the slits is coated on the substrate with a predetermined discharge amount. This slit coating is (1) less liquid loss compared to spin coating, (2) cleaning process is reduced because there is no flying of the coating liquid, and (3) the scattered liquid components are applied to the coating film again. There is an advantage that there is no mixing, (4) the tact time can be shortened because there is no start-up stop time of rotation, and (5) application to a large substrate is easy. From these advantages, slit coating is suitable for producing a color filter for a large-screen liquid crystal display device, and is expected as an advantageous coating method for reducing the amount of coating liquid.

  Since slit coating forms a coating film with a much larger area than spin coating, it is necessary to maintain a certain relative speed between the coater and the object to be coated when discharging the coating liquid from the wide slit exit. is there. For this reason, good fluidity is required for the coating liquid used in the slit coating method. In addition, the slit coating is particularly required to keep the conditions of the coating solution supplied to the substrate from the slit of the coating head constant over the entire coating width. Insufficient liquid properties such as fluidity and viscoelastic properties of the coating liquid tend to cause coating unevenness, making it difficult to keep the coating thickness constant in the coating width direction and obtaining a uniform coating film. The problem of not being able to occur.

  For these reasons, many attempts have been made to improve the fluidity and viscoelastic properties of the coating solution in order to obtain a uniform coating film without unevenness. However, as mentioned above, the molecular weight of the polymer is reduced, a polymer having excellent solubility in a solvent is selected, various solvents are selected to control the evaporation rate, and a surfactant is used. Means have been proposed.

<Color filter>
(Photosensitive resin layer)
The color filter of the present invention is characterized by excellent contrast. In the present invention, the contrast represents the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and when it is vertical. (See “The 7th Color Optical Conference in 1990, 512-color display 10.4” size TFT-LCD color filter, Ueki, Koseki, Fukunaga, Yamanaka ”, etc.)
The high contrast of the color filter means that the contrast of light and darkness can be increased when combined with the liquid crystal, which is a very important performance in order to replace the liquid crystal display with a CRT.

  When the color filter of the present invention is used for a television, the chromaticities of all the single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in the table below ( Hereinafter, in the present invention, the difference (ΔE) from the “target chromaticity”) is preferably in the range of 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

x y Y
------------------------
R 0.656 0.336 21.4
G 0.293 0.634 52.1
B 0.146 0.088 6.90
------------------------

  In the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. The difference from the target chromaticity is represented by a color difference of the La * b * color system.

  The color filter of the present invention can be produced by a method such as a method in which a photosensitive resin layer is formed on a substrate, and exposure and development are repeated for the number of colors. If necessary, the boundary may be divided by a black matrix.

Japanese Patent Application Laid-Open No. 2003-33061 does not describe any color filter production in which reprecipitation pigment is used and an image is formed on an OHP sheet or copy paper by inkjet. When the present inventors used the inkjet recording liquid described in JP-A No. 2003-33061 for the production of a pixel for a color filter, the solvent and heating used during the production produced the dissolution of the pixel and the surface shape. “That” occurred and the color filter could not be produced.
On the other hand, in the method for producing the color filter of the present invention, as a method for forming the photosensitive resin layer on the substrate, (a) each of the photosensitive resin compositions is applied by a normal coating apparatus or the like. A color filter can be satisfactorily manufactured by using a method and (b) the above-described photosensitive resin transfer material and a method of attaching with a laminator.

(A) Application by coating apparatus When the color filter of the present invention is produced, a normal coating apparatus can be used for coating the photosensitive resin composition, and in particular, already (preparation of photosensitive resin transfer material). The slit coater described in the section of “Method” can be preferably used. The preferred specific example of the slit coater is the same as described above. When the photosensitive resin layer is formed by coating, the film thickness is preferably 1.0 to 3.0 μm, more preferably 1.0 to 2.5 μm, and particularly preferably 1.5 to 2.5 μm.

(B) Pasting with a laminator Using the photosensitive resin transfer material of the present invention, the photosensitive resin layer formed in a film shape is heated and / or pressurized on a substrate to be described later with a roller or a flat plate. Or it can affix by thermocompression bonding. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. In addition, the preferable film thickness in the case of forming the photosensitive resin layer with the photosensitive resin transfer material of the present invention is the same as the preferable film thickness described in the section <Photosensitive resin transfer material>.

(substrate)
In the present invention, as the substrate on which the color filter is formed, for example, a transparent substrate is used, and a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, etc. Or a plastic film etc. can be mentioned.
Moreover, the said board | substrate can make contact | adherence with the photosensitive resin composition or the photosensitive resin transfer material still better by performing a coupling process previously. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. Although not particularly limited, the film thickness of the substrate is generally preferably 700 to 1200 μm, and particularly preferably 500 to 1100 μm.

(Oxygen barrier membrane)
In the color filter of the present invention, when the photosensitive resin layer is formed by application of the photosensitive resin composition, an oxygen blocking film can be further provided on the photosensitive resin layer, thereby increasing the exposure sensitivity. can do. Examples of the oxygen blocking film include those already described in the section of (Interlayer) of <Photosensitive resin transfer material>. Although not particularly limited, the thickness of the oxygen blocking film is generally preferably 0.5 to 3.0 μm.

(Exposure and development)
A predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and then exposed from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer, and then developed with a developer. By repeating this process for the number of colors, the color filter of the present invention can be obtained.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

Moreover, there is no restriction | limiting in particular as said developing solution, Normal developing solutions, such as a thing of Unexamined-Japanese-Patent No. 5-72724, can be used. The developer is preferably one in which the photosensitive resin layer exhibits a dissolution type development behavior. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. A small amount of a miscible organic solvent may be added.
Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a normal surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

As a development method, methods such as paddle development, shower development, shower & spin development, and dip development can be used.
Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the exposed photosensitive resin layer by shower. In addition, it is preferable to spray an alkaline liquid having low solubility of the photosensitive resin layer by a shower or the like before development to remove the thermoplastic resin layer, the intermediate layer, or the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

In addition, when manufacturing the color filter of the present invention, as described in JP-A Nos. 11-248921 and 3255107, a base is formed by overlapping the photosensitive resin composition forming the color filter. It is preferable from the viewpoint of cost reduction to form a spacer by forming a transparent electrode on top and further overlapping projections for split orientation.
When the photosensitive resin composition is sequentially applied and stacked, the film thickness becomes thin each time it is stacked due to the leveling of the coating solution. For this reason, it is preferable to overlap the four colors of K (black), R, G, and B, and further overlap the divisional alignment protrusions. On the other hand, in the case of using a transfer material having a thermoplastic resin layer, it is preferable that three or two colors be overlapped because the thickness is kept constant.
The size of the base is preferably 25 μm or more, and particularly preferably 30 μm or more, from the viewpoint of preventing deformation of the photosensitive resin layer when the transfer material is laminated and laminating and maintaining a certain thickness.

<Display device>
The display device of the present invention is not particularly limited as long as it includes the color filter of the present invention described above, and a display device such as a liquid crystal display device, a plasma display display device, an EL display device, a CRT display device, etc. Say. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).

  Among the display devices of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  In addition to the color filter, the liquid crystal display device is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC 1994)” and “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

  The display device of the present invention includes ECB (Electrically Controlled Birefringence), TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), and OCB (Optic Liquid Bistic). Various display modes such as (Vertical Aligned), HAN (Hybrid Aligned Nematic), and GH (Guest Host) can be adopted. It is characterized by using the color filter as described above, and it has no display unevenness when mounted on a TV or monitor, and can have a wide color reproduction range and a high contrast ratio. It can be suitably used for a large-screen display device or the like.

  The present invention will be described below in more detail based on examples, but the present invention is not limited thereto. In the following examples, “%” and “parts” represent “mass%” and “parts by mass” unless otherwise specified, and the molecular weight indicates the mass average molecular weight.

[Example 1]
<Y pigment dispersion 1>
Pigment Dispersant A, a binder and a solvent (propylene glycol monomethyl ether acetate, hereinafter abbreviated as PGMEA) are blended as shown in Table 1 below, and after premixing, Motor Mill M-50 (Eiger Japan) Y pigment dispersion 1 was prepared by using zirconia beads having a diameter of 0.65 mm for 4 hours at a peripheral speed of 9 m / s. Similarly, Y pigment dispersions 2 to 9 were prepared by changing the pigment, dispersant, binder and dispersion time shown in Table 1.

  The viscosity was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd .; ELD, cone rotor angle: 1 ° 34 '). In addition, pigments 1 to 3 and pigment dispersants A to D in Table 1 are shown below.

Pigment 1: Yellow Pigment E4GN-GT (manufactured by LANXESS)
Pigment 2: Compound represented by formula (1) Pigment 3: Compound represented by formula (2)

The composition of binder A in Table 1 is shown below.
・ Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, mass average molecular weight 37,000) ... 27 parts ・ Propylene glycol monomethyl ether acetate 73 parts

From the viscosities of Y pigment dispersions 1 to 5 in Table 1, by using the pigment and the pigment dispersant having an amino group in the present invention, the viscosity after dispersion is low, and the pigment dispersion is small even after 3 days. It can be seen that
Further, from the viscosity of the Y pigment dispersion 6, even when the pigment in the present invention is used, when the nonionic pigment dispersant D having no amino group is used, the viscosity after dispersion is somewhat large, It can be seen that the viscosity increases and the viscosity stability is insufficient.
The Y pigment dispersion 9 to which no pigment dispersant was added had a viscosity of 1200 mPa · s or more and could not be dispersed.

<Production of color filter>
-Production of photosensitive resin transfer material-
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, a photosensitive resin composition K1 having a composition of formulation K1 shown in Table 2 below is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm is formed on the temporary support, and a dry film thickness is A 1.6 μm intermediate layer and a photosensitive resin layer having a dry film thickness of 2.4 μm were provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
In this way, a photosensitive resin transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer are integrated is prepared, and the sample name is the photosensitive resin transfer material. It was set as K1.

(Coating solution for thermoplastic resin layer: Formulation H1)
-Methanol ... 11.1 parts-Propylene glycol monomethyl ether acetate ... 6.36 parts-Methyl ethyl ketone ... 52.4 parts-Methyl methacrylate / 2-ethylhexyl acrylate /
Benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 55 / 11.7 / 4.5 / 28.8, mass average molecular weight = 100,000, Tg≈70 ° C.)
... 5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37,
(Mass average molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts ・ A compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (made by Shin-Nakamura Chemical Co., Ltd.)
Product name: 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane)
・ ・ ・ 9.1 parts ・ Surfactant 1 (Dainippon Ink Chemical Co., Ltd., trade name: Megafac F780F)
... 0.54 parts

(Coating liquid for intermediate layer: prescription P1)
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts Polyvinylpyrrolidone (APS Japan Co., Ltd., K-30)
・ ・ ・ 14.9 parts ・ Distilled water ・ ・ ・ 524 parts ・ Methanol ・ ・ ・ 429 parts

  Next, the photosensitive resin composition K1 used in the production of the photosensitive resin transfer material K1 is changed to the following photosensitive resin compositions R1, G1, and B1 having the compositions shown in Tables 2 and 3 below. Other than that, photosensitive resin transfer materials R1, G1, and B1 were prepared in the same manner as described above.

In Table 2 and Table 3,
The composition of K pigment dispersion 1 is
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.)
... 13.1 parts-Pigment dispersant A ... 0.65 parts-Polymer (benzyl methacrylate / methacrylic acid = 72/28
(Random copolymer of molar ratio, mass average molecular weight 37,000)
... 6.72 parts · Propylene glycol monomethyl ether acetate ... 79.53 parts.

The composition of the R pigment dispersion 1 is
・ C. I. P. R. 254 (trade name: Irgaphor Red B-CF,
Ciba Specialty Chemicals Co., Ltd.) 8 parts, Pigment Dispersant A 0.8 parts Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, mass average molecular weight 37,000) ... 8 parts / propylene glycol monomethyl ether acetate ... 83.2 parts.

The composition of the R pigment dispersion 2 is
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, mass average molecular weight 37,000) ... 12 parts propylene glycol monomethyl ether acetate ... 70 parts.

The composition of the R pigment dispersion 3 is
・ C. I. P. R. 254 (trade name: Irgaphor Red B-CF,
Ciba Specialty Chemicals Co., Ltd.) 8 parts, Pigment Dispersant A 0.8 parts Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, mass average molecular weight 37,000)... 6.4 parts, propylene glycol monomethyl ether acetate 84.8 parts.

As the G pigment dispersion 1, “trade name: GT-2” manufactured by FUJIFILM Electronics Materials Co., Ltd., which is a halogenated copper phthalocyanine compound, was used.
As the Y pigment dispersion 10, “trade name: CF EX3393” manufactured by Mikuni Color Co., Ltd. was used.

As the B pigment dispersion 1, “trade name: CF Blue EX3357” manufactured by Mikuni Color Co., Ltd. was used.
As the B pigment dispersion 2, “trade name: CF Blue EX3383” manufactured by Mikuni Color Co., Ltd. was used.

The composition of binder 1 is
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22
Random copolymer of molar ratio, mass average molecular weight 37,000) ... 27 parts propylene glycol monomethyl ether acetate ... 73 parts.
The composition of binder 2 is
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate)
= Random copolymer of 38/25/37 molar ratio,
(Mass average molecular weight 38,000) 27 parts propylene glycol monomethyl ether acetate 73 parts.
The composition of binder 3 is
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate)
= Random copolymer with a molar ratio of 36/22/42,
(Mass average molecular weight 38,000) 27 parts propylene glycol monomethyl ether acetate 73 parts.
The composition of the binder 4 is
・ Polymer (benzyl methacrylate / methacrylic acid = 72/28
Random copolymer of molar ratio, mass average molecular weight 37,000) ... 27 parts propylene glycol monomethyl ether acetate ... 73 parts.

The composition of the DPHA solution is
・ Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) ・ ・ ・ 76 parts ・ Propylene glycol monomethyl ether acetate ・ ・ ・ 24 parts Surfactant 1 (Dainippon The composition of “Ink Chemical Industries,“ trade name: MegaFuck F780F ”)
And _{· C 6 F 13 CH 2 CH} 2 OCOCH = CH 2 40 parts,
H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH═CH ₂ 55 parts;
Copolymer with 5 parts of H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ ,
The weight average molecular weight is 30,000... 30 parts and methyl ethyl ketone is 70 parts.
Additive 1 is a phosphate ester-based additive (manufactured by Enomoto Kasei Co., Ltd., “trade name: HIPLAAD ED152”).

-Formation of black (K) image-
Cleaning solution (phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, adjusted to 25 ° C on alkali-free glass substrate, trade name: T-SD1 10 times with pure water from Fuji Film Co., Ltd. Was washed with a rotating brush having nylon bristles while being sprayed for 20 seconds by showering, and after pure water shower washing, silane coupling liquid (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3) A mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating apparatus and sent to the next laminator (Note that T-SD1 was used as the cleaning solution here, but T-SD2 may be used similarly).

After peeling off the protective film of the photosensitive resin transfer material K1, a substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Industries (Lamic II)), a rubber roller temperature of 130 ° C., a linear pressure of 100 N / The laminate was laminated with a transfer speed of 2.2 m / min.
After the temporary support is peeled off at the interface with the thermoplastic resin layer, the substrate and mask (quartz exposure mask with image pattern) are removed with a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. While standing vertically, the distance between the exposure mask surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

  Next, a triethanolamine developer (containing 30% by mass of triethanolamine, 0.1% by mass in total of polypropylene glycol, glycerol monostearate, polyoxyethylene sorbitan monostearate and stearyl ether, trade name: T -PD2, manufactured by FUJIFILM Corporation) with pure water (30 ° C) diluted 12 times (mixed at a ratio of 1 part by mass of T-PD2 and 11 parts by mass of pure water) for 50 seconds, Shower development was performed with a flat nozzle at a pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were removed. Subsequently, after air was blown off on the upper surface of the substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.

Subsequently, Na carbonate-based developer (0.38 mol / liter sodium hydrogen carbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer included , Trade name: T-CD1, manufactured by Fuji Film Co., Ltd., diluted 5 times with pure water) and shower-developed at 29 ° C. for 30 seconds with a cone type nozzle pressure of 0.15 MPa to form a photosensitive resin layer. Development was performed to obtain a patterning image.
Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name: T-SD1, manufactured by Fuji Film Co., Ltd.) was used after diluting 10 times with pure water. Sprayed with a shower at a temperature of 20 ° C. and a cone-type nozzle pressure of 0.02 MPa, and further removed the residue by rubbing the image formed with a rotating brush having nylon bristles to obtain a black (K) image (note that Here, T-SD1 was used as the cleaning solution, but T-SD2 may be used similarly).
Thereafter, the substrate was subjected to post-exposure with an ultrahigh pressure mercury lamp from both sides at an exposure amount of 500 mJ / cm ² and then heat treated at 220 ° C. for 15 minutes.
The substrate on which the K image was formed was washed again with a brush as described above, and after pure water shower washing, the silane coupling solution was not used and was sent to a substrate preheating device.

-Formation of red (R) pixels-
Using the photosensitive resin transfer material R1, a red (R) pixel was obtained on a substrate on which a black (K) image was formed, in the same process as the photosensitive resin transfer material K1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate-based developer was 35 ° C. for 35 seconds.
The photosensitive resin layer R1 has a thickness of 2.0 μm. I. Pigment red 254 and C.I. I. Pigment Red. The coating amount of 177 was 0.88 and 0.22 g / m ² , respectively.
The substrate on which the R pixel was formed was again cleaned with a brush as described above, and after pure water shower cleaning, the substrate was heated at 100 ° C. for 2 minutes without using a silane coupling solution.

-Formation of green (G) pixels-
Using the photosensitive resin transfer material G1, green (G) pixels were obtained on the substrate on which the red (R) pixels were formed, in the same process as the photosensitive resin transfer material R1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate-based developer was 34 ° C. and 45 seconds.
The photosensitive resin layer G1 has a thickness of 2.0 μm. I. The coating amounts of Pigment Green 36 and Y pigment were 1.12 and 0.48 g / m ² , respectively.
The substrate on which the R and G images were formed was washed again with a brush as described above, and after pure water shower washing, the substrate was heated at 100 ° C. for 2 minutes by a substrate preheating device without using a silane coupling solution.

-Formation of blue (B) pixels-
Using the photosensitive resin transfer material B1, a blue (B) pixel is obtained on the substrate on which the red (R) pixel and the green (G) pixel are formed in the same process as the photosensitive resin transfer material R1. It was. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate developer was 36 ° C. for 40 seconds.
The photosensitive resin layer B1 has a thickness of 2.0 μm. Pigment Blue 15: 6 and C.I. I. The coating amounts of Pigment Violet 23 were 0.63 and 0.07 g / m ² , respectively.
The substrate on which the R, G, B pixel and K images are formed is again cleaned with a brush as described above, and after pure water shower cleaning, without using a silane coupling solution, Heated for 2 minutes.
The substrate on which the R, G, B pixel and K images were formed was baked at 240 ° C. for 50 minutes to obtain the target color filter 1.

  Further, in the production of the color filter, the contrast coefficient evaluation glass substrate 1 formed only in green was produced using only the photosensitive resin transfer material G1 without forming the K image, R pixel, and B pixel.

―Production of display device―
A transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above. Separately, a glass substrate was prepared as a counter substrate, and patterning was performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, respectively.
A photo spacer was provided in a portion corresponding to the upper part of the partition wall on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.
After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided so as to surround the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV and then heat treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a cold cathode tube was constructed and arranged on the side of the liquid crystal cell provided with the polarizing plate, and the liquid crystal display device of Example 1 was obtained.

[Examples 2 to 5]
In the formation of green pixels, the color filters 2 to 5 were prepared in the same manner as in Example 1 except that the photosensitive resin transfer materials G2 to G5 were prepared using the photosensitive resin compositions G2 to G5 shown in Table 3. It produced and produced the liquid crystal display device of Examples 2-5, and produced the glass substrates 2-5 for contrast coefficient evaluation.

[Examples 6 to 10]
The formation method of K image and RGB pixel was changed to the following coating method, and in the formation of green pixel, color filters 6 to 10 were prepared using the photosensitive resin compositions G1 to G5 shown in Table 3, and carried out. The liquid crystal display device of Examples 6-10 was produced.

<Production of color filter (production by application using slit-like nozzle)>
-Formation of black (K) image-
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the photosensitive resin composition K1 having the composition shown in Table 2 was applied using a glass substrate coater (made by Hirata Kiko Co., Ltd.) having a slit-like nozzle. did. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus: manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2.4 μm. The photosensitive resin layer K1 was obtained.
In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the photosensitive resin The distance between the layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .
Next, pure water is sprayed with a shower nozzle to uniformly moisten the surface of the photosensitive resin layer K1, and then a KOH developer (KOH, containing nonionic surfactant, trade names: CDK-1, Fuji). Film Electromaterials Co., Ltd.) was subjected to shower development at 23 ° C. for 80 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water is sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove residues, and then ultrapure water is sprayed from both sides with a shower nozzle to adhere the developer and the photosensitivity. The resin layer dissolved matter was removed, and the liquid was drained with an air knife to obtain a black (K) image. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

-Formation of red (R) pixels-
Using the photosensitive resin composition R1 having the composition shown in Table 2 on the substrate on which the K image was formed, heat-treated R pixels were formed in the same process as the formation of the black (K) image. .
The photosensitive resin layer R3 has a thickness of 1.6 μm. I. Pigment red 254 and C.I. I. The application amounts of Pigment Red 177 were 0.88 and 0.22 g / m ² , respectively.

-Formation of green (G) pixels-
In the same process as the formation of the black (K) image, the photosensitive resin compositions G1 to G5 having the composition described in Table 3 are used for the substrate on which the K image and the R pixel are formed. A finished G pixel was formed.
The photosensitive resin layers G1 to G5 have a thickness of 1.6 μm. I. The coating amounts of Pigment Green 36 and Y pigment were 1.12 and 0.48 g / m ² , respectively.

-Formation of blue (B) pixels-
Using the photosensitive resin composition B1 having the composition shown in Table 2 above on the substrate on which the K image, R and G pixels are formed, heat treatment is performed in the same process as the formation of the black (K) image. B pixels were formed.
The photosensitive resin layer B1 has a thickness of 1.6 μm. I. Pigment blue 15: 6 and C.I. I. The coating amounts of Pigment Violet 23 were 0.63 and 0.07 g / m ² , respectively.

[Examples 11 to 16]
In the production of the photosensitive transfer material in Example 1, photosensitive transfer materials R2 to R6 were produced using the photosensitive resin compositions R2 to R6 shown in Table 2 instead of the photosensitive resin composition R1, and photosensitive. Photosensitive transfer materials B2 to B6 were prepared using the photosensitive resin compositions B2 to B6 described in Table 2 instead of the photosensitive resin composition B1, and described in Table 3 instead of the photosensitive resin composition G1. Photosensitive transfer materials G9 to G13 were prepared using the photosensitive resin compositions G9 to G13.
Using the photosensitive transfer materials R2 to R6, B2 to B6, and G9 to G13 prepared as described above, Example Color Filters 11 to 16 were prepared in the same manner as Example 1 according to the combinations shown in Table 4, While producing the liquid crystal display device of Examples 11-16, the glass substrates 11-16 for contrast coefficient evaluation were produced.

[Comparative Examples 1-3]
In the formation of green pixels, Comparative Example color filters 17 to 16 were prepared in the same manner as in Example 1 except that photosensitive resin transfer materials G6 to G8 were prepared using the photosensitive resin compositions G6 to G8 shown in Table 3. 19 were produced, and the liquid crystal display devices of Comparative Examples 1 to 3 were produced, and contrast coefficient evaluation glass substrates 17 to 19 were produced.
[Comparative Examples 4 to 6]
The KRGB pixel formation method was changed to the above coating method, and in the formation of green pixels, the photosensitive resin compositions G6 to G8 described in Table 3 were used to produce comparative color filters 20 to 22, and comparative examples 4-6 liquid crystal display devices were produced.

[Evaluation]
<Evaluation of contrast coefficient>
The contrast coefficient was measured as follows using the glass substrate for contrast coefficient evaluation prepared in Examples and Comparative Examples.
Using a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Corp.) as a backlight unit and using a diffusion plate, a contrast coefficient between two polarizing plates (G1220DUN manufactured by Nitto Denko Corporation) The evaluation glass substrates 1 to 5 and 11 to 19 are installed, and the chromaticity Y value of the light that passes when the polarizing plate is installed in parallel Nicols, the chromaticity of the light that passes when installed in crossed Nicols. The contrast was determined by dividing by the Y value. A color luminance meter (BM-5 manufactured by Topcon Corporation) was used for the measurement of chromaticity.
Two polarizing plates, a glass substrate, and a color luminance meter were installed at a position 13 mm from the backlight, a polarizing plate at a position 40 mm to 60 mm, and a cylinder 11 mm in diameter and 20 mm in length. Light was irradiated to a measurement sample installed at a position of 65 mm, and the transmitted light was measured with a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed. The results are shown in Table 3.

<Evaluation of color filter contrast>
Similarly, the contrast of the color filter was measured using the color filters 1 to 22 in place of the contrast coefficient evaluation glass substrates 1 to 5 and 11 to 19.
Furthermore, the color filter produced according to the following evaluation criteria was evaluated. The results are shown in Table 4.
A: The contrast was 2000 or more.
A: The contrast was 1200 or more and less than 2000.
X: The contrast was less than 1200.

<Evaluation of viscosity>
The viscosity of the green photosensitive resin compositions G1 to G13 is stored immediately after preparation using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd .; ELD, cone rotor angle: 1 ° 34 ') at room temperature for 10 days. And then measured respectively. The results are shown in Table 3.

Table 4 shows that a liquid crystal display device provided with a color filter produced by a transfer method or a coating method using the photosensitive resin compositions G1 to G5 and G9 to G13 of the present invention exhibits good contrast.
It can be seen that when the photosensitive resin composition G6, which is a comparative example using the Y pigment dispersion 6 using a pigment dispersant having no amino group, is used, the contrast is lowered.
Comparison using Y pigment dispersion 7 in which a ligand is a metal complex having a structure similar to that of the example of the present invention, but a compound different from the metal complex is not inserted in the crystal. When the photosensitive resin composition G7 which is an example is used, it turns out that contrast falls.
Table 3 also shows that the green photosensitive composition of the present invention has a low liquid viscosity after preparation and suppresses the increase in liquid viscosity over time.

Claims (7)

It contains a pigment, a pigment dispersant, a photopolymerizable compound, and a photopolymerization initiator, and the pigment has a tautomer of an azo compound represented by the following general formula (I) as a ligand. Metal Complex (1) A compound having a crystal structure in which a compound different from the metal complex is inserted in the crystal and a copper halide phthalocyanine compound , and the pigment dispersant is a compound having an amino group, A green photosensitive resin composition having a contrast coefficient of 3800 or more.


[In the formula, the total of the intra-ring and exocyclic double bonds in the rings represented by A and B is 3, respectively.
X, Y, Z and W are independently of each other, a carbonyl group, a thiocarbonyl ^{group, -C (= NR 7) -} , = C (N (R 6) R 7) -, = C (OR 6) - , = C (SR ⁶ )-, = C (CO ₂ R ⁶ )-, = C (CN)-, = C (CON (R ⁶ ) R ⁷ )-, = C (SO ₂ R ⁸ )-or = C (R ⁶ ) —
R ¹ , R ² , R ³ , R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,
R ⁵ represents —OH, —N (R ⁶ ) R ⁷ , an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group,
R ⁷ represents a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group,
R ⁸ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group,
R ¹ and Y, R ² and Y, R ³ and W, R ⁴ and W may be bonded to each other to form a 5- or 6-membered ring, and other rings are condensed to this ring. Often,
The substituents R ^{1 to} R ⁸ having a CH bond may be further substituted,
m, n, o, and p each independently represent 1 or 0 when a double bond comes out from a ring nitrogen atom. ] A metal complex having a tautomer of the azo compound represented by the general formula (I) as a ligand (1) A compound having a crystal structure in which a compound different from the metal complex is inserted into a crystal is Yellow. It is Pigment E4GN-GT, The green photosensitive resin composition of Claim 1 characterized by the above-mentioned. Furthermore, the pigment contains an iron compound (2) different from the metal complex (1) and / or a metal compound (3) different from the metal complex (1) and the iron compound (2). The green photosensitive resin composition of Claim 1 or 2 characterized by these.   The photosensitive resin transfer material which provided the photosensitive resin layer on the temporary support body using the green photosensitive resin composition of any one of Claims 1-3.   The photosensitive resin transfer material according to claim 4, wherein a thermoplastic resin layer and an intermediate layer are provided between the temporary support and the photosensitive resin layer.   A color filter formed using the green photosensitive resin composition according to any one of claims 1 to 3 or the photosensitive resin transfer material according to claim 4 or 5.   A display device comprising the color filter according to claim 6.