JP2015069181A - Radiation-sensitive resin composition, cured film, method for forming the same and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition for forming a black pattern which sufficiently satisfies general characteristics such as sensitivity and has high adhesiveness to a substrate and sufficient light shielding properties, and to provide a cured film obtained from the radiation-sensitive resin composition, a method for producing the same and a display element having the cured film.SOLUTION: There is provided a radiation-sensitive resin composition which comprises a binder polymer (A), a photopolymerization initiator (B) and a light-shielding agent (C), where the light-shielding agent (C) is composed of a perylene-based black pigment and the other pigments and the mass% of the other pigments in the total mass of the light-shielding agent is in the range of 20 to 90 mass%.

Description

  The present invention relates to a radiation-sensitive resin composition, a cured film, a method for forming the same, and a display element. In particular, the present invention relates to a radiation-sensitive resin composition for a spacer suitable as a material for forming a spacer for a display element, a spacer formed therefrom, and a display element.

  Conventionally, liquid crystal display panels use spacer particles such as glass beads and plastic beads having a predetermined particle size in order to keep the distance (cell gap) between two substrates constant. Since particles are randomly distributed on a transparent substrate such as a glass substrate, the presence of spacer particles in the pixel formation region may cause a phenomenon of spacer particle reflection or scattering of incident light, resulting in a contrast of the liquid crystal panel. There was a problem of lowering.

In order to solve these problems, a method of forming a spacer by photolithography has been adopted. In this method, a photosensitive resin composition is applied onto a substrate, exposed to ultraviolet rays through a predetermined mask, and then developed to form dot-like or stripe-like spacers. Since the spacer can be formed only at a predetermined location, the above-described problem is basically solved (Patent Document 1).
Recent color liquid crystal display elements are required to have stricter dimensional accuracy than conventional ones, and slight gap unevenness causes display defects. Further, there is a problem of adverse effects on display performance such as burn-in and display unevenness when a display panel is formed, and a spacer material that can avoid such adverse effects is strongly desired. Furthermore, there is a need for a radiation-sensitive resin composition that forms a spacer that has sufficient heat resistance, chemical resistance, strength, and adhesion and does not deteriorate display performance.

  In recent years, a so-called black column spacer in which the spacer is provided with a light shielding property by a light shielding agent such as carbon black has also been proposed (Patent Document 2).

Since the black column spacer contains a black colorant, it is difficult to form a fine pattern with high sensitivity. Furthermore, depending on the structure of the display element, it may be required to adjust and form the height of the black column spacer in a single exposure. In that case, it is proposed to perform exposure through a halftone mask. (Patent Document 3).
However, since the adhesion to the substrate is low, peeling of the spacer occurs during rubbing, or the amount of black pigment is reduced too much to give priority to developability during patterning, so that sufficient light shielding properties cannot be obtained. There was a problem.

JP 2001-302712 A JP 2011-170075 A JP 2013-134263 A

  The present invention has been made based on the circumstances as described above, and its purpose is to sufficiently satisfy general characteristics such as sensitivity, and to have a black pattern having sufficient adhesion to a substrate and sufficient light shielding properties. An object of the present invention is to provide a radiation-sensitive resin composition for formation, and to provide a cured film formed from the radiation-sensitive resin composition, a method for forming the cured film, and a display element including the cured film.

The invention made to solve the above problems is
(A) a binder polymer, (B) a photopolymerization initiator, and (C) a radiation-sensitive resin composition containing a light-shielding agent, wherein (C) the light-shielding agent comprises a perylene black pigment and other dyes, C) It is achieved by the radiation sensitive resin composition in which the mass% of other pigments is in the range of 20 to 90 mass% in the total mass of the light shielding agent.
The present invention further provides a polymer obtained by reacting the compound (A) having a fluorene skeleton represented by the following general formula (1) with a tetrabasic acid dianhydride, the following general formula ( The polymer obtained by adding the compound represented by 2) is achieved by the radiation-sensitive resin composition according to claim 1.

(In formula (1), ring Z ¹ and ring Z ² represent a monocyclic or condensed polycyclic hydrocarbon ring, R ^1a and R ^1b represent a hydrogen atom or an alkyl group, and R ^2a and R ^2b represent carbonized. A substituent selected from a hydrogen group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, or a cyano group; R ^3a and R ^3b represent a hydrogen atom or a methyl group; and k1 and k2 each independently , 0-4, m1 and m2 each independently represent an integer of 0-3, n1 and n2 each independently represent an integer of 0-10, and p1 and p2 each independently represent 0-4. Indicates an integer.
However, when the ring Z ¹ and the ring Z ² are monocyclic hydrocarbon rings, p 1 and p 2 are each independently an integer of 1 to 3, and the ring Z ¹ and the ring Z ² are condensed polycyclic hydrocarbon rings. If the sum of p2 included in the sum and ring Z ² of p1 contained in the ring Z ¹ is 1 or more, respectively. )

(In formula (2), R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms. X ¹ represents an epoxy group or 3,4-epoxycyclohexyl. A group, one selected from groups represented by the following formula (3-1) or formula (3-2), and * represents a binding site.

Moreover, another invention made | formed in order to solve the said subject contains the display element provided with the cured film formed from the said radiation sensitive resin composition, and the said cured film.

Furthermore, another invention made to solve the above problems is
(1) The process of forming a coating film on a board | substrate using the said radiation sensitive resin composition,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) A pattern forming method comprising: a step of developing the coating film irradiated with the radiation; and (4) a step of heating the developed coating film.

    The present invention provides a radiation-sensitive resin composition for forming a black pattern that sufficiently satisfies general characteristics such as sensitivity, has high adhesion to a substrate, and has sufficient light-shielding properties. A cured film formed from an object, a method for forming the cured film, and a display element including the cured film can be provided. Therefore, the said radiation sensitive resin composition, the said cured film, its formation method, and the said display element can be used suitably for manufacturing processes, such as a liquid crystal display device.

<Radiation sensitive resin composition>
The radiation sensitive resin composition of the present invention is a radiation sensitive resin composition containing (A) a binder polymer, (B) a photopolymerization initiator, and (C) a light shielding agent, and (C) the light shielding agent is perylene. A radiation-sensitive resin composition comprising a black pigment and other dyes, wherein (C) the weight percentage of the other dyes is in the range of 20 to 90% by weight in the total weight of the light-shielding agent. The said radiation sensitive resin composition may contain another arbitrary component in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.
<(A) Binder polymer>
The radiation sensitive resin composition of the present invention can contain (A) a binder polymer. Thereby, the alkali developability of a radiation sensitive resin composition, the binding property to a board | substrate, sclerosis | hardenability, storage stability, etc. can be improved. Such a binder polymer is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (E1) ”) and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as“ unsaturated monomer (e2) ”).

  As said unsaturated monomer (e1), the said compound group (alpha) can be mentioned, for example.

  An unsaturated monomer (e1) can be used individually or in mixture of 2 or more types.

  Moreover, as said unsaturated monomer (e2), the said compound group (beta) can be mentioned, for example.

  An unsaturated monomer (e2) can be used individually or in mixture of 2 or more types.

  In the copolymer of the unsaturated monomer (e1) and the unsaturated monomer (e2), the copolymerization ratio of the unsaturated monomer (e1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (e1) within such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (e1) and the unsaturated monomer (e2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Copolymers disclosed in JP-A-10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like. Can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder polymer.

  The binder polymer in the present invention has a polystyrene-equivalent weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000. Further, the ratio of the weight average molecular weight of the binder polymer in the present invention to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0 to 5.0, more preferably 1.0. ~ 3.0.

  The binder polymer in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

The (A) binder polymer is represented by the following general formula (2) to a polymer obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) with a tetrabasic acid dianhydride. A polymer obtained by adding a compound is preferred.

In formula (1), ring Z ¹ and ring Z ² represent a monocyclic or condensed polycyclic hydrocarbon ring, R ^1a and R ^1b represent a hydrogen atom or an alkyl group, and R ^2a and R ^2b represent a hydrocarbon. Represents a substituent selected from a group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group or a cyano group, R ^3a and R ^3b represent a hydrogen atom or a methyl group, and k1 and k2 each independently represent: M1 and m2 each independently represent an integer from 0 to 3, n1 and n2 each independently represent an integer from 0 to 10, and p1 and p2 each independently represent an integer from 0 to 4 Indicates.
However, when the ring Z ¹ and the ring Z ² are monocyclic hydrocarbon rings, p 1 and p 2 are each independently an integer of 1 to 3, and the ring Z ¹ and the ring Z ² are condensed polycyclic hydrocarbon rings. If the sum of p2 included in the sum and ring Z ² of p1 contained in the ring Z ¹ is 1 or more, respectively. )

In formula (2), R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents a single bond, a methylene group, or an alkylene group having 2 to 12 carbon atoms. X ¹ represents ^one selected from an epoxy group, a 3,4-epoxycyclohexyl group, and a group represented by the following formula (3-1) or formula (3-2). * Indicates a binding site. )

In the above formula (1), the hydrocarbon corresponding to the hydrocarbon ring represented by the ring Z ¹ and the ring Z ² is monocyclic or condensed polycyclic, for example, monocyclic carbonization such as benzene. Hydrogen, condensed bicyclic hydrocarbons (for example, C8-20 condensed bicyclic hydrocarbons such as indene and naphthalene, preferably C10-16 condensed bicyclic hydrocarbons), condensed tricyclic hydrocarbons (anthracene, phenanthrene, etc.) And condensed 2- to 4-cyclic hydrocarbons. Examples of hydrocarbons that are particularly preferred in applications requiring high refractive index and heat resistance include condensed polycyclic aromatic hydrocarbons (such as naphthalene and anthracene), and naphthalene is particularly preferable. In addition, benzene is preferred in applications that require particularly high solubility, compatibility, and low solution viscosity. Ring Z ¹ and ring Z ² may be the same or different rings, and may usually be the same ring.

In the above formula (1), the substituent represented by R ^1a and R ^1b is not particularly limited, but is usually an alkyl group. Examples of the alkyl group include C1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group (for example, C1-4 alkyl group, particularly methyl group). The groups R ^1a and R ^1b may be different from each other or the same. When k1 (or k2) is 2 or more, the groups R ^1a (or R ^1b ) may be different or the same in the same benzene ring. Note that the bonding position (substitution position) of the group R ^1a (or R ^1b ) with respect to the benzene ring constituting the fluorene skeleton is not particularly limited. Preferred substitution numbers k1 and k2 are 0 or 1, in particular 0. The substitution numbers k1 and k2 may be different but are usually the same.

Substituents R ^2a and R ^2b substituted on ring Z ¹ and ring Z ² include alkyl groups (carbon such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, and t-butyl groups. An alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group (such as a cyclopentyl group and a cyclohexyl group). 10 cycloalkyl groups, preferably cycloalkyl groups having 5 to 8 carbon atoms), aryl groups [phenyl groups, alkylphenyl groups (methylphenyl groups (tolyl groups), dimethylphenyl groups (xylyl groups), etc.), etc.) Group, aralkyl group (benzyl group, phenethyl group, etc.), etc .; alkoxy group having 1 to 12 carbon atoms, acyl group, alkoxy group Carbonyl group, a halogen atom, a nitro group, and a cyano group.

Preferred substituents R ^2a (or R ^2b ) are alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups, aryl groups, and aralkyl groups, and alkyl groups having 1 to 12 carbon atoms are particularly preferable. Substituents R2a (or R ^2b) can be substituted on the benzene ring alone or in combination. The groups R ^2a and R ^2b may be the same or different from each other, but are usually the same. When m1 (or m2) is 2 or more, the groups R ^2a (or R ^2b ) may be different or the same in the same hydrocarbon ring.

The substitution position of the substituent R ^2a (or R ^2b ) is not particularly limited, and depends on the substitution position of a hydroxyl group or a hydroxy (poly) alkyleneoxy group (hereinafter sometimes referred to as a hydroxyl group-containing group). Thus, the phenyl group constituting the phenol skeleton can be substituted at the 2-6 position (for example, the 2-position, 5-position, 2,5-position, etc.).

The substitution numbers m1 and m2 of the substituents R ^2a and R ^2b are preferably 0 to 2, more preferably 0 to 1 (particularly 0), although depending on the number of substitutions of the hydroxyl group-containing group. The substitution numbers m1 and m2 may be different but are usually the same in many cases.

The substituent represented by R ^3a and R ^3b of the hydroxyl group-containing group is hydrogen or a methyl group. R ^3a and R ^3b may be the same or different from each other, but are usually the same.

  The addition numbers n1 and n2 of the (poly) alkyleneoxy group are the same or different and can be selected from the range of 0 to 10, preferably 0 to 8 (for example, 1 to 8), more preferably 0 to 6 (for example, 1 to 6), particularly about 0 to 4 (for example, 1 to 4). Moreover, the sum (n1 + n2) of n1 and n2 can be selected from the range of 0-20, Preferably it is 0-16 (for example, 2-12), More preferably, it is 0-12 (for example, 2-12), Especially 0 About 8 (for example, 2-8) may be sufficient. When n1 (or n2) is 2 or more, the (poly) alkyleneoxy group may be composed of the same alkoxy group, and different types of alkoxy groups (for example, ethoxy group and propyleneoxy group) are mixed. Usually, it is often composed of the same alkoxy group.

The substitution numbers p1 and p2 of the hydroxyl group-containing group are in the range of 0 to 4, preferably 1 to 4, particularly preferably 1 to 2. However, the ring ^{Z 1} and the ring ^{Z 2} is the case of the monocyclic hydrocarbon ring p1 and p2 is 1 to 3, ring Z1 and the ring Z2 may condensed polycyclic hydrocarbon ring, contained in the ring Z1 p1 And the sum of p2 contained in ring Z2 are each 1 or more. Moreover, 2-8 are preferable and, as for the sum (p1 + p2) of p1 and p2, More preferably, it is 2-4. In particular, p1 and p2 are preferably 2 to 3 in applications in which the crosslink density of the cured product is required. The substitution numbers p1 and p2 may be different but are usually the same in many cases. The substitution position of the hydroxyl group-containing group is not particularly limited, and can be selected from the 2 to 6 positions of the phenyl group substituted at the 9 position of fluorene according to the number of p1 (or p2), and p1 (or p2) is 2 In this case, for example, it may be 3,4-position, 3,5-position, and the like. One hydroxyl group-containing group may be generally substituted at the 4-position.

  In addition, the several hydroxyl group containing group which comprises the same phenol frame | skeleton may be the same, and may differ. For example, the plurality of hydroxyl group-containing groups may be composed of (i) a hydroxyl group alone where n1 = 0 (n2 = 0) (except when p1 and p2 are 2), and (ii) n1 = 0 (n2 = 0) and a hydroxyl (poly) alkoxy group (such as 2-hydroxyethoxy group) in which n1 ≠ 0 (n2 ≠ 0) may be formed, and (iii) n1 (Iv) different hydroxy (poly) alkoxy groups [n 2 ≠ 0 (n 2 ≠ 0)] [for example, 2 -Hydroxyethoxy group and 2- (2-hydroxyethoxy) ethoxy group].

  Specific examples include 9,9-bis (hydroxyalkoxynaphthyl) fluorenes and 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes. As 9,9-bis (hydroxyalkoxynaphthyl) fluorenes, for example, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {for example, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] Fluorene, 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [ 9,9-bis (hydroxyC2-4alkoxynaphthyl) fluorene etc. such as 5- (2-hydroxypropoxy) -1-naphthyl] fluorene} and the like.

  Examples of 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes include, for example, 9,9-bis (hydroxydialkoxynaphthyl) fluorene [for example, 9,9-bis {6- [2- (2-hydroxy Ethoxy) ethoxy] -2-naphthyl} fluorene, 9,9-bis {6- [2- (2-hydroxypropoxy) propoxy] -2-naphthyl} fluorene, 9,9-bis {5- [2- (2 9,9-bis (hydroxydi-C2- such as -hydroxyethoxy) ethoxy] -1-naphthyl} fluorene, 9,9-bis {5- [2- (2-hydroxypropoxy) propoxy] -1-naphthyl} fluorene 4,9-bis (hydroxydialkoxynaphthyl) fluorenes such as 4alkoxynaphthyl) fluorene, etc .; these compounds Corresponding, such as n1, n2, n3, n4 is 3 or more compounds in the general formula (3).

    Of these, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene and the like are preferable.

  A tetrabasic acid dianhydride is used as a compound to be reacted with the compound having the fluorene skeleton.

  Specific examples of the tetrabasic dianhydride include butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic Acid dianhydride, cyclohexane tetracarboxylic dianhydride, cycloheptane tetracarboxylic dianhydride, norbornane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic acid Dianhydride, biphenyl ether tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2, 5-Dioxotetrahydrofuran-3-yl) -1,2,3,4-tetra Dronaphthalene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,4,9 , 10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and the like, and one or more of these are used. Among these, pyromellitic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, benzophenonetetracarboxylic dianhydride Biphenyltetracarboxylic dianhydride is preferred.

  A polymer compound constituting the photosensitive resin of the present invention can be obtained by subjecting the compound having a fluorene skeleton to an addition reaction with tetrabasic dianhydride. In this addition reaction, the ratio of tetrabasic dianhydride to 1 mol of the compound having a fluorene skeleton is preferably 0.5 mol to 1.5 mol, and more preferably 0.65 mol to 1.25 mol. When the ratio of tetrabasic acid dianhydride is less than 0.5 mol and exceeds 1.5 mol, sufficient molecular weight may not be obtained.

  A catalyst may be used in the addition reaction between the compound having a fluorene skeleton and tetrabasic acid dianhydride. The catalyst to be used is not particularly limited as long as it promotes the reaction. Examples thereof include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N , N-dimethylaniline, N, N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, , 5-diazabicyclo [4,3,0] nonene-5, etc., quaternary ammonium compounds such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, Fins, triphenylphosphine and the like and mixtures thereof. The amount of the catalyst to be used is not particularly limited, but a range of 0.1 to 2.0 parts by mass is preferable with respect to 100 parts by mass in total of the compound having a fluorene skeleton and the tetrabasic acid dianhydride. If the amount of the catalyst is more than 2.0 parts by mass, the electrical characteristics and storage stability of the photosensitive resin may be adversely affected.

  Further, in the addition reaction, a solvent may be used for the purpose of dissolving the reaction raw materials and reducing the viscosity. The type of solvent is not particularly limited as long as it does not inhibit the reaction. Examples include glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. Glycol ether acetates such as, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol ethers such as propylene glycol diethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ete Propylene glycol ether acetates such as acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, dimethyl Examples include sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixtures thereof.

  Although there is no restriction | limiting in particular also in the quantity of the solvent to be used, The range of 25-150 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a fluorene skeleton, and tetrabasic acid dianhydride. If it is less than 25 parts by mass, the viscosity may not be sufficiently reduced. On the other hand, when the amount exceeds 150 parts by mass, the reaction concentration may decrease too much and the reaction rate may decrease.

  Addition of a solvent or catalyst to the compound having a fluorene skeleton and tetrabasic acid dianhydride, if necessary, is allowed to carry out an addition reaction. In the reaction, it is preferable to heat, the raw material is dissolved by heating, and the reaction rate is also accelerated. The The heating temperature can be appropriately set according to the type of the compound having a fluorene skeleton and the tetrabasic acid dianhydride and the apparatus to be used, but it is generally preferably in the range of 60 to 220 ° C. More preferably, it is the range of 90-160 degreeC. When the reaction temperature is lower than 60 ° C., it may take time to complete the reaction. On the other hand, when the reaction temperature is higher than 220 ° C., side reactions such as coloring may occur, or the reaction rate may decrease due to an equilibrium in which the acid anhydride is closed.

  The photosensitive resin of the present invention can be obtained by adding a carboxylic acid reactive (meth) acrylate compound represented by the following general formula (2) to the polymer compound obtained as described above.

(In formula (2), R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms. X ¹ represents an epoxy group or 3,4-epoxycyclohexyl. A group, one selected from groups represented by the following formula (3-1) or formula (3-2), and * represents a binding site.

Specific examples of the carboxylic acid reactive (meth) acrylate represented by the general formula (2) include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate (meth) acrylic acid [3, 4-epoxytricyclo (5.2.1.0 ^2,6 ) decan-9-yl].

    In the reaction between the polymer compound and the carboxylic acid reactive (meth) acrylate compound, a catalyst may be used for the purpose of promoting the reaction. The type of the catalyst differs depending on the type of the carboxylic acid reactive (meth) acrylate compound, so it cannot be generally stated, but as an example, pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4 , 0] -7-undecene, 1,5-diazabicyclo [4,3,0] nonene-5, etc., tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide Quaternary ammonium compounds, tributylphosphine, triphenylphosphine and the like and mixtures thereof.

  Moreover, there is no restriction | limiting in particular also in the quantity of the catalyst to be used, However, The range of 0.1-2.0 mass parts is preferable with respect to 100 mass parts of compounds which have the said fluorene skeleton. If the amount of the catalyst is too large, the electrical properties and storage stability of the photosensitive resin may be adversely affected.

  Moreover, when making a carboxylic-acid reactive (meth) acrylate compound react, it is preferable to add a polymerization inhibitor. The type of the polymerization inhibitor is not particularly limited as long as it suppresses the reaction of unsaturated bond. Examples thereof include hydroquinone, hydroquinone monomethyl ether, t-butyl hydroquinone, t-butyl catechol, N-methyl-N-nitroso. Aniline or N-nitrosophenylhydroxylamine / ammonium salt (Wako Pure Chemical Industries, Ltd .: Q-1300), N-nitrosophenylhydroxylamine / aluminum salt (Wako Pure Chemical Industries, Ltd .: Q-1301), 2, Examples include 2,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. In particular, N-nitrosophenylhydroxylamine aluminum salt and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl are preferable. The amount of the polymerization inhibitor varies depending on the type and reaction conditions, and cannot be generally stated, but is preferably in the range of 5 to 2000 ppm with respect to the entire photosensitive resin. If it is less than this range, unsaturated bonds may react during production to cause gelation, and if it is more than this range, the sensitivity may decrease, which is not preferable.

  When adding the carboxylic acid reactive (meth) acrylate compound, it is preferable to heat for the purpose of improving the reaction rate. The heating temperature can be appropriately set depending on the type and apparatus of the carboxylic acid reactive (meth) acrylate compound, but is generally preferably in the range of 60 to 150 ° C. When the reaction temperature is lower than 60 ° C., it may take time to complete the reaction. On the other hand, if the reaction temperature is higher than 150 ° C., side reactions such as coloring may occur, or unsaturated bonds may react to cause gelation.

  The binder polymer in the present invention has a polystyrene-equivalent weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000. Further, the ratio of the weight average molecular weight of the binder polymer in the present invention to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0 to 5.0, more preferably 1.0. ~ 3.0.

  The binder polymer in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

In this invention, (A) binder polymer can be used individually or in mixture of 2 or more types.
<(B) Photopolymerization initiator>
(B) The photopolymerization initiator is a compound represented by the following formula (4).

In formula (4), R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or Represents a heterocyclic group having 2 to 20 carbon atoms, and the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group is further OR ⁹ , COR ⁹ , SR ⁹ , NR ⁹ , CN group, halogen atom, R ⁹ may be substituted with a hydroxyl group, and R ⁹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. )
Preferable specific examples of the photopolymerization initiator represented by the general formula (4) include the following compound No. 1-No. N o. 30 compounds are mentioned. However, the present invention is not limited by the following compounds.

  In this invention, 0.01-120 mass parts is preferable with respect to 00 mass parts of (A) binder polymers, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may not be sufficiently obtained. On the other hand, if the content is too large, the formed pattern tends to be detached from the substrate during development.

  In this invention, the photoinitiator shown below can be used with the said photoinitiator.

  In the present invention, together with the above photopolymerization initiator, for example, thioxanthone compound, acetophenone compound, biimidazole compound, triazine compound, O-acyloxime compound, onium salt compound, benzoin Examples thereof include benzophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, and imide sulfonate compounds.

In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photo radical generator in the present invention, a thioxanthone compound, an acetophenone compound, a biimidazole compound, It is preferable to contain at least one selected from the group of triazine compounds and O-acyloxime compounds.
<(C) Shading agent>
A black column spacer formed using the photosensitive resin composition is preferable since it contains a perylene pigment because it can easily improve the adhesion of the black column spacer to the substrate. (C) The light-shielding agent comprises a perylene-based black pigment and other dyes, and (C) the total mass of the light-shielding agent is preferably in the range of 20 to 90% by mass of the other dyes. It is particularly preferably 100% by mass or more. When the perylene pigment is 85% by mass or more with respect to the total mass of the (C) light-shielding agent, the maximum transmittance in the wavelength region from 400 nm to 500 nm exceeds 2% when the thickness of the cured film is 3 μm, There is a tendency that the light shielding property at 400 nm to 500 nm is insufficient.

  Specific examples of the perylene pigment include a perylene pigment represented by the following general formula (d-1) and a perylene pigment represented by the following general formula (d-2). In addition, commercially available products such as product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, and 34 can be preferably used.

(In formula (d-1), R ^d1 and R ^d2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^d3 and R ^d4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or acetyl. Represents a group.)

(In formula (d-2), R ^d5 and R ^d6 each independently represent an alkylene group having 1 to 7 carbon atoms.)
The compound represented by the general formula (d-1) and the compound represented by the general formula (d-2) are, for example, the methods described in JP-A Nos. 62-1753 and 63-26784. Can be synthesized. That is, perylene-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and an amine are used as raw materials, and a heating reaction is performed in water or an organic solvent. The target product can be obtained by reprecipitation of the obtained crude product in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

  Moreover, in order to disperse | distribute a perylene pigment favorably in the photosensitive resin composition, it is preferable that the average particle diameter of a perylene pigment is 10-1000 nm.

In addition, (C) the light-shielding agent can be used in combination with a black pigment and a dye having a hue such as red, blue, green, yellow, and purple for the purpose of adjusting the color tone. A dye having a hue other than the black pigment can be appropriately selected from known dyes.
The pigment may be either an organic pigment or an inorganic pigment, and examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists). . Specific examples include those with the following color index (CI) names.
C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;
C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;
C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;
C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

Examples of the inorganic pigment include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean curd (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.
The dye can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, and the like, and for example, the following color index (CI) names are given. Things can be mentioned.
C. I. Solvent Yellow 4, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162, C.I. I. Solvent yellow 179;
C. I. Solvent Red 45, C.I. I. Solvent red 49;
C. I. Solvent Orange 2, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 11, C.I. I. Solvent Orange 15, C.I. I. Solvent Orange 26, C.I. I. Solvent orange 56;
C. I. Solvent Blue 35, C.I. I. Solvent Blue 37, C.I. I. Solvent Blue 59, C.I. I. Solvent blue 67;
C. I. Acid Yellow 17, C.I. I. Acid Yellow 29, C.I. I. Acid Yellow 40, C.I. I. Acid Yellow 76;
C. I. Acid Red 91, C.I. I. Acid Red 92, C.I. I. Acid Red 97, C.I. I. Acid Red 114, C.I. I. Acid Red 138, C.I. I. Acid Red 151;
C. I. Acid Orange 51, C.I. I. Acid Orange 63;
C. I. Acid Blue 80, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90;
C. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Acid Green 25, C.I. I. Acid Green 27.

  In this invention, a coloring agent can be used individually or in mixture of 2 or more types.

The content of the (C) light-shielding agent in the photosensitive resin composition can be appropriately selected within a range that does not impair the object of the present invention, and is typically 5 to 50 mass based on the solid content of the photosensitive resin composition. % Is preferred. By using a light-shielding agent in such an amount, the light-shielding property of the cured film obtained using the photosensitive resin composition is improved, and the exposure failure and the curing failure when the photosensitive resin composition is exposed. Easy to suppress.
<Other optional components>
The radiation-sensitive resin composition is a polyfunctional acrylate, a compound having a cyclic ether group, an acid diffusion controller, a surfactant, an adhesion assistant, a dispersant, as long as the effects of the present invention are not impaired. You may contain other arbitrary components, such as a solvent. Other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.
<Multifunctional acrylate>
Polyfunctional acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate , Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy) Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly ( ) Acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

The content of the polyfunctional acrylate is usually 150 parts by mass or less, preferably 0.5 parts by mass or more and 100 parts by mass or less, and preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the (A) binder polymer. More preferably, it is more preferably 10 parts by mass or more and 25 parts by mass or less. By using in this range, the hardness of the cured film formed from the radiation-sensitive resin composition can be further increased, and the radiation sensitivity of the radiation-sensitive resin composition can be increased.
<Compound having a cyclic ether group>
The compound having a cyclic ether group is a compound having a cyclic ether group and different from the polymer that the (A) binder polymer has. The radiation-sensitive resin composition contains a compound having a cyclic ether group, thereby promoting cross-linking of the (A) binder polymer or the like due to the thermal reactivity of the compound having a cyclic ether group, and the radiation-sensitive resin composition. While the hardness of the cured film formed from a thing can be raised more, the radiation sensitivity of the said radiation sensitive resin composition can be improved.

  The compound having a cyclic ether group is preferably a compound having two or more epoxy groups (oxiranyl group, oxetanyl group) in the molecule.

Examples of the compound having two or more oxiranyl groups in the molecule include:
Bisphenol type diglycidyl ethers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ethers;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; phenol novolac epoxy resins;
Cresol novolac type epoxy resin; Polyphenol type epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids; glycidyl esters of higher fatty acids;
Aliphatic polyglycidyl ethers; epoxidized soybean oil, epoxidized linseed oil and the like. These compounds having a cyclic ether group may be used alone or in combination of two or more.

  Examples of the compound having a cyclic ether group having two or more oxetanyl groups in the molecule include bis [(3-ethyloxetane-3-yl) methyl] isophthalate, 1,4-bis [(3-ethyloxetane). -3-yl) methoxymethyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [1-ethyl- (3-oxetanyl) methyl] ether (also known as bis (3 -Ethyl-3-oxetanylmethyl) ether), 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 '-[1,3- (2-methylenyl) propanediylbis (oxymethylene) ] Bis- (3-ethyloxetane), 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl 3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3 -Oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3 -Oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, xylenebisoxetane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris ( -Ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl- 3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3- Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated Bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, etc. Is mentioned.

  Among these, the compound having a cyclic ether group is preferably a compound having two or more oxetanyl groups in the molecule, such as bis [(3-ethyloxetane-3-yl) methyl] isophthalate, 1,4- Bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene is more preferred.

As content of the compound which has a cyclic ether group, it is 150 mass parts or less normally with respect to 100 mass parts of (A) binder polymers, 0.5 mass part or more and 100 mass parts or less are preferable, and 1 mass part or more 50 More preferred is 10 parts by mass or more and 25 parts by mass or less. The hardness of the cured film formed from the said radiation sensitive resin composition can be raised more by making content of the compound which has a cyclic ether group into the said range.
<Surfactant>
Surfactant is a component which improves the film-forming property of the said radiation sensitive resin composition. By containing the surfactant, the radiation sensitive resin composition can improve the surface smoothness of the coating film. As a result, the film thickness uniformity of the cured film formed from the radiation sensitive resin composition can be improved. It can be improved.

  Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. These surfactants may be used alone or in combination of two or more. As the surfactant, an acid diffusion controlling agent described in JP 2011-18024 A can be used.

The content of the surfactant is usually 3 parts by mass or less, preferably 0.01 parts by mass or more and 2 parts by mass or less, and 0.05 parts by mass or more and 1 part by mass with respect to 100 parts by mass of the (A) binder polymer. Part or less is more preferable. By making content of surfactant into the said range, the film thickness uniformity of the coating film formed can be improved more.
<Adhesion aid>
The adhesion assistant is a component that improves the adhesion between the film formation target such as a substrate and the cured film. The adhesion assistant is particularly useful for improving the adhesion between the inorganic substrate and the cured film. Examples of the inorganic substance include silicon compounds such as silicon, silicon oxide, and silicon nitride, and metals such as gold, copper, and aluminum.

  As the adhesion assistant, a functional silane coupling agent is preferable. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group. These adhesion assistants may be used alone or in combination of two or more. Examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycidoxypropyl. Examples include trimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Among these, as the functional silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane is preferred.

The content of the adhesion assistant is usually 30 parts by mass or less, preferably 0.5 parts by mass or more and 20 parts by mass or less, and preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the (A) binder polymer. Is more preferable. By setting the content of the adhesion assistant in the above range, the adhesion between the formed cured film and the substrate is further improved.
<Dispersant>
In the present invention, when a pigment is used as a light-shielding agent, it can be used together with a dispersant and a dispersion aid as desired. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, an acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be given.

  Such a dispersant can be obtained commercially. For example, as an acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Corporation (BYK)), As polyurethane, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Corp.), polyethylene As imine, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) and as polyester, Ajisper PB821, Ajisper PB822, Ajisper PB880 ( Mention may be made of the Moto Fine-Techno Co., Ltd.), and the like.

  These dispersants can be used alone or in admixture of two or more.

  Content of a dispersing agent is 100 mass parts or less normally with respect to 100 mass parts of pigments, Preferably it is 1-70 mass parts, More preferably, it is 10-50 mass parts. When there is too much content of a dispersing agent, there exists a possibility that developability etc. may be impaired.

Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The content of the dispersion aid can be appropriately determined within a range that does not impair the object of the present invention.
<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition is dissolved or dispersed by mixing (A) a binder polymer and (B) a photopolymerization initiator, (C) a light-shielding agent, if necessary, a suitable component, and other optional components in a solvent. To be prepared. For example, the said radiation sensitive resin composition can be prepared by mixing each component in a predetermined ratio in a solvent.
<Solvent>
As the solvent, a solvent that uniformly dissolves or disperses other components in the radiation-sensitive resin composition and does not react with the other components is preferably used. Examples of such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, Aromatic hydrocarbons, ketones, other esters and the like can be mentioned. As the solvent, the solvents described in JP2011-232632 can be used.
<Method for forming cured film for display element>
The radiation-sensitive resin composition is preferable for forming a cured film for a display element. Moreover, the cured film for display elements formed from the said radiation sensitive resin composition is suitably contained in this invention.

The method for forming a cured film for a display element of the present invention is as follows.
(1) The process of forming a coating film on a board | substrate using the said radiation sensitive resin composition,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation; and (4) a step of heating the developed coating film.

According to the forming method of the present invention, it is possible to form a cured film for a display element that is excellent in compression performance, transmittance, light resistance, voltage holding ratio, development resistance, heat resistance and solvent resistance. Hereinafter, each process is explained in full detail.
[Step (1)]
In this step, a transparent conductive film is formed on one surface of the transparent substrate, and a coating film of the radiation-sensitive resin composition is formed on the transparent conductive film. Examples of the transparent substrate include glass substrates such as soda lime glass and alkali-free glass, and resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

  Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO2), an ITO film made of indium oxide-tin oxide (In2O3-SnO2), and the like.

  When a coating film is formed by a coating method, the coating film is preferably formed by heating (pre-baking) the coated surface after coating the solution of the radiation sensitive resin composition on the transparent conductive film. Can do. As solid content concentration of the composition solution used for a coating method, 5 mass%-50 mass% are preferable, 10 mass%-40 mass% are more preferable, 15 mass%-35 mass% are especially preferable. Examples of the application method of the radiation sensitive resin composition include spraying, roll coating, spin coating (spin coating), slit coating (slit die coating), bar coating, and ink jet coating. An appropriate method can be adopted. Of these, spin coating or slit coating is preferred.

The prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but are preferably 70 ° C. to 120 ° C. and about 1 to 15 minutes. The film thickness after pre-baking of the coating film is preferably 0.5 μm to 10 μm, and more preferably about 1.0 μm to 7.0 μm.
[Step (2)]
In this step, radiation is applied to at least a part of the formed coating film. At this time, when irradiating only a part of the coating film, for example, a method of irradiating through a photomask having a predetermined pattern can be used.

  Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

Radiation dose (exposure dose), as a value measured by a luminometer intensity at a wavelength 365nm of the radiation emitted (OAI model 356, Optical Associates Ltd. ^{Inc.), 100J / m 2 ~5,000J} / m 2 is Preferably, 200 J / m ^{2 to} 3,000 J / m ² is more preferable.

The radiation-sensitive resin composition has a higher sensitivity than conventionally known compositions, and a desired film thickness even when the radiation dose is 700 J / m ² or less, and even 600 J / m ² or less. A cured film for a display element having a good shape, excellent adhesion and high hardness can be obtained.
[Step (3)]
In this step, the coated film after irradiation is developed to remove unnecessary portions and form a predetermined pattern. Examples of the developer used for the development include aqueous solutions of alkaline compounds such as inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant may be added to the aqueous solution of the alkaline compound.

The developing method may be any of a liquid filling method, a dipping method, a shower method, and the like, and the developing time is preferably about 10 seconds to 180 seconds at room temperature. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern is obtained by air drying with compressed air or compressed nitrogen.
[Step (4)]
In this step, a cured film for display element is obtained by heating the obtained patterned coating film with a suitable heating device such as a hot plate or oven. The heating temperature is about 100 ° C to 250 ° C. The heating time is, for example, about 5 to 30 minutes on a hot plate and about 30 to 180 minutes for an oven.
<Method for manufacturing display element>
A display element provided with the said cured film for display elements is also suitably contained in this invention. As a method for manufacturing a display element, first, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition is formed on the transparent conductive film of one of the substrates. Is used to form a spacer or a protective film or both in accordance with the method described above. Subsequently, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the display element of the present invention is bonded to both outer surfaces of the liquid crystal cell such that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. can get.

  As another method, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film, a spacer, or both, and an alignment film are formed are prepared in the same manner as described above. After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, and then the liquid crystal is dropped in the form of fine droplets using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. . Then, both the substrates are sealed by irradiating the sealing agent part with ultraviolet rays using a high-pressure mercury lamp. Finally, the display element of the present invention is obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in each of the above methods include nematic liquid crystal and smectic liquid crystal. In addition, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or an H film Examples thereof include a polarizing plate made of itself.

<Synthesis of binder polymer>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 3 parts by mass of 2,2′-azobisisobutyronitrile and 235 parts by mass of propylene glycol monomethyl ether acetate, followed by 20 parts by mass of methacrylic acid and 12 parts by mass of N-phenylmaleimide. , 14 parts by mass of benzyl methacrylate, 10 parts by mass of styrene, 15 parts by mass of 2-hydroxyethyl methacrylate, 29 parts by mass of 2-ethylhexyl methacrylate and 5 parts by mass of α-methylstyrene dimer (chain transfer agent) The reaction solution was heated to 80 ° C. while gently stirring, and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by mass of 2,2′-azobisisobutyronitrile was added, and the polymerization was further continued for 1 hour to obtain a binder resin solution (solid content concentration). = 30% by mass). The obtained binder polymer was Mw = 10,000 and Mn = 5,600. This binder polymer solution is referred to as “binder polymer solution (A-1)”.
<Preparation of pigment dispersion>
Preparation Example 1
As perylene black-based black pigments, C.I. I. 12 parts by weight of Pigment Black 788, 6 parts by weight of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration = 40% by weight), 4 parts by weight of a binder polymer solution (A-1) solution as a binder polymer A pigment dispersion (C-1) was prepared by treating with 78 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and using a bead mill.
Preparation Examples 2-6
In Preparation Example 1, pigment dispersions (C-2) to (C-6) were prepared in the same manner as Preparation Example 1, except that the type and mixing ratio of the colorant were changed as shown in Table 1.

In Table 1, “R242” means C.I. I. Pigment Red 242, “R254” means C.I. I. Pigment Red 254, “Y139” is C.I. I. Pigment Yellow 139, “Y185” is C.I. I. Pigment Yellow 185, “B15: 6” is C.I. I. Pigment Blue 15: 6 is shown respectively.
<Preparation of radiation-sensitive resin composition>
[Examples 1-7 and Comparative Examples 1-2]
The types and amounts of (A) binder polymer shown in Table 2 and (C) a pigment dispersion as a light shielding agent are added, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as a polyfunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.) , KAYARAD DPHA), (B) As a photopolymerization initiator, Compound No. 4 is mixed with 10 parts by mass, and a silicone surfactant (SH8400 FLUID, manufactured by Toray Dow Corning, Silicone) is further mixed as a surfactant, and propylene glycol monomethyl ether is added so that the solid content concentration is 25% by mass. A radiation sensitive resin composition was prepared using acetate (PGMEA).

  Table 2 shows the details of the composition of the radiation sensitive resin composition and the evaluation results shown below.

In Table 2,
A-1: Binder resin of Synthesis Example 1 A-2: Cardo resin Ogsol CR-1030 (manufactured by Osaka Gas Chemicals) (solid content concentration = 50 mass%)
A-3: Epoxy acrylate resin ZCR-1797H (manufactured by Nippon Kayaku) (solid content concentration = 65 mass%) is shown.
<Evaluation of cured film>
Using the radiation-sensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 and 2, a cured film was formed as follows, and the characteristics were evaluated.
(Evaluation of transmittance)
After applying the radiation sensitive resin composition prepared in Examples 1 to 7 and Comparative Examples 1 and 2 to a glass substrate (“Corning (registered trademark) 7059” (manufactured by Corning)) using a spinner, A coating film was formed by prebaking on a plate at 90 ° C. for 2 minutes. After these substrates were cooled to room temperature, each coating film was irradiated with radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 2,000 J / m 2 without using a photomask using a high-pressure mercury lamp. . (Hereinafter, it is also referred to as exposure.) Thereafter, a developer consisting of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. was discharged at a development pressure of 1 kgf / cm 2 (nozzle diameter 1 mm) on these substrates. Shower development was performed for 60 seconds. Thereafter, this substrate is washed with ultrapure water, air-dried, and further post-baked in a clean oven at 230 ° C. for 30 minutes, whereby a cured film for evaluation having a post-baked film thickness of 3.0 μm is obtained. Formed. About the glass substrate in which this cured film was formed, the light transmittance of the wavelength range of 400 nm-800 nm was measured using the spectrophotometer "150-20 type double beam" (made by Hitachi, Ltd.), and each glass substrate The maximum value of the light transmittance in the wavelength range of 400 nm to 500 nm was evaluated. When this light transmittance was 2% or less, it was judged that the light shielding property was particularly good. The evaluation results are collectively shown in Table 2 as “maximum transmittance (%) of 400 to 500 nm” and “light shielding”.
(Evaluation of adhesion)
After applying the radiation sensitive resin composition prepared in Examples 1 to 7 and Comparative Examples 1 and 2 to a glass substrate (“Corning (registered trademark) 7059” (manufactured by Corning)) using a spinner, A coating film was formed by prebaking on a plate at 90 ° C. for 2 minutes. Next, after cooling the substrate to room temperature, using a high-pressure mercury lamp, the coating film is irradiated with radiation containing wavelengths of 365 nm, 405 nm, and 436 nm through a photomask having a circular pattern with different mask sizes as openings. Irradiation was performed with an exposure dose of 500 J / m ² . Then, shower development was performed by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. to the substrate at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm). The development time was set to about 1.5 times the BT on the basis of the time until the unexposed area was completely dissolved (BT: break time). The substrate was washed with ultrapure water and air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes to form a spacer. Then, the minimum mask dimension capable of forming a spacer at an exposure amount of 500 J / m ² was examined and used as an adhesion index.
If a pattern having a mask size of 15 μm or less was in close contact with the substrate in the above evaluation, it was determined that the adhesion was good. The results are shown in Table 2.

As is clear from the results in Table 2, compared to Examples 1 to 7, Comparative Example 1 had a low light shielding property, and Comparative Example 2 had poor adhesion.
When the light-shielding agent is composed of a perylene-based black pigment and other dyes, and (C) the total mass of the light-shielding agent is such that the mass% of the other dyes is in the range of 20 to 90 mass%, the adhesion and the light-shielding properties are high (Examples 1 to 7).
On the other hand, when the perylene pigment is 85% by mass or more with respect to the total mass of the (C) light-shielding agent (Comparative Examples 1 and 2), it is clear that both adhesion and light-shielding properties cannot be achieved at a high level. Became.

Claims (8)

(A) a binder polymer, (B) a photopolymerization initiator, and (C) a radiation-sensitive resin composition containing a light-shielding agent, wherein (C) the light-shielding agent comprises a perylene black pigment and other dyes, C) A radiation-sensitive resin composition, wherein, in the total mass of the light-shielding agent, mass% of other pigments is in the range of 20 to 90 mass%. The (A) binder polymer is represented by the following general formula (2) to a polymer obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) with a tetrabasic acid dianhydride. The radiation-sensitive resin composition according to claim 1, which is a polymer obtained by adding a compound.

(In formula (1), ring Z ¹ and ring Z ² represent a monocyclic or condensed polycyclic hydrocarbon ring, R ^1a and R ^1b represent a hydrogen atom or an alkyl group, and R ^2a and R ^2b represent carbonized. A substituent selected from a hydrogen group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, or a cyano group; R ^3a and R ^3b represent a hydrogen atom or a methyl group; and k1 and k2 each independently , 0-4, m1 and m2 each independently represent an integer of 0-3, n1 and n2 each independently represent an integer of 0-10, and p1 and p2 each independently represent 0-4. Indicates an integer.
However, when the ring Z ¹ and the ring Z ² are monocyclic hydrocarbon rings, p 1 and p 2 are each independently an integer of 1 to 3, and the ring Z ¹ and the ring Z ² are condensed polycyclic hydrocarbon rings. If the sum of p2 included in the sum and ring Z ² of p1 contained in the ring Z ¹ is 1 or more, respectively. )

(In formula (2), R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms. X ¹ represents an epoxy group or 3,4-epoxycyclohexyl. A group, one selected from groups represented by the following formula (3-1) or formula (3-2), and * represents a binding site.
The radiation sensitive resin composition according to claim 1, wherein the (B) photopolymerization initiator is a compound represented by the following formula (4).

(In Formula (4), R6, R7, and R8 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom. Represents a heterocyclic group of formula 2 to 20, and the hydrogen atom of the alkyl group, aryl group, arylalkyl group and heterocyclic group is further represented by OR ⁹ , COR ⁹ , SR ⁹ , NR ⁹ , CN group, halogen atom and hydroxyl group. R 9 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.   The radiation sensitive resin composition according to any one of claims 1 to 3, wherein the other colorant of the (C) light-shielding agent is at least one selected from a red pigment and a yellow pigment. It is a cured film formed from the radiation sensitive resin composition as described in any one of Claims 1-4, Comprising: The maximum transmittance | permeability in the wavelength range of 400 nm to 500 nm in the film thickness of a cured film is 3 micrometers. A cured film that is 2% or less.   The radiation-sensitive resin composition according to any one of claims 1 to 4, which is used for pattern formation of a display element. (1) The process of forming a coating film on a board | substrate using the radiation sensitive resin composition of Claim 6,
(2) A step of irradiating a part of the coating film with radiation,
(3) A method for forming a pattern comprising a step of developing the coating film irradiated with the radiation, and (4) a step of heating the developed coating film. A display element provided with the pattern formed from the pattern formation method of Claim 7.