JP2018189877A - Polymerizable composition, photosensitive composition for black matrix, and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable composition capable of giving a cured product having high light-shielding properties and high adhesive strength.SOLUTION: The polymerizable composition contains: an ethylenically unsaturated compound (A) having one or more structures selected from the group consisting of a dendrimer structure, a hyperbranched structure, and a structure derived from a polyglycerol; a colorant (B); an alkali-developable compound (C) excluding the ethylenically unsaturated compound (A); and a polymerization initiator (D). The colorant (B) is preferably a black pigment.SELECTED DRAWING: None

Description

  Conventionally, color filters have been widely used for the purpose of colorization of liquid crystal display devices and the like, and in general, red, green, and blue pixels are arranged in a mosaic pattern. As a method for producing this color filter, a dyeing method, a printing method, an ink jet method, an electrodeposition method, a colorant dispersion method and the like are known. In particular, a colorant dispersion method in which fine pixels are formed by photolithography using a color polymerizable composition for a color filter in which a colorant is dispersed together with a photosensitive polymer and / or a photosensitive monomer is used to improve pixel flatness. Because of its superiority, it has become the mainstream color filter manufacturing method.

The color filter coloring composition contains a pigment, a solvent, a dispersant, a photopolymerizable unsaturated compound, a photopolymerization initiator, and the like. Since the coloring composition containing a photopolymerization initiator can be polymerized and cured by irradiation with ultraviolet rays or an electron beam, it is useful for a filter segment constituting a color filter. The filter segment is formed by removing excess solvent from a coated product obtained by applying a photosensitive material on a glass substrate or the like, and then exposing the coated material to active energy by exposure through a photomask for pixel formation. It is formed by applying a heat of 230 ° C. or more called post-baking after irradiating a wire, increasing the curing (negative type) or increasing the alkali solubility (positive type), and then removing the portion dissolved with an alkali solution or the like.
In the case of using a pigment in the color filter coloring composition, it is general to prepare a pigment dispersion in which the pigment is previously dispersed in a resin or a dispersion medium when the coloring composition is prepared.

  In recent years, there has been a strong demand for high-definition display panels reflecting the high quality of color imaging devices and color liquid crystal televisions. Therefore, a highly adhesive black matrix photosensitive composition that has a high light-shielding property and can ensure sufficient adhesion even in a BM with a low line width has been studied. However, the existing black matrix photosensitive composition has a problem that a black matrix having both light shielding properties and high adhesiveness cannot be obtained.

  Patent Document 1 discloses a low curing shrinkage curable resin composition excellent in adhesive strength and heat resistance, containing second to fifth generation dendrimers having at least two polymerizable groups in the molecule. . Patent Document 2 discloses a radiation-sensitive composition for forming a colored layer that contains a dendrimer or a hyperbranched polymer and can form a pixel and a black matrix having excellent solvent resistance.

JP 2013-18810 A 2009-198751

Edited by Yasuhiko Okada, "Science and Function of Dendrimers", IPC, 2000

  However, the inventions described in Patent Documents 1 and 2 have low light shielding properties and low adhesion to glass. Therefore, the problem to be solved by the present invention is that there has been no polymerizable composition having high light shielding properties and excellent adhesion to glass.

  Accordingly, an object of the present invention is to provide a polymerizable composition, a BM photosensitive composition, a BCS photosensitive composition, a BM photosensitive composition, and a BM photosensitive composition that are excellent in light-shielding properties and adhesive strength to glass. It is in providing the cured | curing material obtained from this, the cured | curing material obtained from this, a display display apparatus, and the method of manufacturing this cured | curing material.

  As a result of intensive studies by the inventors of the present invention, it has been found that the above problems can be solved by providing the following [1] to [9].

[1]
Excluding the ethylenically unsaturated compound (A), the colorant (B), and the ethylenically unsaturated compound (A) having at least one structure selected from the group consisting of a dendrimer structure, a hyperbranched structure and a polyglycerin derived structure A polymerizable composition comprising an alkali developable compound (C) and a polymerization initiator (D).

[2]
The polymerizable composition according to [1], wherein the colorant (B) is a black pigment.

[3]
The alkali-developable compound (C) is subjected to an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (I) and a polybasic acid anhydride. The polymerizable composition according to [1] or [2], which is an unsaturated compound having a structure to be obtained.

(In the formula, M represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO ₂ —, —SS—, —SO—, —CO—, —OCO— or Represents a substituent selected from the group represented by formula (a), (b), (c) or (d);
The hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms represented by M may be substituted with a halogen atom,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ (hereinafter also referred to as R ^{1 to} R ⁸ ) are each independently a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. Represents a hydrocarbon group or a halogen atom,
The methylene group in the group represented by R ^{1 to} R ⁸ may be substituted with an unsaturated bond, —O— or —S—,
n is a number from 0 to 10,
When n ≧ 1, a plurality of R ^{1 to} R ⁸ and M may be the same or different. )

(Wherein R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms,
R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ (hereinafter also referred to as R ^{10 to} R ³⁸ ), respectively, Independently, it represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocyclic ring, or a halogen atom,
The methylene group in the group represented by R ^{10 to} R ³⁸ may be substituted with an unsaturated bond, —O— or —S—,
R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ²² and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ³⁰ and R ²³ , R ²³ And R ²⁴ , R ²⁴ and R ²⁵ , R ³⁸ and R ³¹ , R ³¹ and R ³² , R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ^36, and R ³⁶ and R ³⁷ are combined to form a ring. May form
* In the groups represented by the above formulas (a), (b), (c) and (d) represents a bond. )

[4]
The polymerizable composition according to any one of [1] to [3], wherein the polymerization initiator (D) is a polymerization initiator having a group represented by the following general formula (II).

(In the formula, R ⁴¹ and R ⁴² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring. Represents
Hydrogen atom of the group having 2 to 20 carbon atoms containing heterocyclic ring represented by a hydrocarbon group or ^{R 41} and ^{R 42} having 1 to 20 carbon atoms represented by R ⁴¹ and ^{R 42} is a halogen atom, a nitro Group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group, hydrocarbon group having 1 to 20 carbon atoms or heterocyclic ring may be substituted with groups having 2 to 20 carbon ^atoms, containing hetero ring represented by a hydrocarbon group or ^{R 41} and ^{R 42} having 1 to 20 carbon atoms represented by ^{R 41} and ^{R 42} a methylene group in the group having a carbon number of 2~20 -O -, - CO -, - COO -, - OCO -, - NR 43 -, - NR 43 CO -, - S -, - CS -, - SO ₂ -, - SC -, - COS -, - OCS- or CSO- in some cases be substituted,
R ⁴³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
m represents 0 or 1;
* In the formula represents a bond. )

[5]
[1] A photosensitive composition for a black matrix comprising the polymerizable composition according to any one of [4].

[6]
[1] A photosensitive composition for a black column spacer comprising the polymerizable composition according to any one of [4].

[7]
Light irradiation of the polymerizable composition according to any one of [1] to [4], the photosensitive composition for black matrix according to [5], or the photosensitive composition for black column spacer according to [6]. Or the method of manufacturing hardened | cured material hardened by heating.

[8]
Curing of the polymerizable composition according to any one of [1] to [4], the photosensitive composition for black column spacer according to [5], or the photosensitive composition for black column spacer according to [6]. object.

[9]
[8] A display device containing the cured product according to [8].

  The cured product obtained from the polymerizable composition, the photosensitive composition for BM, or the photosensitive composition for BCS of the present invention has high light shielding properties and high adhesive strength. The cured product is particularly useful for BM and BCS, and can be preferably used for a display device containing the BM or the BCS.

  Hereinafter, the polymerizable composition of the present invention will be described in detail based on preferred embodiments.

  The polymerizable composition of the present invention comprises an ethylenically unsaturated compound (A) having a structure selected from the group consisting of a dendrimer structure, a hyperbranched structure and a structure derived from polyglycerin (hereinafter simply referred to as an ethylenically unsaturated compound). (Also referred to as (A)), a colorant (B), an alkali-developable compound (C) excluding the ethylenically unsaturated compound (A) (hereinafter also simply referred to as an alkali-developable compound (C)), and a polymerization initiator (D) is contained. Hereinafter, each component will be described in order.

<Ethylenic unsaturated compound (A)>
The polymerizable composition of the present invention contains an ethylenically unsaturated compound (A). The ethylenically unsaturated compound (A) may contain an ethylenically unsaturated compound having at least one structure selected from the group consisting of a dendrimer structure, a hyperbranched structure, and a structure derived from polyglycerin. Not limited. Because of the high reactivity, the ethylenically unsaturated compound (A) preferably has an ethylenically unsaturated group having an acrylic group or a methacrylic group, and particularly preferably has an acrylic group.

The above-mentioned dendrimer structure is a polymer that is synthesized stepwise, has a single molecular structure, repeats repeating units including a branched structure from the central core through a functional group, and is linked to a terminal group. Usually, the number of repetitions of a repeating unit including a branch structure is expressed as “generation” (1 generation, 2 generations,...). Dendrimers have various functions depending on the structure of the repeating unit, the number of generations, the type of terminal structure (terminal group), and the like. The dendrimer is described in, for example, “Science and function of dendrimer, edited by Akihiko Okada (2000), IPC” (Non-patent Document 1).
The ethylenically unsaturated compound (A) having a dendrimer structure is a compound having an ethylenically unsaturated group, preferably an acryl group or a methacryl group as a polymerizable group at the end of the dendrimer structure.

  The central core of the dendrimer structure is not particularly limited, but must have at least two bonding points. Further, from the viewpoint of easy availability, the central core preferably has an oxygen atom or a nitrogen atom.

The ethylenically unsaturated compound (A) having a dendrimer structure preferably has 5 to 30 ethylenically unsaturated groups such as an acryl group or a methacryl group, and more preferably 10 to 15 groups. When the number of ethylenically unsaturated groups of the ethylenically unsaturated compound (A) having a dendrimer structure is in the above range, the sensitivity of the polymerizable composition is increased, and the sealing strength of the cured product is increased, which is preferable.
The number of ethylenically unsaturated groups in the ethylenically unsaturated compound (A) having the dendrimer structure is measured by, for example, the iodine value of the ethylenically unsaturated compound (A) by a known method and the weight average molecular weight by GPC. From the measured iodine value and weight average molecular weight, it can be calculated using the following formula.

(Number of ethylenically unsaturated groups) = (iodine value) /253.8×100/ (weight average molecular weight)

  The ethylenically unsaturated compound (A) having a dendrimer structure preferably has a weight average molecular weight of 500 to 5000, more preferably 1000 to 3000. When the weight average molecular weight of the ethylenically unsaturated compound (A) having a dendrimer structure is in the above range, the sensitivity of the polymerizable composition is increased, and the sealing strength of the cured product is increased, which is preferable. The weight average molecular weight of the ethylenically unsaturated compound (A) having the dendrimer structure can be measured by, for example, GPC.

  The ethylenically unsaturated compound (A) having the dendrimer structure can be produced by a known method. Moreover, a commercial item can also be used as an ethylenically unsaturated compound (A) which has the said dendrimer structure. Commercially available products include, for example, Biscoat 1000, Biscoat 1020, STAR-501, STAR-502, SIRIUS-501, SUBARU-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-HBR-5 (Shin Nakamura Chemical Co., Ltd.). Manufactured).

The hyperbranched structure means a multi-branched polymer structure synthesized by polymerizing an ABx type monomer that is a polyfunctional monomer having two or more kinds of functional groups, has a molecular weight distribution, and has a dendrimer structure. In comparison, it has a random branch structure.
The ethylenically unsaturated compound (A) having a hyperbranched structure is a compound having an ethylenically unsaturated group, preferably an acrylic group or a methacrylic group as a polymerizable group at the end of the hyperbranched structure.

The ethylenically unsaturated compound (A) having the hyperbranched structure preferably has 5 to 30 ethylenically unsaturated groups such as an acryl group or a methacryl group, and more preferably 10 to 15 ethylenically unsaturated groups. When the number of ethylenically unsaturated groups in the ethylenically unsaturated compound (A) having a hyperbranched structure is in the above range, the sensitivity of the polymerizable composition is increased, and the sealing strength of the cured product is increased, which is preferable.
The number of ethylenically unsaturated groups in the ethylenically unsaturated compound (A) having the hyperbranched structure is measured by, for example, the iodine value of the ethylenically unsaturated compound (A) by a known method and the weight average molecular weight by GPC. From the measured iodine value and weight average molecular weight, it can be calculated using the following formula.

(Number of ethylenically unsaturated groups) = (iodine value) /253.8×100/ (weight average molecular weight)

  The ethylenically unsaturated compound (A) having the hyperbranched structure preferably has a weight average molecular weight of 500 to 5000, more preferably 1000 to 3000. When the weight average molecular weight of the ethylenically unsaturated compound (A) having a hyperbranched structure is in the above range, the sensitivity of the polymerizable composition is increased, and the sealing strength of the cured product is increased, which is preferable. It can be measured by the weight average molecular weight of the ethylenically unsaturated compound (A) having the hyperbranched structure, for example, GPC.

  The ethylenically unsaturated compound (A) having the hyperbranched structure can be produced by a known method. Moreover, a commercial item can also be used as an ethylenically unsaturated compound which has the said hyperbranch structure. As a commercial item, CN2300, CN2301, CN2302, CN2303, CN2304 (above, the Sartomer Japan company make) etc. can be mentioned, for example.

  The ethylenically unsaturated compound (A) having a structure derived from polyglycerin means a compound obtained by an esterification reaction of polyglycerin and acrylic acid or methacrylic acid. The polyglycerin preferably has an average degree of polymerization of 5 to 100, and particularly preferably 10 to 50. Examples thereof include diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin and the like. There is no restriction | limiting in particular as a method of esterifying a polyglycerol and acrylic acid or methacrylic acid, A well-known method is employable.

The ethylenically unsaturated compound (A) having a structure derived from polyglycerin preferably has 5 to 30 ethylenically unsaturated groups such as an acryl group or a methacryl group, and more preferably 5 to 15. When the number of ethylenically unsaturated groups of the ethylenically unsaturated compound (A) having a structure derived from the polyglycerin is in the above range, the sensitivity of the polymerizable composition is increased, and the sealing strength of the cured product is increased, which is preferable. .
The number of ethylenically unsaturated groups in the ethylenically unsaturated compound (A) having a structure derived from the polyglycerin is, for example, a known method for determining the iodine value of the ethylenically unsaturated compound (A), and the weight average molecular weight. It can be calculated by the following calculation formula from the measured iodine value and weight average molecular weight by GPC.

(Number of ethylenically unsaturated groups) = (iodine value) /253.8×100/ (weight average molecular weight)

  The ethylenically unsaturated compound (A) having a structure derived from the polyglycerol preferably has a weight average molecular weight of 1000 to 10,000, more preferably 2000 to 4000. When the weight average molecular weight of the ethylenically unsaturated compound (A) having a structure derived from the polyglycerin is in the above range, the sensitivity of the polymerizable composition is increased, and the sealing strength of the cured product is increased, which is preferable. The weight average molecular weight of the ethylenically unsaturated compound (A) having a structure derived from the polyglycerol can be measured by, for example, GPC.

  Examples of the ethylenically unsaturated compound having a structure derived from the polyglycerol include polyglycerol diacrylate and polyglycerol dimethacrylate.

  Among the ethylenically unsaturated compounds (A), an ethylenically unsaturated compound having a dendrimer structure is particularly preferable because it exhibits high adhesive strength to glass.

In the polymerizable composition of the present invention, the content of the ethylenically unsaturated compound (A) is not particularly limited, but the ethylenically unsaturated compound (A), the colorant (B), and the alkali developable compound. Preferably it is 1-30 mass parts with respect to a total of 100 mass parts of (C) and a polymerization initiator (D), More preferably, it is 3-20 mass parts, More preferably, it is 5-15 mass parts. is there. When content of an ethylenically unsaturated compound (A) is in said range, it is preferable from the adhesive strength of the hardened | cured material obtained being excellent.
For example, when forming a cured product having a thickness of 2 to 5 μm, the content of the ethylenically unsaturated compound (A) is not particularly limited, but the ethylenically unsaturated compound (A), the colorant ( Preferably, the total amount of B), the alkali-developable compound (C) and the polymerization initiator (D) is 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and still more preferably. 5 to 15 parts by mass.

  The polymerizable composition of the present invention has one of technical features in that the ethylenically unsaturated compound (A) and the alkali developable compound (C) are used in combination. By using the ethylenically unsaturated compound (A) and the alkali-developable compound (C) in combination, the resulting cured product has high light shielding properties and high adhesive strength. In particular, as an alkali-developable compound (C), an esterification of an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I) and a polybasic acid anhydride When an unsaturated compound having a structure obtained by the reaction is used, the above effect becomes even more remarkable.

<Colorant (B)>
The polymerizable composition of the present invention contains a colorant (B).
As the colorant (B) used in the polymerizable composition of the present invention, pigments and dyes can be used. As the pigment and the dye, an inorganic color material or an organic color material can be used, respectively, and these can be used alone or in admixture of two or more. Here, the pigment refers to a colorant that is insoluble in a solvent to be described later, and includes inorganic or organic colorants that are insoluble in a solvent, or those obtained by rake formation of an inorganic or organic dye.

Examples of the pigment include carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black, a carbon black prepared or coated with an epoxy resin, and the carbon black In which a resin is dispersed in a resin in advance and coated with 20 to 200 mg / g of resin, an acid or alkaline surface treatment of the above carbon black, an average particle size of 8 nm or more, and a DBP oil absorption of 90 ml / 100 g or less of carbon black, the total amount of oxygen calculated from CO and CO ₂ in the volatile content at 950 ° C. is, carbon black is surface area 100 m ² per 9mg above, graphitized carbon black, graphite, activated carbon, carbon fibers, carbon nanotubes, Kabonma Black coil represented by crocoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, lactam black and perylene black, chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series, ferrocyan Fluoride, ultramarine blue, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, synthetic iron black, amber, lake pigment And organic or inorganic pigments.

  Among the above pigments, a black pigment is preferably used because of its high light shielding properties, and carbon black is particularly preferably used for BM applications.

  For BCS applications that require low liquid crystal contamination, it is more preferable to use organic black pigments such as lactam black and perylene black as the pigment.

  A commercial item can also be used as said pigment, for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97. 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223 224, 226, 227, 254, 228, 240 and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64 , 65 and 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 9 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168 175, 180 and 185; Pigment Green 7, 10, 36 and 58; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24 56, 60, 61, 62 and 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50, and the like.

  Examples of the dye include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthanthrones. Compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids, azo dyes, metal complex compounds of cyanine dyes, and the like.

In the polymerizable composition of the present invention, the content of the colorant (B) is not particularly limited, but is preferably 100 to 500 mass with respect to 100 mass parts of the following alkali developable compound (C). Parts, more preferably 150 to 400 parts by mass, and still more preferably 200 to 350 parts by mass. When the content of the colorant (B) is within the above range, it becomes a polymerizable composition having excellent storage stability without aggregation of the colorant, and the cured product of the polymerizable composition has high light shielding properties. To preferred.
For example, when forming a cured product having a thickness of 1 to 3 μm, the content of the colorant (B) is not particularly limited, but is preferably based on 100 parts by mass of the alkali-developable compound (C). Is 100 to 500 parts by mass, more preferably 150 to 400 parts by mass, and still more preferably 200 to 350 parts by mass.

<Alkali developable compound (C)>
The composition of the present invention contains an alkali developable compound (C).
The alkali-developable compound (C) used in the present invention is not particularly limited as long as it has a hydrophilic group and exhibits alkali-developability, and those conventionally used can be used.
Examples of the hydrophilic group include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amide group or a salt thereof, and the alkali developable compound (C) having a hydroxyl group and a carboxyl group has high alkali developability. Therefore, it is preferable.
The preferable functional group equivalent (mass of the high molecular compound containing 1 equivalent of hydrophilic group) of the hydrophilic group in an alkali developable compound (C) is 50-10000.
The preferred molecular weight of the alkali developable compound (C) is 1000 to 500,000.

The alkali-developable compound (C) has an acid value of preferably 10 to 200 mg / KOH, more preferably 30 to 150 mg / KOH. If the acid value is less than 10 mg / KOH, sufficient alkali developability may not be obtained, and if it is greater than 200 mg / KOH, it may be difficult to produce the polymer compound.
Here, the acid value is based on JIS K 0050 and JIS K 0211.

Specific examples of the alkali-developable compound (C) include copolymers of acrylic acid esters, phenol and / or cresol novolac epoxy resins, polyphenylmethane type epoxy resins having polyfunctional epoxy groups, epoxy acrylate resins, Resins obtained by allowing an unsaturated monobasic acid to act on an epoxy compound group such as an epoxy compound represented by the above general formula (I) and further causing a polybasic acid anhydride to act can be used.
Among these, it is an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I), or the epoxy addition compound and a polybasic acid anhydride. An alkali-developable compound, which is an unsaturated compound having a structure obtained by an esterification reaction, is preferred because the sensitivity of the polymerizable composition is increased, and a cured product obtained from the polymerizable composition is excellent in elastic recovery.
Moreover, it is preferable that the said alkali developable compound contains 0.2-1.0 equivalent of unsaturated groups.

  Since the dispersibility and heat resistance of the colorant (B) are good, the alkali developable compound (C) is represented by the epoxy compound represented by the general formula (I); represented by the general formula (I). An unsaturated compound having a structure [the following (e)] obtained by esterifying an epoxy compound and an unsaturated monobasic acid; or a structure obtained by further esterifying a polybasic acid anhydride to the unsaturated compound [the following ( f)] is desirable.

Wherein Y ¹ represents an unsaturated monobasic acid residue, Y ² represents a polybasic acid anhydride residue,
* In the formula represents a group represented by these formulas, and the * part represents a bond. )

  The hydrocarbon group having 1 to 20 carbon atoms represented by M in the general formula (I) is not particularly limited, but is preferably an alkylene group having 1 to 20 carbon atoms and 2 carbon atoms. Represents an alkenylene group having 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. Among these, since the sensitivity when used as the alkali-developable compound (C) is good, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, and 3 to 10 carbon atoms. A cycloalkylene group or an arylene group having 6 to 10 carbon atoms is more preferable.

  Examples of the alkylene group having 1 to 20 carbon atoms represented by M in the general formula (I) include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. Nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, icosylene group, and the like.

  Examples of the alkenylene group having 2 to 20 carbon atoms represented by M in the general formula (I) include 1,2-ethenediyl group (also referred to as ethenylene group or vinylene group), 2-butene-1,4. -Diyl group, 1,2-dimethyl-1,2-ethenediyl group and the like can be mentioned.

  Examples of the cycloalkylene group having 3 to 20 carbon atoms represented by M in the general formula (I) include a cyclopropylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group. .

  Examples of the arylene group having 6 to 20 carbon atoms represented by M in the general formula (I) include a phenylene group, a tolylene group, a xylylene group, a naphthylene group, a biphenylene group, a fluorene group, and an indane group.

  Examples of the halogen atom for substituting the hydrocarbon group having 1 to 20 carbon atoms represented by M in the general formula (I) include fluorine, chlorine, bromine and iodine.

The hydrocarbon group having 1 to 20 carbon atoms represented by M and R ^{1 to} R ³⁸ in the general formula (I) is not particularly limited, but is preferably an alkyl having 1 to 20 carbon atoms. Groups, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkylalkyl groups having 4 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and 7 to 7 carbon atoms 20 arylalkyl groups and the like are represented. Since sensitivity is good when used as an alkali developable compound (C), an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and the like are more preferable.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, amyl group, isoamyl group, t -Amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, t-octyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, An octadecyl group, an icosyl group, etc. are mentioned. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, amyl group, isoamyl group, t -Amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, t-octyl group, nonyl group, isononyl group, decyl group, isodecyl group and the like.

  Examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, 2-propenyl group, 3-butenyl group, 2-butenyl group, 4-pentenyl group, 3-pentenyl group, 2-hexenyl group, 3- Hexenyl group, 5-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 3-octenyl group, 3-nonenyl group, 4-decenyl group, 3-undecenyl group, 4-dodecenyl group, 3- Examples include a cyclohexenyl group, a 2,5-cyclohexadienyl-1-methyl group, and a 4,8,12-tetradecatrienylallyl group. Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, 2-propenyl group, 3-butenyl group, 2-butenyl group, 4-pentenyl group, 3-pentenyl group, 2-hexenyl group, 3-hexenyl group, Examples include a hexenyl group, a 5-hexenyl group, a 2-heptenyl group, a 3-heptenyl group, a 4-heptenyl group, a 3-octenyl group, a 3-nonenyl group, and a 4-decenyl group.

  The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, adamantyl group, decahydronaphthyl group, octahydropentalene group, bicyclo [1.1.1. ] A pentanyl group, a tetradecahydroanthracenyl group, etc. are mentioned. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, an adamantyl group, and a decahydronaphthyl group. An octahydropentalene group, a bicyclo [1.1.1] pentanyl group, and the like.

  The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with a cycloalkyl group. For example, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, cycloheptylmethyl group, cyclooctylmethyl group, cyclononylmethyl group, cyclodecylmethyl group, 2-cyclobutylethyl group, 2-cyclopentyl Ethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 2-cyclononylethyl group, 2-cyclodecylethyl group, 3-cyclobutylpropyl group, 3-cyclopentylpropyl group, 3-cyclohexylpropyl group, 3-cycloheptylpropyl group, 3-cyclooctylpropyl group, 3-cyclononylpropyl group, 3-cyclodecylpropyl group, 4-cyclobutylbutyl group, 4-cyclopentylbutyl group, 4-cyclohexyl Butyl , 4-cycloheptyl-butyl group, 4-cyclooctyl-butyl group, 4-cyclopropyl-nonyl-butyl group, 4-cyclopropyl-decyl-butyl group, 3-3-adamantyl propyl and deca hydro-naphthylpropyl group and the like. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a cyclononylmethyl group, 2-cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 2-cycloheptylethyl group, 2-cyclooctylethyl group, 3-cyclobutylpropyl group, 3-cyclopentylpropyl group, 3-cyclohexylpropyl Group, 3-cycloheptylpropyl group, 4-cyclobutylbutyl group, 4-cyclopentylbutyl group, 4-cyclohexylbutyl group and the like.

  Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, a phenanthrenyl group, the alkyl group, the alkenyl group, and a carboxyl group, Phenyl group, biphenylyl group, naphthyl group, anthryl group, etc. substituted with one or more halogen atoms, such as 4-chlorophenyl group, 4-carboxylphenyl group, 4-vinylphenyl group, 4-methylphenyl group, 2, Examples include 4,6-trimethylphenyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and the like, the alkyl group, the alkenyl group, a carboxyl group, a halogen atom, and the like. The substituted phenyl group, biphenylyl group, naphthyl group, anthryl group, etc., for example, 4-chlorophenyl group, 4-carboxylphenyl group, 4-vinylphenyl group, 4-methylphenyl group, 2,4,6-trimethylphenyl Groups and the like.

  The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which a hydrogen atom of the alkyl group is replaced with an aryl group. Examples include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenylethyl group and naphthylpropyl group. The arylalkyl group having 7 to 10 carbon atoms means a group having 7 to 10 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group. For example, a benzyl group, α-methylbenzyl Group, α, α-dimethylbenzyl group, phenylethyl group and the like.

The group having 2 to 20 carbon atoms containing the heterocyclic ring represented by R ^{10 to} R ³⁸ in the general formula (I) is not particularly limited, and examples thereof include a pyrrolyl group, a pyridyl group, and a pyridyl group. Ethyl group, pyrimidyl group, pyridazyl group, piperazyl group, piperidyl group, pyranyl group, pyranylethyl group, pyrazolyl group, triazyl group, triazylmethyl group, pyrrolidyl group, quinolyl group, isoquinolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, Furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, Thiomorpholinyl group 2-pyrrolidinon-1-yl group, 2-piperidone-1-yl group, 2,4-dioxyimidazolidin-3-yl group, 2,4-dioxyoxazolidin-3-yl group, and the like. Specific examples including substituents include groups having the following structures.

(In the above formulae, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. Represents a bond in the * part of the group represented by these formulas.)

Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include those having 1 to 6 carbon atoms among those exemplified as the alkyl group having 1 to 20 carbon atoms described above. it can.
Examples of the alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include those having 1 to 6 carbon atoms among those exemplified as the alkylene group having 1 to 20 carbon atoms. it can.

Examples of the halogen atom represented by R ^{1 to} R ⁸ and R ^{10 to} R ³⁸ include fluorine, chlorine, bromine, and iodine.

Examples of the unsaturated bond that may substitute the methylene group in the groups represented by R ^{1 to} R ⁸ and R ^{10 to} R ³⁸ include —C═C— and —C≡C—.

In the above general formula (I), R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ²² and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ³⁰ and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ³⁸ and R ³¹ , R ³¹ and R ³² , R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ^36, and R ³⁶ and R ³⁷ are combined Examples of the ring formed as described above include cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone ring, lactam ring, and other 5- to 7-membered rings, naphthalene and anthracene, etc. And the like.

The unsaturated monobasic acid is an acid having an unsaturated bond in the structure and having one hydrogen atom per molecule that can be ionized to form a hydrogen ion.
Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid and hydroxyethyl methacrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, and dicyclopentadiene / malate. Is mentioned.

  In addition, the polybasic acid anhydride that acts on the epoxy addition compound obtained by allowing the unsaturated monobasic acid to act on the epoxy compound represented by the general formula (I) is biphenyltetracarboxylic dianhydride. , Tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol Bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5 -(2,5-dioxotetrahydrofuryl) -3-methyl- Examples include 3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, and methyl hymic anhydride.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, the epoxy addition compound is preferably added such that the carboxyl group of the unsaturated monobasic acid is in a ratio of 0.1 to 1.0 with respect to one epoxy group of the epoxy compound. The ethylenically unsaturated compound is preferably such that the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 with respect to one hydroxyl group of the epoxy adduct. .
Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.

  In order to improve the developability of the polymerizable composition of the present invention by adjusting the acid value, the alkali developable compound (C) is used after adjusting the acid value by further reacting with a monofunctional or polyfunctional epoxy compound. You can also The alkali-developable compound (C) preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and the usage amount of the monofunctional or polyfunctional epoxy compound is selected so as to satisfy the acid value. Is preferred.

  Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the following epoxy compounds No. 1, no. 2 etc. are mentioned.

As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers, because a polymerizable composition with better characteristics can be obtained.
As the bisphenol type epoxy compound, an epoxy compound represented by the general formula (I) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds can also be used.

  As the alkali developable resin (C), a commercially available product can also be suitably used. Examples of the commercially available products include SPC1000, SPC-2000, SPC-3000, SPRR-1X, SPRR-2X, SPRR-3X, SPRR-5X, SPRR-6X, SPRR-7X, SPRR-8X, SPRR-9X, SPRR-10X, SPRR-11X, SPRR-12X, SPRR-13X, SPRR-14X, SPRR-15X, SPRR-16X, SPRR-17X, SPRR-18X, SPRR-19X, SPRR-20X, SPRR-21X (above, Showa Denko Co., Ltd.), JET2000, AGOR1060, AGOR3060, ORGA1060, ORGA2060 (above, manufactured by Osaka Organic Chemical Co., Ltd.), CCR-1171H (manufactured by Nippon Kayaku Co., Ltd.), and the like.

In the polymerizable composition of the present invention, the content of the alkali developable compound (C) is not particularly limited, but the ethylenically unsaturated compound (A), the colorant (B), the alkali developable compound ( Preferably it is 5-50 mass parts with respect to a total of 100 mass parts of C) and a polymerization initiator (D), More preferably, it is 10-40 mass parts, More preferably, it is 10-30 mass parts. . When content of an alkali developable compound (C) exists in said range, it is preferable from the alkali developability of polymeric composition being favorable.
For example, when forming a cured film having a thickness of 2 to 5 μm, the content of the alkali-developable compound (C) is not particularly limited, but the ethylenically unsaturated compound (A), the colorant (B ), Preferably 100 to 50 parts by weight, more preferably 10 to 40 parts by weight, and still more preferably 100 parts by weight in total of the alkali-developable compound (C) and the polymerization initiator (D). 10 to 30 parts by mass.

<Polymerization initiator (D)>
The polymerizable composition of the present invention contains a polymerization initiator (D).
As the polymerization initiator (D) used in the polymerizable composition of the present invention, a conventionally known radical polymerization initiator can be used.

  The radical polymerization initiator is a photo radical polymerization initiator and a thermal radical polymerization initiator. In the present invention, it is preferable to use a radical photopolymerization initiator because of its high reactivity.

  The radical photopolymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and a conventionally known compound can be used. For example, acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, oxime ester compounds, and the like can be exemplified as preferable examples.

  Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2. -Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzoy Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 1-one etc. are mentioned.

  Examples of the benzyl compound include benzyl.

  Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone and 4-benzoyl-4′-methyldiphenyl sulfide. .

  Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

  Examples of the oxime ester compound include a compound having a group represented by the general formula (II). Among the photoradical polymerization initiators, since the sensitivity is good, a compound having a group represented by the general formula (II) can be preferably used in the polymerizable composition of the present invention.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴³ in the general formula (II) is the same as the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{1 to} R ³⁸ , respectively. It is. The group having 2 to 20 carbon atoms containing a halogen atom and a heterocyclic ring represented by R ⁴¹ and R ⁴² is 2 to 20 carbon atoms containing a halogen atom and a heterocyclic ring represented by R ^{10 to} R ^38. It is the same as the group of

Which may replace the hydrogen atom of the group having 2 to 20 carbon atoms having a hydrocarbon group and heterocyclic ring having 1 to 20 carbon atoms represented by R ⁴¹ and R ⁴² in the general formula (II) , A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a group having 2 to 20 carbon atoms containing a heterocyclic ring are a halogen atom represented by R ^{10 to} R ³⁸ , and a carbon atom having 1 to 20 carbon atoms. This is the same as the group having 2 to 20 carbon atoms containing a hydrogen group and a heterocyclic ring. In addition, a carbon group having 1 to 20 carbon atoms that may be substituted for a hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ and R ⁴² and a group having 2 to 20 carbon atoms containing a heterocyclic ring. A methylene group in a group having 2 to 20 carbon atoms containing a hydrogen group and a heterocyclic ring is —O—, —CO—, —COO—, —OCO—, —NR ⁴³ —, provided that they are not adjacent to each other. , —NR ⁴³ CO—, —S—, —CS—, —SO ₂ —, —SCO—, —COS—, —OCS—, or CSO— may be substituted. is there.

  Among the compounds having the group represented by the above general formula (II), the compound represented by the following general formula (III) is preferably used in the polymerizable composition of the present invention because it has particularly high sensitivity.

^(Wherein, R ^{41, R 42} and m are the same as ^{R 41, R 42} and m, respectively, in formula (II),
R ⁵¹ and R ⁵² are each independently a hydrogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
X ¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁵³ R ⁵⁴ , CO, NR ⁵⁵ or PR ⁵⁶ ,
X ² represents absence, a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, CO,
R ^{53 to} R ⁵⁶ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and represented by R ^{53 to} R ^56. The hydrogen atom in the group may be substituted with a halogen atom, a nitro group, a cyan group, a hydroxyl group, a carboxyl group or a heterocyclic group,
The methylene group in the group represented by R ^{51 to} R ⁵⁶ may be substituted with —O— under the condition that oxygen is not adjacent.
R ^{51 to} R ⁵⁶ may each independently form a ring together with one of the adjacent benzene rings,
g represents a number from 0 to 4,
h represents the number of 0-3. )

In the above general formula (III), the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms and the heterocyclic ring represented by R ⁵¹ and R ⁵² The group having 2 to 20 carbon atoms containing is the same as R ^{10 to} R ³⁸ .

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^{53 to} R ⁵⁶ in the general formula (III) is a hydrocarbon group having 1 to 20 carbon atoms represented by R ^{1 to} R ³⁸ , respectively. It is the same.

The group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R ^{53 to} R ⁵⁶ in the general formula (III) is 2 carbon atoms containing a heterocyclic ring represented by R ^{10 to} R ^38. It is the same as the group of ~ 20.

The hydrocarbon group having 1 to 20 carbon atoms represented by X ² in the general formula (III) is the same as the hydrocarbon group having 1 to 20 carbon atoms represented by M.

When g is a number from 2 to 4, R ⁵¹ may be the same or different. When h is a number from 2 to 3, R ⁵² may be the same or different. In this invention, it is preferable that g is a number of 1-5. When g is a number from 1 to 5, at least one of R ⁵¹ is preferably a nitro group.

  Preferred examples of the radical photopolymerization initiator include compound No. shown below. D1-No. D15 is mentioned. Examples of the compound represented by the general formula (III) include compound No. shown below. D1 and No. D3-No. D15 is mentioned. However, the radical photopolymerization initiator used in the present invention is not limited by the following compounds.

X ² is to be absent in the general formula (III), 2 benzene rings means that are connected via only X ^1.
In the present invention, when X ¹ is a sulfur atom and X ² is absent, the compound represented by the general formula (III) is the compound No. 1 above. It becomes an oxime ester compound having a diphenyl sulfide skeleton represented by D1 to 8, and is preferable in that a polymerizable composition having good sensitivity can be obtained.

In the present invention, when X ¹ is NR ⁵⁵ and X ² is a direct bond, the compound represented by the general formula (III) is the compound No. 1 above. It becomes an oxime ester type | system | group compound which has a carbazole skeleton represented by D9-15, and is especially preferable at the point from which the polymerizable composition with a favorable sensitivity is obtained.

  Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr-1). -Yl)] Titanocene compounds such as titanium.

  Commercially available radical initiators include Adekaoptomer N-1414, N-1717, N-1919, Adeka Arcles NCI-831, NCI-930 (above, manufactured by ADEKA); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OX 01, IRGACURE OXE 02, IRGACURE 784 (above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (above, manufactured by Troly);

  The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used. For example, azo compounds, peroxides and persulfates are preferable. It can be illustrated as a thing.

  Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'- And azobis (1-acetoxy-1-phenylethane).

  Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate.

  Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

  Among the polymerization initiators, a polymerization initiator having a nitro group is preferable because a polymerizable composition having high sensitivity can be obtained.

  Among the polymerization initiators, a polymerization initiator having a hydroxyl group is particularly preferable because it can provide a display device having low liquid crystal contamination and excellent electrical characteristics.

  The said polymerization initiator (D) can mix and use 1 type, or 2 or more types illustrated so far.

In the polymerizable composition of the present invention, the content of the polymerization initiator (D) is not particularly limited, but the ethylenically unsaturated compound (A), the colorant (B), the alkali developable compound ( Preferably, it is 0.3 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to the total 100 parts by mass of C) and the polymerization initiator (D). More preferably, it is 3-8 mass parts. When the content of the polymerization initiator (D) is within the above range, it is preferable because a polymerizable composition having good curability and excellent storage stability without precipitation of the polymerization initiator is obtained.
For example, when forming a cured film having a thickness of 2 to 5 μm, the content of the polymerization initiator (D) is not particularly limited, but the ethylenically unsaturated compound (A) and the colorant (B) The total amount of the alkali-developable compound (C) and the polymerization initiator (D) is preferably 0.3 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and more. Preferably it is 3-8 mass parts.

  The polymerizable composition of the present invention may further contain a solvent. As the solvent, the above-mentioned components [ethylenically unsaturated compound (A), colorant (B), alkali developable compound (C), polymerization initiator (D) and the like] are usually dissolved or dissolved as necessary. A dispersible solvent can be used. For example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-di Ether solvents such as ethoxyethane and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, iso- or n-butanol And alcohol solvents such as amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl Ether ester solvents such as ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as D-limonene and pinene; mineral spirit, Swazol # 310 (above, manufactured by Cosmo Matsuyama Oil); and Solvesso # 100 ( Paraffinic solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbons such as chlorobenzene Solvents: carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. These solvents can be used as one or two or more mixed solvents. Among these, ketones and ether ester solvents, etc., particularly PGMEA and cyclohexanone are preferable because the compatibility of the resist and the polymerization initiator is good in the polymerizable composition.

In the polymerizable composition of the present invention, the content of the solvent is not particularly limited, but is preferably 30 to 95% by mass, more preferably 50 to 95% in the total amount of the polymerizable composition. % By mass.
When the content of the solvent is in the above range, handling properties (viscosity and wettability of the polymerizable composition), reduction of unevenness during drying, and liquid stability (without precipitation or sedimentation of components contained in the composition) It is preferable because the excellent polymerizable composition and the thickness of the cured product can be appropriately controlled.

  In the polymerizable composition of the present invention, if necessary, the ethylenically unsaturated compound (A) and the ethylenically unsaturated compound not belonging to the alkali developable compound (C) (hereinafter also referred to as ethylenically unsaturated compound). Description), epoxy compound, alkali developability imparting agent, dispersant, latent additive, organic polymer, inorganic compound, coupling agent, chain transfer agent, sensitizer, surfactant and melamine compound, p-anisole, Thermal polymerization inhibitors such as hydroquinone, pyrocatechol, t-butylcatechol and phenothiazine; plasticizers; adhesion promoters; fillers; antifoaming agents; leveling agents; surface conditioners; antioxidants; A conventional additive such as a coagulation inhibitor, a catalyst, an effect promoter, a crosslinking agent, a thickener, and the like can be added.

As the ethylenically unsaturated compound, a compound having an ethylenically unsaturated bond can be used. For example, unsaturated compounds such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, etc. Aliphatic hydrocarbons; glycidyl (meth) acrylate; 1-No. 4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Noxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol te Unsaturated monobasic acids such as la (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-maleic anhydride Insic acid adducts, acid anhydrides of unsaturated polybasic acids such as dodecenyl succinic anhydride, methyl hymic anhydride; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, cyanide Unsaturated nitriles such as allyl; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylphenol, vinylbenzyl methyl ether, vinylbenzyl Unsaturated aromatic compounds such as glycidyl ether; Unsaturated ketones such as methyl vinyl ketone; Unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; Vinyl alcohols such as allyl alcohol and crotyl alcohol Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; indene, 1-methylindene, etc. Indenes; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Monomers at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane Macromonomers having a (meth) acryloyl group; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl Examples include ruimidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, a vinyl urethane compound of a polyisocyanate compound, and a vinyl epoxy compound of a polyepoxy compound.
An ethylenically unsaturated compound can be used individually or in mixture of 2 or more types.

  A commercial item can also be used as said ethylenically unsaturated compound, for example, Kayrad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (above, Nippon Kayaku make) ); Aronix M-215, M-350 (above, manufactured by Toagosei Co., Ltd.); NK ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (above, Shin-Nakamura Chemical Co., Ltd.).

  Examples of the epoxy compound include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, phenyl-2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, Glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, 4-phenylphenol glycidyl ether, cresyl glycidyl ether, dibromocresyl ether Glycidyl ether, decyl glycidyl ether, methoxy polyethylene glycol Monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetrakis (glycidyloxyphenyl) ethane and pentaerythritol tetraglycidyl ether; glycidyl acetate, glycidyl stearate Glycidyl esters such as Rate; 2- (3,4-epoxycyclohexyl-5,5-spiro 3,4-epoxy) cyclohexane-metadioxane, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxy) Cyclohexyl) propane, ethylenebis (3,4-epoxycyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy -1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl 6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3- Methylsiku Hexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4-epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadiene diepoxide, 3,4-epoxy-6-methylcyclohexylcarboxylate, α-pinene oxide, styrene oxide, cyclohexene oxide and cyclopentene oxide Type compounds and N-glycidylphthalimide.

  An epoxidized polyolefin can also be used as the epoxy compound. The epoxidized polyolefin is a polyolefin having an epoxy group introduced by modifying the polyolefin with an epoxy group-containing monomer. It can be produced by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, another monomer by either a copolymerization method or a graft method. . Ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and other monomers may be polymerized alone or in combination with other monomers. Moreover, the double bond of the nonconjugated polybutadiene which has a hydroxyl group at the terminal can also be obtained by epoxidizing by a peracetic acid method, and what has a hydroxyl group in a molecule | numerator may be used. It is also possible to urethanize a hydroxyl group with an isocyanate and introduce an epoxy group by reacting with a primary hydroxyl group-containing epoxy compound.

  Examples of the ethylene or α-olefin having 3 to 20 carbon atoms include ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, and 2,3-dimethyl-1,3. -Butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and the like.

  Examples of the epoxy group-containing monomer include glycidyl ester of α, β-unsaturated acid, vinylbenzyl glycidyl ether, and allyl glycidyl ether. Specific examples of the glycidyl ester of α, β-unsaturated acid include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate, and glycidyl methacrylate is particularly preferable.

Commercially available products can also be used as the epoxy compound.
Suitable commercial products include, for example, Epolite 40E, 1500NP, 1600, 80MF, 4000 and 3002 (manufactured by Kyoeisha Chemical Co., Ltd.); Adekaglycilol ED-503, ED-503D, ED-503G, ED-523T, ED- 513, ED-501, ED-502, ED-509, ED-518, ED-529, Adeka Resin EP-4000, EP-4005, EP-4080 and EP-4085 (above, manufactured by ADEKA); Denacol EX-201, EX-203, EX-211, EX-212, EX-221, EX-251, EX-252, EX-711, EX-721, Denacol EX-111, EX-121, EX-141, EX-142, EX -145, EX-146, EX-147, EX-171, EX-192 and E -731 (manufactured by Nagase ChemteX); EHPE-3150, Celoxide 2021P, 2081, 2000 and 3000 (manufactured by Daicel); Epiol M, EH, L-41, SK, SB, TB and OH (many, day Epolite M-1230 and 100MF (above, manufactured by Kyoeisha Chemical Co., Ltd.); Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211 and OXT-212 (above, Toagosei Co., Ltd.) Etanacol OXBP and OXTP (above Ube Industries); 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 4-hydroxybutyl vinyl ether (above Maruzen Petrochemical); Denacol EX-121, EX-141, EX- 142, EX-14 , EX-146, EX-147, EX-201, EX-203, EX-711, EX-721, on-coat EX-1020, EX-1030, EX-1040, EX-1050, EX-1051, EX-1010 EX-1011 and 1012 (above, manufactured by Nagase ChemteX); Ogsol PG-100, EG-200, EG-210, and EG-250 (above, manufactured by Osaka Gas Chemical); HP4032, HP4032D, and HP4700 (above, manufactured by DIC) ESN-475V (manufactured by Toto Kasei); Marproof G-0105SA and G-0130SP (above, manufactured by NOF Corporation); Epicron N-665 and HP-7200 (above, manufactured by DIC); EOCN-1020, EOCN-102S , EOCN-103S, EOCN-104S, XD-1000, N -3000, EPPN-501H, EPPN-501HY, EPPN-502H and NC-7000L (manufactured by Nippon Kayaku Co., Ltd.) and the like.

  The alkali developability-imparting agent is a compound that does not have radical polymerizability and imparts alkali developability. As such a compound, any compound that has an acid value and is soluble in an aqueous alkali solution can be used. Although not particularly limited, a typical example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”). The novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used, and among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-kis Renoru, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferable. These phenols are used alone or in combination of two or more.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde and p N-butylbenzaldehyde and the like are used, and among these compounds, formaldehyde Rudehydr, acetaldehyde, benzaldehyde and the like are preferable. These aldehydes may be used alone or in combination of two or more. Aldehydes are preferably used in a proportion of 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenol.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid. The amount of these acid catalysts used is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol per mol of phenols. In the condensation reaction, water is usually used as a reaction medium. However, if the phenols used in the condensation reaction do not dissolve in an aqueous solution of aldehydes and become heterogeneous from the beginning of the reaction, the reaction medium is hydrophilic. A solvent can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, or cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. Although the reaction temperature of a condensation reaction can be suitably adjusted according to the reactivity of a reaction raw material, it is 10-200 degreeC normally, Preferably it is 70-150 degreeC. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally raised to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure. Next, the melted novolac resin is collected on a steel belt or the like.
After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane and n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.

  Examples other than the novolak resin include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, and polyvinylhydroxybenzoate.

  The dispersing agent may be anything as long as it can disperse and stabilize the colorant (B), and a commercially available dispersing agent, for example, BYK series, BYK series, etc. can be used, polyester having a basic functional group, A polymer dispersant comprising a polyether or polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / g Those are preferably used.

The latent additive is inactive at room temperature, in the light exposure step and in the pre-bake step, and is protected at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. Is activated by desorption. Examples of the effects obtained by activation include oxidation prevention, ultraviolet absorption, antifouling property, recoatability and adhesion.
As the latent additive, those described in the pamphlet of WO2014 / 021023 can be preferably used.

  A commercial item can be used as said latent additive, for example, Adeka Arcles GPA-5001 etc. are mentioned.

Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, etc. are mentioned. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, epoxy resin are used. Masui.
By using the organic polymer together with the alkali developable compound (C), the properties of the cured product can be improved.
When using an organic polymer, the usage-amount is preferably 10-500 mass parts with respect to 100 mass parts of said alkali developable compounds (C).

  The inorganic compound can be contained. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver and copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable.

By containing an inorganic compound in the polymerizable composition of the present invention, it can be used as a photosensitive paste composition. The photosensitive paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
These inorganic compounds are also suitably used as, for example, fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, and ink repellent agents.

  In the polymerizable composition of the present invention, when an inorganic compound is added, the content of the inorganic compound is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the alkali developable compound (C). Preferably it is 0.5-20 mass parts, and these inorganic compounds can use 1 type (s) or 2 or more types.

Examples of the coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, Such as 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane ( T) Acrylic acid ester functional alkoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3 , 4-epoxycyclohexyl) propyltrimethoxysilane and other epoxy functional alkoxysilanes, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Aminofunctional alkoxysilanes such as trimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate functional alkoxysilanes such as 3-isocyanatopropyltriethoxysilane, 3-ureidopropyl Ureido functional alkoxysilanes such as trialkoxysilane, isocyanurate functional alkoxysilanes such as tris- (trimethoxysilylpropyl) isocyanurate, titanium alkoxides such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium dioctyloxy Titanium chelates such as bis (octylene glycolate) and titanium diisopropoxy bis (ethylacetoacetate), zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, zirconium tributoxymonostearate, etc. Zirconium acylates and isocyanate silanes such as methyl triisocyanate silane can be used.
Addition of a coupling agent is preferable because it improves the adhesion between the cured product and the substrate.

  A commercial item can be used as said coupling agent, for example, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM- 502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-903, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007, KBM-04, KBE-04, KBM-13, KBE-13, KBE-22, KBE- 103, HMDS-3, KBM-3063, KBM-3103C, KPN 3504 and KF-99 (manufactured by Shin-Etsu Silicone), and the like.

  As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate); iodo such as disulfide compounds obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropanesulfonic acid Alkyl compound; trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1, -Dimethyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropioate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, the following compound No. C1, Showa Denko Karenz PE1 and NR1 and the like.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, amphoteric surfactants and silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

  In the polymerizable composition of the present invention, other than the ethylenically unsaturated compound (A), the colorant (B), the alkali developable compound (C), the polymerization initiator (D), the ethylenically unsaturated compound, the solvent and the inorganic compound. The content of the optional component is appropriately selected according to the purpose of use, and is not particularly limited as long as the effects of the present invention are not impaired. Preferably, the ethylenically unsaturated compound (A), the colorant (B ), The alkali-developable compound (C), the polymerization initiator (D), and the ethylenically unsaturated compound in a total of 100 parts by mass, a total of 20 parts by mass or less.

  The photosensitive composition for BM of the present invention contains, as essential components, an ethylenically unsaturated compound (A), a colorant (B), an alkali developable compound (C) and a polymerization initiator (D), and is photosensitive. And a composition that has alkali developability and is particularly suitable for forming BM.

  The photosensitive composition for BCS of the present invention contains an ethylenically unsaturated compound (A), a colorant (B), an alkali developable compound (C) and a polymerization initiator (D) as essential components, and is photosensitive. And a composition that has alkali developability and is particularly suitable for forming BCS.

  A method for producing a cured product by light irradiation or heating using the polymerizable composition, the photosensitive composition for BM, or the photosensitive composition for BCS of the present invention will be described in detail below.

  The polymerizable composition of the present invention and the photosensitive composition for BCS are soda glass, quartz glass, and semiconductor by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing and dipping. The present invention can be applied on a support substrate such as a substrate, metal, paper, or plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  Further, as a light source for energy rays used for curing the polymerizable composition of the present invention and the photosensitive composition for BCS, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, mercury vapor Electromagnetic wave energy or electron beam having a wavelength of 2000 angstrom to 7000 angstrom obtained from arc lamp, xenon arc lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc. Although high energy rays such as X-rays and radiation can be used, preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp and the like that emit light having a wavelength of 300 to 450 nm are exemplified. .

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser. In addition, lasers that emit light in the visible to infrared region such as various semiconductor lasers and YAG lasers are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

  Moreover, the polymerizable composition and photosensitive composition for BCS of the present invention can be cured by heating. Examples of the curing condition include, but are not limited to, 230 ° C. × 1 hour.

The cured product of the present invention is particularly useful as BCS. BCS is (1) a step of forming a coating film of the photosensitive composition for BCS of the present invention on a substrate, (2) a step of irradiating the coating film with radiation through a mask having a predetermined pattern shape, ( It is preferably formed by 3) a baking step after exposure, (4) a step of developing the coating after exposure, and (5) a step of heating the coating after development.
As the mask, a multi-tone mask such as a halftone mask or a gray scale mask can be used.

  The polymerizable composition, the photosensitive composition for BM or the photosensitive composition for BCS, and the cured product of the present invention are curable paint, varnish, curable adhesive, printed circuit board, display display device (color television, PC monitor, Color filters for color display liquid crystal display panels such as portable information terminals and digital cameras, color filters for various display applications, color filters for CCD image sensors, touch panels, electroluminescent display devices, plasma display panels, organic EL black barriers ), Powder coatings, printing inks, printing plates, adhesives, gel coats, photoresists for electronics, electroplating resists, etching resists, solder resists, insulating films, black matrices, and to form structures in LCD manufacturing processes For encapsulating resist, electrical and electronic components Manufacture 3D objects by composition, solder resist, magnetic recording material, micro mechanical parts, waveguide, optical switch, plating mask, etching mask, color test system, glass fiber cable coating, stencil for screen printing, stereolithography Material, holographic recording material, image recording material, fine electronic circuit, decoloring material, decoloring material for image recording material, decoloring material for image recording material using microcapsules, photoresist material for printed wiring board It can be used for various applications such as photoresist materials for UV and visible laser direct image systems, photoresist materials used for dielectric layer formation in the sequential lamination of printed circuit boards, and protective films. There is no limit, but among the above applications, especially for display devices, Out it is used to apply.

  The display device of the present invention has the same configuration as a conventionally known display device except that it includes the cured product of the present invention (particularly BM and BCS), but the BCS is preferably provided between cells.

  When the polymerizable composition of the present invention is used as a black partition wall of an organic EL, an alkali-developable compound having a weight average molecular weight of 5000 or more is used because the pattern shape is vertical, development adhesion is improved, and heat resistance is improved. More preferably, an alkali developable compound having a weight average molecular weight of 7000 to 15000 is preferably used. Further, the alkali-developable compound is obtained by an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I) and a polybasic acid anhydride. Particularly preferred is an unsaturated compound having the structure shown below.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In addition, the numerical value of the raw material of the polymeric composition in Table 1 and 2 is a mass part.

[Production Example 1] Carbon Black No. Production of 1 150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 3000 ml of a deionized aqueous solution of sodium peroxodisulfate (concentration 2.0 N) were mixed and stirred at 60 ° C. for 10 hours. The resulting slurry was neutralized with sodium hydroxide and treated by diafiltration, and the resulting solid was dried at 75 ° C. overnight to obtain carbon black No. 4 as a black powder. 1 was obtained.

[Production Example 2] Carbon Black Dispersion No. Production of carbon black No. 1 20 g, polymerizable compound No. 1 1g 2g, DISPERBYK-161 (manufactured by BYK Chemie, dispersant) 100g, PGMEA 100g, weighed together, processed by bead mill, carbon black dispersion No. 1 (solid content 20%) was obtained.

[Production Example 3] Carbon Black Dispersion No. Preparation of 2 20 g of MA100 (manufactured by Mitsubishi Chemical Corp.) as carbon black, 12.5 g of BYK16 1 (manufactured by BYK Corporation) as a dispersant (solid content concentration 40% by mass), 92.5 g of PGMEA as a solvent, and bead mill The carbon black dispersion No. 2 (20% solids) was prepared.

[Production Example 4] Preparation of alkali-developable compound PGMEA solution C-1 184 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 58 g of acrylic acid, 2,6-di-tert -0.26 g of butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide and 105 g of PGMEA were charged and stirred at 120 ° C for 16 hours. The reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and after stirring at 120 ° C. for 4 hours, at 100 ° C. for 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C. for 11 hours, 128 g of PGMEA was added, The alkali-developable compound C-1 was obtained as (solid content 45 mass%) (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mgKOH / g). Content of the alkali developable compound C-1 in the alkali developable compound PGMEA solution was 45 mass%.

[Production Example 5] Production of alkali-developable compound PGMEA solution C-2 9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p -Cresole 0.273g, tetrabutylammonium chloride 0.585g, and PGMEA 65.9g were prepared, and stirred at 90 ° C for 1 hour, 100 ° C for 1 hour, 110 ° C for 1 hour, and 120 ° C for 14 hours. The mixture was cooled to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Furthermore, 9,9-bis (4-glycidyloxyphenyl) fluorene 30.0 g, 2,6-di-t-butyl-p-cresol 0.269 g, and PGMEA 1.50 g were added, and 90 minutes at 90 ° C. After stirring at 120 ° C. for 4 hours, 122.2 g of PGMEA was added to obtain the target alkali-developable compound C-2 as a PGMEA solution (solid content: 45%) (Mw = 4190, Mn = 2170, acid value ( Solid content) 52 mg · KOH / g). Content of the alkali developable compound C-2 in the alkali developable compound PGMEA solution was 45 mass%.

[Examples 1 to 7 and Comparative Examples 1 and 2] Preparation of polymerizable composition
Each component was mixed according to the mixing | blending of [Table 1] and [Table 2], and polymeric composition (Examples 1-7 and Comparative Examples 1-2) was obtained. In addition, the numerical value of the mixing | blending in a table | surface represents a mass part.
Moreover, the code | symbol of each component in a table | surface represents the following component.
A-1 Biscote 1000
(Dendrick acrylate, 10-15 functional, weight average molecular weight 1840; manufactured by Osaka Organic Chemical Co., Ltd.)
A-2 A-HBR-5
(Dendrick acrylate, 10-15 functional, weight average molecular weight 1830; manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-3 A-PG5027E
(Polyglycerin acrylate, 9 functional, weight average molecular weight 2200; manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-4 A-PG5054E
(Polyglyceryl acrylate, 9 functional, weight average molecular weight 3400; manufactured by Shin-Nakamura Chemical Co., Ltd.)
A'-5 M450
(Pentaerythritol tetraacrylate, tetrafunctional, manufactured by Toa Gosei Co., Ltd.)
A'-6 DPHA
(Dipentaerythritol hexaacrylate, hexafunctional, manufactured by Nippon Kayaku Co., Ltd.)
B-1 Carbon Black Dispersion No. 1 (Oxidized CB black)
B-2 Carbon Black Dispersion No. 2 (CB black without acid value treatment) C-1 Alkali developable compound PGMEA solution C-1
C-2 Alkali developable compound PGMEA solution C-2
D-1 Compound No. D9
D-2 Compound No. D10
E-1 PGMEA
F-1 KBM-403 (alkoxysilane coupling agent; manufactured by Shin-Etsu Chemical Co., Ltd.)

[Evaluation of cured product obtained from polymerizable composition]
The sensitivity of the polymerizable compositions of Examples 1 to 7 and Comparative Examples 1 and 2 and the cured products obtained were evaluated for light shielding properties (OD value) and seal strength according to the following procedures. The results are shown in [Table 1] and [Table 2].

(sensitivity)
The polymerizable composition or the comparative polymerizable composition was spin-coated (300 rpm, 7 seconds) on the substrate and dried, and then pre-baked at 100 ° C. for 100 seconds. After exposure at 40 mJ / cm ² (measured with a 365 nm sensor) using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, the film was developed by immersing in a 0.04% KOH aqueous solution at 23 ° C. for 30 seconds and thoroughly washed with water. After washing with water and drying, baking was performed at 230 ° C. for 30 minutes. The pattern was fixed as A, and the pattern was not fixed as B.

(OD value)
The polymerizable composition and the comparative polymerizable composition were spin-coated (300 rpm, 7 seconds) and dried on a glass substrate, and then prebaked at 90 ° C. for 100 seconds. After exposure using an ultrahigh pressure mercury lamp as a light source, the cured product was prepared by baking at 230 ° C. for 30 minutes. The OD value of the obtained film was measured using a Macbeth transmission densitometer, and the OD value per film thickness was calculated by dividing the OD value by the film thickness after post-baking.
A cured product having an OD value of 3.0 or more per film thickness can be used as BM, and a cured product having an OD value of 3.5 or more per film thickness can be preferably used as BM. A cured product having an OD value of 4.0 or more can be particularly preferably used as BM. A cured product having an OD value per film thickness of less than 1.0 cannot be used as a BM.

(Seal strength)
Apply a thermosetting adhesive (sealing agent: XN-21S manufactured by Mitsui Chemicals) in an area of 6 mm x 3.5 mm to a glass substrate, create a substrate A, and then apply the polymerizable composition to another glass substrate, A glass substrate B having a resin black matrix layer prepared by thermosetting at 230 ° C. for 1 hour was prepared. The thermosetting adhesive-coated surface of the obtained glass substrate A and the resin black matrix layer forming surface of the glass substrate B were bonded together and heated at 150 ° C. for 2 hours to adhere the glass substrate A and the glass substrate B.
This sample was subjected to a three-point support bending test using Shimadzu EZ-Graph, and the seal strength was measured.

  From [Table 1] and [Table 2], the cured product obtained from the polymerizable composition, the photosensitive composition for BM, or the photosensitive composition for BCS of the present invention is sensitive, light-shielding (OD value), and seal strength. Therefore, it is useful as BM and BCS.

Claims (9)

  Excluding the ethylenically unsaturated compound (A), the colorant (B), and the ethylenically unsaturated compound (A) having at least one structure selected from the group consisting of a dendrimer structure, a hyperbranched structure and a polyglycerin derived structure A polymerizable composition comprising an alkali developable compound (C) and a polymerization initiator (D).   The polymerizable composition according to claim 1, wherein the colorant (B) is a black pigment. The alkali-developable compound (C) is subjected to an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (I) and a polybasic acid anhydride. The polymerizable composition according to claim 1, which is an unsaturated compound having a structure to be obtained.
(In the formula, M represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —SO ₂ —, —SS—, —SO—, —CO—, —OCO— or Represents a substituent selected from the group represented by formula (a), (b), (c) or (d);
The hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms represented by M may be substituted with a halogen atom,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ (hereinafter also referred to as R ^{1 to} R ⁸ ) are each independently a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. Represents a hydrocarbon group or a halogen atom,
The methylene group in the group represented by R ^{1 to} R ⁸ may be substituted with an unsaturated bond, —O— or —S—,
n is a number from 0 to 10,
When n ≧ 1, a plurality of R ^{1 to} R ⁸ and M may be the same or different. )
(Wherein R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms,
R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ (hereinafter also referred to as R ^{10 to} R ³⁸ ), respectively, Independently, it represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocyclic ring, or a halogen atom,
The methylene group in the group represented by R ^{10 to} R ³⁸ may be substituted with an unsaturated bond, —O— or —S—,
R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ²² and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ³⁰ and R ²³ , R ²³ And R ²⁴ , R ²⁴ and R ²⁵ , R ³⁸ and R ³¹ , R ³¹ and R ³² , R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ^36, and R ³⁶ and R ³⁷ are combined to form a ring. May form
* In the groups represented by the above formulas (a), (b), (c) and (d) represents a bond. ) The polymerizable composition according to any one of claims 1 to 3, wherein the polymerization initiator (D) is a polymerization initiator having a group represented by the following general formula (II).
(In the formula, R ⁴¹ and R ⁴² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring. Represents
Hydrogen atom of the group having 2 to 20 carbon atoms containing heterocyclic ring represented by a hydrocarbon group or ^{R 41} and ^{R 42} having 1 to 20 carbon atoms represented by R ⁴¹ and ^{R 42} is a halogen atom, a nitro Group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group, hydrocarbon group having 1 to 20 carbon atoms or heterocyclic ring may be substituted with groups having 2 to 20 carbon ^atoms, containing hetero ring represented by a hydrocarbon group or ^{R 41} and ^{R 42} having 1 to 20 carbon atoms represented by ^{R 41} and ^{R 42} a methylene group in the group having a carbon number of 2~20 -O -, - CO -, - COO -, - OCO -, - NR 43 -, - NR 43 CO -, - S -, - CS -, - SO ₂ -, - SC -, - COS -, - OCS- or CSO- in some cases be substituted,
R ⁴³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
m represents 0 or 1;
* In the formula represents a bond. )   The photosensitive composition for black matrices containing the polymeric composition as described in any one of Claims 1-4.   The photosensitive composition for black column spacers containing the polymeric composition as described in any one of Claims 1-4.   The polymerizable composition according to any one of claims 1 to 4, the photosensitive composition for a black matrix according to claim 5, or the photosensitive composition for a black column spacer according to claim 6, or A method for producing a cured product, which is cured by heating.   A polymerizable composition according to any one of claims 1 to 4, a photosensitive composition for a black column spacer according to claim 5, or a cured product of the photosensitive composition for a black column spacer according to claim 6. .   The display apparatus containing the hardened | cured material of Claim 8.