KR102390795B1 - Composition, cured film, and organic el·liquid crystal display device - Google Patents

Abstract

[식 (A1) 중, R¹은 각각 독립적으로 수소 원자 또는 할로겐 원자이고, R²는 치환기를 가져도 좋은 탄화수소기이지만, 단 환상 에테르기를 포함하는 기는 아니다.](Project) The composition which can form the cured film with little generation|occurrence|production of an outgas is provided.
(Solution) Resin having a structural unit (A1) represented by the formula (A1) and a structural unit (A2) containing a cyclic ether group, wherein the content of the structural unit (A1) is 30% by mass or more in 100% by mass of all the structural units A composition containing (A), a reaction initiator (B), and a polyfunctional polymerizable compound (C).

[In formula (A1), R ¹ is each independently a hydrogen atom or a halogen atom, and R ² is a hydrocarbon group which may have a substituent, provided that it is not a group containing a cyclic ether group.]

Description

A composition, a cured film, and organic electroluminescent liquid crystal display element TECHNICAL FIELD

The present invention relates to a composition, a cured film, and an organic EL/liquid crystal display element.

Display elements, such as a liquid crystal display element and an organic electroluminescent (EL) display element, generally have cured films, such as a planarization film, an interlayer insulating film, a partition, a spacer, a protective film, and the adhesive bond layer for color filters (patent document 1, see 2). However, it is known that the reliability of a display element deteriorates with the outgas resulting from a cured film.

Japanese Laid-Open Patent Publication No. 2002-275432 Japanese Laid-Open Patent Publication No. 2015-140435

As a material which forms a cured film, the composition containing resin, a reaction initiator, and a polymeric compound is known. According to the examination of the present inventors, it was found that the resin mainly composed of structural units derived from methacrylic acid esters is easily depolymerized by heat, and the depolymerized component tends to become outgas. The subject of this invention is providing the composition which can form the cured film with little generation|occurrence|production of an outgas.

MEANS TO SOLVE THE PROBLEM The present inventors examined in order to solve the said subject. As a result, it was discovered that the said subject could be solved by the composition which has the following structures, and this invention was completed. The present invention relates to, for example, the following [1] to [9].

[1] a resin having a structural unit (A1) represented by the formula (A1) and a structural unit (A2) containing a cyclic ether group, wherein the content of the structural unit (A1) is 30% by mass or more in 100% by mass of all structural units ( A composition comprising A), a reaction initiator (B), and a polyfunctional polymerizable compound (C).

[In formula (A1), R ¹ is each independently a hydrogen atom or a halogen atom, and R ² is a hydrocarbon group which may have a substituent, provided that it is not a group containing a cyclic ether group.]

[2] The composition of the above [1], wherein R ² in the formula (A1) is a cyclic hydrocarbon group which may have a substituent.

[3] The composition of the above [2], wherein the cyclic hydrocarbon group is at least one alicyclic hydrocarbon group selected from a monocyclic hydrocarbon group, a crosslinked hydrocarbon group and a spiro hydrocarbon group.

[4] The composition according to any one of [1] to [3], wherein the cyclic ether group in the structural unit (A2) is at least one selected from an epoxy ring and an oxetane ring.

[5] The composition according to any one of [1] to [4], wherein the resin (A) is an alkali-soluble resin.

[6] A cured film formed from the composition according to any one of [1] to [5].

[7] The cured film according to the above [6], which is for a display element or a lighting element.

[8] An organic EL device having the cured film according to [6] above.

[9] A liquid crystal display element having the cured film according to [6] above.

ADVANTAGE OF THE INVENTION According to this invention, the composition which can form the cured film with little generation|occurrence|production of an outgas can be provided.

1 : is sectional drawing of one Embodiment of an organic electroluminescent element.
2 : is sectional drawing of one Embodiment of an organic electroluminescent element.
3 : is sectional drawing of one Embodiment of a liquid crystal display element.

(Form for implementing the invention)

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated in detail including suitable aspect. Unless otherwise specified, each component illustrated in this specification may be used individually by 1 type, respectively, and may use 2 or more types together.

[Composition]

The composition of this invention contains resin (A) mentioned later, a reaction initiator (B), and a polyfunctionally polymerizable compound (C). The said composition can contain the at least 1 sort(s) chosen from an adhesion auxiliary|assistant (D), a polymerization inhibitor (E), and another component further. Each of the above components is also described as component (A), component (B), component (C), component (D), and component (E), respectively.

<Resin (A)>

Resin (A) has a structural unit (A1) represented by Formula (A1), and a structural unit (A2) containing a cyclic ether group. Component (A) WHEREIN: Content of a structural unit (A1) is 30 mass % or more in 100 mass % of all structural units.

In the formula (A1), R ¹ each independently represents a hydrogen atom or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, preferably a hydrogen atom. R ² is a hydrocarbon group which may have a substituent, provided that it is not a group containing a cyclic ether group.

In the structural unit (A1), since the group on the carbon atom bonded to the carbonyl group shown in the formula (A1) is a hydrogen atom, depolymerization is difficult to proceed in the component (A), so the generation of outgas from the cured film is reduced. can be suppressed

The upper limit of carbon number of ^R2 becomes like this. Preferably it is 30, More preferably, it is 20, More preferably, it is 16, More preferably, it is 12, Especially preferably, it is 10. If it is such an aspect, the resolution and developability of a composition can be improved.

Examples of the hydrocarbon group for R ² include cyclic hydrocarbon groups such as alicyclic hydrocarbon groups and aromatic ring-containing hydrocarbon groups, and chain hydrocarbon groups. The hydrophobicity of component (A) becomes more suitable, and resolution From a viewpoint of being able to improve developability and the suppression ability of exposure nonuniformity, Preferably it is a cyclic hydrocarbon group, More preferably, it is an alicyclic hydrocarbon group.

It is preferable that the ring carbon of the alicyclic hydrocarbon group in R< ² > couple|bonds with the ester group shown in Formula (A1). In such an aspect, high transparency can be expressed.

Examples of the alicyclic hydrocarbon group include a cycloalkyl group represented by a cyclopentyl group, a cyclohexyl group, a cycloheptanyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, a cyclohexadecanyl group, and a cycloicosan group, and a cyclo monocyclic hydrocarbon groups such as a cycloalkenyl group represented by a pentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclodekenyl group, and a cyclododekenyl group; saturated or unsaturated cross-linked hydrocarbon groups such as norbornyl group, adamantyl group, bicyclo[2.2.1]hepta-2-enyl group, tricyclo[5.2.1.0 ^2,6 ]decanyl group; Saturated or unsaturated spiro hydrocarbon groups, such as a spirobicyclopentanyl group, are mentioned. Among these, a monocyclic hydrocarbon group and a crosslinked hydrocarbon group are preferable.

As an aromatic ring containing hydrocarbon group, For example, Aryl groups, such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group; Aralkyl groups, such as a benzyl group and a phenethyl group, are mentioned.

Examples of the chain hydrocarbon group include chain alkyl groups such as methyl group, ethyl group, butyl group, 2-ethylhexyl group, decyl group, n-lauryl group and n-stearyl group.

The hydrocarbon group for R ² may have a substituent. However, a cyclic ether group is excluded among the substituents. As a substituent, a hydroxyl group and a carboxyl group are mentioned, for example.

Examples of the unsaturated compound that induces the structural unit (A1) include cycloalkyl acrylates such as cyclopentyl acrylate, cyclohexyl acrylate and cyclooctyl acrylate; cycloalkenyl acrylates such as cyclohexenyl acrylate; cross-linked hydrocarbon group-containing acrylates such as norbornyl acrylate, adamantyl acrylate, and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate; aryl acrylates such as phenyl acrylate; Aralkyl acrylates, such as benzyl acrylate; and C _{1-20 alkyl} acrylates such as methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-lauryl acrylate, and n-stearyl acrylate.

In component (A), content of structural unit (A1) is 30 mass % or more in 100 mass % of all the structural units which comprise component (A), Preferably it is 30-75 mass %, More preferably, It is 30-70 mass %. If it is such an aspect, depolymerization of a component (A) will not advance easily, and generation|occurrence|production of the outgas from a cured film can be suppressed.

The structural unit (A2) contains a cyclic ether group. Examples of the cyclic ether group include a 3- to 8-membered ring, preferably a heterocyclic ring composed of a carbon atom and one oxygen atom, particularly a 3-membered or 4-membered heterocyclic ring, specifically is an epoxy ring and an oxetane ring. The epoxy ring also includes an embodiment in which one to two carbon atoms constituting the epoxy ring is a ring carbon atom, and also includes an embodiment in which one to three carbon atoms constituting the oxetane ring is a ring carbon atom. . When a component (A) has a structural unit (A2), the resolution of a composition, the adhesiveness of a cured film, and chemical-resistance can be improved.

The structural unit (A2) is preferably represented by a formula (A2).

In the formula (A2), R ³ each independently represents a hydrogen atom or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, preferably a hydrogen atom. R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group. R ⁵ is a cyclic ether-containing group. X is a single bond or a C1-C12 alkanediyl group, such as a methylene group, an ethylene group, and a propylene group, Preferably it is a single bond or a methylene group.

The cyclic ether group of the structural unit (A2) acts as a crosslinking group. Therefore, the cured film from which deterioration is prevented over a long period of time can be formed by using the composition of this invention.

Examples of the cyclic ether-containing group include an epoxy ring-containing group and an oxetane ring-containing group, and specifically, an oxiranyl group (epoxy group); A group represented by the following formula (1) represented by a 3,4-epoxycyclohexyl group, a group represented by the following formula (2) represented by a 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl group, etc. , a group obtained by epoxidation of an alicyclic hydrocarbon group; The group represented by following formula (3) represented by 3-ethyloxetanyl group is mentioned. These groups may have a substituent, for example, a C1-C15 alkyl group, a hydroxyl group, and a carboxyl group are mentioned. As an alicyclic hydrocarbon group, the example enumerated as R< ² > in Formula (A1) mentioned above is mentioned.

In formulas (1) to (3), * is a bonding site with X, and in formula (3), R is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms.

The cyclic ether-containing group is preferably an epoxy ring-containing group from the viewpoint of cured film physical properties.

Examples of the unsaturated compound from which the structural unit (A2) is derived include cyclic ether group-containing (meth)acrylate, and specifically, glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^{2 ,6} ] epoxy ring-containing (meth)acrylates such as decyl (meth)acrylate; (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate; Oxetane ring containing (meth)acrylates, such as (3-ethyloxetan-3-yl)methyl (meth)acrylate, are mentioned.

In component (A), content of structural unit (A2) is 5-40 mass % normally in 100 mass % of all the structural units which comprise component (A), Preferably it is 10-35 mass %, More preferably Preferably, it is 15-30 mass %. By making content of a structural unit (A2) more than the said lower limit, the hardness and chemical-resistance of a cured film can be improved more, etc. By making content of a structural unit (A2) below the said upper limit, the developability of a composition can be made more favorable.

It is preferable to have a structural unit containing an acidic radical, and, as for a component (A), it is more preferable to have a structural unit containing a carboxyl group. According to this aspect, the composition of the present invention can exhibit good developability with respect to an alkaline developer.

In the component (A), the structural unit (A1) and/or (A2) may contain an acid group, but the component (A) is a structural unit containing an acid group other than the structural units (A1) and (A2). It is preferable to further have (A3). For example, since the cyclic ether group of a structural unit (A2) and the acidic radical of a structural unit (A3) can crosslinking-react, the hardness and chemical-resistance of a cured film can be improved more.

Examples of the unsaturated compound that induces the structural unit (A3) include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid; Unsaturated dicarboxylic acids, such as maleic acid, a fumaric acid, a citraconic acid, a mesaconic acid, and itaconic acid, are mentioned.

In component (A), content of structural unit (A3) is 2-25 mass % normally in 100 mass % of all the structural units which comprise component (A), Preferably it is 4-20 mass %, More preferably Preferably, it is 8-18 mass %. By setting it as such an aspect, the sensitivity and developability of a composition, and hardness of a cured film can be made more favorable.

The component (A) may have a structural unit (A4) other than the structural units (A1) to (A3).

Examples of the unsaturated compound from which the structural unit (A4) is derived include methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate, and the like. of C _{1-20 alkyl} methacrylate; cycloalkyl methacrylates such as cyclopentyl methacrylate, cyclohexyl methacrylate, and cyclooctyl methacrylate; cycloalkenyl methacrylates such as cyclohexenyl methacrylate; cross-linked hydrocarbon group-containing methacrylates such as norbornyl methacrylate, adamantyl methacrylate, and tricyclo[5.2.1.0 ^2,6 ]decan-8-yl methacrylate; aryl methacrylates such as phenyl methacrylate; Aralkyl methacrylates, such as benzyl methacrylate; unsaturated dicarboxylic acid diesters such as diethyl itaconic acid; maleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide; unsaturated aromatic compounds such as styrene, α-methylstyrene, o,m or p-methylstyrene, and p-methoxystyrene; conjugated diene compounds such as 1,3-butadiene and isoprene; In addition, (meth)acrylonitrile, (meth)acrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate are mentioned.

In component (A), the content of the structural unit (A4) is usually 40% by mass or less, preferably 30% by mass or less, more preferably, in 100% by mass of all the structural units constituting the component (A). It is 25 mass % or less. It is preferable that content of the structural unit which replaced the hydrogen atom on the carbon atom couple|bonded with the carbonyl group especially shown in Formula (A1) with a methyl group is below the said value. In addition, the content of a structural unit in which a hydrogen atom on a carbon atom bonded to a carbonyl group represented in the formula (A1) is replaced with a methyl group, and R ² is a cyclic hydrocarbon group optionally having a substituent (especially an alicyclic hydrocarbon group) is the above value It is preferable that it is less than, and it is more preferable that it is 20 mass % or less. If it is such an aspect, depolymerization of a component (A) will not advance easily, and generation|occurrence|production of the outgas from a cured film can be suppressed.

A component (A) may have only one type of structural unit (A1), and may have multiple types of structural unit (A1). A component (A) may have only one type of structural unit (A2), and may have multiple types of structural unit (A2). The same is true for structural units (A3) and (A4). Content of each structural unit can be measured by NMR analysis.

Component (A) may consist of 1 type of resin, and may consist of 2 or more types of resin, as long as content of each structural unit measured by NMR analysis satisfies the said requirements, for example. In the case of two or more types of resins (blend), if the content (measured value) of each structural unit in the entire blend satisfies the above requirements, the blend has a structural unit (A1) or (A2) Resin which is not present, and resin in which content of each structural unit does not satisfy|fill the said requirement may be contained.

It is preferable that a component (A) is alkali-soluble resin. Alkali solubility in a component (A) means that it can melt|dissolve or swell in aqueous alkali solutions, such as a tetramethylammonium hydroxide aqueous solution with a concentration of 2.38 mass %.

The weight average molecular weight (Mw) by the gel permeation chromatography method (GPC method) of a component (A) is 2000-20000 normally, Preferably it is 3000-12000. Moreover, the dispersion degree (weight average molecular weight (Mw)/number average molecular weight (Mn)) of a component (A) is 1.0-4.0 normally, Preferably it is 1.0-2.5. The details of measurement conditions are described in Examples. In such an aspect, a decrease in the developability of the composition can be prevented, and the film formability can be improved.

Content of component (A) is 10-80 mass % normally in solid content of the composition of this invention, Preferably it is 15-75 mass %, More preferably, it is 20-70 mass %. Here, solid content is all components except the solvent mentioned later. If it is such an aspect, the suppression ability and developability of the exposure nonuniformity of a composition can be exhibited more favorably, and the cured film excellent in sclerosis|hardenability and transparency can be formed.

Component (A) is obtained by, for example, a known method such as radical polymerization in the presence of an appropriate solvent, polymerization initiator and chain transfer agent, using an unsaturated compound that induces each structural unit described above, for example. can

<reaction initiator (B)>

A reaction initiator (B) is a component used in order to superpose|polymerize resin, a polyfunctional polymerizable compound, etc. Although it does not specifically limit as a reaction initiator (B), For example, polymerization initiators, such as a radical polymerization initiator and a cationic polymerization initiator, are mentioned. The kind of the reaction initiator (B) can be appropriately selected according to the polymerization form of the polyfunctional polymerizable compound (C). The composition of the present invention may be a radiation-sensitive curing type or a thermosetting type, but from the viewpoint of pattern formation and prevention of deterioration of the element, a radiation-sensitive curing type is preferable. As such, the composition of the present invention is excellent in radiation sensitivity and resolution.

The radical polymerization initiator is not particularly limited as long as it initiates radical polymerization by radiation (light) irradiation, heating, or the like. For example, Radiation-sensitive radical polymerization initiators, such as an oxime ester compound, an alkylphenone compound, an acylphosphine oxide compound, a biimidazole compound, a triazine compound, a benzoin compound, and a benzophenone compound; Thermal radical polymerization initiators, such as a peroxide and an azo compound, are mentioned. Among these, a radiation-sensitive radical polymerization initiator is preferable and an oxime ester compound is more preferable.

As an oxime ester compound, an O-acyl oxime compound is mentioned, for example, Specifically, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl oxime)]; Ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9 H.-carbazol-3-yl)-octane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazol-3-yl ]-Ethan-1-oneoxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazol-3-yl]-ethan-1-one Oxime-O-benzoate, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O -acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime) , ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9.H.-carbazole-3- yl]-1-(O-acetyloxime);

Examples of the oxime ester compound include NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, manufactured by Daitokemix, Inc.), Irgacure OXE01 , OXE02, OXE03 (above, manufactured by BASF), etc. can also be used.

A cationic polymerization initiator will not be specifically limited if it generate|occur|produces a protonic acid or a Lewis acid by radiation (light) irradiation, heating, etc. For example, the initiator of an ionic photoacid generating type|mold and a nonionic photoacid generating type|mold is mentioned.

Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, (2,4-cyclopentadien-1-yl)[(1) -methylethyl)benzene]-Fe salt, etc. onium salt compounds are mentioned, In addition, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound are mentioned. As the onium salt, specifically, the cation moiety is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, or (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene] -Fe is a cation, and the anion moiety is BF ^{4 -} , PF ^{6 -} , SbF ⁶ - ,[BX ₄ ] ^- (X is a phenyl group substituted with two or more fluorine or trifluoromethyl groups), or [PRf ^{6 -} ] and onium salts constituted by (Rf is a fluorinated alkyl group).

Examples of the nonionic photoacid generating type photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, and N-hydroxyimidesulfonate.

By making the composition of the present invention a radiation-sensitive curing type, component (C) is polymerized and cured by irradiation with radiation (ultraviolet rays, far ultraviolet rays, visible rays, etc.), and usually a negative cured film or pattern can be formed. there is.

In the composition of this invention, content of component (B) is 1-20 mass parts normally with respect to 100 mass parts of component (A), Preferably it is 3-18 mass parts, More preferably, 5-15 mass parts am. If it is such an aspect, the suppression ability and developability of the exposure nonuniformity of a composition can be exhibited more favorably, and the cured film excellent in sclerosis|hardenability and transparency can be formed.

< multisensory polymeric compound (C)>

A polyfunctional polymerizable compound (C) is a compound which has a some polymerizable group normally. As a polymeric group, groups containing carbon-carbon unsaturated double bonds, such as a vinyl group and a (meth)acryloyloxy group, are mentioned, for example.

Component (C), Preferably, it is polyfunctional (meth)acrylate which has 2 or more (meth)acryloyloxy groups per molecule, More preferably, it is 2-6 pieces of (meth)acryl per molecule. It is a polyfunctional (meth)acrylate which has a royloxy group. Examples of the polyfunctional (meth)acrylate include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanedi (meth)acrylic acid diesters of alkylene glycol or polyalkylene glycol, such as old-di (meth)acrylate; (meth)acrylic acid diesters of mono- or polycycloalkanedimethanol, such as cyclohexane dimethanol di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate; Trimethylolpropane poly(meth)acrylate, ditrimethylolpropane poly(meth)acrylate, pentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate (meth)acrylic acid polyester; AO-modified or caprolactone of polyhydric alcohols having trivalence or higher, such as pentaerythritol AO-modified poly(meth)acrylate, trimethylolpropane AO-modified poly(meth)acrylate, and dipentaerythritol AO-modified poly(meth)acrylate (meth)acrylic acid polyester of a modified product; In addition, tri(2-(meth)acryloyloxyethyl)phosphate, succinic acid modified pentaerythritol triacrylate, and succinic acid modified dipentaerythritol pentaacrylate are mentioned. Poly here means di, tri, tetra, penta, hexa or more. In this specification, AO modification means alkylene oxide modification|denaturation, such as ethylene oxide (EO) modification and a propylene oxide (PO) modification|denaturation.

In addition, a compound having a straight-chain alkylene group and an alicyclic structure and having two or more isocyanate groups, a compound having one or more hydroxyl groups in the molecule, and three, four or five (meth)acryloyloxy groups Polyfunctional urethane (meth)acrylate obtained by making the compound which has it react is also mentioned.

In the composition of this invention, content of component (C) is 20-200 mass parts normally with respect to 100 mass parts of component (A), Preferably it is 30-150 mass parts, More preferably, 40-100 mass parts am. By making content of a component (C) more than the said lower limit, the sensitivity and resolution of a composition, and the chemical-resistance of a cured film can be improved. By making content of a component (C) or less into the said upper limit, generation|occurrence|production of exposure nonuniformity can be reduced effectively.

<Adhesive aid (D)>

Adhesion adjuvant (D) is a component which improves the adhesiveness of a cured film and a board|substrate. As component (D), the functional silane coupling agent which has reactive functional groups, such as a carboxy group, a methacryloxy group, a vinyl group, an isocyanate group, an oxiranyl group, is preferable. Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, 3-glycan Cydyloxypropyl trimethoxysilane, 2-(3,4-epoxy cyclohexyl) ethyl trimethoxysilane, and phosphoric acid 2-(methacryloxy) ethyl are mentioned.

In the composition of this invention, content of component (D) is 0.01-10 mass parts normally with respect to 100 mass parts of component (A), Preferably it is 0.1-5 mass parts, More preferably, 0.5-4 mass parts. am.

<polymerization ban (E)>

A polymerization inhibitor (E) is a component which improves the storage stability of the composition of this invention. Examples of the component (E) include sulfur, quinones, hydroquinones, polyoxy compounds, amines and nitronitroso compounds, and more specifically, 2,5-di-t-butylhydroquinone. , p-methoxyphenol, and N-nitroso-N-phenylhydroxylamine aluminum.

In the composition of this invention, content of component (E) is 0.01-0.5 mass part normally with respect to 100 mass parts of component (A), Preferably it is 0.01-0.3 mass part, More preferably, 0.01-0.2 mass part am.

<Other ingredients>

The composition of the present invention may further contain components other than the above-mentioned components (A) to (E). As such other components, polymers other than component (A), antioxidant, surfactant, and a chain transfer agent are mentioned, for example.

In addition, in the solid content of the composition of this invention, as an upper limit of content of the sum total of components other than component (A)-(E) component, 10 mass % may be sufficient, 5 mass % may be sufficient, and 1 mass %, for example. also good

<Method for preparing the composition>

The composition of the present invention can be prepared by mixing components (A) to (C) and, if necessary, components (D) to (E) and other components in a predetermined ratio, preferably by dissolving in a suitable solvent. there is. It is preferable to filter the prepared composition with a filter with a pore diameter of about 0.2 micrometer, for example.

As a solvent, the thing which melt|dissolves or disperse|distributes each said component uniformly, and does not react with each said component is used. Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; Ethers, such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, and ethylene diglycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. As a solvent, esters are preferable.

Solid content concentration of the composition of this invention is 10-60 mass %, for example, Preferably it is 20-40 mass %. Here, the solid content concentration is the total concentration of all components excluding the solvent.

[ cured film ]

The cured film of this invention is formed from the composition of this invention mentioned above. The cured film has a characteristic that there is little amount of outgas generated, and in one embodiment, it is excellent in light transmittance, heat resistance, chemical resistance, foaming resistance, voltage retention, and adhesion to a substrate.

Although the thickness of the cured film of this invention can be set suitably according to the use, Preferably it is 0.5-10.0 micrometers, More preferably, it is 1.0-8.0 micrometers, More preferably, it is 1.5-5.0 micrometers.

In one embodiment, the lower limit of the light transmittance in wavelength 400-800 nm of the cured film of this invention becomes like this. Preferably it is 95 %, More preferably, it is 96 %. It is preferable that the light transmittance in wavelength 400-800 nm after heating a cured film at 230 degreeC in clean oven for 5 hours is also more than the said lower limit. According to such an aspect, the element which has favorable optical characteristics can be obtained.

The cured film of the present invention is, for example, a planarizing film that plays a role of flattening surface irregularities caused by members such as TFTs that elements such as display elements and lighting elements have, an interlayer insulating film that insulates between wirings, and a light emitting layer to form It can be used as an adhesive layer for a bank (barrier), a spacer, a protective film, and a color filter defining an area for the purpose. Among these, it is useful as a negative planarization film, and is especially useful as a planarization film which an organic electroluminescent element has.

Hereinafter, as an example, the formation method of the cured film in the case of using a radiation-sensitive curable resin composition is demonstrated. The method for forming a cured film includes a step (1) of forming a coating film on a substrate using the composition of the present invention, a step (2) of exposing at least a portion of the coating film, a step (3) of developing the coating film, and; A step (4) of heating the developed coating film is included.

[Process (1)]

In this process, a coating film is formed on a board|substrate using the composition of this invention. Specifically, the composition is applied to the surface of the substrate, preferably prebaking is performed to remove the solvent to form a coating film.

Examples of the substrate include a glass substrate, a silicon substrate, a plastic substrate, and a substrate in which various thin metal films are formed on the surface. As a plastic substrate, the resin substrate which consists of plastics, such as a polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, a polycarbonate, and a polyimide, is mentioned, for example. Moreover, as a board|substrate, the board|substrate in which TFT was formed may be sufficient.

As a coating method, the spray method, the roll coating method, the spin coating method, the slit-die coating method, the bar coating method, and the inkjet method are mentioned, for example. Among these, the spin coating method, the slit die coating method, and the bar coating method are preferable.

As conditions for a prebaking, although it changes also with the kind of each component, a usage ratio, etc., it is 0.5 to 10 minutes at 60-130 degreeC, for example. As for the film thickness of the coating film to be formed, 1.0-12.0 micrometers is preferable as a value after prebaking.

[Process (2)]

In this step, at least a part of the coating film is irradiated with radiation. Specifically, the coating film formed in step (1) is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation include charged particle beams such as ultraviolet rays, far ultraviolet rays, visible rays, X-rays, and electron beams. Among these, an ultraviolet-ray is preferable, and as an ultraviolet-ray, g line|wire (wavelength 436 nm) and i line|wire (wavelength 365 nm) are mentioned, for example. As an exposure amount of a radiation, 0.1-20,000 J/m<2> is preferable.

[Process (3)]

In this step, the coating film irradiated with radiation is developed. In this method, normally, it becomes negative type development. Specifically, the coating film irradiated with radiation in step (2) is developed with a developer to remove the non-radiation portion.

As a developing solution, the aqueous solution of an alkali (basic compound) is mentioned, for example. Examples of the alkali include sodium hydroxide, tetramethylammonium hydroxide, and other alkalis exemplified in paragraph [0127] of Japanese Patent Application Laid-Open No. 2016-145913 (incorporated herein). As alkali concentration in aqueous alkali solution, 0.1-5.0 mass % is preferable from a viewpoint of obtaining moderate developability.

As a developing method, suitable methods, such as the puddle method, the dipping method, the rocking|fluctuation immersion method, and the shower method, are mentioned, for example. Although development time changes with the composition of a composition, it is 30 to 120 second, for example. Moreover, it is preferable to perform the rinse process by running water washing with respect to the patterned coating film after a developing process.

[Process (4)]

In this step, the developed coating film is heated. For example, it can be heated using heating apparatuses, such as an oven and a hot plate. Heating temperature is 120-250 degreeC, for example. Although heating time changes with the kind of heating equipment, when heat-processing on a hotplate, for example, it is 5-40 minutes, when heat-processing in oven, it is 10-80 minutes. As mentioned above, the target patterned cured film (pattern) can be formed on a board|substrate.

[display element and lighting element]

The display element and lighting element of this invention have the cured film of this invention mentioned above. As said element, For example, Organic electroluminescent elements, such as an organic electroluminescent display element and an organic electroluminescent lighting element; A liquid crystal display element is mentioned. These elements WHEREIN: The said cured film is used as at least 1 sort(s) chosen from a planarization film, an interlayer insulating film, a partition, a spacer, a protective film, and the adhesive bond layer for color filters, for example.

<Organic EL device>

Hereinafter, one Embodiment of an organic electroluminescent element is demonstrated based on FIG. 1 and FIG. The organic EL element 1 can have a top emission structure (refer to FIG. 1) or a bottom emission structure (refer to FIG. 2), and the material of each constituent material can be suitably selected according to the said structure. The organic EL element 1 in Figs. 1 and 2 is an active matrix type having a plurality of pixels formed in a matrix shape.

The organic EL element 1 includes a support substrate 2 , a thin film transistor (hereinafter also referred to as “TFT”) 3 , a planarization film 4 , an anode 5 as a first electrode, a through hole 6 , and a partition wall. (7), the organic light emitting layer 8, the cathode 9 as a 2nd electrode, the passivation film 10, and the sealing substrate 11 are provided.

The support substrate 2 is formed of an insulating material. When the organic EL element 1 is of a bottom emission type, the support substrate 2 is required to have high light transmittance. Therefore, as an insulating material, transparent resins, such as a polyethylene terephthalate, polyethylene naphthalate, polyimide, etc. with high light transmittance, and glass materials, such as alkali free glass, are preferable, for example. On the other hand, when the organic EL element 1 is a top emission type, any insulator can be used as the insulating material, for example, it is possible to use the above-described transparent resin and glass material.

The TFT 3 is an active element in each pixel portion, and is formed on the support substrate 2 . The TFT 3 includes a gate electrode, a gate insulating film, a semiconductor layer, a source electrode, and a drain electrode. It is not limited to the bottom gate type in which a gate insulating film and a semiconductor layer are provided in this order on a gate electrode, but a top gate type in which a gate insulating film and a gate electrode are provided in this order on a semiconductor layer may be used.

The flattening film 4 is an insulating film that plays a role in flattening the surface irregularities of the TFT 3 and, in one embodiment, the color filter 13 . The planarization film 4 is formed so as to cover the entirety of the TFT 3 and the color filter 13 in one embodiment.

The anode 5 forms a pixel electrode. The anode 5 is formed on the planarization film 4 with a conductive material. When the organic EL element 1 is of the bottom emission type, the anode 5 is required to be light-transmissive. Therefore, as a material of the anode 5, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and tin oxide with high light transmittance are preferable. When the organic EL element 1 is of the top emission type, the anode 5 is required to have light reflectivity. Therefore, as the material of the anode 5, Al (aluminum), APC alloy (alloy of silver, palladium, and copper), ARA (alloy of silver, rubidium, and gold), MoCr (of molybdenum and chromium) with high light reflectivity alloy), NiCr (an alloy of nickel and chromium), and a laminate film of these metals and an electrode with high light transmittance (eg, ITO) is preferable.

The through hole 6 is formed in order to connect the anode 5 and the drain electrode of the TFT 3 . The anode 5 and the drain electrode of the TFT 3 are connected by a wiring formed in the through hole 6 .

The barrier rib 7 is formed so as to cover the periphery of the anode 5 , and defines a concave portion 70 defining an arrangement region of the organic light emitting layer 8 . The planarization film 4 and/or the partition 7 are formed from the composition of this invention.

The organic light emitting layer 8 is formed on the anode 5 in the region defined by the partition 7 , that is, the recess 70 . In this way, by forming the organic light emitting layer 8 in the concave portion 70 , the periphery of the organic light emitting layer 8 is surrounded by the barrier rib 7 , and a plurality of adjacent pixels can be partitioned. The organic light emitting layer 8 contains a light emitting material which is an organic material, that is, an organic light emitting material. The organic light emitting material included in the organic light emitting layer may be a low molecular weight organic light emitting material or a high molecular weight organic light emitting material. The organic light emitting layer 8 is located between the anode 5 and the cathode 9 which face each other.

The cathode 9 is formed to cover a plurality of pixels in common, and constitutes a common electrode of the organic EL element 1 . The cathode 9 is made of a conductive member. When the organic EL element 1 is a top emission type, it is preferable that the cathode 9 is a light transmissive electrode, and an ITO electrode and an IZO electrode are mentioned. When the organic EL element 1 is a bottom emission type, the cathode 9 does not need to be a light-transmitting electrode. In that case, as a constituent material of the cathode 9, an alloy containing barium (Ba), barium oxide (BaO), aluminum (Al), and Al is mentioned, for example.

The passivation film 10 suppresses penetration of moisture and oxygen. This passivation film 10 is formed on the cathode 9 .

The sealing substrate 11 is different from the support substrate 2 in the TFT substrate which has the main surface (support substrate 2, TFT3, and planarization film 4) on which the organic light emitting layer 8 is arrange|positioned. opposite side) is sealed. As the sealing substrate 11, glass substrates, such as an alkali free glass substrate, are mentioned. It is preferable to seal the main surface in which the organic light emitting layer 8 is arrange|positioned with the sealing substrate 11 through the sealing layer 12 using the sealing compound apply|coated to the outer peripheral edge part vicinity of a TFT board|substrate. The sealing layer 12 is a layer of inert gas, such as dried nitrogen gas, or a layer of filling materials, such as an adhesive agent, for example.

The organic EL element 1 shown in Fig. 1 is of a top emission type, and a pixel emitting white light is formed in a recess 70, and above it, for example, under the sealing substrate 11, for each pixel. Corresponding color filters 13 for each color such as red, green, blue, or the like are arranged. A black matrix 14 may be formed between each color filter 13 . The white light emitted from the pixel becomes the color light transmitted and selected by the corresponding color filter 13 , and passes through the encapsulation substrate 11 .

The organic EL element 1 shown in Fig. 2 is of a bottom emission type, a pixel emitting white light is formed in a recess 70, and below the pixel, for example, under the planarization film 4, for each pixel. Corresponding color filters 13 for each color such as red, green, blue, or the like are arranged. The white light emitted from the pixel becomes the color light transmitted and selected by the corresponding color filter 13 , and passes through the supporting substrate 2 .

1 and 2, even if the color filter 13 is not formed, for example, each color such as red, green, blue, and the like is applied separately for each pixel, and red, green, and blue pixels of each color are formed in the recesses 70 good.

<Liquid crystal display element>

Hereinafter, an embodiment of the liquid crystal display device will be described with reference to FIG. 3 . A liquid crystal display element has, for example, two board|substrates which are opposingly arranged, the display pixel laminated|stacked on the inner surface side of at least either of these board|substrates, and the liquid crystal layer arrange|positioned between the said board|substrates, This becomes a liquid crystal cell.

The liquid crystal display element 1a is of an active matrix type. The liquid crystal display element 1a has an array substrate 15 serving as a display element substrate, and a color filter substrate 90 disposed opposite to the array substrate 15, and a seal formed around both substrates 15 and 90 . The liquid crystal layer 16 is formed by sealing the liquid crystal between the substrates 15 and 90 by the ash.

The array substrate 15 has a structure in which a substrate 21 , an interlayer insulating film 52 , and a pixel electrode 36 are formed in this order in a pixel region that is a display region in which a plurality of pixels are arranged. Specifically, in the pixel region, the array substrate 15 includes a base coating film 22 , a semiconductor layer 23 , a gate insulating film 24 , and a gate electrode ( 25), an inorganic insulating film 41, a source electrode 34 and a drain electrode 35 made of a first wiring layer 61, an interlayer insulating film 52, a pixel electrode 36 formed for each pixel, and The alignment film 37 formed so as to cover the pixel region has a structure in which it is stacked in this order from the substrate 21 side.

In this way, on the substrate 21 constituting the array substrate 15 , the TFT 29 including the semiconductor layer 23 , the gate insulating film 24 , and the gate electrode 25 , and functioning as a pixel switching element is formed. Each pixel is made by hand. The TFT 29 constitutes a so-called top gate type TFT. The source electrode 34 and the drain electrode 35 made of the first wiring layer 61 are connected to the source/drain region of the semiconductor layer 23 via a contact hole 31f formed in the inorganic insulating film 41 . Further, the pixel electrode 36 is connected to the drain electrode 35 made of the first wiring layer 61 through a contact hole 31g formed in the interlayer insulating film 52 .

The alignment film 37 is formed on the surface of the array substrate 15 in contact with the liquid crystal layer 16 so as to cover at least the pixel region.

In the pixel region, the color filter substrate 90 includes a black matrix 92 comprising a light blocking member formed between each pixel on an insulating substrate 91, and red, green, and blue color filters 93 formed for each pixel. ), a common electrode 94 made of a transparent conductive film, and an alignment film 95 are formed in this order from the substrate 91 side.

Each member constituting the liquid crystal display element 1a can each be formed using a conventionally well-known material, and at least one of the insulating films among each member is formed from the composition of this invention. For example, the interlayer insulating film 52 is formed of the composition of the present invention. As for the film thickness of the interlayer insulating film 52, 1-5 micrometers which can fully exhibit an insulating function and a planarization function are preferable, More preferably, it is 2-4 micrometers.

(Example)

Hereinafter, the present invention will be described more specifically based on Examples, but the present invention is not limited to these Examples. In the description of Examples etc. below, unless otherwise indicated, "part" means "part by mass".

[Weight average molecular weight (Mw), number average molecular weight ( Mn ) and dispersion (Mw/ Mn )]

Mw and Mn of the resin were measured by gel permeation chromatography (GPC method) under the following analysis conditions using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation. The degree of dispersion (Mw/Mn) was calculated from the measurement results of Mw and Mn.

(Analysis Conditions)

Elution solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Sample concentration: 1.0% by mass

Sample injection volume: 100 μL

Column temperature: 40°C

Detector: Differential Refractometer

Standard material: monodisperse polystyrene

[ ¹³ C-NMR analysis]

¹³ C-NMR analysis was performed using the analysis instrument ("JNM-EX400" manufactured by Nippon Electronics Co., Ltd.) using heavy chloroform as the measurement solvent. The content ratio of each structural unit of the resin was calculated as mass% from the area ratio of the peak corresponding to each structural unit in the spectrum obtained by ¹³ C-NMR analysis.

<Synthesis of alkali-soluble resin>

[ Synthesis example One]

To a flask equipped with a cooling tube and a stirrer, 10 parts of 2,2'-azobis-(2,4-dimethylvaleronitrile) and 200 parts of methyl 3-methoxypropionate were charged. Then, 10 parts of methacrylic acid, 25 parts of 3, 4- epoxycyclohexyl methyl methacrylate, and 65 parts of cyclohexyl acrylates were thrown in. After nitrogen substitution, stirring was started slowly. The solution containing alkali-soluble resin (A-1) was obtained by raising the temperature of a solution to 75 degreeC, and preserving this temperature for 5 hours. Solid content concentration of the said solution was 34.2 mass %, Mw of resin (A-1) was 8,300, and Mw/Mn was 2.0.

[ Synthesis example 2-12]

A solution containing alkali-soluble resins (A-2) to (A-12) was obtained in the same manner as in Synthesis Example 1 except that each component of the kind and compounding amount shown in Table 1 was used as a monomer. A result is shown in Table 1.

<Preparation of composition>

[ Example One]

In a solution containing resin (A-1), 4 parts of reaction initiator (B-1), 5 parts of reaction initiator (B-2) with respect to an amount equivalent to 100 parts (solid content) of resin (A-1); 50 parts of polyfunctional polymerizable compound (C-1), 3 parts of methacryloxypropyltrimethoxysilane ("XIAMETER(R) OFS-6030 SILANE" manufactured by Toray Dow Corning) and 2,5-di-t- 0.1 part of butylhydroquinone (Wako Pure Chemical Industries, Ltd.) was mixed, and the obtained mixture was dissolved in a mixed solvent of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate (mass ratio of 50:50) so that the solid content concentration was 30% by mass. Then, it filtered with a membrane filter with a pore diameter of 0.2 micrometer, and the resin composition (S-1) was prepared.

[ Example 2 to 10 and comparative example 1-3]

The resin (A) and other resins, the reaction initiator (B), and the polyfunctional polymerizable compound (C) were operated in the same manner as in Example 1 except that each component of the type and compounding amount shown in Table 2 was used, and the resin Compositions (S-2) to (S-10) and (CS-1) to (CS-3) were prepared.

The meaning of each symbol in Table 2 is as follows.

Resin (A) and other resins

A-1 to A-12: Resins synthesized in Synthesis Examples 1 to 12, respectively

reaction initiator (B)

B-1: 「NCI-930」 from ADEKA

B-2: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (BASF's "Irgacure OXE01")

multisensory polymeric compound (C)

C-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("KAYARAD DPHA" by Nippon Kayaku Corporation)

C-2: 1,9-nonanediol diacrylate (“Light acrylate 1,9ND-A” by Kyoei Sha Chemicals)

<Evaluation>

An insulating film was formed from the resin compositions obtained in Examples and Comparative Examples, and in accordance with the method described below, low outgas properties, negative radiation sensitivity, negative resolution, development adhesion, chemical resistance, light transmittance and Heat-resistant light transmittance was evaluated. Table 2 shows the evaluation results.

[I (低) outgas castle ]

After apply|coating the resin composition obtained by the Example and the comparative example using a spinner on a silicon substrate, it prebaked at 90 degreeC for 2 minute(s) on a hotplate, and the coating film was formed. Next, the coating film was exposed at an exposure amount of 400 J/m 2 using an exposure machine ("PLA-501F" by Canon Corporation: an ultra-high pressure mercury lamp was used). Next, using the tetramethylammonium hydroxide aqueous solution (developing solution) of 2.38 mass % density|concentration, the development process was performed at 25 degreeC by the Puddle method. The time of the developing treatment was 100 seconds. After the developing treatment, the coating film was washed with running water for 1 minute in ultrapure water and dried to form a pattern on the silicon substrate. This silicon substrate was heated at 230 degreeC for 30 minutes in a clean oven, and the insulating film with a film thickness of 2.0 micrometers was obtained.

The insulating film silicon substrate was cut into 1 cm × 5 cm pieces, and for the four cut silicon substrates, a silicon wafer analyzer device (“Heat/Desorption Device JTD-505” manufactured by Nippon Bun Seki Kogyo Co., Ltd., Shimadzu Corporation) Using "Gas Chromatography Mass Spectrometer GCMS-QP2010Plus"), the amount of outgas (ng/cm 2 ) when the temperature was raised to 230° C. at a temperature increase rate of 10° C./min and stored and maintained at the same temperature for 15 minutes was determined.

(Evaluation standard)

A: Less than 200ng/cm2

B: 200ng/cm2 or more and less than 600ng/cm2

C: 600ng/cm2 or more

[ negative radiation sensitivity]

The resin compositions obtained in Examples and Comparative Examples were coated on a glass substrate (“Corning 7059” by Corning Corporation) using a spinner, and then prebaked on a hot plate at 90° C. for 2 minutes to form a coating film having a thickness of 4.0 μm. did.

Next, using an exposure machine ("PLA-501F" by Canon Corporation: using an ultra-high pressure mercury lamp), the exposure amount was changed, and the coating film was exposed through a pattern mask having a plurality of rectangular light-shielding portions (10 µm × 10 µm). . Next, using the tetramethylammonium hydroxide aqueous solution (developing solution) of 2.38 mass % density|concentration, the development process was performed at 25 degreeC by the Puddle method. The time of the developing treatment was 100 seconds. After the developing treatment, the coating film was washed with running water for 1 minute in ultrapure water and dried to form a pattern on the glass substrate. This glass substrate was heated at 230 degreeC in clean oven for 30 minutes, and the insulating film was obtained.

About the film thickness of an insulating film, the exposure amount used as 85 % or more of the residual film ratio (ratio which a patterned thin film remains appropriately) represented by the following formula was calculated|required as a sensitivity, and the following criteria evaluated sensitivity.

Remaining film rate (%) = (film thickness after development / film thickness before development) x 100

(Evaluation standard)

A: 400J/㎡ or less

B: Exceeding 400J/m2 and less than or equal to 600J/m2

[ negative resolution]

An insulating film having a through hole was formed in the same manner as in the evaluation of radiation sensitivity except that the exposure amount was 400 J/m 2 , and the minimum diameter of the through hole of the insulating film was observed with an optical microscope. Resolution was evaluated according to the following criteria.

(Evaluation standard)

A: The minimum diameter of the through hole is 10 µm or more

B: The minimum diameter of the through hole is 8 µm or more and less than 10 µm

C: The minimum diameter of the through hole is 5 µm or more and less than 8 µm

[Development Adhesion]

Using a mask with a line-and-space ratio (L/S) of 1:1 (a line width of 5 to 40 µm and a space width of the same size), the radiation sensitivity was evaluated and In the same manner, an insulating film was formed. About this insulating film, the minimum width of the line which remained without peeling after image development was observed with the optical microscope, and image development adhesiveness was evaluated according to the following criteria.

(Evaluation standard)

A: The minimum width is less than 10㎛

B: Minimum width 10㎛ or more and less than 30㎛

[Chemical resistance]

After apply|coating the resin composition obtained by the Example and the comparative example using a spinner on a silicon substrate, it prebaked at 90 degreeC for 2 minute(s) on a hotplate, and the coating film was formed. Next, the coating film was exposed at an exposure amount of 400 J/m 2 using an exposure machine ("PLA-501F" by Canon Corporation: an ultra-high pressure mercury lamp was used). Next, using the tetramethylammonium hydroxide aqueous solution (developing solution) of 2.38 mass % density|concentration, the development process was performed at 25 degreeC by the Puddle method. The time of the developing treatment was 100 seconds. After the developing treatment, the coating film was washed with running water for 1 minute in ultrapure water and dried. This silicon substrate was heated at 230 degreeC for 30 minutes in a clean oven, and the insulating film with a film thickness of 4.0 micrometers was obtained. This was immersed in N-methyl-2-pyrrolidone heated to 65° C. for 6 minutes, and after immersion, the insulating film was washed in running water for 5 seconds in ultrapure water and dried. The film thickness of the insulating film after the treatment was measured using a stylus type film thickness meter. N-methyl-2-pyrrolidone swelling ratio (%) was calculated according to the following formula, and chemical resistance was evaluated according to the following criteria.

N-methyl-2-pyrrolidone swelling ratio (%)

=100 x {(remaining film after immersion (μm) - remaining film before immersion (μm)) / remaining film before immersion (μm)}

(Evaluation standard)

A: Less than 3%

B: 3% or more and less than 5%

C: 5% or more

[Light transmittance and heat-resistant light transmittance]

After apply|coating the resin composition obtained by the Example and the comparative example using a spinner on a glass substrate ("Corning 7059" by Corning Corporation), it prebaked at 90 degreeC for 2 minute(s) on a hotplate, and formed the coating film.

Subsequently, the coating film was exposed at an exposure amount of 400 J/m 2 using an exposure machine ("PLA-501F" by Canon Corporation: an ultra-high pressure mercury lamp was used). Next, using the tetramethylammonium hydroxide aqueous solution (developing solution) of 2.38 mass % density|concentration, the development process was performed at 25 degreeC by the Puddle method. The time of the developing treatment was 100 seconds. Furthermore, the cured film A with a film thickness of 3.0 micrometers was obtained by heating at 230 degreeC for 30 minutes in clean oven. The cured film B was obtained by heating this cured film A at 230 degreeC for 5 hours further within a clean oven.

About the glass substrate on which the cured film A or the cured film B was formed, the light transmittance (light transmittance) of the range of wavelength 400-800 nm is measured using the spectrophotometer ("150-20 type double beam" by Hitachi Seisakusho) And about each glass substrate, the minimum value (it also called the minimum light transmittance with respect to the cured film A and the minimum heat-resistant light transmittance with respect to the cured film B) of the light transmittance of the range of wavelength 400-800 nm was evaluated. Table 2 shows the lowest light transmittance and the lowest heat-resistant light transmittance.

<Production of liquid crystal display element and evaluation of foaming resistance and voltage retention rate>

[Evaluation of foam resistance]

In this Example, an active matrix type VA mode color liquid crystal display element having the same structure as that of the liquid crystal display element 1a of FIG. 3 was manufactured using a well-known method suitably.

First, the array substrate which comprises a liquid crystal display element was manufactured. First, according to a known method, a TFT having a semiconductor layer made of p-Si on an insulating glass substrate made of alkali-free glass so that the array substrate to be manufactured has the same TFT as the TFT 29 of FIG. 3 described above. A substrate having a TFT was prepared by arranging bare electrodes, wiring, and the like, and an inorganic insulating film made of SiN. Accordingly, in the present embodiment, the TFT of the array substrate is formed according to a known method on a glass substrate by repeating the normal semiconductor film formation and known insulating layer formation, and the like, and repeating the etching by the photolithography method. .

Next, using the resin composition obtained in the Example and the comparative example, it apply|coated with the slit-die coater on the board|substrate with the prepared TFT. Next, on a hot plate, it prebaked at 90 degreeC for 100 second, the organic solvent etc. were evaporated, and the coating film was formed. Next, using a UV (ultraviolet) exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ), 1000 J/m 2 of UV light was irradiated through a pattern mask in which a predetermined pattern can be formed. Then, using the tetramethylammonium hydroxide aqueous solution (developing solution) of 2.38 mass % density|concentration, the development process for 100 second was performed by the puddle method at 25 degreeC. After the development treatment, the coating film is washed in running water for 1 minute in ultrapure water, dried to form a patterned coating film on the substrate, and then heated (post-baked) in an oven at 230°C for 30 minutes (post-baking) to cure, and the cured film on the substrate formed to obtain an interlayer insulating film having a thickness of 4.0 µm. A contact hole was formed in the interlayer insulating film on the substrate by patterning.

Next, on the interlayer insulating film, a film made of ITO was formed using a sputtering method, and a pixel electrode was formed by patterning using a photolithography method. The formed pixel electrode was connected to the TFT through a contact hole.

As described above, an array substrate was manufactured.

Next, the color filter board|substrate manufactured by a well-known method was prepared. In this color filter substrate, a red color filter, a green color filter and a blue color filter, and a black matrix are arranged in a grid shape on a transparent glass substrate to form a color filter, and on the color filter, the color filter An insulating film serving as a planarization layer was formed. In addition, on the insulating film, a transparent common electrode made of ITO was formed.

Next, a liquid crystal aligning agent (trade name: JALS2095-S2, manufactured by JSR Co., Ltd.) is applied to each of the TFT arrangement surface of the array substrate and the color filter arrangement surface of the color filter substrate using a spinner, 80 An alignment film having a film thickness of 60 nm was formed by heating at deg. C for 1 minute and then at 180 deg. C for 1 hour to prepare an array substrate with an alignment film and a color filter substrate with an alignment film.

Next, after applying an ultraviolet curable sealing material to the outer periphery of the pixel region of each substrate, using a dispenser, photopolymerizable to a nematic liquid crystal having negative dielectric anisotropy on the inside of the sealing material The polymerizable liquid crystal composition prepared by adding the polymerizable component which has

Then, the color filter board|substrate was bonded together to the array board|substrate to which the polymeric liquid crystal composition was dripped in vacuum. Next, UV light was irradiated to the sealing material while moving the UV light source along the application area of the sealing material to harden the sealing material. In this way, the polymerizable liquid crystal composition was filled and sealed between the opposing array substrate and the color filter substrate to form a layer of the polymerizable liquid crystal composition.

Next, by applying an alternating voltage between the source electrode of the TFT and the common electrode on the color filter substrate in a state in which the voltage at which the TFT of the array substrate turns on is applied to the gate electrode of the TFT, the polymerizable liquid crystal composition The liquid crystals in the layer were oriented obliquely. Then, while maintaining the state in which the liquid crystal is oriented in an oblique orientation, ultraviolet light is irradiated to the layer of the polymerizable liquid crystal composition using an ultra-high pressure mercury lamp from the side of the array substrate, so that the liquid crystal forms a pretilt angle in a predetermined direction. A liquid crystal layer formed by vertically aligning was formed.

As mentioned above, the color liquid crystal display element of VA mode was manufactured.

Next, using the manufactured liquid crystal display element, the impact was given in the state of high temperature (80 degreeC), and the presence or absence of foaming in a pixel was confirmed. The impact to a liquid crystal display element was provided by making the iron ball (5.5 g) fall from 30 cm above the liquid crystal display element. In the pixel of the liquid crystal display element by the application of an impact, a thing in which foaming does not occur at all is "very good", a thing which foams but has little bubble density is "good", and a thing with a large bubble density is "poor". was evaluated as As for the result of evaluation, A was made into very favorable, B was made into good, and bad was made into C.

[Voltage retention rate]

A SiO ₂ film is formed on the surface to prevent elution of sodium ions, and the resin composition obtained in Examples and Comparative Examples is spin coated on a soda glass substrate on which an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. After carrying out, prebaking was performed for 10 minutes in 90 degreeC clean oven, and the coating film with a film thickness of 2.0 micrometers was formed. Next, it exposed to the coating film with the exposure amount of 400 J/m<2> without passing through the photomask. Then, post-baking was performed at 230 degreeC for 30 minute(s), and the coating film was hardened. Next, after bonding the board|substrate which formed this pixel and the board|substrate which vapor-deposited only the ITO electrode in the predetermined shape with the sealing compound which mixed 0.8 mm glass beads, Merck liquid crystal MLC 6608 was inject|poured, and the liquid crystal cell was produced. Furthermore, the liquid crystal cell was put into a 60 degreeC constant temperature layer, and the voltage retention of a liquid crystal cell was measured with the liquid crystal voltage retention measuring system (VHR-1A type, Toyo Technica Corporation). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Voltage retention (%) is a value calculated|required from a following formula.

Voltage retention rate (%)

= (voltage applied at liquid crystal cell potential difference after 16.7 milliseconds/0 milliseconds) x 100

When the voltage retention of the liquid crystal cell is less than 90%, the liquid crystal cell cannot maintain the applied voltage at a predetermined level for a time of 16.7 milliseconds, meaning that the liquid crystal cannot be sufficiently oriented, and there is a risk of causing "burn-in" such as an afterimage high.

(Evaluation standard)

A: 95% or more

B: 90% or more and less than 95%

C: less than 90%

The insulating film of Comparative Example 1 was inferior in low outgassing property, foaming resistance and voltage retention ratio, the insulating film of Comparative Example 2 was inferior in low outgassing property, and the insulating film of Comparative Example 3 had chemical resistance and voltage retention ratio. this was behind The present invention can provide an insulating film excellent in low outgas properties, chemical resistance, light transmittance, heat-resistant light transmittance, foaming resistance, and voltage retention. Accordingly, the insulating film in the present invention can be suitably used, for example, as a planarization film or an interlayer insulating film included in a display element.

1: organic EL element
2: support substrate
3: thin film transistor (TFT)
4: planarization film
5: Anode as first electrode
6: Through hole
7: bulkhead
8: organic light emitting layer
9: cathode as second electrode
10: passivation film
11: encapsulation substrate
12: encapsulation layer
13 : color filter
14 : Black Matrix
70: recess
1a: liquid crystal display element
15: array substrate
16: liquid crystal layer
21, 91: substrate
22: base coating film
23: semiconductor layer
24: gate insulating film
25: gate electrode
29: TFT
31f, 31g: contact hole
34: source electrode
35: drain electrode
36: pixel electrode
37, 95: alignment layer
41: inorganic insulating film
52: interlayer insulating film
61: first wiring layer
90: color filter substrate
92: Black Matrix
93: color filter
94: common electrode

Claims (9)

Resin (A) having a structural unit (A1) represented by formula (A1) and a structural unit (A2) containing a cyclic ether group, wherein the content of the structural unit (A1) is 30% by mass or more in 100% by mass of all structural units;
a radical polymerization initiator as the reaction initiator (B); and
Polyfunctional polymerizable compound (C)
contains,
A composition characterized in that it is used for the formation of a planarization film or an interlayer insulating film:

[In formula (A1), R ¹ is each independently a hydrogen atom or a halogen atom, and R ² is a hydrocarbon group which may have a substituent, provided that it is not a group containing a cyclic ether group]. According to claim 1,
A composition in which R ² in the formula (A1) is a cyclic hydrocarbon group which may have a substituent. 3. The method of claim 2,
The composition wherein the cyclic hydrocarbon group is at least one alicyclic hydrocarbon group selected from a monocyclic hydrocarbon group, a cross-linked hydrocarbon group and a spiro hydrocarbon group. According to claim 1,
The composition in which the cyclic ether group in the said structural unit (A2) is at least 1 sort(s) chosen from an epoxy ring and an oxetane ring. According to claim 1,
The composition in which the said resin (A) is alkali-soluble resin. A cured film which is a planarization film or an interlayer insulating film formed from the composition of any one of claims 1 to 5. 7. The method of claim 6,
A cured film which is a planarization film or an interlayer insulating film for use in a display element or a lighting element. An organic EL device having a cured film which is the planarization film or interlayer insulating film according to claim 6 . The liquid crystal display element which has a cured film which is the planarization film of Claim 6 or an interlayer insulating film.

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