JP5992059B2 - Photosensitive resin composition, method for producing cured film, cured film, organic EL display device and liquid crystal display device - Google Patents

Description

The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “photosensitive resin composition” or “composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening | curing the photosensitive composition, and various image display apparatuses using the said cured film.
More specifically, a photosensitive resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state image sensor, and the use thereof The present invention relates to a method for producing a cured film.

  Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In forming this interlayer insulating film, a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained (for example, patents). Literatures 1-3).

JP-A-5-165214 JP 2008-256974 A JP-A-8-62847

An important characteristic of the photosensitive resin composition constituting the interlayer insulating film is adhesion to the substrate. In recent years, it has become difficult to perform fine pattern processing as display devices have higher performance and higher definition, and an improvement in adhesion of the interlayer insulating film material after curing is also required.
In particular, since the substrate itself is made of a plurality of types of materials, the interlayer insulating film material formed on the surface of the wiring substrate is also provided with adhesion to the types of substrates.
The interlayer insulating film is exposed to a resist stripping solution used for forming a pattern of the transparent electrode film after the interlayer insulating film is formed, and NMP (N-methylpyrrolidone) used for forming the liquid crystal alignment film. Therefore, sufficient resistance to general chemicals used for these interlayer insulating films is required.
Here, when this inventor earnestly examined the prior art, for example, patent document 3 contains 1-cyclohexyl-3- (2-morpholinoethyl) -2-thiourea in a photosensitive composition. Although it is disclosed that adhesion in etching with a hydrochloric acid-based etchant is improved, it is difficult to achieve both adhesion to various substrates at the time of development and when used as a cured film. I understood. Moreover, since the photosensitive composition disclosed in Patent Document 3 is not high in resistance (chemical resistance) to chemicals such as a stripping solution and NMP, display defects are likely to occur in a liquid crystal display device, and improvement is required. It was.

  The present invention aims to solve the above-mentioned problems, and is a cured photosensitive resin composition having excellent adhesion to various substrates in the state of development and cured film, and excellent chemical resistance. The purpose is to provide goods. Furthermore, it aims at providing the manufacturing method of a cured film using such a photosensitive resin composition, a cured film, an organic electroluminescence display, and a liquid crystal display device.

As a result of intensive studies by the present inventors under such circumstances, the photosensitive resin composition contains a polymer containing a repeating unit having an acid group and a repeating unit having a crosslinkable group, and a coordination atom in one molecule. By including a compound having a structure containing and a thiourea structure, the adhesion to various substrates in the state of developing the photosensitive resin composition and when the photosensitive resin composition is a cured film is improved, It has been found that the chemical resistance is improved when the photosensitive resin composition is used for an interlayer insulating film, and the present invention has been completed.
Specifically, the above-mentioned problem has been solved by the following means <1>, preferably <2> to <17>.
<1> (A) (a1) a polymer containing a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group,
(B) A photosensitive resin composition containing a quinonediazide compound and (C) a compound having a structure containing a coordination atom and a thiourea structure in one molecule.
<2> The photosensitive resin composition according to <1>, wherein the component (C) is a compound containing at least one nitrogen atom as the coordination atom.
<3> The photosensitive resin composition according to <1> or <2>, wherein the component (C) is a compound represented by the following general formula (S).
General formula (S)
(In general formula (S), R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group.)
<4> In the general formula (S), R ¹ is represented by —NR ³ R ⁴ (R ³ and R ⁴ are each an organic group, and may be bonded to each other to form a ring). The photosensitive resin composition as described in <3> which is group to be made.
<5> The photosensitive resin composition according to <3> or <4>, wherein R ¹ in the general formula (S) is a 5-membered or 6-membered cyclic group.
<6> The photosensitive resin composition according to any one of <3> to <5>, wherein R ¹ in the general formula (S) is a morpholino group.
<7> The photosensitive resin composition according to any one of <3> to <6>, which has a hydrocarbon group at the end of R ^{2 in} the general formula (S).
<8> The photosensitive resin composition according to any one of <1> to <7>, wherein the structural unit (a1) is a repeating unit having a carboxyl group and / or a phenolic hydroxyl group.
<9> From the group consisting of the group represented by the structural unit (a2) represented by an epoxy group, an oxetanyl group and —NH—CH ₂ —O—R (wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The photosensitive resin composition in any one of <1>-<8> containing the structural unit containing at least 1 selected.
<10> The blending amount of the component (B) in the photosensitive resin composition is more than 10% by mass and 40% by mass or less with respect to the total solid content in the photosensitive resin composition. <9> The photosensitive resin composition according to any one of the above.
<11> The photosensitive resin composition according to any one of <1> to <10>, wherein the photosensitive resin composition is a positive photosensitive resin composition.
<12> (1) The process of apply | coating the photosensitive resin composition in any one of <1>-<11> on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
The manufacturing method of the cured film containing this.
<13> The method for producing a cured film according to <12>, including a step of (6) exposing the developed photosensitive resin composition to the entire surface after the developing step and before the post-baking step.
<14> The method for producing a cured film according to <12> or <13>, including a step of performing dry etching on a substrate having a cured film obtained by thermosetting in the post-baking step.
<15> A cured film formed by the method for producing a cured film according to any one of <12> to <14>.
<16> The cured film according to <15>, which is an interlayer insulating film.
<17> An organic EL display device or a liquid crystal display device having the cured film according to <15> or <16>.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in the adhesiveness with respect to various board | substrates in the state at the time of image development and a cured film, and excellent in chemical resistance can be provided.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In addition, in the description of groups (atomic groups) in the present specification, the description that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The organic EL element in the present invention refers to an organic electroluminescence element.

<Photosensitive resin composition>
The composition of the present invention comprises (A) (a1) a repeating unit having an acid group, (a2) a polymer containing a repeating unit having a crosslinkable group, (B) a quinonediazide compound, and (C) in one molecule. And a compound having a structure containing a coordination atom and a thiourea structure (hereinafter also referred to as component (C)).
The inventor of the present application contains (A) a polymer containing (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group and (C) component in the photosensitive resin composition. When the photosensitive resin composition is developed and when the photosensitive resin composition is used as a cured film, the adhesion to various substrates is improved and the photosensitive resin composition is used for an interlayer insulating film. It has been found that chemical resistance is also improved.
Although this mechanism is not clear, by introducing the repeating unit (a2) having a crosslinkable group into the polymer (A), the crosslinkable group and the component (C) interact with each other, and the component (C) As a result of more adsorbing to the substrate, it is presumed that the adhesion to various substrates is improved during development of the photosensitive resin composition and when the photosensitive resin composition is used as a cured film. In addition, although this mechanism is not clear, by introducing a repeating unit having (a2) a crosslinkable group into the polymer (A), the crosslink density when the photosensitive resin composition is a cured film is improved. In addition, as a result of the structure containing the coordination atom contained in the component (C) promoting the crosslinking reaction of the cured film, it is estimated that the chemical resistance is improved when the photosensitive resin composition is used for an interlayer insulating film. Is done. Therefore, when the said (C) component is contained in the photosensitive resin composition, it is estimated that chemical resistance improves compared with the case where the said (C) component is not contained in the photosensitive resin composition. Is done. The composition of the present invention can be preferably applied to a positive photosensitive resin composition.

<(A) Polymer>
In the polymer containing (A) (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group used in the present invention, (a1) the repeating unit having an acid group is a carboxyl group and / or A repeating unit having a phenolic hydroxyl group is preferred. In addition, the repeating unit (a2) having a crosslinkable group is an epoxy group, an oxetanyl group, or a group represented by —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). It is preferable to contain a structural unit containing at least one selected from the group consisting of:
(A) A polymer becomes a main component of the component except the solvent of the composition of this invention, and it is preferable to occupy 60 mass% or more of a total solid.

  (A) The polymer is, for example, a compound (a1-1) that provides a carboxyl group-containing structural unit as a repeating unit having an acid group (a1) in the presence of a polymerization initiator in a solvent (hereinafter referred to as “(a1-1 And (a2) a compound that gives an epoxy group-containing structural unit as a repeating unit having a crosslinkable group (hereinafter, sometimes referred to as “(a2) compound”). Can be manufactured. In addition, (a1) as a repeating unit having an acid group, a hydroxyl group-containing unsaturated compound that gives a hydroxyl group-containing structural unit (hereinafter sometimes referred to as “(a1-2) compound”) is further added, can do. Further, in the production of the polymer (A), together with the compound (a1) and the compound (a2), the compound (a3) (a structural unit other than the structural unit derived from the compounds (a1) and (a2)) is given. A saturated compound) can be further added to form a copolymer.

[(A1-1) Compound]
As the (a1-1) compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, anhydride of unsaturated dicarboxylic acid, mono [(meth) acryloyloxyalkyl] ester of polyvalent carboxylic acid, carboxyl group at both ends and Examples thereof include mono (meth) acrylates of polymers having a hydroxyl group, unsaturated polycyclic compounds having a carboxyl group, and anhydrides thereof.

Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid and the like;
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .; examples of the unsaturated dicarboxylic acid anhydride include, for example, anhydrides of the compounds exemplified as the above dicarboxylic acid; Examples of acid mono [(meth) acryloyloxyalkyl] esters include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like; Examples of mono (meth) acrylates of polymers having a hydroxyl group and ω-carboxypolycaprolactone mono (meth) acrylates; unsaturated polycyclic compounds having a carboxyl group and their anhydrides include, for example, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicar Xibicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5, Examples include 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.

  Of these, monocarboxylic acids and dicarboxylic anhydrides are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an aqueous alkali solution, and availability. These (a1-1) compounds may be used alone or in combination of two or more.

  The proportion of (a1-1) compound used is 5 to 5 based on the total of (a1-1) compound and (a2) compound (optional (a1-2) compound and (a3) compound as required). 30 mass% is preferable and 7-25 mass% is more preferable. (A1-1) By making the usage-amount of a compound into the said range, while optimizing the solubility with respect to the aqueous alkali solution of (A) polymer, the photosensitive resin composition excellent in a sensitivity is obtained.

[(A1-2) Compound]
Examples of the (a1-2) compound include a (meth) acrylic acid ester having a hydroxyl group, a phenolic hydroxyl group-containing unsaturated compound represented by the following formula (3), and the like.

In the above formula (3), R ¹⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^{18 to} R ²² are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, —COO—, or —CONH—. p is an integer of 0-3. However, at least one of R ^{18 to} R ²² is a hydroxyl group.

  Examples of the (meth) acrylic acid ester having a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene glycol. (N = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methacryloxyethylglycoside and the like. .

  Examples of the phenolic hydroxyl group-containing unsaturated compound represented by the above formula (3) include compounds represented by the following formulas (3-1) to (3-5) according to the definitions of Y and p. .

In the above formula (3-1), q is an integer of 1 to 3. R < ¹⁷ > -R < ²² > is synonymous with the said Formula (3).

In said formula (3-2), R < ¹⁷ > -R < ²² > is synonymous with the said Formula (3).

In the above formula (3-3), r is an integer of 1 to 3. R < ¹⁷ > -R < ²² > is synonymous with the said Formula (3).

In said formula (3-4), R < ¹⁷ > -R < ²² > is synonymous with the said Formula (3).

In the above formula (3-5), R ¹⁷ to R ²² is as defined in the above formula (3).

  Of these compounds, 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable. These compounds may be used alone or in combination of two or more.

  The proportion of the (a1-2) compound used is 5 to 5 based on the sum of the (a1-2) compound, the (a2) compound, and the (a1-1) compound (optional (a3) compound if necessary). 30 mass% is preferable and 7-25 mass% is more preferable. (A1-2) By making the usage-amount of a compound into the said range, the cured film which has the outstanding solvent resistance etc. can be formed.

[(A2) Compound]
The crosslinkable group in the compound (a2) is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. As a preferred embodiment of the structural unit having a crosslinkable group, an epoxy group, an oxetanyl group, a group represented by —NH—CH ₂ —O—R (where R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene And a structural unit containing at least one selected from the group consisting of an unsaturated group, an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R is a hydrogen atom or a carbon number of 1 to 20). And at least one selected from the group consisting of an ethylenically unsaturated group. Among them, in the composition used in the present invention, the component (A) preferably includes a structural unit containing at least one of an epoxy group and an oxetanyl group.

Four
Examples of the unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylate-3, 4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid-3,4-epoxycyclohexylmethyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl , O-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, compounds containing an alicyclic epoxy skeleton described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443, and the like. these Contents of which are incorporated herein.

Moreover, the unsaturated compound which has an oxiranyl group can also be used as an unsaturated compound which has an epoxy group.
Examples of unsaturated compounds having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and glycidyl α-n-butyl acrylate. 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethylacrylic-6,7-epoxyheptyl, o-Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-Epoxycyclohexyl is preferable from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the cured film.

Examples of the unsaturated compound having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- ( (Acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2, 2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxy) Ethyl) oxetane, 3- 2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-acryloyl) Oxyethyl) -2-pentafluoroethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluorooxetane, 3- (2-acryloyloxy) Ethyl) -2,2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane and the like; 3-ethyl-3-methacryloyloxymethyloxetane , 3- (Methacryloyloxymethyl) oxetane 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2 -Pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluoro Oxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacrylo Yloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (2-methacryloyl) Oxyethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane, 3- (2-methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (2 -Methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane and the like. These (a2) compounds may be used alone or in admixture of two or more.
In addition to the unsaturated compound having an oxetanyl group, specific examples of the radical polymerizable monomer used to form a structural unit having an oxetanyl group include, for example, JP-A-2001-330953 Examples include (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016, and the contents thereof are incorporated herein.

In the unsaturated compound having a group represented by —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), R is preferably an alkyl group having 1 to 9 carbon atoms, An alkyl group having 1 to 4 carbon atoms is more preferable. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. More preferable examples of the unsaturated compound having a group represented by —NH—CH ₂ —O—R include compounds represented by the following general formula (a2-30).
Formula (a2-3)
(In general formula (a2-3), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
R ² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.

  As an unsaturated compound which has an ethylenically unsaturated group, description of paragraph number 0072-0090 of Unexamined-Japanese-Patent No. 2011-215580 can be referred, for example, The content of these is integrated in this-application specification.

(A2) As a use ratio of a compound, 5-70 mass% is preferable based on the sum total of (a1) compound and (a2) compound, and 20-65 mass% is more preferable. (A2) By making the usage-amount of a compound into the said range, the cured film which has the outstanding solvent resistance etc. can be formed.
[(A3) Compound]
The compound (a3) is not particularly limited as long as it is an unsaturated compound other than the compounds (a1) and (a2). Examples of the compound (a3) include methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Bicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, unsaturated compound containing skeleton represented by the following formula (4), and other unsaturated compounds Compounds and the like.

In the formula (4), R ²³ is a hydrogen atom or a methyl group. s is an integer of 1 or more.

  Examples of the chain alkyl ester of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and n-methacrylate. Examples include lauryl, tridecyl methacrylate, and n-stearyl methacrylate.

Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2.1]. .0 ^2,6] decan-8-yl oxy ethyl, and isobornyl methacrylate.

  Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. Examples include lauryl, tridecyl acrylate, and n-stearyl acrylate.

Examples of acrylic acid cyclic alkyl esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5.2.1.0 ^2,6. ] Decan-8-yloxyethyl acrylate, isobornyl acrylate and the like.

  Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

  Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.

  Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

  Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1]. Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 -Cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2 2.1] Hept- -Ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2 ′ -Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2. 2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, and the like.

  Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  Examples of unsaturated compounds containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene- 2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2- Yl-hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one, etc. Is mentioned.

  Examples of unsaturated compounds containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one , 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like.

  Examples of unsaturated compounds containing a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran and 4- (1,5-dioxa-6-oxo. -7-octenyl) -6-methyl-2-pyran and the like.

  Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, acryloylmorpholine, p-vinylbenzyl 2,3-epoxypropyl ether, and the like.

Among these (a3) compounds, it has a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a skeleton represented by the above formula (4). Unsaturated compounds, unsaturated aromatic compounds and acrylic acid cyclic alkyl esters are preferred. Among these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, p-methoxystyrene, 2- Methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one From the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution, it is more preferable. These (a3) compounds may be used alone or in admixture of two or more.

  (A3) As a use ratio of a compound, 0-70 mass% is preferable based on the sum total of (a1) compound and (a3) compound (and arbitrary (a2) compound), and 0-50 mass% is more preferable. . (A3) By making the use ratio of a compound into the said range, the cured film excellent in solvent resistance etc. can be formed.

In addition, a molecular weight modifier may be added to the (A) polymer. The molecular weight modifier is not particularly limited, and examples thereof include pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), and α-methylstyrene dimer. Only one type of molecular weight regulator may be used, or two or more types may be used in combination.
As a usage-amount of a molecular weight modifier, 0.5-10 mass% is preferable in a polymer (A), and 1-5 mass% is more preferable.
The polymer (A) used in the present invention is particularly preferably an acrylic polymer containing the (a1) repeating unit having an acid group and the (a2) repeating unit having a crosslinkable group.

<(A) Polymer Synthesis Method>
(A) The synthesis | combination of a polymer can consider description of the paragraph numbers 0067-0073 of Unexamined-Japanese-Patent No. 2012-88549, and this content is integrated in this-application specification.

<(B) Quinonediazide compound>
As the (B) quinonediazide compound used in the composition of the present invention, a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.
Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3 , 4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone, and the like.
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone.
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone and 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone.
Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxy). Phenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-) 4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl) -4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like.
Examples of other mother nuclei include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1- (4 -Hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4 , 6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, and the like.

  Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2. -Naphthoquinonediazide-4-sulfonic acid amide etc. are also used suitably.

  These (B) quinonediazide compounds can be used alone or in combination of two or more. The proportion of the (B) quinonediazide compound used in the photosensitive resin composition is preferably 5 to 100% by mass, more than 10% by mass and 40% by mass or less, based on the total solid content in the photosensitive resin composition. More preferably, it is more than 12 mass% and 40 mass% or less. (B) By setting the use ratio of the quinonediazide compound within the above range, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution serving as the developer is large, the patterning performance is improved, and the cured film obtained The solvent resistance is improved.

<(C) Compound having a structure containing a coordination atom and a thiourea structure in one molecule (hereinafter also referred to as component (C))>
The composition of the present invention contains a compound having a structure containing a coordination atom and a thiourea structure in one molecule. It is presumed that such a basic site (for example, a structure containing a coordination atom) contained in the component (C) promotes the crosslinking reaction of the cured film.
Here, the coordination atom is, for example, an inorganic material constituting the base substrate to which the composition of the present invention is applied, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, gold, copper, molybdenum, titanium, aluminum, or the like. An atom capable of forming a coordination bond with the metal is preferable. Specifically, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are more preferable, and a nitrogen atom or an oxygen atom is particularly preferable.
Moreover, the structure containing a coordination atom is preferably a structure containing at least one nitrogen atom, and more preferably a structure containing 1 to 3 nitrogen atoms.
Specific examples of the structure containing a coordination atom include, for example, morpholino group, hydrazino group, pyridyl group, imidazolyl group, quinolyl group, piperidyl group, pyrrolidinyl group, pyrazonyl group, oxazolyl group, thiazolyl group, benzooxazolyl group, Examples thereof include a benzimidazolyl group, a benzthiazolyl group, a pyrazinyl group, and a diethylamino group. Among these, morpholino group, piperidyl group, imidazolyl group and diethylamino group are preferable, morpholino group, piperidyl group and imidazolyl group are more preferable, and morpholino group is more preferable.
By using such a component (C), the interaction between the composition of the present invention and the base substrate can be strengthened, and the adhesion to various substrates in the state of development and cured film is improved. It is thought that.
Furthermore, in the post-bake process, a cured film having a higher crosslinking density is formed by promoting the reaction between the acid group and the crosslinking group of the polymer contained in the composition of the present invention. Used for forming a pattern of a transparent electrode film after the formation of an interlayer insulating film or a liquid crystal alignment film. It is considered that the resistance to NMP can be improved.

The component (C) is preferably a compound containing at least one nitrogen atom as a coordination atom, and more preferably a compound represented by the following general formula (S).
General formula (S)
(In general formula (S), R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group.)

R ¹ represents a group containing at least one nitrogen atom, preferably a group containing 1 to 3 nitrogen atoms, and more preferably a group represented by —NR ³ R ⁴ .
R ¹ preferably contains 1 to 10 carbon atoms and 1 to 3 heteroatoms including a nitrogen atom and / or an oxygen atom. In this case, examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, and a nitrogen atom and an oxygen atom are preferable. R ¹ is preferably a cyclic group, more preferably a 5-membered or 6-membered cyclic group.
R ³ and R ⁴ each represents an organic group. As the organic group, an alkyl group, an alkenyl group, or a group composed of at least one of these and —O—, —S—, and —N— is preferable. R ³ and R ⁴ are each preferably a group having 1 to 3 carbon atoms. R ³ and R ⁴ may be bonded to each other to form a ring, and preferably form a ring. In particular, R ³ and R ⁴ are bonded to each other to form a 5-membered or 6-membered ring. Is preferably formed.

Preferred embodiments of R ¹ include the following embodiments.
(1) An embodiment in which R ¹ is a group represented by —NR ³ R ⁴ and R ³ and R ⁴ are bonded to each other to form a ring, or R ³ and R ⁴ are respectively , A linear, branched or cyclic aliphatic hydrocarbon group.
(2) An embodiment in which R ¹ is a group represented by —NR ³ R ⁴ and R ³ and R ⁴ are bonded to each other to form a 5-membered or 6-membered ring, or R ³ and R ⁴ Are respectively a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms.
(3) R ¹ is a group represented by —NR ³ R ⁴ , and R ³ and R ⁴ are bonded to each other to form two or more heteroatoms (at least one is a nitrogen atom and the rest are oxygen atoms or A mode in which a 5-membered ring or a 6-membered ring is formed, or R ³ and R ⁴ are each a straight-chain aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aspect which is.

Specific examples of R ¹ include, for example, morpholino group, hydrazino group, pyridyl group, imidazolyl group, quinolyl group, piperidyl group, pyrrolidinyl group, pyrazonyl group, oxazolyl group, thiazolyl group, benzoxazolyl group, benzimidazolyl group, A benzthiazolyl group, a pyrazinyl group, a diethylamino group, etc. are mentioned. Among these, morpholino group, piperidyl group, imidazolyl group and diethylamino group are preferable, morpholino group, piperidyl group and imidazolyl group are more preferable, and morpholino group is more preferable.

R ² represents an organic group. The organic group is preferably a hydrocarbon group or a group consisting of a hydrocarbon group and at least one of —O— and —C (═O) —, particularly an aliphatic hydrocarbon group or an aliphatic group. A group composed of a hydrocarbon group and at least one combination of —O— and —C (═O) — is more preferable. The number of carbon atoms in R ² is preferably from 1 to 20, 1 to 10 is more preferable.
R ² preferably has a hydrocarbon group at the terminal. When R ² has a hydrocarbon group at the terminal, the hydrophobicity is further improved, and the effects of the present invention are more effectively exhibited.
Specifically, R ² is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, or a group composed of at least one of —O— and —C (═O) —. Further preferred. These groups may have a substituent, and examples of the substituent include a halogen atom.
When R ² is an alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group is preferable. When R ² is a cyclic alkyl group, a 5-membered or 6-membered cyclic alkyl group is preferred.
When R ² is an aryl group, a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable.

Preferred embodiments of R ² include the following embodiments.
(1) The aspect which is a C1-C4 (preferably 2 or 3) linear alkylene group.
(2) Aspect of being a 5- or 6-membered cyclic alkyl group (3) an aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably 2 to 4 carbon atoms), -O- and -C (= O) An embodiment in which the group is a combination of-and the terminal is a hydrocarbon group

A represents a divalent linking group, such as a hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —NR—, —CO—, —COO—, —NRCO—, —SO ₂ — and the like. Examples thereof include a divalent group or a divalent group composed of a combination of these groups. Here, R represents a hydrogen atom or an alkylene group having 1 to 4 carbon atoms. Among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable, a hydrocarbon group having 1 to 10 carbon atoms is more preferable, and a hydrocarbon group having 2 to 6 carbon atoms is more preferable. Examples of the hydrocarbon group include an alkylene group and an arylene group, and an alkylene group is preferable. The alkylene group is preferably a linear or branched alkylene group, and more preferably a linear alkylene group.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a cyclohexylene group, and a cyclopentylene group. Examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a naphthylene group. In the present invention, a methylene group, an ethylene group, and a propylene group are particularly preferable, and an ethylene group or a propylene group is more preferable.

Preferred embodiments of A include the following embodiments.
(1) The aspect which is a C1-C4 linear or branched alkyl group, a 5-membered ring or a 6-membered cyclic alkyl group, or a phenyl group.

The compound represented by the general formula (S) is exemplified as a particularly preferable embodiment in which the preferred embodiment of R ¹ , the preferred embodiment of R ² , and the preferred embodiment of A are combined.

More preferably, the compound represented by the general formula (S) is represented by the general formula (S1).
General formula (S1)
(In general formula (S1), R ² represents an organic group, and A represents a divalent linking group.)
R ² has the same meaning as R ² in formula (S), and the preferred range is also the same.
A is synonymous with A in the formula (S), and the preferred range is also the same.
In particular, in the general formula (S1), the following embodiments are preferable.
(1) A mode in which A is a linear alkylene group having 1 to 4 carbon atoms, and R ² is a linear, branched, or cyclic alkyl group.
(2) A mode in which A is an alkylene group having 2 or 3 carbon atoms, and R ² is a linear, branched, or cyclic alkyl group having 2 to 6 carbon atoms.

Specific examples of the general formula (S) include the following compounds, but the present invention is not particularly limited thereto. In the following exemplary compounds, Et represents an ethyl group.

150-1000 are preferable and, as for the molecular weight of the said (C) component, 200-500 are more preferable.
The composition of the present invention preferably contains the component (C) in a proportion of 0.001 to 10 parts by mass, and in a proportion of 0.003 to 7.5 parts by mass with respect to 100 parts by mass of the total solid content. Is more preferable, and it is further more preferable to contain in the ratio of 0.005-5 mass parts. (C) Only 1 type may be sufficient as a component and 2 or more types may be sufficient as it. In the case of two or more types, the total is preferably in the above range.

<Other optional components>
In addition to the (A) polymer, the (B) quinonediazide compound, the (C) component, the composition of the present invention includes a silane coupling agent, a surfactant, Optional components such as an adhesion aid, a heat resistance improver, and a heat-sensitive acid generator can be contained. These optional components may be used alone or in combination of two or more. Details of these compounds can be referred to the description of paragraph numbers 0201 to 0224 of JP2012-88459A, the contents of which are incorporated herein.

Silane coupling agent The silane coupling agent used in the composition of the present invention preferably contains an alkoxysilane compound. When an alkoxysilane compound is used, the adhesion between the film formed from the composition used in the present invention and the substrate can be further improved, or the properties of the film formed from the composition used in the present invention can be adjusted. it can. The alkoxysilane compound that can be used in the composition of the present invention includes an inorganic material as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, molybdenum, titanium, or aluminum, and an insulating film. It is preferable that it is a compound which improves adhesiveness. Specifically, a known silane coupling agent or the like is also effective.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.

Moreover, the compound represented with the following general formula can also be employ | adopted preferably.
_{^{(R 1) 4-n -Si-}} (OR 2) n
In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group, R ² is an alkyl group or a phenyl group having 1 to 3 carbon atoms, n represents an integer of 1 to 3 It is.
Specific examples thereof include the following compounds.

  In the above, Ph is a phenyl group.

  As for content of the alkoxysilane compound in the composition of this invention, 0.1-30 mass parts is preferable with respect to 100 mass parts of total solids in a photosensitive composition, and 0.5-20 mass parts is more preferable. .

Surfactant It does not specifically limit as surfactant used for the composition of this invention, For example, what was described in Unexamined-Japanese-Patent No. 2012-8859, paragraph number 0201-0205 can be used. Only one surfactant may be used, or two or more surfactants may be used in combination, but two or more surfactants are preferably used in combination.
The content of the surfactant in the composition of the present invention is preferably 0.01 to 1 part by mass, and 0.05 to 0.5 part by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition. More preferred.

<Solvent>
The composition of the present invention may further contain a solvent. As the solvent used in the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.

  Among such solvents, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether from the viewpoint of solubility of each component, reactivity with each component, ease of film formation, and the like. , Ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono -N-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (Poly) alkylene glycol monoalkyl ethers of

  Acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid ethylene glycol mono-n-propyl ether, acetic acid ethylene glycol mono-n-butyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-propyl Acetic acid (poly) alkylene glycol monoalkyl ethers such as ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate ;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, 3-methyl-3-methoxybutylpropio Nate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 2 -Other esters such as ethyl oxobutyrate;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

  Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate Le acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate are preferred. The solvent can be used alone or in combination of two or more.

  In addition to the above solvents, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination. The said high boiling point solvent can use single or 2 types or more.

  Although it is not limited as content of a solvent, the total density | concentration of each component remove | excluding the solvent of the said photosensitive resin composition from viewpoints of the applicability | paintability of a photosensitive resin composition obtained, stability, etc. is 5-50 mass%. The quantity which becomes is preferable, and the quantity used as 10-40 mass% is more preferable. When the photosensitive resin composition is prepared in a solution state, the solid content concentration (components other than the solvent in the composition solution) can be set to any concentration (for example, 5 depending on the purpose of use, a desired film thickness value, etc.). ˜50 mass%). A more preferable solid content concentration varies depending on a method of forming a film on the substrate, which will be described later. The composition solution thus prepared can be used after being filtered using a Millipore filter or the like having a pore diameter of about 0.5 μm.

<Method for preparing photosensitive resin composition>
The composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, and stirring and dissolving. For example, the resin composition can be prepared by mixing each component in a predetermined ratio after preparing each solution in advance in the above-described solvent. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore size of 0.2 μm.

[Method for producing cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the composition of this invention on a board | substrate;
(2) A step of removing the solvent from the applied photosensitive resin composition;
(3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays;
(4) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5) A post-baking step of thermosetting the developed photosensitive resin composition.
Each step will be described below in order.

In the coating step (1), it is preferable to apply the composition of the present invention on a substrate to form a wet film containing a solvent. Before applying the photosensitive resin resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like.
These substrates are rarely used in the above-described form, and usually a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.
The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP 2009-145395 A.
The wet film thickness when applied is not particularly limited and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 μm.

  In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. In particular, an embodiment in which the solvent is removed from the film by heating to form a dry coating film on the substrate is preferable. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.

In the exposure step (3), the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mj / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, since the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, PEB is not necessarily performed. A positive image can also be formed by development.

In the developing step (4), a polymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
Preferred examples of the developer include 0.4% aqueous solution, 0.5% aqueous solution, 0.7% aqueous solution and 2.38% aqueous solution of tetraethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The developing time is preferably 30 to 500 seconds, and the developing method may be any of a liquid piling method and a dipping method. After development, washing with running water is usually performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

In the post-baking step of (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and then crosslinked with a crosslinkable group, a crosslinking agent or the like. A cured film can be formed. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on a hot plate, 30 to 120 minutes for an oven. It is preferable to By proceeding with such a crosslinking reaction, it is possible to form a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking step). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

  Furthermore, the cured film obtained from the composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

[Curing film]
The cured film of the present invention is a cured film obtained by curing the composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
By the composition of the present invention, an interlayer insulating film having excellent transparency and high transparency even when baked at a high temperature can be obtained. Since the interlayer insulating film using the composition of the present invention has high transparency and excellent cured film properties, it is useful for applications of organic EL display devices and liquid crystal display devices. For details of the organic EL display device and the liquid crystal display device, paragraphs 0209-0210 of JP2011-209681A and the description of FIGS. 1 and 2 can be referred to, and the contents thereof are incorporated in the present specification.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
In the following synthesis examples, the weight average molecular weight Mw of the copolymer was measured by gel permeation chromatography (GPC) under the following apparatus and conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Detector: Differential refractometer Standard material: Monodisperse polystyrene

<(A) Synthesis of polymer>
(Synthesis of P-1)
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 12 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 4 parts by weight of N-cyclohexylmaleimide, 15 parts by weight of tetrahydrofurfuryl methacrylate, 5 parts by weight of acryloylmorpholine, 8 parts by weight of 3- (2-methacryloyloxyethyl) oxetane. And 2 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) were charged and purged with nitrogen, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and the polymerization was started when the reaction solution temperature reached 70 ° C. Thereafter, 3 parts by mass of N-cyclohexylmaleimide 30 minutes after the start of polymerization, and 3 parts by mass of N-cyclohexylmaleimide were added dropwise to the reaction solution 1 hour later. Then, the polymer solution containing a copolymer (P-1) was obtained by hold | maintaining for 3 hours. The polystyrene equivalent weight average molecular weight (Mw) of the copolymer P-1 was 9,000, and the molecular weight distribution (Mw / Mn) was 2.0.

  Other polymers were synthesized in the same manner as P-1 using the monomers listed in the following table (monomer components (raw materials of (a1) to (a3))), a polymerization initiator, a molecular weight regulator, and a solvent. did.

<Preparation of photosensitive resin composition>
Dissolve and mix (A) component, (B) component, (C) component, silane coupling agent and surfactant in a solvent until the solid content ratio is 32% so that the solid content ratio shown in the following table is obtained. Then, the mixture was filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of various examples and comparative examples.

<(A) component>
The polymers of P-1 to P-11 described above were used.
<(B) component>
B-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate with sulfonic acid chloride (3.0 mol) B-2: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (2.0 mol) B-3: 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44) Mole)

<(C) component>
The following compounds (C-1) to (C-12) were used.

(Silane coupling agent)
D-1: 3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Surfactant)
W-1: Silicone surfactant ("SH 8400 FLUID" manufactured by Toray Dow Corning Co., Ltd.)
W-2: Fluorosurfactant FTX-218 (manufactured by Neos Co., Ltd.)

  The following evaluation was performed about the obtained composition.

<Evaluation of adhesion during development>
A glass substrate (10 cm × 10 cm) in which a Mo (molybdenum) thin film is formed on a half region (10 cm × 5 cm) of one surface of the substrate and a SiNx thin film is formed on the other half region (10 cm × 5 cm) of the same surface. 10 cm × 0.5 mm) is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition solution is applied using a spin coater so that the dry film thickness becomes 3 μm. The solvent was volatilized by pre-baking on a hot plate at 2 ° C. for 2 minutes. Then, after exposing to an integrated dose of 40 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line) using an ultra-high pressure mercury lamp through a mask capable of reproducing a 10 μm line / 10 μm space, an alkali developer Development was performed at 23 ° C. for 60 seconds with (0.4 mass% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 1 minute. The obtained substrate was observed with an optical microscope, and the Mo part and the SiNx part were observed for chipping and peeling of the 10 μm line / 10 μm space pattern. The results are shown in the following table. Less peeling is preferable, and A or B is preferable.
A: No chipping or peeling B: Chipping or peeling 30% or less C: Chipping or peeling over 30% to 60% D: Chipping or peeling over 60% to 100% or less

<Hardened film adhesion: Mo>
After exposing a glass substrate (10 cm × 10 cm × 0.5 mm) on which a Mo (molybdenum) thin film was formed under hexamethyldisilazane (HMDS) vapor for 30 seconds, and then spin-coating each photosensitive resin composition And a pre-baking on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 3 μm. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
Next, the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the numerical value, the higher the adhesion to the base substrate, and A or B is preferred.
A: The transferred area is less than 1% B: The transferred area is 1% or more and less than 5% C: The transferred area is 5% or more and less than 10% D: The transferred area is 10% or more and less than 50% E : The transferred area is 50% or more

<Hardened film adhesion: Ti>
After exposing a glass substrate (10 cm × 10 cm × 0.5 mm) on which a Ti (titanium) thin film was formed under hexamethyldisilazane (HMDS) vapor for 30 seconds and then spin-coating each photosensitive resin composition And a pre-baking on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 3 μm. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
Next, the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the numerical value, the higher the adhesion to the base substrate, and A or B is preferred.
A: The transferred area is less than 1% B: The transferred area is 1% or more and less than 5% C: The transferred area is 5% or more and less than 10% D: The transferred area is 10% or more and less than 50% E : The transferred area is 50% or more

<Hardened film adhesion: SiNx>
A glass substrate (10 cm × 10 cm × 0.5 mm) on which a SiNx (silicon nitride) thin film was formed was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition was spin-coated. Then, the solvent was volatilized by pre-baking on a hot plate at 90 ° C. for 2 minutes to form a photosensitive resin composition layer having a thickness of 3 μm. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
Next, the cured film was cut using a cutter at intervals of 1 mm vertically and horizontally, and a tape peeling test (100 mask loss cut method: conforming to JIS 5600) was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the numerical value, the higher the adhesion to the base substrate, and A or B is preferred.
A: The transferred area is less than 1% B: The transferred area is 1% or more and less than 5% C: The transferred area is 5% or more and less than 10% D: The transferred area is 10% or more and less than 50% E : The transferred area is 50% or more

<Evaluation of stripping solution resistance>
The glass substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition is spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C./120 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 3.0 μm was formed. Subsequently, using an ultra-high pressure mercury lamp, exposure was performed so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and this substrate was heated in an oven at 230 ° C./30 minutes, Furthermore, it heated at 230 degreeC / 2 hours in oven.
The film thickness (T1) of the obtained cured film was measured. And after immersing the board | substrate with which this cured film was formed in peeling liquid (mixed liquid of a monoethanolamine and dimethylsulfoxide (DMSO)) temperature-controlled at 80 degreeC for 10 minutes, The film thickness (t1) was measured, and the film thickness change rate {| t1-T1 | / T1} × 100 [%] due to immersion was calculated. The results are shown in the table below. A smaller value is preferable, and A and B are at a level causing no problem in practical use.
A: Less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4% D: 4% or more and less than 6% E: 6% or more

<Evaluation of NMP resistance>
The glass substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition is spin-coated on the substrate, and then pre-baked on a hot plate at 90 ° C./120 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 3.0 μm was formed. Subsequently, using an ultra-high pressure mercury lamp, exposure was performed so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and this substrate was heated in an oven at 230 ° C./30 minutes, Furthermore, it heated at 230 degreeC / 2 hours in oven.
The film thickness (T1) of the obtained cured film was measured. And after immersing the board | substrate with which this cured film was formed in NMP temperature-controlled at 80 degreeC for 10 minutes, the film thickness (t1) of the cured film after immersion was measured, and the film thickness change rate by immersion { | T1−T1 | / T1} × 100 [%] was calculated. The results are shown in the table below. A smaller value is preferable, and A and B are at a level causing no problem in practical use.
A: Less than 2% B: 2% or more and less than 3% C: 3% or more and less than 4% D: 4% or more and less than 6% E: 6% or more

As apparent from the above results, the composition of the present invention comprises (A) (a1) a repeating unit having an acid group, (a2) a polymer containing a repeating unit having a crosslinkable group, (B) a quinonediazide compound, and (C) In one molecule, since it contains a compound having a structure containing a coordination atom and a thiourea structure, it has excellent adhesion to various substrates in the state of development and as a cured film, The resist stripping solution and NMP were also excellent in resistance (chemical resistance).
In Comparative Example 1, since the component (C) was not used, the adhesion of the cured film to various substrates, the adhesion to various substrates during development, and the chemical resistance were inferior to those of the Examples.
In Comparative Example 2, a compound different from the compound (C-1) only in that S was replaced with O was used. However, the adhesion of the cured film to various substrates and the adhesion to various substrates during development were different from those of the compound (C-1). It was greatly inferior to Example 12 using (C-1).
In Comparative Example 3, a compound different from the compound (C-1) only in that NH was replaced with O was used, but the adhesion of the cured film to various substrates and the adhesion to various substrates during development were different from those of the compound (C-1). It was greatly inferior to Example 12 using (C-1).
In Comparative Example 4, a compound different from the compound (C-1) only in that R ¹ was replaced from a morpholino group to a cyclohexyl group was used, but the adhesion of the cured film to various substrates and the adhesion to various substrates during development The properties and chemical resistance were greatly inferior to those of Example 12 using the compound (C-1).
In Comparative Example 5, a compound different from the compound (C-1) only in that R ¹ was replaced from a morpholino group to an aryl group was used. However, the adhesion of the cured film to various substrates and the adhesion to various substrates during development were used. And chemical resistance were greatly inferior to Example 12 using the compound (C-1).
In Comparative Example 6, a compound having a thiouracil structure was used as the component (C). However, since the compound does not contain a structure containing a coordination atom, the adhesion of the cured film to various substrates, during development The adhesion to various substrates and chemical resistance were greatly inferior.
In Comparative Example 7, the polymer containing the repeating unit (a2) having a crosslinkable group was not used as the component (A), and the adhesion and chemical resistance of the cured film to various substrates were greatly inferior.
In Comparative Example 8, as the component (A), a polymer containing (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group was not used, and a phenol resin (novolak resin) was used. Since it was used, the adhesion of the cured film to various substrates and the chemical resistance were greatly inferior. Although this mechanism is not clear, since the photosensitive resin composition of Comparative Example 8 uses a polymer that does not contain a crosslinkable group, that is, a phenol resin, it is crosslinked as in the photosensitive resin composition of the examples. Since the functional group and the component (C) do not interact, for example, when the developer (TMAH) touches a substrate such as Mo, Ti, or SiNx, the surface of the substrate is modified and partially dissolved. As a result of the penetration of the developer into the interface between the substrate and the cured film, the adhesion to the substrate in the state when developing the photosensitive resin composition and when the photosensitive resin composition is a cured film is reduced. Estimated Further, although this mechanism is not clear, since the photosensitive resin composition of Comparative Example 8 uses a polymer that does not contain a crosslinkable group, an implementation using a polymer containing a repeating unit having a crosslinkable group is used. As an example, it is presumed that the chemical resistance when the photosensitive resin composition was used for an interlayer insulating film was lowered as a result of the inability to improve the cross-linking density when a cured film was formed.

<Production of organic EL display device>
An organic EL display device using a TFT was manufactured by the following method (see, for example, FIG. 1 of JP 2011-209681 A).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 8 on a substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. After irradiating i-line with 100 mJ / cm ² using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 220 ° C. for 60 minutes. The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average level difference of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film was 2000 nm.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and DMSO). The first electrode thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating layer 8 having a shape covering the periphery of the first electrode was formed. For the insulating layer, the photosensitive resin composition of Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating layer, it is possible to prevent a short circuit between the first electrode and the second electrode formed in the subsequent process.

  Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

<Production of liquid crystal display device>
In the active matrix type liquid crystal display device shown in FIGS. 1 and 2 of Japanese Patent No. 3321003, a liquid crystal display device is manufactured according to a conventional method using the photosensitive resin composition of Example 1 of the present invention as the interlayer insulating film 17. did.

  When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

Claims (17)

(A) (a1) a polymer containing a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group,
(B) a quinonediazide compound, and (C) a photosensitive resin composition containing, in one molecule, a compound having a structure containing a coordination atom and a thiourea structure;
However, it is a photosensitive resin composition containing an alkali-soluble resin containing a structural unit represented by the following general formula (1) and a radiation-sensitive acid generator, and satisfies the following (1) and / or (2): Excluding the photosensitive resin composition;
(1) The alkali-soluble resin containing the structural unit represented by the general formula (1) has an acid labile group;
(2) The photosensitive resin composition includes a resin having an acid labile group;
General formula (1)
In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 9 carbon atoms.   The photosensitive resin composition according to claim 1, wherein the component (C) is a compound containing at least one nitrogen atom as the coordination atom. The photosensitive resin composition of Claim 1 or 2 whose said (C) component is a compound represented by the following general formula (S).
General formula (S)
(In general formula (S), R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group.) In the general formula (S), R ¹ is a group represented by —NR ³ R ⁴ (R ³ and R ⁴ are each an organic group and may be bonded to each other to form a ring). The photosensitive resin composition of Claim 3 which is. The photosensitive resin composition of Claim 3 or 4 whose R < ¹ > is a 5-membered ring or a 6-membered cyclic group in the said general formula (S). The photosensitive resin composition of any one of Claims 3-5 whose R < ¹ > is a morpholino group in the said general formula (S). In the general formula (S), having a hydrocarbon group at the terminal of R ^2, the photosensitive resin composition according to any one of claims 3-6.   The photosensitive resin composition of any one of Claims 1-7 whose said structural unit (a1) is a repeating unit which has a carboxyl group and / or a phenolic hydroxyl group. The structural unit (a2) was selected from the group consisting of an epoxy group, an oxetanyl group, and a group represented by —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The photosensitive resin composition of any one of Claims 1-8 containing the structural unit containing at least one.   The amount of the component (B) in the photosensitive resin composition is more than 10% by mass and 40% by mass or less with respect to the total solid content in the photosensitive resin composition. 2. The photosensitive resin composition according to item 1.   The photosensitive resin composition of any one of Claims 1-10 whose said photosensitive resin composition is a positive photosensitive resin composition. (1) The process of apply | coating the photosensitive resin composition of any one of Claims 1-11 on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
The manufacturing method of the cured film containing this.   The manufacturing method of the cured film of Claim 12 including the process of exposing the developed photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process.   The manufacturing method of the cured film of Claim 12 or 13 including the process of dry-etching with respect to the board | substrate which has a cured film obtained by thermosetting at the said post-baking process. The cured film formed by hardening the photosensitive resin composition of any one of Claims 1-11 .   The cured film according to claim 15, which is an interlayer insulating film.   An organic EL display device or a liquid crystal display device having the cured film according to claim 15 or 16.