TWI587092B - Positive-type photo-sensitive resin composition, method for forming cured film, cured film, organic el display device, and liquid crystal display device - Google Patents

Description

Positive photosensitive resin composition, method of forming cured film, and hardening Film, organic EL display device, and liquid crystal display device

The present invention relates to a positive photosensitive resin composition (hereinafter, simply referred to as "photosensitive resin composition" and "composition of the present invention"). Further, the present invention relates to a method for producing a cured film using the positive photosensitive resin composition, a cured film obtained by curing a positive photosensitive composition, and various image display devices using the cured film.

More specifically, the present invention relates to a positive photosensitive resin composition and a method for producing a cured film using the same, wherein the positive photosensitive resin composition is suitable for forming a liquid crystal display device or an organic electroluminescence (Electroluminescence). EL) A flattening film, a protective film, or an interlayer insulating film of an electronic component such as a display device, an integrated circuit element, or a solid-state image sensor.

In an organic EL display device, a liquid crystal display device or the like, an interlayer insulating film formed by patterning is provided. When forming the interlayer insulating film, it is used to obtain a necessary pattern. A photosensitive resin composition is widely used in terms of the number of steps of the shape of the case, and sufficient flatness is obtained (International Publication No. 2007/122929, Japanese Patent Laid-Open No. 2011-48064).

The inventors of the present application conducted a study on the above-mentioned International Publication No. 2007/122929, and found that sensitivity, transparency, and adhesion to a substrate are obtained when the disulfide compound described in the International Publication No. 2007/122929 is used. The performance required for the photosensitive resin composition for forming the interlayer insulating film is insufficient.

The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a positive photosensitive resin composition having high sensitivity, excellent adhesion to a substrate, and excellent transparency.

In the above-mentioned circumstances, the inventors of the present invention conducted an effort to find that a thioether compound containing a ruthenium atom is used in a positive photosensitive resin composition, and it is possible to provide a high sensitivity and excellent adhesion to a substrate. The positive photosensitive resin composition having excellent transparency has completed the present invention.

Specifically, the above problem is solved by the means of the following <1>, preferably <2> to <15>.

<1> A positive photosensitive resin composition containing: (Component A) an alkali-soluble resin; (Component B) 1,2-quinonediazide compound; and (Component X) of the following formula (I) Compound represented;

(In the formula (I), R ¹ to R ⁶ each independently represent a hydrocarbon group or an alkoxy group, and L ¹ and L ² each independently represent an alkylene group, an extended aryl group or a group containing a combination of the groups, n represents an integer from 2 to 4).

The positive-type photosensitive resin composition as described in <1>, wherein the alkali-soluble resin is a copolymer containing (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group; .

<3> The positive photosensitive resin composition as described in <2>, wherein the structural unit (a1) is a repeating unit having a carboxyl group and/or a phenolic hydroxyl group.

<4> The positive photosensitive resin composition as described in <2>, wherein the structural unit (a2) is a repeating unit having an epoxy group and/or an oxetanyl group.

The positive photosensitive resin composition as described in any one of the above-mentioned (component X), wherein the compounding amount of the above-mentioned (component X) is 1 mass% to 25 mass in the total solid content of the composition. %.

<6> The <1> to <5> The positive-type photosensitive resin composition according to any one of claims, wherein R ¹ ~ R ⁶ are each independently alkyl having 1 to 6 carbon atoms or 1 to 6 Alkoxy group.

<7> The <1> to <6> positive type photosensitive resin composition according to any one of claims, wherein L ¹ and L ² are each independently an alkylene group having a carbon number 1 to 8, or phenylene A group comprising a combination of such groups.

The positive photosensitive resin composition as described in any one of <1> to <7>, wherein n is 3 or 4.

<9> A method of forming a cured film, comprising the steps of: (1) applying a positive photosensitive resin composition according to any one of <1> to <8> to a substrate; (2) a prebaking step of baking the positive photosensitive resin composition to be applied; (3) a step of exposing the baked positive photosensitive resin composition by actinic rays or radiation; (4) a step of developing the exposed positive photosensitive resin composition by an aqueous developing solution; and (5) a post-baking step of thermally curing the developed positive photosensitive resin composition.

<10> The method for forming a cured film according to <9>, wherein the step of performing comprehensive exposure of the developed positive photosensitive resin composition after (6) after the developing step and before the post-baking step .

<11> The method for forming a cured film according to <9> or <10>, further comprising the step of dry etching the substrate having the cured film obtained by thermal curing.

The method for forming a cured film according to any one of the above aspects, wherein the heat curing is performed at 200 ° C or higher.

<13> A cured film formed by the method for forming a cured film according to any one of <9> to <12>.

<14> The cured film according to <13>, which is an interlayer insulating film.

<15> An organic EL display device or a liquid crystal display device having the cured film as described in <13> or <14>.

In addition, the present invention is also achieved by the following means.

<16> The positive photosensitive resin composition according to any one of the preceding claims, wherein the alkali-soluble resin contains a fat derived from two or more linked members having an alicyclic 5-membered ring, an alicyclic 6-membered ring, or a member ring. A repeating unit of a compound of a ring structure.

<17> The positive photosensitive resin composition according to any one of the above, wherein the alkali-soluble resin contains a carboxyl group as an acid group.

<18> The positive photosensitive resin composition according to any one of the above, wherein the alkali-soluble resin contains a repeating unit having an aromatic structure.

<19> The positive photosensitive resin composition according to any one of the above, further comprising an adhesion improving agent and a surfactant.

<20> The positive photosensitive resin composition according to any one of the above, wherein the alkali-soluble resin contains (a2) a repeating unit having a crosslinkable group.

According to the present invention, it is possible to provide a positive photosensitive resin composition having high sensitivity, excellent adhesion to a substrate, and excellent transparency.

1‧‧‧TFT (thin film transistor)

2‧‧‧Wiring

3‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

8‧‧‧Insulation film

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

16‧‧‧TFT

17‧‧‧ hardened film

18‧‧‧Contact hole

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

FIG. 1 is a conceptual diagram showing an example of an organic EL display device. This is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.

FIG. 2 is a conceptual diagram showing an example of a liquid crystal display device. It shows a schematic cross-sectional view of an active matrix substrate in a liquid crystal display device, and has a cured film 17 as an interlayer insulating film.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be performed according to a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the specification of the present application, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit. Further, the term "organic EL element" as used in the present invention means an organic electroluminescence element.

In addition, in the expression of the group (atomic group) in the present specification, it is not described that the substituted and unsubstituted expressions include those having no substituent, and also include 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 positive photosensitive resin composition of the present invention contains (component A) an alkali-soluble resin, (component B) 1,2-quinonediazide compound, and (component X) represented by the following formula (I) Compound (sulfur-containing compound). Hereinafter, the details of these components will be described.

<Component A: Alkali Soluble Resin>

The alkali-soluble resin of the present invention is preferably an addition polymerization type resin, more preferably It is a polymer containing a structural unit derived from (meth)acrylic acid and/or its ester. Further, a structural unit other than the structural unit derived from (meth)acrylic acid and/or an ester thereof, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound may be contained.

The alkali-soluble resin of the present invention is a polymer containing a (meth)acrylic repeating unit, and is not particularly limited as long as it is a resin which has an alkali-soluble group in the molecule and is soluble in an aqueous alkaline solution. A resin which is rendered alkali-soluble by having a carboxyl group or a phenolic hydroxyl group as an alkali-soluble group is preferably used.

The ratio of the acrylic repeating unit contained in the alkali-soluble resin of the present invention is preferably 20 mol% (% by mole) to 100 mol%, and more preferably 35 mol% to 100 mol, from the viewpoint of forming a pattern having a high transmittance. %, especially preferably 50 mol% to 100 mol%.

The alkali-soluble resin of the present invention is preferably a copolymer containing (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group. The alkali-soluble resin may also contain other repeating units as needed.

(a1) a repeating unit having an acid group

The alkali-soluble resin of the present invention preferably contains a repeating unit having an acid group, and preferably contains a repeating unit (a1-1) having a carboxyl group, from the viewpoint of improving the solubility of the photosensitive resin composition in the developer. And a repeating unit (a1-2) having a carbon-unsaturated bond group and a carboxyl group, and a repeating unit (a1-3) having a phenolic hydroxyl group.

- repeating unit having a carboxyl group (a1-1) -

The repeating unit (a1-1) having a carboxyl group is, for example, a repeating unit derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid.

As the unsaturated carboxylic acid for obtaining the repeating unit (a1-1) having a carboxyl group, those enumerated below can be used.

That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

Further, examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

Further, the unsaturated polycarboxylic acid used to obtain the repeating unit (a1-1) having a carboxyl group may also be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester of a polyvalent carboxylic acid, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and succinic acid. Mono(2-methylpropenyloxyethyl)ester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate Wait.

Further, the unsaturated polycarboxylic acid may be a mono(meth)acrylate whose both ends are a dicarboxy polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone. Methacrylate and the like.

Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, monoalkyl maleate, monoalkyl fumarate, 4-carboxystyrene, etc. may be used. .

Among them, in terms of developability, in order to form a repeat having a carboxyl group The unit (a1-1) is preferably an acid anhydride of acrylic acid, methacrylic acid or an unsaturated polycarboxylic acid.

The repeating unit (a1-1) having a carboxyl group may be composed of a single one or may be composed of two or more kinds.

- a repeating unit (a1-2) having an unsaturated bond between carbon and a carboxyl group -

The repeating unit (a1-2) having an unsaturated bond between carbon and a carboxyl group is preferably a hydroxyl group which is present in the repeating unit (a2-1) having an unsaturated bond between carbons, and reacts with an acid anhydride. The resulting repeating unit.

As the acid anhydride, a known one may be used, and specific examples thereof include a dibasic acid anhydride such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or chlorobridge anhydride. An anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride or biphenyltetracarboxylic anhydride. Among these acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride or succinic anhydride is preferred from the viewpoint of developability.

The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably from 10 mol% to 100 mol%, and more preferably from 30 mol% to 100 mol%, from the viewpoint of developability.

- repeating unit having a phenolic hydroxyl group (a1-3) -

The repeating unit (a1-3) having a phenolic hydroxyl group may be exemplified by a molecule derived from hydroxystyrene, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide. a repeating unit of at least one phenolic hydroxyl compound.

(a1) The repeating unit having an acid group may be composed of a single one of (a1-1), (a1-2), and (a1-3), or may be composed of a mixture of these. This hair In the present invention, a repeating unit (a1-1) having a carboxyl group or a repeating unit (a1-3) having a phenolic hydroxyl group is preferred, and a repeating unit (a1-1) having a carboxyl group is more preferred.

From the viewpoint of developability, the content of the repeating unit having an acid group in (a1) in the alkali-soluble resin of the present invention is preferably from 1 mol% to 50 mol%, more preferably from 3 mol% to 45 mol%, further preferably from 5 mol%. ~40mol%. Here, the content of the repeating unit (a1) having an alkali-soluble group means the total content of (a1-1), (a1-2) and (a1-3).

(a2) a repeating unit having a crosslinkable group

In the alkali-soluble resin of the present invention, it is preferred to contain (a2) a repeating unit having a crosslinkable group. A repeating unit (a2-1) having a phenolic hydroxyl group, an acid anhydride group, an aldehyde group, a hydroxymethyl group, a maleidino group, a thiol group, or an intercarbon unsaturated group as a crosslinkable group, or a repeating unit (a2-2) having an epoxy group and/or an oxetanyl group as a crosslinkable group, and having a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) a repeating unit (a2-3) or the like as a crosslinkable group; preferably a repeating unit (a2-1) having an unsaturated bond between carbons or a repeat having an epoxy group and/or an oxetanyl group The unit (a2-2), the repeating unit (a2-3) having a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms), more preferably having an epoxy group and/or Or a repeating unit (a2-2) of an oxetanyl group, a repeating unit (a2-3) having a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms), and further A repeating unit (a2-2) having an epoxy group and/or an oxetanyl group is preferred.

The details of these repeating units will be described below.

- a repeating unit having a carbon-unsaturated bond (a2-1) -

The repeating unit (a2-1) having an inter-carbon unsaturated bonding group may be a repeating unit derived from a monomer having an inter-carbon unsaturated bonding group (polymerizable group). From the viewpoint of reactivity, the carbon-unsaturated bonding group (polymerizable group) is preferably a (meth)acrylonitrile group, an allyl group, more preferably a (meth)acrylylene group, and most preferably an acrylonitrile group. base. The repeating unit (A2-1) having an inter-carbon unsaturated bonding group is preferably a repeating unit having a structure in which an epoxy ring and a carboxyl group are added to a compound having an epoxy ring and an unsaturated bond between carbons, or A repeating unit having a structure in which a carboxyl group and an epoxy ring are added to a compound having a carboxyl group and an unsaturated bond between carbon atoms. More specifically, it is preferably a repeating unit obtained by reacting an epoxy ring in a compound containing an epoxy ring and an unsaturated bond between carbons and a carboxyl group of the repeating unit (a1-1) having a carboxyl group, or A repeating unit obtained by reacting a carboxyl group of a compound having a carboxyl group and an unsaturated bond with carbon (such as (meth)acrylic acid) with an epoxy ring derived from a repeating unit derived from an epoxy ring-containing monomer described later.

The compound containing an epoxy ring and an unsaturated bond between carbon atoms may be a compound containing one or more epoxy rings and an unsaturated bond between carbon atoms, and examples thereof include glycidyl acrylate and glycidyl methacrylate. A compound such as an ester, (3,4-epoxycyclohexyl)methyl acrylate, (3,4-epoxycyclohexyl)methyl methacrylate, or allyl glycidyl ether.

Among these compounds, glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl)methyl acrylate, (3,4-epoxycyclohexyl)methyl methacrylate, From the viewpoint of solvent resistance and heat resistance, glycidyl methacrylate, acryl-(3,4-epoxycyclohexyl)methyl ester, methacrylic acid (3,4-) are preferred. Epoxycyclohexyl)methyl ester.

The repeating unit (a2-1) having an inter-carbon unsaturated bonding group may be composed of a single one or two or more.

The content of the repeating unit (a2-1) having an inter-carbon unsaturated bonding group in the alkali-soluble resin of the present invention is preferably from 0 mol% to 60 mol%, more preferably in terms of various resistance and developability. 0 mol% to 50 mol%, and further preferably 0 mol% to 40 mol%.

a repeating unit (a2-2) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group -

The repeating unit (a2-2) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group may be exemplified by an epoxy group-containing unsaturated compound and an oxetane group. a repeating unit of a group of unsaturated compounds.

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, and α-n-butyl acrylate shrinkage. Glyceride, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate , α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. Among these compounds, glycidyl methacrylate, methacrylic acid-6,7-epoxy can be preferably used in terms of improving copolymerization reactivity and heat resistance and surface hardness of the obtained interlayer insulating film. Heptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacryl Acid-3,4-epoxycyclohexylmethyl ester and the like.

Examples of the oxetanyl group-containing unsaturated compound include (meth) acrylate having an oxetanyl group. Examples of the oxetanyl group-containing unsaturated compound include a (meth) acrylate having an oxetanyl group described in Paragraph No. 0011 to Paragraph No. 0016 of JP-A-2001-330953. As such a compound, in view of the wide process margin of the obtained photosensitive resin composition and the improvement of the chemical resistance of the obtained interlayer insulating film, specifically, it is preferable to use 3- (methacryloxymethyl) oxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxyloxy) Methyl)-2-phenyloxetane, 2-(methacryloxymethyl)oxetane, 2-(methacryloxymethyl)-4-trifluoromethyl Oxycyclobutane and the like. These compounds may be used singly or in combination.

The repeating unit (a2-2) may contain only one type, and may contain two or more types. The content of the repeating unit (a2-2) in the alkali-soluble resin of the present invention is preferably from 0 mol% to 50 mol%, more preferably from 0 mol% to 45 mol%, in terms of various resistances and transparency of the formed film. And further preferably from 0 mol% to 40 mol%.

a repeating unit (a2-3) having a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) -

In the copolymer used in the present invention, a repeating unit (a2-3) having a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) is also preferable. By containing the repeating unit (a2-3), a hardening reaction can be caused by a slow heat treatment, and a cured film excellent in various characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group. The repeating unit (a2) is more preferably a structural unit having a group represented by the following formula (1).

(In the above formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents 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. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group.

Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a cyclohexyl group, and a n-hexyl group. Among them, isobutyl, n-butyl and methyl groups are preferred.

The repeating unit (a2-3) may contain only one type, and may contain two or more types. The content of the repeating unit (a2-3) in the alkali-soluble resin of the present invention is preferably from 0 mol% to 50 mol%, more preferably from 0 mol% to 45 mol%, in terms of various resistances and transparency of the formed film. And further preferably from 0 mol% to 40 mol%.

In the present invention, it is preferred that the alkali-soluble resin contains the repeating unit (a2), and when the alkali-soluble resin contains the repeating unit (a2), the repeating unit (a2) preferably accounts for 5 mol% of the repeating unit in the alkali-soluble resin. ~50mol%, more preferably 8 Mol%~40mol%.

-Other repeating units (a3)-

The alkali-soluble resin used in the present invention may further contain other structural units other than the copolymer including (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group. The repeating unit which may be contained in the alkali-soluble resin is not particularly limited, and examples thereof include a repeating unit derived from a vinyl monomer, a repeating unit containing an alicyclic structure, or a repeating unit containing an aromatic ring structure.

By containing other repeating units (a3), the pattern formation property of the alkali-soluble resin may be improved.

The vinyl monomer which can form the other repeating unit (a3) is a vinyl monomer as described in Paragraph No. 0046 to Paragraph No. 0051 of JP-A-2009-98691.

Further, the alkali-soluble resin used in the present invention has an alicyclic structure in the molecule, from the viewpoint of high transmittance of the formed resin composition film and low relative dielectric constant.

The alicyclic structure is preferably an alicyclic 5-membered ring, an alicyclic 6-membered ring, or an alicyclic structure in which two or more of the member rings are bonded, and specific examples thereof include a cyclohexyl group and a t-butylcyclohexyl group. A heat resistance, an insulation stability, and indium tin oxide of a film obtained by using a photosensitive resin composition, such as a dicyclopentenyl group, a dicyclopentenyloxyethyl group, a dicyclopentyl group, or an isobornyl group ( Indium Tin Oxide (ITO) is preferably a cyclohexyl group, a dicyclopentenyl group, a dicyclopentenyloxyethyl group or a dicyclopentyl group in terms of sputtering suitability.

The alkali-soluble resin of the present invention may contain a repeating unit having an aromatic ring structure from the viewpoint of improving the developability of the film pattern formed of the photosensitive resin composition.

The repeating unit having an aromatic ring structure is preferably derived from the monomer shown below.

That is, phenyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, and β-phenoxyethoxy (meth)acrylate Ethyl ethyl ester, nonylphenoxy polyethylene glycol (meth)acrylate, tribromophenyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate, styrene, methyl styrene, Dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, ethoxylated styrene , chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, a group deprotectable by an acidic substance (for example, tert-Butyloxycarbonyl (tert-Boc), etc.) The protected hydroxystyrene, methyl benzoate and α-methylstyrene are preferably benzyl (meth) acrylate or styrene.

The other repeating unit (a3) may be composed of a single one or two or more.

The content of the other repeating unit (a3) in the alkali-soluble resin of the present invention is preferably from 0 mol% to 50 mol%, more preferably from 0 mol% to 45 mol%, and further preferably from the viewpoint of having various resistances and developability. 0 mol% to 40 mol%.

The alkali-soluble resin used in the present invention is preferably an alkali-soluble resin having at least one group selected from the group consisting of an epoxy group and/or an oxetanyl group in the molecule. Preferred examples of such a resin include, for example, methacrylic acid/tricyclomethacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester/-2-methylcyclohexyl acrylate/methacrylic acid Glycidyl ester/N-(3,5-dimethyl-4-hydroxybenzyl)methacrylamide copolymer, methacrylic acid/tetrahydrofurfuryl methacrylate/glycidyl methacrylate/N- Cyclohexylmaleimide/lauryl methacrylate/α-methyl-p-hydroxystyrene copolymer, styrene/methacrylic acid/glycidyl methacrylate/methacrylic acid (3-ethyloxalate) Cyclobutane-3-yl)ester/tricyclomethacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester copolymer, methacrylic acid/methacrylic acid tricyclic [5.2.1.0 ^2,6 ] Decane-8-yl ester/N-cyclohexylmaleimide/glycidyl methacrylate/styrene copolymer, methacrylic acid/methacrylic acid-3,4-epoxycyclohexylmethyl ester/benzene Ethylene/methacrylic acid tricyclo [5.2.1.0 ^2,6 ]decane-8-yl ester copolymer and the like.

Hereinafter, such an alkali-soluble resin is exemplified, but the present invention is not limited thereto.

Further, the alkali-soluble resin exemplified below has a weight average molecular weight of 5,000 to 80,000.

The polystyrene-equivalent weight average molecular weight obtained by Gel Permeation Chromatography (GPC) of the alkali-soluble resin used in the present invention (hereinafter referred to as "Mw" from the viewpoint of development margin or sensitivity It is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 × 10 ⁴ .

In addition, the molecular weight distribution (hereinafter referred to as "Mw/Mn") which is a ratio of the Mw to the polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") is preferably 5.0 or less. More preferably 3.0 or less.

The positive photosensitive resin composition for an interlayer insulating film containing the above-described alkali-soluble resin does not generate a development residue at the time of development, and can easily form a predetermined pattern shape.

The content of the alkali-soluble resin in the photosensitive resin composition of the present invention is preferably 20% by mass to 90% by mass, more preferably 25% by mass to 85% by mass, based on the total solid content of the photosensitive resin composition. Good is 30% by mass to 80% by mass. When the content is in this range, the pattern formation property at the time of development becomes good.

<B component: 1,2-quinonediazide compound>

The photosensitive resin composition of the present invention contains a 1,2-quinonediazide compound. The (B) 1,2-quinonediazide compound of the present invention is a compound having a 1,2-quinonediazide moiety structure, and it is required to have at least one 1,2-quinonediazide moiety structure in a molecule, preferably It has two or more 1,2-quinonediazide partial structures.

(B) The 1,2-quinonediazide compound suppresses the alkali solubility of the photosensitive resin composition coating film in the unexposed portion, and enhances the photosensitive resin composition coating film by generating a carboxylic acid in the exposed portion. The alkali solubility is such that positive pattern formation can be performed.

The 1,2-quinonediazide compound is obtained, for example, by subjecting a 1,2-quinonediazidesulfonium chloride to a condensation reaction with a hydroxy compound or an amine compound in the presence of a dehydrochlorinating agent.

Examples of the 1,2-quinonediazide compound include 1,2-benzoquinonediazidesulfonate, 1,2-naphthoquinonediazidesulfonate, and 1,2-benzoquinonediazidesulfonate. Amine, 1,2-naphthoquinonediazidesulfonamide, and the like. Specifically, J. Kosar's "Light-Sensitive Systems" (pp. 339-pp. 352 (1965), John Wiley & Sons, New York, USA) (New York)) or WS De Forest's "Photoresist" 50 (1975) (McGraw-Hill, Inc., New York) The 1,2-quinonediazide compound described in (New York), Japanese Patent Laid-Open No. 2004-170566, Japanese Patent Laid-Open No. 2002-40653, Japanese Patent Laid-Open No. 2002-351068, and Japanese Patent The 1,2-quinonediazide compound described in Japanese Laid-Open Patent Publication No. 2004-271975, and the like. It is also preferred to recite in paragraph number 0066 to paragraph number 0081 of Japanese Patent Laid-Open Publication No. 2008-224970. This is incorporated into the specification of the present application.

In the present invention, among the 1,2-quinonediazide compounds, a compound having a 1,2-naphthoquinonediazide group is also preferred. When a compound having a 1,2-naphthoquinonediazide group is used, the sensitivity is high and the developability is improved.

Among the compounds having a 1,2-naphthoquinonediazide group, a compound having the following structure can be preferably used because its sensitivity is particularly high.

Further, the most preferable compound having a 1,2-naphthoquinonediazide group is the following compound. The ratio of the H to the 1,2-naphthoquinonediazide group (mol ratio) in D is preferably from 50:50 to 1:99 in terms of sensitivity and transparency.

In the photosensitive resin composition of the present invention, when the total amount of the alkali-soluble resin is 100 parts by mass, in terms of the difference in the dissolution rate between the exposed portion and the unexposed portion and the allowable range of the sensitivity, 1, 2 The amount of the quinonediazide compound is preferably from 1 part by mass to 100 parts by mass, more preferably from 3 parts by mass to 80 parts by mass, even more preferably from 5 parts by mass to 30 parts by mass. The 1,2-quinonediazide compound may be used alone or in combination of two or more. Further, it may be used in combination with a photoacid generator.

The photoacid generator can be appropriately selected from a photo-cationic polymerization photoinitiator, a photoradical polymerization photoinitiator, a dye-based photo-decolorizer, a photochromic agent, a micro resist, or the like. A known compound which produces an acid by irradiation with actinic rays or radiation, or a mixture thereof.

Specific examples of the photoacid generator include a diazonium salt compound, an onium salt compound, an onium salt compound, an onium salt compound, a sulfhydryl sulfonate compound, an oxime sulfonate compound, and a diazodiamine compound. Diterpenoid compound, o-nitrobenzyl sulfonate compound.

The photoacid generator is preferably a sulfonic acid having a pKa of 2 or less, or an alkyl or aryl carboxylic acid substituted by an electron withdrawing group, and similarly substituted by an electron withdrawing group. Disulfonimide or the like is used as an acid generating compound. Here, examples of the electron-withdrawing group include a halogen atom such as a F atom, a halogenated alkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

Further, as the photoacid generator, a compound which generates an acid by irradiation with actinic rays or radiation or a compound which is introduced into a main chain or a side chain of a resin may be used, for example, the specification of U.S. Patent No. 3,849,137. German Patent No. 3914407, Japanese Patent Laid-Open No. Sho 63-26653, Japanese Patent Laid-Open No. Sho 55-164824, Japanese Patent Laid-Open No. Sho 62-69263, Japanese Patent Laid-Open No. 63-146038, Japanese Patent No. The compound described in each of the publications of Japanese Laid-Open Patent Publication No. SHO-63-153- 053, No. Sho. This is incorporated into the specification of the present application.

Further, as the photoacid generator, a compound which generates an acid by light as described in each of the specifications of U.S. Patent No. 3,779,778 and European Patent No. 126,712 can also be used.

The amount of the photoacid generator added is preferably from 0.5 part by mass to 15 parts by mass, more preferably from 1 part by mass to 5 parts by mass, per 100 parts by mass of the solid content of the photosensitive resin composition.

Further, in the photosensitive resin composition of the present invention, when a sulfonium salt compound is added as a photoacid generator, it is preferred to add a sensitizer in order to promote decomposition thereof.

The amount of the sensitizer added is preferably from 20 parts by mass to 200 parts by mass, more preferably from 30 parts by mass to 150 parts by mass, per 100 parts by mass of the onium salt compound.

<X component: sulfur-containing compound>

In the present invention, the compound represented by the formula (I) is contained as X. Minute. By blending the compound represented by the formula (I), it is possible to provide a positive photosensitive resin composition having high sensitivity, excellent adhesion to a substrate, and excellent transparency. Further, it has been surprisingly found that the panel display performance when used for various panels is also excellent.

(In the formula (I), R ¹ to R ⁶ each independently represent a hydrocarbon group or an alkoxy group, and L ¹ and L ² each independently represent an alkylene group, an extended aryl group or a group containing a combination of the groups, n represents an integer from 2 to 4)

R ¹ to R ⁶ represent a hydrocarbon group or an alkoxy group. The hydrocarbon group means an aliphatic hydrocarbon group and an aromatic hydrocarbon group, preferably an alkyl group and an aryl group, and more preferably an alkyl group.

The alkyl group of R ¹ to R ⁶ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a carbon number of 1. ~3 alkyl. The alkyl group may be linear, branched or cyclic, and is preferably linear. Further, the alkyl group may have a substituent, but preferably has no substituent. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecane group. Base, cetyl, octadecyl, eicosyl, isopropyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, An isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group, a 2-norbornyl group and the like, among which a methyl group, an ethyl group, a propyl group and an isopropyl group are preferred, and more preferably Methyl or ethyl.

The aryl group of R ¹ to R ⁶ is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms. The aryl group may have a more substituent, but preferably has no substituent. Specific examples of the aryl group include a phenyl group, a p-methylphenyl group, a naphthyl group, and an anthracenyl group. Among them, a phenyl group and a naphthyl group are preferable.

Examples of the substituent which the alkyl group and/or the aryl group may have include an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a cyano group, and a halogen atom (a fluorine atom, a chlorine atom, and a bromine atom). Atom, iodine atom, etc.

The alkoxy group of R ¹ to R ⁶ is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, particularly It is preferably an alkoxy group having 1 to 3 carbon atoms. The alkoxy group may be linear, branched or cyclic, and is preferably linear. The alkoxy group may have a substituent, but preferably has no substituent. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an isopropoxy group, an isobutoxy group, a second butoxy group, and the like. A tributyloxy group, an isopentyloxy group, a neopentyloxy group or the like is preferable, and among them, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group is preferred, and a methoxy group or an ethoxy group is more preferred. The alkoxy group may have the same substituent as the alkyl group or the aryl group.

In these, R ¹ to R ⁶ are each independently preferably an alkyl group or an alkoxy group, more preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

R ¹ to R ⁶ may be the same or different, and it is preferred that at least two of R ¹ to R ^{3 have} the same structure, and it is preferred that at least two of R ⁴ to R ^{6 have} the same structure.

L ¹ and L ² each independently represent an alkylene group, an aryl group or a group containing a combination of the groups, preferably an alkyl group or a group containing a combination of an alkyl group and an extended aryl group, more preferably It is an alkyl group. When an alkylene group is used, the adhesion to the substrate tends to be further improved.

The alkylene group of L ¹ and L ² is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms, and further It is preferably an alkyl group having a carbon number of 2 to 4. The alkylene group may have a substituent, but preferably has no substituent. Further, the alkylene group may be any of a straight chain, a branched chain, and a cyclic group, and is preferably a linear alkylene group. Examples of the alkylene group include a methylene group, an ethyl group, a propyl group, a butyl group and the like.

The aryl group is preferably an extended aryl group having 6 to 20 carbon atoms, more preferably an alkylene group having 6 to 14 carbon atoms, and more preferably an extended aryl group having 6 to 10 carbon atoms, and more preferably a phenyl group. The extended aryl group may have a substituent, but preferably has no substituent. Examples of the extended aryl group include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, and naphthyl. In the present invention, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and more preferably a 1,4-phenylene group are preferable.

The alkylene group and the extended aryl group may have the same substituents as the alkyl group or the aryl group.

In these, L ¹ and L ² are each independently preferably a C 1-8 alkyl group, a phenyl group or a group containing a combination of the groups, more preferably a C 2 to 4 alkylene group. a group, a phenyl group or a group comprising a combination of such groups.

n represents an integer of 2 to 4, preferably 3 or 4.

The molecular weight of the compound represented by the general formula (I) used in the present invention is relatively Good for 200~800, better for 400~500.

The compound represented by the formula (I) which can be preferably used in the present invention is shown below, but the present invention is of course not limited to these compounds. Further, Me represents a methyl group, and Et represents an ethyl group.

The method for producing the compound represented by the formula (I) used in the present invention is not limited, and can be synthesized, for example, by referring to the literature such as US Publication No. 2006/106240 A1.

In the present invention, the amount of the component (component X) is preferably from 5% by mass to 25% by mass, and more preferably from 8% by mass to 22% by mass based on the total solid content of the composition.

In addition, it is preferable to contain (component X) in a ratio of 1 part by mass to 10 parts by mass, and more preferably in a ratio of 1 part by mass to 5 parts by mass, based on 100 parts by mass of the total amount of the polymer component ( Ingredient X).

<crosslinker>

The photosensitive resin composition of the present invention may contain a crosslinking agent in order to improve the curability. The details will be described below.

- (C-1) a crosslinking agent having at least one group selected from the group consisting of epoxy groups and oxetanyl groups -

The photosensitive resin composition of the present invention may further contain a crosslinking agent (C-1) having at least one selected from the group consisting of an epoxy group and an oxetanyl group. Group. Particularly, when the alkali-soluble resin does not contain the repeating unit (A2-2), it is preferred to use (C-1). Thus, from the viewpoint of storage stability, it is preferred to separate the epoxy group and the oxetanyl group from the alkali-soluble resin.

Examples of the crosslinking agent (C-1) include a copolymer having at least one group selected from the group consisting of an epoxy group and an oxetanyl group (hereinafter sometimes referred to as a copolymer (C1)). ). In addition, from the viewpoint of easiness of reaction, an epoxy group is preferred, and from the viewpoint of storage stability of the composition or heat resistance of the cured product, oxetanyl group is preferred.

The copolymer (C1) may contain an alicyclic structure in its structure from the viewpoints of transparency, developability, and insulation stability of the cured film formed using the photosensitive resin composition.

In the present invention, the copolymer (C1) is a repeating unit (C1-1). The copolymer, the above repeating unit (C1-1) has at least one group selected from the group consisting of an epoxy group and an oxetanyl group. In addition, (C1-2) other repeating units may be contained as needed. However, the copolymer (C1) does not contain a carboxyl group or a phenolic hydroxyl group in its structure. Further, the copolymer (C1) is preferably an acrylic copolymer in terms of transparency and insulation stability.

[Repeating unit (C1-1) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group]

The repeating unit (C1-1) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group may be exemplified by having a group selected from the group consisting of an epoxy group and an oxetanyl group. A repeating unit of a monomer of at least one group in the group.

Specific examples of the monomer having an epoxy group include glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, allyl glycidyl ether, ( Methyl)acrylic acid-3,4-epoxycyclohexylethyl ester, 3,4-epoxycyclohexyl n-propyl (meth) acrylate, (meth)acrylic acid-3,4-epoxycyclohexyl isopropyl Ester, 1-vinyl-2,3-epoxycyclohexane, 1-vinyl-3,4-epoxycyclohexane, 1-allyl-2,3-epoxycyclohexane, 1- A compound such as allyl-3,4-epoxycyclohexane is preferably a glycidyl (meth)acrylate or a (meth)acrylic acid from the viewpoint of solvent resistance and heat resistance. 4-epoxycyclohexyl)methyl ester.

The monomer having an oxetanyl group is, for example, a (meth) acrylate having an oxetanyl group described in Paragraph No. 0011 to Paragraph No. 0016 of JP-A-2001-330953. Specifically, the monomer is obtained The photosensitive resin composition has a wide process margin and improves the chemical resistance of the obtained interlayer insulating film, preferably 3-(methacryloxymethyl)oxetane, 3 -(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 2-( Methyl propylene methoxymethyl) oxetane, 2-(methacryloxymethyl)-4-trifluoromethyl oxetane, and the like.

The repeating unit (C1-1) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group may be composed of a single type or two or more types.

The copolymer (C1) of the present invention has a group selected from the group consisting of an epoxy group and an oxetanyl group in terms of solvent resistance and heat resistance of the cured film formed using the photosensitive resin composition. The content of the repeating unit (C1-1) of at least one group in the group is preferably from 20 mol% to 98 mol%, more preferably from 30 mol% to 95 mol%, still more preferably from 40 mol% to 90 mol%.

[(C1-2) Other repeating units]

The copolymer (C1) of the present invention may also contain other repeating units (C1-2). The other repeating unit (C1-2) is not particularly limited, and from the viewpoint of compatibility with the alkali-soluble resin, it is preferred to contain a hydroxyl group or a polyethylene oxide group. Further, a repeating unit derived from a vinyl monomer may be contained.

The vinyl monomer which can form another repeating unit (C1-2) is a vinyl monomer as described in Paragraph No. 0046 to Paragraph No. 0051 of JP-A-2009-98691.

Among these, (meth)acrylates or styrenes are preferable. Best Among the (meth) acrylates and (meth) acrylates, 2-hydroxyethyl (meth) acrylate and (methyl) are preferred from the viewpoint of pattern formation and transparency obtained by development. Diethylene glycol monomethyl ether, diethylene glycol monoethyl (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl (meth)acrylate, (methyl) ) Polyethylene glycol monomethyl ether, polyethylene glycol monoethyl (meth)acrylate.

Further, the cured film formed may have a repeating unit having an alicyclic structure in terms of transparency and insulation stability.

Specific examples of the monomer having an alicyclic structure include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and (meth)acrylic acid. Cyclopentenyloxyethyl ester, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, etc., among which cyclohexyl (meth)acrylate and dicyclopentyl (meth)acrylate are preferred. An enester, dicyclopentenyloxyethyl (meth)acrylate, or dicyclopentanyl (meth)acrylate.

The other repeating unit (C1-2) may be composed of a single one or two or more.

The content of the other repeating unit (C1-2) in the copolymer (C1) of the present invention is preferably 0 mol% in terms of transparency and developability of the cured film formed using the photosensitive resin composition. 50 mol%, more preferably 3 mol% to 40 mol%, and further preferably 5 mol% to 30 mol%.

The copolymer (C1) as described above can be synthesized by copolymerizing at least a monomer which can form a repeating unit of (C1-1) and optionally a repeating unit of (C1-2) at the time of polymerization.

Hereinafter, the copolymer (C1) which can be preferably used in the present invention is exemplified, but the present invention is not limited thereto. Further, the weight average molecular weight of the following exemplified compounds is from 4,000 to 41,000.

The molecular weight of the copolymer (C-1) used in the present invention is not particularly limited, and it is preferably in terms of weight average molecular weight from the viewpoint of alkali dissolution rate or film physical property. It is 2,000 to 50,000, more preferably 3,000 to 30,000.

The crosslinking agent of the present invention may also be a compound having at least one group selected from the group consisting of an epoxy group and an oxetanyl group other than the above copolymer (C-1). For example, Celloxide 2021P, Celloxide 3000, Epolead GT401, EHPE 3150, EHPE 3150E (above manufactured by Daicel Chemical Industry Co., Ltd.), JER157S70, JER157S65 ( A commercially available product described in paragraph 0189 of Japanese Laid-Open Patent Publication No. 2011-221494, and the like.

Also listed are: ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP -4011S (above is made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above ADEKA) () manufacturing), Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, generation Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-411, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-211, Dina Denacol EX-212, Denacol EX-810, Denacol EX-811, Denacol EX-850, Dinacol (Denacol) EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841 , Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931, Dina Kaul ( Denacol) EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L, Denacol DLC-201, Denacol DLC-203, Denacol DLC-204, Denacol DLC-205, Denacol ) DLC-206, Denacol DLC-301, Denacol DLC-402 (above produced by Nagase Chemtex), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above is manufactured by Nippon Steel Chemical Co., Ltd.), Aron Oxetane OXT-121, Yalong Oxetane (Aron Oxetane) OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (above, manufactured by East Asia Synthetic Co., Ltd.), and the like.

The crosslinking agent (C-1) of the present invention may be used alone or in combination of two or more. When the total amount of the alkali-soluble resin described above is set to 100 parts by mass, the amount of the crosslinking agent of the present invention added to the photosensitive resin composition of the present invention is preferably from 5 parts by mass to 120 parts by mass. More preferably, it is 10 mass parts - 100 mass parts. When the amount of addition is within this range, the cured film formed using the photosensitive resin composition is excellent in solvent resistance, heat resistance, and insulation stability.

<(C-2) Alkoxymethyl group-containing crosslinking agent>

Other preferred examples of the crosslinking agent of the present invention include (C-2) an alkoxymethyl group-containing crosslinking agent. The alkoxymethyl group-containing crosslinking agent (C-2) used as a crosslinking agent is preferably an alkoxymethylated melamine, an alkoxymethylated benzoguanamine or an alkoxymethyl group. Glycoluril and alkoxymethylated urea, and the like. These cross-linking agents are each obtained by converting a methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril and methylolated urea to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and examples thereof include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, etc., and generation of out gas. From a quantitative point of view, it is especially preferred to be a methoxymethyl group.

Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzene melamine, and alkoxymethylated glycoluril are preferred crosslinkable compounds, and transparency is considered. In particular, alkoxymethylated glycoluril is preferred.

The (C-2) alkoxymethyl group-containing crosslinking agent can be obtained as a commercially available product, and for example, can be preferably used: Cymel 300, Cymel 301, Seime Cymel 303, Cymel 370, Cymel 325, Cymel 327, Cymel 701, Cymel 266, Semel ( Cymel) 267, Cymel 238, Cymel 1141, Cymel 272, Cymel 202, Cymel 1156, Cymel 1158, Cymel 1123, Cymel 1170, Cymel 1174, Cymel UFR65, Cymel 300 (above Mitsui Cyanamid) ) (share) manufacturing), Nikalac Mx-750, Nikalac Mx-032, Nikalac Mx-706, Nikalac Mx-708, Nikalac Mx-40, Nikalac Mx-31, Nikalac Mx-270, Nikalac Mx-280, Nikalac Mx-290, Nikalac Ms-11, Nikalac Mw-30HM, Nikalac Mx-100LM, Nikalac Mx-390 (above, manufactured by Sanwa Chemical Co., Ltd.), and the like.

The amount of the (C-2) alkoxymethyl group-containing crosslinking agent to be added is preferably 0.05 parts by mass to 50 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass per 100 parts by mass of the alkali-soluble resin. Parts by mass. By adding (C-2) an alkoxymethyl group-containing crosslinking agent in this range, it is possible to obtain a preferable alkali solubility at the time of development and an excellent solvent resistance of the film after curing.

In addition to the above, the photosensitive resin composition of the present invention may further contain an antioxidant, a thermal radical generator, an adhesion promoter (preferably a decane coupling agent), a surfactant, and a thermosensitive acid, depending on the purpose. Any compound such as a compound, a polymerizable compound having at least one ethylenically unsaturated double bond, or a solvent.

Hereinafter, arbitrary components will be described.

<antioxidant>

The composition of the present invention may contain a known antioxidant. By adding an antioxidant, there is an advantage that the coloration of the cured film can be prevented or the film thickness due to decomposition can be reduced. Examples of such an antioxidant include phosphorus-based antioxidants, anthraquinones, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, and ascorbic acid. Zinc sulfate, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among them, from the viewpoint of coloring of the cured film and thinning of the film thickness, a phenol-based antioxidant or a sulfur-based antioxidant is particularly preferable. These antioxidants may be used singly or in combination.

Commercial products of phenolic antioxidants include, for example, Adekastab AO-60 (made by ADEKA) and Adekastab AO-80 (ADEKA). ) Manufacturing), the trade name is Irganox 1098 (manufactured by Ciba Japan).

The content of the antioxidant is preferably from 0.1% by mass to 6% by mass, more preferably from 0.2% by mass to 5% by mass, most preferably from 0.5% by mass to 4% by mass based on the total solid content of the photosensitive resin composition. By setting it as this range, sufficient transparency of the formed film can be obtained, and the sensitivity is also exhibited at the time of pattern formation.

In addition, as the additive other than the antioxidant, various ultraviolet absorbers, metal deactivators, and the like described in "New Development of Polymer Additives (Nikko Kogyo Co., Ltd.)" may be added to the photosensitive resin composition of the present invention.

<Thermal free radical generator>

The photosensitive resin composition of the present invention may further contain a thermal radical generating agent.

The thermal radical generating agent of the present invention can be known by using a usual radical generating agent. The thermal radical generating agent is a compound which generates a radical by thermal energy, and initiates and accelerates a polymerization reaction with a polymerizable compound such as an alkali-soluble resin. By adding a thermal radical generator, the obtained cured film becomes stronger, and heat resistance and solvent resistance are improved.

Hereinafter, the thermal radical generating agent will be described in detail, but the present invention is not limited by the description.

In the present invention, preferred examples of the thermal radical generating agent include aromatic ketones, phosphonium salt compounds, organic peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketooxime ester compounds, and boric acid ester compounds. An azinium compound, a metallocene compound, an active ester compound, a compound having a carbon halogen bond, an azo compound, a bibenzyl compound, or the like.

In the present invention, from the viewpoint of heat resistance and solvent resistance of the obtained cured film, an organic peroxide, an azo compound or a bibenzyl compound is more preferable, and a bibenzyl compound is particularly preferable.

Further, the bibenzyl compound is preferably a compound represented by the following formula (1).

In the above formula (1), a plurality of R ³ present independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom.

Specific examples of the compound represented by the formula (1) include 2,3-dimethyl-2,3-diphenylbutane, α,α'-dimethoxy-α,α'-diphenyl linkage. Benzyl, α,α'-diphenyl-α-methoxybibenzyl, α,α'-dimethoxy-α,α'-dimethylbibenzyl, α,α'-dimethoxy linkage Benzyl, 3,4- Dimethyl-3,4-diphenyl-n-hexane, 2,2,3,3-tetraphenylsuccinic acid nitrile, bibenzyl, and the like.

The thermal radical generator of the present invention may be used alone or in combination of two or more.

In the case where the alkali-soluble resin is used in an amount of 100 parts by mass, the amount of the thermal radical generating agent added to the photosensitive resin composition of the present invention is preferably 0.01 parts by mass to 50 parts by mass. More preferably, it is 0.1 mass part - 10 mass parts, and further preferably 1 mass part - 5 mass parts.

<Intimate accelerator>

In the photosensitive resin composition of the present invention, an adhesion promoter such as an organic hydrazine compound, a decane coupling agent or a leveling agent may be added as needed in order to impart adhesion to a solid surface.

Examples of the adhesion promoters include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, vinyltriethoxydecane, and 3-methylpropenyloxyl. Propyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methyl Propylene methoxypropyl methyl diethoxy decane, γ-glycidoxypropyl triethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, urea propyl triethoxy Base decane, tris(acetonitrile)aluminum, acetamidineacetate, aluminum diisopropylate, and the like.

When the adhesion promoter is used for the photosensitive resin composition, the adhesion promoter is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, per 100 parts by mass of the alkali-soluble resin.

<Surfactant>

In the photosensitive resin composition of the present invention, a surfactant may be contained in order to improve coatability. As the surfactant, a fluorine-based surfactant, an anthrone-based surfactant, or a non-ionic surfactant can be preferably used. For example, various surfactants described in JP-A-2001-330953 can be used. .

These surfactants may be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, the surfactant is preferably 0.001 parts by mass to 20 parts by mass, more preferably 0.01% by weight based on 100 parts by mass of the alkali-soluble resin. The mass fraction is preferably 5 parts by mass, and more preferably 0.01 parts by mass to 2 parts by mass.

<Thermal acid generating compound>

The thermosensitive acid generating compound can be used to further improve the heat resistance or hardness of the resulting interlayer insulating film. Examples thereof include an onium salt such as a phosphonium salt, a benzothiazolium salt, an ammonium salt or a phosphonium salt.

Examples of the above-mentioned onium salt include an alkyl phosphonium salt, a benzyl phosphonium salt, a dibenzyl phosphonium salt, a substituted benzyl phosphonium salt, and a benzothiazolium salt.

As the sensible acid generating compound, a sulfonium salt or a benzothiazole oxime salt can be preferably used, and particularly, 4-ethyl methoxy phenyl dimethyl sulfonium hexafluoro arsenate or benzyl-4-hydroxy benzene is preferably used. Methyl hydrazine hexafluoroantimonate, 4-ethenyloxyphenylbenzylmethyl hexafluoroantimonate, dibenzyl-4-hydroxyphenyl hexafluoroantimonate, 4-ethyl oxime Phenylphenylbenzylphosphonium hexafluoroantimonate or 3-benzylbenzothiazolium hexafluoroantimonate.

Such commercially available products include, for example, Sun-aid SI-L85, Sun-aid SI-L110, Sun-aid SI-L145, Sandy Aide (Sun-aid) SI-L150, Sun-aid (SI-Lid) (the above is manufactured by Sanshin Chemical Industry Co., Ltd.).

The use ratio of the (H) component in the photosensitive resin composition of the present invention is preferably 20 parts by mass or less, more preferably 5 parts by mass, based on 100 parts by mass of the alkali-soluble resin, from the viewpoint of heat resistance and hardness. the following.

<Polymerizable compound having at least one ethylenically unsaturated double bond>

A polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter referred to as "polymerizable compound (I)" as appropriate) may, for example, be a monofunctional (meth) acrylate, a difunctional (meth) acrylate or three. A functional (meth) acrylate.

Examples of the above monofunctional (meth) acrylate include 2-hydroxyethyl (meth)acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, and (meth) acrylate. 3-methoxybutyl acrylate, 2-(methyl) propylene methoxyethyl 2-hydroxypropyl phthalate, and the like.

Examples of the above difunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexane diol di(meth) acrylate, and 1,9-nonanediol di(methyl). Acrylate, polypropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenoxyethanol oxime diacrylate, bisphenoxyethanol oxime diacrylate, and the like.

Examples of the above trifunctional or higher (meth) acrylate include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris((meth)acryloxyethylethyl phosphate). An ester, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, or the like.

Among these, a trifunctional or higher (meth) acrylate can be preferably used. Among them, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate or dipentaerythritol hexa(meth)acrylate is particularly preferable. These monofunctional, difunctional or trifunctional or higher (meth) acrylates may be used singly or in combination.

The use ratio of the polymerizable compound (I) in the photosensitive resin composition of the present invention is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin. By containing the component (I) in such a ratio, the heat resistance and surface hardness of the interlayer insulating film obtained from the photosensitive resin composition of the present invention can be improved.

<solvent>

The solvent for preparing the photosensitive resin composition of the present invention can be used by uniformly dissolving an alkali-soluble resin, a 1,2-quinonediazide compound, and a component X, and optionally blending other components, without reacting with the components. By.

Among them, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester or the like can be preferably used in terms of solubility of each component, reactivity with each component, easiness of formation of a coating film, and the like. Diethylene glycol. Among these solvents, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate can be preferably used. , diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate or ethoxypropyl Ethyl acetate.

Further, in order to increase the in-plane uniformity of the film thickness, a high boiling point solvent may be used in combination with the above solvent. Examples of the high-boiling solvent which can be used in combination include N-methylformamide, N,N-dimethylformamide, N-methylformanilide, and N- Methyl acetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid , octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate, Phenolic cellosolve acetate and the like. Among these high boiling solvents, N-methylpyrrolidone, γ-butyrolactone or N,N-dimethylacetamide are preferred.

When the solvent for preparing the photosensitive resin composition of the present invention is used in combination, the amount of use may be 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass based on the total amount of the solvent. %the following. When the amount of the high boiling point solvent used exceeds the amount used, the film thickness uniformity, sensitivity, and residual film ratio of the coating film may be lowered.

When the photosensitive resin composition of the present invention is prepared in a solution state, the solid content concentration of the component other than the solvent in the solution can be arbitrarily set depending on the purpose of use or the desired film thickness, etc., preferably 5 The mass % to 50% by mass, more preferably 10% by mass to 40% by mass, and further preferably 12% by mass to 35% by mass. The composition solution prepared in this manner can also be used after being filtered using a millipore filter having an opening having a pore diameter of about 0.2 μm.

[Pattern forming method]

The method of forming a patterned cured film using the photosensitive resin composition of the present invention can be carried out by using a pattern forming method in which: (1) the photosensitive resin composition of the present invention is applied (preferably coated) to a suitable substrate. (2) baking (pre-baking) the applied substrate; (3) performing exposure under actinic rays or radiation; (4) post-heating as needed; (5) development with an aqueous developing solution; (6) full exposure as needed; and (7) thermal hardening (post-baking) and the like. By using the pattern forming method, a cured film of a desired shape (pattern) can be formed on a substrate.

Further, in the above pattern forming method, the post-heating of (4) and the total exposure of (6) are arbitrary steps, and may be carried out as needed.

(1) The photosensitive resin composition of the present invention is applied to a semiconductor element or a glass substrate so that the thickness after curing is a desired thickness (for example, 0.1 μm to 30 μm), as described above. By performing (2) prebaking, (3) exposure, (5) development, and (7) thermal curing, a patterned cured film for an organic EL display device or a liquid crystal display device can be formed.

Hereinafter, the pattern forming method will be described in more detail.

The photosensitive resin composition (1) of the present invention is applied to a suitable substrate.

The substrate may be selected according to the use of the formed cured film. For example, a semiconductor substrate such as a germanium wafer or a ceramic substrate, or a substrate containing glass, metal or plastic may be used. When the cured film is used for a semiconductor device, a germanium wafer is usually used, and when the cured film is used for a display device, a glass substrate is usually used.

In the application method, spray coating, spin coating, slit coating, offset printing, roll coating, screen printing, extrusion coating, liquid level can be used. Meniscus coating, curtain coating, dip coating, etc., but are not limited to these methods.

Forming a photosensitive resin composition on the substrate by the (1) application step Layer of matter.

After the application step (1), in order to evaporate the solvent remaining in the photosensitive resin composition layer, (2) prebaking is performed. The (2) prebaking is preferably carried out at a temperature of from 70 ° C to 130 ° C in the range of from several minutes to 30 minutes.

Then, the photosensitive resin composition layer dried by (2) prebaking is used, and (3) exposure using actinic rays or radiation is performed through a mask having a desired pattern. The exposure energy is usually preferably from 10 mJ/cm ² to 500 mJ/cm ² . X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used for the actinic rays or radiation. The optimum radiation is 436 nm (g-ray), 405 nm (h-ray), and 365 nm (i-ray). In addition, exposure can also be performed by laser irradiation such as ultraviolet laser. By the (3) exposure step, a region to be developed and a region where no development is performed are formed on the photosensitive resin composition layer on the substrate.

(4) Heating (post-heating) of the substrate exposed by actinic rays or radiation. The heating may be carried out at a temperature of 70 ° C or higher, preferably to a high temperature of 150 ° C or higher, more preferably to 180 ° C to 250 ° C, and particularly preferably to 200 ° C to 240 ° C. Further, in the present invention, by heating at 200 ° C or higher, a crosslinkable group (for example, a hydroxyl group, a methylol group or an isocyanate group) other than an epoxy group or an oxetanyl group can be crosslinked to form a crosslinkable group. A stronger cross-linking structure. The post-heating is carried out in a short time, usually a few seconds to a few minutes. This step is generally referred to in the art as post-exposure bake.

Then, the photosensitive resin composition layer (5) after (3) exposure ((4) post-heating) is developed with an aqueous developing solution. Photosensitive resin by the development The exposed portion of the composition layer is developed by an aqueous developing solution, and the unexposed portion remains on the substrate, thereby forming a photosensitive resin composition layer having a desired shape (pattern).

Among the aqueous developing solutions, there are alkaline solutions using inorganic bases (such as potassium hydroxide, sodium hydroxide, aqueous ammonia), primary amines (such as ethylamine, n-propylamine), and secondary amines (such as diethylamine, two). N-propylamine), tertiary amines (such as triethylamine), alcohol amines (such as triethanolamine), quaternary ammonium salts (such as tetramethylammonium hydroxide, tetraethylammonium hydroxide), and mixtures thereof. The preferred developer contains tetramethylammonium hydroxide. Further, an appropriate amount of a surfactant may be added to the developer.

Alternatively, development can be carried out by dipping, spraying, puddling or other similar development methods.

(5) After the development step, the photosensitive resin composition layer remaining on the substrate may be washed with deionized water as the case may be.

Then, after the (5) development step, the photosensitive resin composition layer remaining on the substrate is subjected to (6) full exposure as necessary. The exposure energy of the full exposure is preferably from 100 mJ/cm ² to 1000 mJ/cm ² .

When the cured film for a display device is formed by the (6) full exposure, it is preferable because the transparency is improved.

Then, (5) the photosensitive resin composition layer remaining on the substrate after the development step is subjected to (7) thermal hardening treatment in order to obtain a final patterned cured film. This thermosetting is carried out in order to form a cured film having high heat resistance, chemical resistance, and film strength. When a usual photosensitive polyimide intermediate precursor composition is used, heat hardening is performed at a temperature of about 300 ° C to 400 ° C. On the other hand, the feeling of the present invention When the photosensitive resin composition is heated to 150 ° C or higher, a cured film having a film physical property equal to or higher than that of the conventional photosensitive polyimide precursor composition can be obtained. The heating is preferably carried out to a temperature of from 180 ° C to 250 ° C, more preferably from 200 ° C to 240 ° C. Further, in the present invention, by heating at 200 ° C or higher, a crosslinkable group (for example, a hydroxyl group, a methylol group or an isocyanate group) other than an epoxy group or an oxetanyl group can be crosslinked to form a crosslinkable group. A stronger cross-linking structure.

According to the photosensitive resin composition of the present invention, a cured film which is excellent in insulating properties and has high transparency even when baked at a high temperature can be obtained.

In addition, it can also be used as a dry etching resist.

The organic EL display device or the liquid crystal display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic compounds having various structures can be used. EL display device or liquid crystal display device.

[hardened film]

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.

The cured film of the present invention can be preferably used as an interlayer insulating film. Further, the cured film of the present invention is preferably a cured film obtained by the method for forming a cured film of the present invention.

According to the photosensitive resin composition of the present invention, an interlayer insulating film which is excellent in insulating properties and has high transparency even when baked at a high temperature can be obtained. The interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and a cured film Since it is excellent in physical properties, it is useful for the use of an organic EL display device or a liquid crystal display device.

[Organic EL display device, liquid crystal display device]

The organic EL display device and the liquid crystal display device of the present invention are characterized by comprising the cured film of the present invention.

The organic EL display device or the liquid crystal display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic compounds having various structures can be used. EL display device or liquid crystal display device.

Specific examples of the thin film transistor (TFT) included in the organic EL display device and the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be used in combination with these TFTs.

Further, examples of the liquid crystal display device that can be adopted in the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and a coplanar switching (In-Plane-Switching, IPS) mode, Fringes Field Switching (FFS) mode, Optical Compensated Bend (OCB) mode, etc.

Moreover, the specific alignment of the liquid crystal alignment film which can be taken by the liquid crystal display device of the present invention is, for example, a rubbing alignment method or a photoalignment method. Further, the polymer alignment support can be carried out by the Polymer Sustained Alignment (PSA) technique described in JP-A-2003-149647 or JP-A-2011-257734.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used in various applications. For example, in addition to the planarization film or the interlayer insulating film, it may be preferably used for a protective film of a color filter or a spacer for holding a liquid crystal layer to a certain thickness in a liquid crystal display device, or A microlens or the like provided on a color filter in the solid-state image sensor.

FIG. 1 is a conceptual diagram showing an example of an organic EL display device. This is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.

A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed to cover the state of the TFT 1. After the contact hole (not shown) is formed in the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. The wiring 2 is a wiring for connecting the organic EL element formed between the TFTs 1 or in the subsequent steps to the TFT 1.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarization layer 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is filled.

On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 including ITO is formed on the planarizing film 4 by being connected to the wiring 2 via the contact hole 7. Further, the first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 having a shape covering the edge of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Furthermore, although not shown in FIG. 1, it is covered by a desired pattern, in order. A hole transport layer, an organic light-emitting layer, and an electron transport layer are provided by vapor deposition, and then a second electrode including A1 is formed on the entire upper surface of the substrate, and is bonded using a sealing glass plate and an ultraviolet curable epoxy resin. This is sealed to obtain an active matrix type organic EL display device in which the organic EL elements are connected to drive the TFTs 1 of the organic EL elements.

FIG. 2 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and an element of the TFT 16 is disposed in the liquid crystal panel. The elements of the TFT 16 and the two glass substrates 14 and the glass substrate 15 on which the polarizing film is attached are disposed. All pixels between them correspond. The wiring of the ITO transparent electrode 19 on which the pixel electrode is formed is formed by the contact hole 18 formed in the cured film 17 for each element formed on the glass substrate. A layer of the liquid crystal 20 and a red green blue (RGB) color filter 22 in which a black matrix is disposed are provided on the ITO transparent electrode 19.

The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white light emitting diode (LED), a multicolor LED such as blue/red/green, a fluorescent lamp (cold cathode tube), an organic EL, or the like can be given.

In addition, the liquid crystal display device can be set to three-dimensional (3D, stereoscopic) type, or can be set to a touch panel type.

The photosensitive resin composition of the present invention is excellent in flatness and transparency, and can be used, for example, in forming a bank layer (16) and a planarizing film described in Fig. 2 of JP-A-2011-107476. (57), the partition wall (12) and the flat body shown in Fig. 4 (a) of Japanese Patent Laid-Open Publication No. 2010-9793 The bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of Japanese Patent Laid-Open Publication No. 2010-27591, and FIG. 4 of Japanese Patent Laid-Open No. 2009-128577 ( The second interlayer insulating film (125) and the third interlayer insulating film (126) described in a), the planarizing film (12) and the pixel separating insulating film described in FIG. 3 of JP-A-2010-182638 (14) and so on.

Example

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are the quality standards.

(synthesis example)

<Alkyl Soluble Resin: Synthesis of A-1>

Using methacrylic acid (hereinafter referred to as MAA) 12.05 g (35 mol%), styrene 4.17 g (10 mol%), dicyclopentanyl methacrylate 13.22 g (15 mol%), glycidyl methacrylate 22.74 g (40 mol) %) As a monomer component for forming a copolymer, 2.57 g of azobisisobutyronitrile (AIBN) was used as a radical polymerization initiator, and the components were made into a solvent propylene glycol monomethyl ether acetate (PGMEA) 115 g. The polymerization reaction was carried out at 70 ° C for 4 hours, whereby a PGMEA solution of A-1 (solid content concentration: 30% by mass) was obtained.

The obtained styrene-equivalent weight average molecular weight measured by GPC of A-1 was 15,000.

<Alkyl Soluble Resin: Synthesis of A-2>

12.05 g (35 mol%) of methacrylic acid, 4.17 g (10 mol%) of styrene, 13.22 g (15 mol%) of dicyclopentanyl methacrylate, and 3-ethyl-3-oxetanyl methacrylate 29.48 g (40 mol%) as a monomer component for forming a copolymer, using azobisisobutyronitrile (AIBN) 2.57 g as a radical polymerization initiator to make the components in a solvent propylene glycol monomethyl ether acetate (PGMEA) 135 g was subjected to a polymerization reaction at 70 ° C for 4 hours, whereby a PGMEA solution of A-2 (solid content concentration: 30% by mass) was obtained.

The obtained styrene-converted weight average molecular weight measured by GPC of A-2 was 13,000.

<Production of photosensitive resin composition>

The alkali-soluble resin (component A), the 1,2-quinonediazide compound (component B), the X component, the adhesion improver, and the surfactant are dissolved and mixed in the PGMEA so as to have a solid content ratio as described in the following table. The photosensitive resin composition of each of Examples and Comparative Examples was obtained by filtration through a filter made of polytetrafluoroethylene having a pore diameter of 0.2 μm until the solid content concentration was 32% by mass. The blending amount of each component in the following table is expressed in parts by mass.

The details of the abbreviations of the respective compounds used in the examples and comparative examples are as follows.

<B ingredient>

B-1: TAS-200 (Toyo Synthetic Manufacturing)

TAS-200 (esterification rate is 65%)

<X ingredient>

C-7: bis(triethoxydecylpropyl) disulfide, trade name Z-6920, manufactured by Toray Dow Corning Acne

C-9: bis(triethoxydecylpropyl)tetrasulfide, trade name KBE-864, manufactured by Shin-Etsu Chemical Co., Ltd.

<Comparative component of X component>

R-1: 1,3-bis(triethoxydecyl)ethane, KBE-3026, manufactured by Shin-Etsu Chemical Co., Ltd.

R-2: bis(2-benzamide phenyl) disulfide, manufactured by Tokyo Chemical Industry Co., Ltd.

R-3: Dithiobisphenol, manufactured by Tokyo Chemical Industry Co., Ltd.

R-4: 2-hydroxyethyl disulfide, manufactured by Wako Pure Chemical Industries Co., Ltd.

<Close Agent>

G-1: 3-glycidoxypropyltrimethoxydecane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Surfactant>

H-1: a perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by Diane Health (DIC))

The obtained composition was subjected to the following evaluation.

<Evaluation of sensitivity>

A glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and was coated by spin coating. Each of the photosensitive resin compositions was prebaked on a hot plate at 90 ° C for 120 seconds to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3.0 μm.

Then, using the MPA 5500CF (high-pressure mercury lamp) manufactured by Canon, the obtained photosensitive resin composition layer was exposed through a predetermined mask set to a hole having a diameter of 5 μm. Then, the exposed photosensitive resin composition layer was developed with an alkali developer (0.4% aqueous tetramethylammonium hydroxide solution) at 23 ° C for 60 seconds, and then rinsed with ultrapure water for 20 seconds. Will be solved by these operations The optimum i-ray exposure amount (Eopt) when the 5 μm hole was analyzed was taken as the sensitivity.

A: 80 mJ/cm ² or more and less than 100 mJ/cm ²

B: 100 mJ/cm ² or more and less than 160 mJ/cm ²

C: 160 mJ/cm ² or more and less than 250 mJ/cm ²

D: 250mJ/cm ² or more

<Adhesion evaluation>

After each of the photosensitive resin compositions was slit-coated on a Mo (molybdenum) substrate, the solvent was removed by heating on a hot plate at 90 ° C for 120 seconds to form a photosensitive resin having a film thickness of 4.0 μm. Composition layer. The obtained photosensitive resin was composed of a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd. in a manner that the cumulative irradiation amount was 300 mJ/cm ² (illuminance: 20 mW/cm ² , i-ray). The layer was exposed, and then the substrate was heated in an oven at 230 ° C for 1 hour to obtain a cured film. Using a cutter, the slit was cut into the cured film at intervals of 1 mm in the longitudinal and lateral directions, and the tape peeling test was performed using Scotch tape. The adhesion between the cured film and the substrate was evaluated based on the area of the cured film transferred to the back surface of the tape. The smaller the value, the higher the adhesion to the underlying substrate, and preferably A or B.

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

<Transparency evaluation>

A coating film having a film thickness of 3.0 μm was formed on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)). Then, the exposure was performed through a predetermined mask using an i-ray stepper (manufactured by Canon Co., Ltd.). The solution was developed by an alkaline developer (2.38 mass% aqueous solution of tetramethylammonium hydroxide) at 23 ° C for 65 seconds, and then rinsed with ultrapure water for 1 minute. An ultrahigh pressure mercury lamp was used for the developed coating film, and after irradiating light of 300 mJ/cm ² at a wavelength of 365 nm, it was heated in an oven at 220 ° C for 45 minutes. The transmittance of the cured film was measured at a wavelength of 400 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.).

A: 95% or more

B: 93% or more and less than 95%

C: 90% or more and less than 93%

D: 85% or more and less than 90%

E: less than 80%

<Panel display suitability evaluation>

In the active matrix type liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a liquid crystal display device is obtained by using the interlayer insulating film of the present invention. A driving voltage was applied to the obtained liquid crystal display device to evaluate the presence or absence of crosstalk or afterimage. If the insulating property of the interlayer insulating film is poor, problems such as crosstalk or residual image are likely to occur.

A: No crosstalk or afterimage is generated at all.

B: Only extremely rare crosstalk or afterimages are produced

C: only rare crosstalk or afterimages are generated

D: often produces crosstalk or afterimage

E: Frequent crosstalk or afterimage

As is apparent from the above results, the photosensitive resin composition of the present invention has high sensitivity, excellent adhesion to a substrate, and high transparency. Further, it is surprising that the panel display is excellent in suitability. On the other hand, when the X component does not contain a sulfur atom (Comparative Example 2), the sensitivity, transparency, and panel display suitability were inferior. On the other hand, when the X component did not contain a ruthenium atom (Comparative Example 3 to Comparative Example 5), the panel display was inferior in performance in addition to sensitivity or adhesion. In particular, Comparative Examples 2 to 5 have a tendency to be worse than Comparative Example 1 which does not contain the X component, and therefore the photosensitive resin composition of the present invention has a high technical significance.

<Production of organic EL display device>

An organic EL display device using a TFT was fabricated by the following method (see FIG. 1).

A bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. Then, after the contact hole (not shown) is formed in the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. This wiring 2 is a wiring for connecting the organic EL element formed between the TFTs 1 or in the subsequent steps to the TFT 1.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarization layer 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is filled. The formation of the planarizing film 4 on the insulating film 3 was performed by spin-coating the photosensitive resin composition of Example 8 on a substrate, prebaking on a hot plate (90 ° C, 2 minutes), and self-masking. After i-rays of 100 mJ/cm ² were irradiated with a high-pressure mercury lamp, development was carried out using an alkaline aqueous solution to form a pattern, and heat treatment was performed at 220 ° C for 60 minutes. The coating property when the photosensitive resin composition was applied was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and firing. Further, the average step of the wiring 2 was 500 nm, and the film thickness of the produced planarizing film was 2000 nm.

Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 containing ITO is formed on the planarization film 4 via the contact hole 7 and connected to the wiring 2. Thereafter, a resist is applied and pre-baked, and exposed and developed through a mask of a desired pattern. This resist pattern was used as a mask, and pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was peeled off using a resist stripper (a mixture of monoethanolamine and DMSO). The first electrode thus obtained corresponds to the anode of the organic EL element.

Then, an insulating layer 8 covering the shape of the edge of the first electrode is formed. With respect to the insulating layer, the insulating film 8 was formed by the same method as described above using the photosensitive resin composition of Example 1. By providing the insulating layer, a short circuit between the first electrode and the second electrode formed in the subsequent step can be prevented.

Further, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by vapor deposition in a vacuum vapor deposition apparatus through a desired pattern mask. Then, a second electrode including A1 is formed on the entire upper surface of the substrate. The obtained substrate was taken out from the vapor deposition machine, and sealed by bonding using a glass plate for sealing and an ultraviolet curable epoxy resin.

An active matrix type organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to the respective organic EL elements is obtained as described above. When a voltage is applied via a driving circuit, the result shows good display characteristics, which is known as reliability. High organic EL display device.

<Production of liquid crystal display device>

In the active matrix liquid crystal display device described in FIG. 1 and FIG. 2 of the Japanese Patent No. 3321003, the photosensitive resin composition of the first embodiment of the present invention is used for the interlayer insulating film 17, and the conventional method is used. A liquid crystal display device is produced.

When a driving voltage was applied to the obtained liquid crystal display device, it was found to have good display characteristics, and it was found to be a highly reliable liquid crystal display device.

1‧‧‧TFT (thin film transistor)

2‧‧‧Wiring

3‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

8‧‧‧Insulation film

Claims (18)

A positive photosensitive resin composition comprising: (Component A) an alkali-soluble resin, wherein the alkali-soluble resin is a copolymer containing (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group (Component B) 1,2-quinonediazide compound; and (Component X) a compound represented by the following formula (I); (In the formula (I), R ¹ to R ⁶ each independently represent a hydrocarbon group or an alkoxy group, and L ¹ and L ² each independently represent an alkylene group, an extended aryl group or a group containing a combination of the groups, n represents an integer from 2 to 4). The positive photosensitive resin composition according to claim 1, wherein the structural unit (a1) is a repeating unit having a carboxyl group and/or a phenolic hydroxyl group. The positive photosensitive resin composition according to claim 1, wherein the structural unit (a2) is a repeating unit having an epoxy group and/or an oxetanyl group. The positive photosensitive resin composition according to the first aspect of the invention, wherein the amount of the component (component X) is from 1% by mass to 25% by mass based on the total solid content of the composition. The positive photosensitive resin composition according to claim 1, wherein R ¹ to R ⁶ are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. The positive photosensitive resin composition according to claim 1, wherein L ¹ and L ² are each independently an alkylene group having 1 to 8 carbon atoms, a phenyl group or a group containing a combination of the groups. group. The positive photosensitive resin composition as described in claim 1, wherein n is 3 or 4. The positive photosensitive resin composition according to claim 1, wherein the structural unit (a1) is a repeating unit having a carboxyl group and/or a phenolic hydroxyl group, and the structural unit (a2) has an epoxy group and / or repeating unit of oxetanyl. The positive photosensitive resin composition according to claim 1, wherein R ¹ to R ⁶ are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and L ¹ and L ^{2 is} independently an alkylene group having 1 to 8 carbon atoms, a phenyl group or a group containing a combination of these groups. The positive photosensitive resin composition according to claim 1, wherein R ¹ to R ⁶ are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and L ¹ and L ^{2 is} independently an alkylene group having 1 to 8 carbon atoms, a phenyl group or a group containing a combination of the groups, and n is 3 or 4. A method of forming a cured film, comprising: (1) a step of applying a positive photosensitive resin composition according to any one of claims 1 to 10 to a substrate; (2) a pre-baking step of baking the positive photosensitive resin composition applied; (3) consisting of a baked positive photosensitive resin by actinic rays or radiation a step of exposing the object; (4) a step of developing the exposed positive photosensitive resin composition by an aqueous developing solution; and (5) after thermally curing the developed positive photosensitive resin composition Baking steps. The method for forming a cured film according to claim 11, wherein after the developing step and before the post-baking step, the step of (6) performing full exposure of the developed positive photosensitive resin composition is included. . The method for forming a cured film according to claim 11, which further comprises the step of dry etching the substrate having the cured film obtained by thermosetting. The method for forming a cured film according to claim 11, wherein the thermal hardening is performed at 200 ° C or higher. A cured film formed by a method of forming a cured film according to claim 11 or 12. The cured film according to claim 15, which is an interlayer insulating film. An organic EL display device having the cured film according to claim 15 of the patent application. A liquid crystal display device having the cured film according to claim 15 of the patent application.