JP5914668B2 - Positive photosensitive resin composition, method for producing cured film, cured film, organic EL display device and liquid crystal display device - Google Patents

Description

The present invention relates to a positive photosensitive resin composition (hereinafter, simply referred to as “photosensitive resin composition” or “composition of the present invention”). The present invention also relates to a method for producing a cured film using the positive photosensitive resin composition, a cured film obtained by curing the positive photosensitive composition, and various image display devices using the cured film.
More specifically, a positive photosensitive resin composition suitable for forming a flattening film, a protective film, and an interlayer insulating film of electronic components such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state imaging device, and the same The present invention relates to a method for producing a cured film using the above.

  Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained (Patent Document 1). Patent Document 2).

International Publication No. 2007/122929 Pamphlet JP 2011-48064 A

When the inventor of the present application has studied the above Patent Document 1, when the disulfide compound described in Patent Document 1 is used, a photosensitive resin for forming an interlayer insulating film such as sensitivity, transparency, adhesion to a substrate, etc. It has been found that the performance required for the composition is not sufficient.
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.

Under such circumstances, as a result of intensive studies by the present inventor, by using a sulfide compound containing a silicon atom in the positive photosensitive resin composition, the sensitivity is high and the adhesiveness with the substrate is excellent. The present inventors have found that a positive photosensitive resin composition excellent in transparency can be provided, and completed the present invention.
Specifically, the above problem has been solved by the following means <1>, preferably by means <2> to <15>.
<1> (Component A) an alkali-soluble resin,
A positive photosensitive resin composition containing (Component B) 1,2-quinonediazide compound and (Component X) a compound represented by the following general formula (I).
(I)
(In general formula (I), R ^{1 to} R ⁶ each independently represents a hydrocarbon group or an alkoxy group, and L ¹ and L ² each independently represent an alkylene group, an arylene group, or a combination thereof. And n represents an integer of 2 to 4.)
<2> The positive photosensitive resin composition according to <1>, wherein the alkali-soluble resin is a copolymer comprising (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group. .
<3> The positive photosensitive resin composition according to <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 according to <2> or <3>, wherein the structural unit (a2) is a repeating unit having an epoxy group and / or an oxetanyl group.
<5> The positive photosensitive resin composition according to any one of <1> to <4>, wherein the blending amount of (Component X) is 1 to 25% by mass in the total solid content of the composition.
<6> The positive photosensitive resin according to any one of <1> to <5>, 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. Resin composition.
<7> The positive type according to any one of <1> to <6>, wherein L ¹ and L ² are each independently a group consisting of an alkylene group having 1 to 8 carbon atoms, a phenylene group, or a combination thereof. Photosensitive resin composition.
<8> The positive photosensitive resin composition according to any one of <1> to <7>, wherein n is 3 or 4.
<9> (1) A step of applying the positive photosensitive resin composition according to any one of <1> to <8> on a substrate,
(2) a pre-baking step of baking the applied positive photosensitive resin composition;
(3) a step of exposing the baked positive photosensitive resin composition with actinic rays or radiation;
(4) a step of developing the exposed positive photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed positive photosensitive resin composition;
A method for forming a cured film comprising:
<10> The method for forming a cured film according to <9>, including a step of (6) exposing the entire surface of the developed positive photosensitive resin composition 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 a step of performing dry etching on a substrate having a cured film obtained by thermosetting.
<12> The method for forming a cured film according to any one of <9> to <11>, wherein the thermosetting 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 according to <13> or <14>.

It was also achieved by the following means.
<16> In any one of the positive photosensitive resin compositions described above, the alkali-soluble resin is derived from a compound having an alicyclic 5-membered ring, an alicyclic 6-membered ring, or a compound having an alicyclic structure in which two or more of them are connected. A positive photosensitive resin composition containing units.
<17> The positive photosensitive resin composition according to any one of the above-described positive photosensitive resin compositions, wherein the alkali-possible resin includes a carboxyl group as an acid group.
<18> The positive photosensitive resin composition as described above, wherein the alkali-soluble resin has a repeating unit having an aromatic structure.
<19> The positive photosensitive resin composition according to any one of the above, further comprising an adhesion improver and a surfactant.
<20> The positive photosensitive resin composition as described above, wherein the alkali-soluble resin includes a repeating unit (a2) 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 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.

  In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have 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 comprises (Component A) an alkali-soluble resin, (Component B) a 1,2-quinonediazide compound, and (Component X) a compound (sulfur-containing) represented by the following formula (I) Compound). Details of these will be described below.

<A component: alkali-soluble resin>
The alkali-soluble resin in the present invention is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.

The alkali-soluble resin in the present invention is a polymer containing a (meth) acrylic repeating unit, and is particularly limited as long as it is a resin having an alkali-soluble group in the molecule and soluble in an aqueous alkali solution. However, a resin to which alkali solubility is imparted by having a carboxyl group or a phenolic hydroxyl group as the alkali-soluble group is preferably used.
The proportion of the acrylic repeating unit contained in the alkali-soluble resin of the present invention is preferably 20 to 100 mol%, more preferably 35 to 100 mol%, particularly preferably from the viewpoint that a pattern with high transmittance can be formed. It is 50-100 mol%.

  The alkali-soluble resin in 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. This alkali-soluble resin may contain other repeating units as necessary.

(A1) Repeating Unit Having Acid Group The alkali-soluble resin in the present invention preferably contains a repeating unit having an acid group, and has a carboxyl group, from the viewpoint of improving the solubility of the photosensitive resin composition in the developer. It is preferable to include any of the unit (a1-1), the repeating unit (a1-2) having both a carbon-carbon unsaturated bond group and a carboxyl group, and the repeating unit (a1-3) having a phenolic hydroxyl group. .

-Repeating unit having a carboxyl group (a1-1)-
Examples of the repeating unit (a1-1) having a carboxyl group include unsaturated carboxylic acids having at least one carboxyl group in the molecule, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid. The repeating unit derived from is mentioned.

As the unsaturated carboxylic acid used for obtaining the repeating unit (a1-1) having a carboxyl group, those listed below are used.
That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

  Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the repeating unit (a1-1) which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.

  Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.

  As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.

  Among these, from the viewpoint of developability, in order to form the repeating unit (a1-1) having a carboxyl group, it is preferable to use acrylic acid, methacrylic acid, an unsaturated polycarboxylic acid anhydride, or the like.

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

-Repeating unit (a1-2) having both an intercarbon unsaturated bond group and a carboxyl group-
The repeating unit (a1-2) having both a carbon-carbon unsaturated bond group and a carboxyl group is a hydroxyl group and an acid anhydride present in the repeating unit (a2-1) having a carbon-carbon unsaturated bond group described later. It is preferable that it is the repeating unit obtained by making it react.
As the acid anhydride, known ones can be used. Specific examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride. Examples include basic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 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 has at least one phenolic hydroxyl group in the molecule such as hydroxystyrene, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like. Examples include a repeating unit derived from a compound.

  (A1) The repeating unit having an acid group may be composed of one of (a1-1), (a1-2), and (a1-3), or a mixture of these. May be. In this invention, the repeating unit (a1-1) which has a carboxyl group, or the repeating unit (a1-3) which has a phenolic hydroxyl group is preferable, and the repeating unit (a1-1) which has a carboxyl group is more preferable.

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

(A2) Repeating Unit Having Crosslinkable Group The alkali-soluble resin in the present invention preferably contains (a2) a repeating unit having a crosslinkable group. Examples of the crosslinkable group include a phenolic hydroxyl group, an acid anhydride group, an aldehyde group, a methylol group, a maleimide group, a thiol group, a repeating unit (a2-1) having an unsaturated bond group between carbons, an epoxy group and / or oxetanyl. Examples thereof include a repeating unit (a2-2) having a group, a repeating unit (a2-3) having a group represented by —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms), and the like. , A repeating unit (a2-1) having an unsaturated bond group between carbons, a repeating unit (a2-2) having an epoxy group and / or an oxetanyl group, -NH-CH ₂ -O-R (R is carbon number 1 repeating unit (a2-3) is preferable to have a group represented by the alkyl group) of 20, the repeating unit having an epoxy group and / or an oxetanyl group (a2-2), - NH-CH 2 - The repeating unit (a2-3) having a group represented by —R (R is an alkyl group having 1 to 20 carbon atoms) is more preferable, and the repeating unit (a2-2) having an epoxy group and / or an oxetanyl group is further included. preferable.
Hereinafter, these details will be described.

-Repeating unit (a2-1) having an unsaturated bond group between carbon atoms-
Examples of the repeating unit (a2-1) having an intercarbon unsaturated bond group include a repeating unit derived from a monomer having an intercarbon unsaturated bond group (polymerizable group). As the intercarbon unsaturated bond group (polymerizable group), from the viewpoint of reactivity, a (meth) acryloyl group and an allyl group are preferable, a (meth) acryloyl group is more preferable, and an acryloyl group is most preferable. As the repeating unit (A2-1) having an unsaturated bond group between carbons, a repeating unit having a structure in which an epoxy ring in a compound containing an epoxy ring and an unsaturated bond group between carbons is added to a carboxyl group, or The repeating unit having a structure in which a carboxyl group in a compound containing a carboxyl group and an intercarbon unsaturated bond group is added to an epoxy ring is preferred. More specifically, a repeating unit obtained by reacting an epoxy ring in a compound containing an epoxy ring and an intercarbon unsaturated bond group with the carboxyl group of the repeating unit (a1-1) having a carboxyl group, or It is a repeating unit obtained by reacting a carboxyl group of a compound containing a carboxyl group such as (meth) acrylic acid and an intercarbon unsaturated bond group with an epoxy ring in a repeating unit derived from a monomer having an epoxy ring described later. Is preferred.

The compound containing an epoxy ring and an intercarbon unsaturated bond group may be a compound having at least one epoxy ring and an intercarbon unsaturated bond group, for example, glycidyl acrylate, glycidyl methacrylate, (3, Examples include compounds such as 4-epoxycyclohexyl) methyl acrylate, (3,4-epoxycyclohexyl) methyl methacrylate, and allyl glycidyl ether.
Among these, glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl acrylate, (3,4-epoxycyclohexyl) methyl methacrylate are preferable, glycidyl methacrylate, 3,4-epoxycyclohexyl) methyl acrylate, ( 3,4-epoxycyclohexyl) methyl methacrylate is most preferred from the viewpoints of solvent resistance and heat resistance.

  The repeating unit (a2-1) having an unsaturated bond group between carbons may be composed of one kind alone, or may be composed of two or more kinds.

  In the present invention, the content of the repeating unit (a2-1) having an unsaturated bond group between carbons in the alkali-soluble resin is preferably 0 to 60 mol% from the viewpoint of compatibility between various resistances and developability, and 0 to 50 mol%. The mol% is more preferable, and 0 to 40 mol% is more preferable.

-Repeating unit (a2-2) having at least one group selected from the group consisting of epoxy group and oxetanyl group-
Examples of the repeating unit (a2-2) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group include repeating units derived from an epoxy group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound.
Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylate 3,4. -Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinyl Examples thereof include benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether. Among these, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, etc. However, it is preferably used from the viewpoint of increasing the copolymerization reactivity, the heat resistance of the resulting interlayer insulating film, and the surface hardness.

Examples of the oxetanyl group-containing unsaturated compound include (meth) acrylic acid ester having an oxetanyl group. Examples of the oxetanyl group-containing unsaturated compound include (meth) acrylic acid esters having an oxetanyl group described in JP-A-2001-330953, paragraphs 0011 to 0016. Specific examples of such compounds include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- ( Methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. have a wide process margin of the resulting photosensitive resin composition and increase the chemical resistance of the resulting interlayer insulating film Are preferably used. These may be used alone or in combination.
The repeating unit (a2-2) may contain only 1 type and may contain 2 or more types. The content of the repeating unit (a2-2) in the alkali-soluble resin in the present invention is preferably 0 to 50 mol%, more preferably 0 to 45 mol%, from the viewpoint of various resistances and transparency of the formed film. 0 to 40 mol% is more preferable.

Repeating unit (a2-3) having a group represented by —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms) —
The copolymer used in the present invention is also preferably a repeating unit (a2-3) having a group represented by —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms). By having the repeating unit (a2-3), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The repeating unit (a2) is more preferably a structural unit having a group represented by the following general formula (1).
General 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. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.

The repeating unit (a2-3) may contain only one type or may contain two or more types. The content of the repeating unit (a2-3) in the alkali-soluble resin in the present invention is preferably 0 to 50 mol%, more preferably 0 to 45 mol%, from the viewpoints of various resistances and transparency of the formed film. 0 to 40 mol% is more preferable.
In the present invention, the alkali-soluble resin preferably contains the repeating unit (a2). When the alkali-soluble resin contains the repeating unit (a2), the repeating unit (a2) is a repeating unit in the alkali-soluble resin. It is preferable to occupy 5 to 50 mol%, and more preferably 8 to 40 mol%.

-Other repeating units (a3)-
The alkali-soluble resin used in the present invention may contain (a1) a repeating unit having an acid group and (a2) another constituent unit other than a copolymer containing a repeating unit having a crosslinkable group. Although what is contained in alkali-soluble resin does not have a restriction | limiting in particular, The repeating unit derived from a vinyl monomer, the repeating unit containing an alicyclic structure, the repeating unit containing an aromatic ring structure, etc. are mentioned.

By including other repeating units (a3), the pattern-forming property of the alkali-soluble resin may be improved.
Examples of the vinyl monomer that can form the other repeating unit (a3) include vinyl monomers described in Paragraph Nos. 0046 to 0051 of JP-A No. 2009-98691.

In addition, the alkali-soluble resin used in the present invention has an alicyclic structure in the molecule from the viewpoint that the formed resin composition film has a high transmittance and a low relative dielectric constant. it can.
As the alicyclic structure, an alicyclic 5-membered ring, an alicyclic 6-membered ring, or an alicyclic structure in which two or more of them are connected is preferable. Specific examples include cyclohexyl, tert-butylcyclohexyl, dicyclopentenyl, dicyclo Examples thereof include cyclopentenyloxyethyl, dicyclopentanyl, isobonyl, etc. Among them, from the viewpoint of heat resistance, insulation stability, and ITO sputtering suitability of a film formed using the photosensitive resin composition, cyclohexyl, dicyclopentenyl, Dicyclopentenyloxyethyl and dicyclopentanyl are preferred.
The alkali-soluble resin in 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 from the photosensitive resin composition.
The repeating unit having an aromatic ring structure is preferably derived from the monomers shown below.
Namely, phenyl (meth) acrylate, 3-methoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate , Tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, Hydroxystyrene protected with an acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, or a group that can be deprotected by an acidic substance (eg, tert-Boc) Emissions, methyl vinyl benzoate, and α- methyl styrene and the like, these, (meth) acrylate, benzyl styrene is preferred.

  The other repeating unit (a3) may be composed of one kind alone, or may be composed of two or more kinds.

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

Preferred examples of the alkali-soluble resin used in the present invention include an alkali-soluble resin having in the molecule thereof at least one group selected from the group consisting of an epoxy group and / or an oxetanyl group. Preferable specific examples of such a resin include, for example, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / 2-methylcyclohexyl acrylate / glycidyl methacrylate / 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 / (3-ethyloxetane-3-yl) methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate copolymer, methacrylic acid / tricyclo [5.2. 1.0 ^2,6] decan-8-Irume Acrylate / N- cyclohexyl maleimide / glycidyl methacrylate / styrene copolymer, methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / styrene / tricyclo [5.2.1.0 ^2,6] decan-8-yl methacrylate copolymer A polymer etc. can be mentioned.
Hereinafter, although such alkali-soluble resin is illustrated, this invention is not limited to this.
In addition, the weight average molecular weight of the alkali-soluble resin exemplified below is 5000 to 80000.

The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) by GPC of the alkali-soluble resin used in the present invention is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably from the viewpoint of development margin and sensitivity. 5 × 10 ^{3 to} 5 × 10 ⁴ .
The molecular weight distribution (hereinafter referred to as “Mw / Mn”), which is the ratio between Mw and polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”), is preferably from the viewpoint of improving the pattern shape. 5.0 or less, more preferably 3.0 or less.
The positive-type photosensitive resin composition for interlayer insulating films containing the alkali-soluble resin can easily form a predetermined pattern shape without causing a development residue during development.

  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, and preferably 25% by mass to 85% by mass with respect to the total solid content of the photosensitive resin composition. %, More preferably 30% by mass to 80% by mass. When the content is within this range, the pattern formability upon development is 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 in the present invention is a compound having a 1,2-quinonediazide partial structure, and requires at least one 1,2-quinonediazide partial structure in the molecule. What has the above is preferable.
(B) The 1,2-quinonediazide compound suppresses the alkali solubility of the photosensitive resin composition coating film in the unexposed area, and generates carboxylic acid in the exposed area to generate an alkali in the photosensitive resin composition coating film. By improving the solubility, a positive pattern can be formed.
A 1,2-quinonediazide compound can be obtained, for example, by subjecting 1,2-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound, or the like in the presence of a dehydrochlorinating agent.
Examples of the 1,2-quinonediazide compound include 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2-benzoquinonediazidesulfonic acid amide, and 1,2-naphthoquinonediazidesulfonic acid amide. Etc. Specifically, J. et al. Kosar, “Light-Sensitive Systems”, pp. 339-352 (1965), John Wiley & Sons (New York) and W.C. S. 1,2-quinonediazide compounds described in “Photoresist” 50 (1975) by De Forest, McGraw-Hill, Inc, (New York), JP-A 2004-170566, JP-A 2002-40653, JP Examples thereof include 1,2-quinonediazide compounds described in JP-A No. 2002-351068, JP-A No. 2004-4233, JP-A No. 2004-271975, and the like. Those described in JP-A-2008-224970, paragraph numbers 0066 to 0081 are also preferable. These contents are incorporated herein.

In the present invention, among 1,2-quinonediazide compounds, compounds having a 1,2-naphthoquinonediazide group are preferred. When a compound having a 1,2-naphthoquinonediazide group is used, high sensitivity and developability are obtained.
Among the compounds having a 1,2-naphthoquinonediazide group, compounds having the following structures can be preferably used because they have particularly high sensitivity.

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

  In the photosensitive resin composition of the present invention, the amount of the 1,2-quinonediazide compound is 100 parts by mass with respect to the total amount of the alkali-soluble resin from the viewpoint of the difference in dissolution rate between the exposed part and the unexposed part and the allowable range of sensitivity. 1 part by mass to 100 parts by mass is preferable, 3 parts by mass to 80 parts by mass is more preferable, and 5 parts by mass to 30 parts by mass is more preferable. As the 1,2-quinonediazide compound, one kind may be used alone, or two or more kinds may be used in combination. Furthermore, you may use together with a photo-acid generator.

  Photoacid generators include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, irradiation with actinic rays or radiation used in microresists, etc. A known compound that generates an acid or a mixture thereof can be appropriately selected and used.

Specific examples of photoacid generators include, for example, diazonium salt compounds, phosphonium salt compounds, sulfonium salt compounds, iodonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, o-nitrobenzyl sulfonate compounds. Can be mentioned.
As the photoacid generator, a compound that generates a sulfonic acid, an alkyl or arylcarboxylic acid substituted with an electron withdrawing group, a disulfonylimide substituted with an electron withdrawing group, or the like having a strong pKa of 2 or less as the generated acid. preferable. Here, examples of the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

  Further, as a photoacid generator, a group capable of generating an acid upon irradiation with actinic rays or radiation, or a compound having a compound introduced into the main chain or side chain of the resin, for example, US Pat. No. 3,849,137, German Patent No. 3914407, and JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, The compounds described in JP-A Nos. 62-153853 and 63-146029 can also be used. These contents are incorporated herein.

Further, as a photoacid generator, compounds capable of generating an acid by light described in each specification such as US Pat. No. 3,779,778 and European Patent 126,712 can also be used.
0.5-15 mass parts is preferable with respect to 100 mass parts of solid content of the photosensitive resin composition, and, as for the addition amount of a photo-acid generator, 1-5 mass parts is more preferable.

  Moreover, in the photosensitive resin composition of this invention, when adding a sulfonium salt compound as a photo-acid generator, it is preferable to add a sensitizer in order to accelerate | stimulate the decomposition | disassembly.

  The addition amount of the sensitizer is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass with respect to 100 parts by mass of the sulfonium salt compound.

<X component: sulfur-containing compound>
In this invention, the compound represented by general formula (I) is included as X component. By compounding the compound represented by the general formula (I), it is possible to provide a positive photosensitive resin composition having high sensitivity, excellent adhesion to the substrate, and excellent transparency. Surprisingly, it has been found that the panel display is excellent when used in various panels.
(In general formula (I), R ^{1 to} R ⁶ each independently represents a hydrocarbon group or an alkoxy group, and L ¹ and L ² each independently represent an alkylene group, an arylene group, or a combination thereof. And n represents an integer of 2 to 4.)

R ^{1 to} R ^{6 each} represents a hydrocarbon group or an alkoxy group. The hydrocarbon group represents 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 in 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, still more preferably an alkyl group having 1 to 6 carbon atoms, and 1 carbon atom. An alkyl group of ˜3 is particularly preferred. The alkyl group may be linear, branched or cyclic, but is preferably linear. In addition, the alkyl group may have a substituent, but preferably has no substituent. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, A cyclopentyl group, 2-norbornyl group, etc. are mentioned, Among these, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable, and a methyl group or an ethyl group is more preferable.
The aryl group in 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 further have a 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 anthranyl group, and among them, a phenyl group and a naphthyl group are preferable.

  Examples of the substituent that the alkyl group and / or 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, a halogen atom (a fluorine atom, a chlorine atom, Bromine atom, iodine atom) and the like.

The alkoxy group in 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, still more preferably an alkoxy group having 1 to 6 carbon atoms, and 1 carbon atom. Particularly preferred are ˜3 alkoxy groups. The alkoxy group may be linear, branched or cyclic, but is preferably linear. The alkoxy group may have a substituent, but preferably has no substituent. Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, isopropoxy group, isobutoxy group, s-butoxy group, tert-butoxy group, isopentoxy group, and neopentoxy group. Among them, a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group are preferable, and a methoxy group or an ethoxy group is more preferable. The substituent that the alkoxy group may have is the same as the substituent that the alkyl group or aryl group may have.

Among these, as R < ¹ > -R < ⁶ >, an alkyl group or an alkoxy group is respectively independently preferable, and a C1-C6 alkyl group or a C1-C6 alkoxy group is preferable.

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

L ¹ and L ² each independently represent an alkylene group, an arylene group or a group consisting of a combination thereof, an alkylene group or a group consisting of a combination of an alkylene group and an arylene group is preferred, and an alkylene group is more preferred. When an alkylene group is used, the adhesion to the substrate tends to be further improved.
The alkylene group in 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, still more preferably an alkylene group having 1 to 8 carbon atoms, and 2 to 2 carbon atoms. Even more preferred is an alkylene group of 4. The alkylene group may have a substituent, but preferably has no substituent. The alkylene group may be any of linear, branched or cyclic, but a linear alkylene group is preferred. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.
As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, an alkylene group having 6 to 14 carbon atoms is more preferable, an arylene group having 6 to 10 carbon atoms is further preferable, and a phenylene group is further more preferable. The arylene group may have a substituent, but preferably has no substituent. Examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a naphthylene group. In the present invention, 1,2-phenylene group, 1,3-phenylene group and 1,4-phenylene group are particularly preferable, and 1,4-phenylene group is more preferable.
The substituent that the alkylene group and arylene group may have is the same as the substituent that the alkyl group or aryl group may have.

Among these, L ¹ and L ² are preferably each independently an alkylene group having 1 to 8 carbon atoms, a phenylene group or a group consisting of a combination thereof, and an alkylene group having 2 to 4 carbon atoms or a phenylene group. Or the group which consists of these combination is more preferable.

  n represents an integer of 2 to 4, and 3 or 4 is preferable.

  200-800 are preferable and, as for the molecular weight of the compound represented with general formula (I) used by this invention, 400-500 are more preferable.

Although the compound represented with general formula (I) preferably used for this invention below is shown, it cannot be overemphasized that this invention is not limited to these. Me represents a methyl group, and Et represents an ethyl group.

The compound represented by the general formula (I) used in the present invention can be synthesized with reference to documents such as US Publication No. 2006/106240 A1, for example.
In this invention, it is preferable that the compounding quantity of (component X) is 5-25 mass% of the total solid of a composition, and it is more preferable that it is 8-22 mass%.
Moreover, it is preferable to be contained in the ratio of 1-10 mass parts with respect to a total of 100 mass parts of a polymer component, and it is more preferable to be contained in the ratio of 1-5 mass parts.

<Crosslinking agent>
The photosensitive resin composition of the present invention may contain a crosslinking agent for the purpose of improving curability. Details will be described below.

-(C-1) Crosslinking agent having at least one group selected from the group consisting of epoxy group and oxetanyl group-
The photosensitive resin composition of the present invention may contain a crosslinking agent (C-1) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group. In particular, when the alkali-soluble resin does not contain the repeating unit (A2-2), it is preferable to use (C-1). Thus, it is preferable from the viewpoint of storage stability 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 copolymer (C1)). Can do. An epoxy group is preferable from the viewpoint of easy reaction, and an oxetanyl group is preferable from the viewpoint of storage stability of the composition and heat resistance of the cured product.
As the copolymer (C1), an alicyclic structure is included in the structure from the viewpoint that transparency, developability, and insulation stability of a cured film formed using the photosensitive resin composition are improved. It can be a thing.

  In the present invention, the copolymer (C1) is a copolymer containing a repeating unit (C1-1) having at least one group selected from the group consisting of an epoxy group and an oxetanyl group. Furthermore, (C1-2) other repeating units may be included as necessary. However, the copolymer (C1) does not contain a carboxyl group or a phenolic hydroxyl group in its structure. The copolymer (C1) is preferably an acrylic copolymer from the viewpoint of transparency and insulation stability.

[Repeating unit (C1-1) having at least one group selected from the group consisting of epoxy group and 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 is derived from a monomer having at least one group selected from the group consisting of an epoxy group and an oxetanyl group. Repeat units are mentioned.
Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexyl-n-bromo (meth) acrylate, 3,4-epoxycyclohexyl-i-propyl (meth) acrylate, 1-vinyl-2,3-epoxycyclohexane, 1-vinyl-3 , 4-epoxycyclohexane, 1-allyl-2,3-epoxycyclohexane, 1-allyl-3,4-epoxycyclohexane, and the like. Among them, glycidyl (meth) acrylate, (3,4-epoxy (Cyclohexyl) methyl (meth) acryle DOO, but solvent resistance, from the viewpoint of heat resistance.

  Examples of the monomer having an oxetanyl group include (meth) acrylic acid esters having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953. Specific examples of such a monomer include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- ( From the point that the process margin of the photosensitive resin composition from which methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane and the like are obtained is wide, and the chemical resistance of the resulting interlayer insulating film is increased. preferable.

  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 one kind alone, or may be composed of two or more kinds.

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

[(C1-2) Other repeating units]
The copolymer (C1) in the present invention may contain other repeating units (C1-2). Although there is no limitation in particular as this other repeating unit (C1-2), It is preferable that a hydroxyl group and a polyethylene oxide group are included from a compatible viewpoint with alkali-soluble resin. Moreover, the repeating unit derived from a vinyl monomer can be included.
Examples of vinyl monomers that can form other repeating units (C1-2) include vinyl monomers described in paragraph numbers 0046 to 0051 of JP-A No. 2009-98691.

Among these, (meth) acrylic acid esters or styrenes are preferable. Most preferred are (meth) acrylic esters, and among (meth) acrylic esters, 2-hydroxyethyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl (meth) acrylate Ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether form pattern by development From the viewpoints of safety and transparency.
Furthermore, the repeating unit which has an alicyclic structure can be included from the point that the transparency and insulation stability of the cured film to be formed are excellent.
Specific examples of the monomer having an alicyclic structure include cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (Meth) acrylic acid dicyclopentanyl, (meth) acrylic acid isobonyl, etc. are mentioned, among them, (meth) acrylic acid cyclohexyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyloxyethyl, (Meth) acrylic acid dicyclopentanyl is preferred.

Other repeating units (C1-2) may be composed of one kind alone, or may be composed of two or more kinds.
The content of the other repeating unit (C1-2) in the copolymer (C1) in the present invention is excellent in transparency and developability of a cured film formed using the photosensitive resin composition. 0 mol%-50 mol% are preferable, 3 mol%-40 mol% are more preferable, 5 mol%-30 mol% are further more preferable.

  The copolymer (C1) as described above is synthesized by copolymerizing monomers capable of forming at least a repeating unit of (C1-1) and, if necessary, a repeating unit of (C1-2) when polymerized. can do.

Hereinafter, although the example of the copolymer (C1) which can be used conveniently for this invention is given, this invention is not limited to this. In addition, the weight average molecular weight of the compound illustrated below is 4000-41000.

Although there is no restriction | limiting in particular in the molecular weight of the copolymer (C-1) used by this invention, 2,000-50,000 are preferable at a weight average molecular weight from a viewpoint of an alkali dissolution rate or film | membrane physical property, and 3,000. ~ 30,000 is more preferred.
As the crosslinking agent in the present invention, a compound having at least one group selected from the group consisting of an epoxy group other than the copolymer (C-1) and an oxetanyl group can also be used. For example, Celoxide 2021P, 3000, Epolide GT401, EHPE3150, EHPE3150E (manufactured by Daicel Chemical Industries, Ltd.), JER157S70, JER157S65 (manufactured by Mitsubishi Chemical Corporation), paragraph 0189 of JP2011-221494A The commercial item of description etc. are mentioned.
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX- 832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX- 14L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (above, Nagase ChemteX Corporation) YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, manufactured by Nippon Steel Chemical Co., Ltd.), Aron Oxetane OXT-121, OXT-221, OX -SQ, PNOX (above, manufactured by Toagosei Co., Ltd.) and the like.
The crosslinking agent (C-1) in this invention may be used individually by 1 type, and may use 2 or more types together. The addition amount of the crosslinking agent in the present invention to the photosensitive resin composition of the present invention is preferably 5 parts by mass to 120 parts by mass, preferably 10 parts by mass when the total amount of the alkali-soluble resin and alkali-soluble resin is 100 parts by mass. Part to 100 parts by mass is more preferable. When the addition amount is within this range, the cured film formed using the photosensitive resin composition has excellent solvent resistance, heat resistance, and insulation stability.

<(C-2) Alkoxymethyl group-containing crosslinking agent>
Other preferred examples of the crosslinking agent in the present invention include (C-2) an alkoxymethyl group-containing crosslinking agent. As the alkoxymethyl group-containing crosslinking agent (C-2) used as the crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril and methylolated urea into alkoxymethyl groups, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group and the like. A methyl group is preferred.
Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable crosslinkable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.

  These (C-2) alkoxymethyl group-containing crosslinking agents are available as commercial products, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202. , 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, -032, -706, -708, -40, -31, -270, -280 , -290, Nicarak Ms-11, Nicarak Mw-30HM, -100LM, -390 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

  The addition amount when used as these (C-2) alkoxymethyl group-containing crosslinking agents is preferably 0.05 to 50 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. It is. By adding within this range, preferable alkali solubility during development and excellent solvent resistance of the cured film can be obtained.

In addition to the above, the photosensitive resin composition of the present invention comprises an antioxidant, a thermal radical generator, an adhesion promoter (preferably a silane coupling agent), a surfactant, a thermosensitive acid generating compound, and at least one ethylene. An optional component such as a polymerizable compound having a polymerizable unsaturated double bond and a solvent may be further contained depending on the purpose.
Hereinafter, arbitrary components will be described.

<Antioxidant>
The composition of the present invention can contain a known antioxidant. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented or reduction in film thickness due to decomposition can be reduced. Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, Examples thereof include thiosulfate and hydroxylamine derivatives. Of these, phenol-based antioxidants and sulfur-based antioxidants are particularly preferable from the viewpoints of coloring the cured film and reducing the film thickness. These may be used alone or in combination.

Examples of commercially available phenolic antioxidants include ADK STAB AO-60 (manufactured by ADEKA), ADK STAB AO-80 (manufactured by ADEKA), and trade name Irganox 1098 (manufactured by Ciba Japan).
The content of the antioxidant is preferably 0.1% by mass to 6% by mass and more preferably 0.2% by mass to 5% by mass with respect to the total solid content of the photosensitive resin composition. Preferably, 0.5% by mass to 4% by mass is optimal. By setting it in this range, sufficient transparency of the formed film can be obtained, and sensitivity can be exhibited even during pattern formation.
In addition, as an additive other than the antioxidant, the various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun)”, metal deactivators and the like are used in the photosensitive resin composition of the present invention. You may add to.

<Thermal radical generator>
The photosensitive resin composition of the present invention may contain a thermal radical generator.
As the thermal radical generator in the present invention, those generally known as radical generators can be used. A thermal radical generator is a compound that generates radicals by heat 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 tougher and heat resistance and solvent resistance are improved.

Hereinafter, although a thermal radical generator is explained in full detail, this invention is not restrict | limited by these description.
In the present invention, preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, activity Examples thereof include an ester compound, a compound having a carbon halogen bond, an azo compound, and a bibenzyl compound.
In the present invention, from the viewpoint of heat resistance and solvent resistance of the obtained cured film, organic peroxides, azo compounds, and bibenzyl compounds are more preferable, and bibenzyl compounds are particularly preferable.
Moreover, as a bibenzyl compound, the compound represented by following General formula (1) is preferable.

In the general formula (1), a plurality of R ³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, or a halogen atom. Represents an atom.

  Specific examples of the compound represented by the general formula (1) include 2,3-dimethyl-2,3-diphenylbutane, α, α′-dimethoxy-α, α′-diphenylbibenzyl, α, α ′. -Diphenyl-α-methoxybibenzyl, α, α'-dimethoxy-α, α'dimethylbibenzyl, α, α'-dimethoxybibenzyl, 3,4-dimethyl-3,4-diphenyl-n-hexane, 2 2, 3, 3-tetraphenyl succinic acid nitrile, dibenzyl and the like.

The thermal radical generator in the present invention may be used alone or in combination of two or more.
The addition amount of the thermal radical generator to the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass when the alkali-soluble resin is 100 parts by mass from the viewpoint of improving film properties. More preferably, it is 1 mass part-10 mass parts, and it is still more preferable that it is 1 mass part-5 mass parts.

<Adhesion promoter>
If necessary, an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent may be added to the photosensitive resin composition of the present invention to provide adhesion to a solid surface.
Examples of these are, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl. Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, tris ( Acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like.
When using an adhesion promoter for the photosensitive resin composition, 0.1 to 20 parts by mass is preferable and 0.5 to 10 parts by mass is more preferable with respect to 100 parts by mass of the alkali-soluble resin.

<Surfactant>
The photosensitive resin composition of the present invention can contain a surfactant in order to improve applicability. As the surfactant, a fluorine-based surfactant, a silicone-based surfactant, or a nonionic surfactant can be suitably used. For example, various surfactants described in JP-A-2001-330953 can be used. it can.
These surfactants may be used alone or in combination of two or more.
In the photosensitive resin composition of the present invention, these surfactants are preferably 0.001 to 20 parts by mass, and 0.01 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin, from the viewpoint of improving coatability. Is more preferable, and 0.01 to 2 parts by mass is even more preferable.

<Heat-sensitive acid generating compound>
The heat-sensitive acid generating compound can be used to further improve the heat resistance and hardness of the resulting interlayer insulating film. Examples thereof include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts.
Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, and benzothiazonium salts.
As the heat-sensitive acid generating compound, a sulfonium salt or a benzothiazonium salt is preferably used, and in particular, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl Benzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate or 3-benzylbenzothiazolium hexafluoroantimonate are preferably used.
Examples of these commercially available products include Sun-Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.).
The proportion of the component (H) in the photosensitive resin composition of the present invention is preferably 20 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the alkali-soluble resin from the viewpoint of heat resistance and hardness. is there.

<Polymerizable compound having at least one ethylenically unsaturated double bond>
Examples of the polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter appropriately referred to as “polymerizable compound (I)”) include, for example, monofunctional (meth) acrylate, bifunctional (meth) acrylate, A trifunctional or higher functional (meth) acrylate can be preferably mentioned.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.

Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Of these, trifunctional or higher functional (meth) acrylates are preferably used, among which trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate or dipentaerythritol hexa (meth) acrylate is particularly preferable. These monofunctional, bifunctional, or trifunctional or higher (meth) acrylates are used alone or in combination.
The proportion of the polymerizable compound (I) used in the photosensitive resin composition of the present invention is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, with respect to 100 parts by mass of the alkali-soluble resin. By containing (I) component in such a ratio, the heat resistance and surface hardness of the interlayer insulation film obtained from the photosensitive resin composition of this invention can be improved.

<Solvent>
As a solvent used for the preparation of the photosensitive resin composition of the present invention, an alkali-soluble resin, a 1,2-quinonediazide compound, component X, and other components optionally blended are uniformly dissolved, and these Those that do not react with the other components are used.
Among these, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester or diethylene glycol is preferably used from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, Purpylene glycol monomethyl ether acetate, methyl methoxypropionate or ethyl ethoxypropionate can be used particularly preferably.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone or N, N-dimethylacetamide is preferred.

  When a high boiling point solvent is used in combination as a solvent for preparing the photosensitive resin composition of the present invention, the amount used is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass, based on the total amount of the solvent. It can be as follows. If the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may decrease.

When preparing the photosensitive resin composition of the present invention in a solution state, the solid content concentration of components other than the solvent in the solution can be arbitrarily set according to the purpose of use, the value of the desired film thickness, and the like. However, Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%, More preferably, it is 12-35 mass%.
The composition solution thus prepared may be used after being filtered using a Millipore filter having an opening having a pore diameter of about 0.2 μm.

[Pattern formation method]
As a method for forming a patterned cured film using the photosensitive resin composition of the present invention, (1) the photosensitive resin composition of the present invention is applied (preferably applied) on an appropriate substrate, ( 2) Bake (pre-bake) this applied substrate, (3) Expose with actinic rays or radiation, (4) Post-heat if necessary, (5) Develop with aqueous developer, (6) Necessary A pattern forming method is used in which the entire surface is exposed, and (7) thermosetting (post-baking) is performed. By using this pattern forming method, a cured film having a desired shape (pattern) can be formed on the substrate.

  In the pattern forming method, the post-heating in (4) and the entire surface exposure in (6) are optional steps and may be performed as necessary.

  As in the pattern formation method described above, (1) the photosensitive resin composition of the present invention is formed on a semiconductor element or a glass substrate so that the thickness after curing becomes a desired thickness (for example, 0.1 to 30 μm). After the coating, at least (2) pre-baking, (3) exposure, (5) development, and (7) thermosetting, a patterned cured film for an organic EL display device or a liquid crystal display device is obtained. Can be formed.

Hereinafter, the pattern forming method will be described in more detail.
The photosensitive resin composition of the present invention is (1) applied on a suitable substrate.
The substrate may be selected according to the use of the cured film to be formed. For example, a semiconductor substrate such as a silicon wafer or a ceramic substrate, or a substrate made of glass, metal, or plastic is used. If the cured film is for a semiconductor device, a silicon wafer is generally used, and if the cured film is for a display device, a glass substrate is generally used.
Application methods include, but are not limited to, spray coating, spin coating, slit coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and dip coating.
By this (1) application process, the photosensitive resin composition layer is formed on the substrate.

  After the (1) application step, (2) pre-baking is performed to evaporate the solvent remaining in the photosensitive resin composition layer. This (2) pre-bake is preferably performed at a temperature of 70 ° C. to 130 ° C. for several minutes to 30 minutes.

Next, (2) the photosensitive resin composition layer dried by pre-baking is subjected to (3) exposure using actinic rays or radiation through a mask having a desired pattern. It is preferred exposure energy is typically ^{10mJ / cm 2 ~500mJ / cm 2} . As the actinic ray or radiation, X-ray, electron beam, ultraviolet ray, visible ray or the like can be used. Most preferred radiation is one having a wavelength of 436 nm (g-line), 405 nm (h-line), and 365 nm (i-line). Further, exposure can be performed by a laser method such as an ultraviolet laser. By this (3) exposure step, a developed region and a non-developed region are formed in the photosensitive resin composition layer on the substrate.

  (3) The substrate exposed by actinic rays or radiation is (4) heated (post-heated). This heating can be performed at a temperature of 70 ° C. or higher, preferably 150 ° C. or higher, more preferably 180 to 250 ° C., and particularly preferably 200 to 240 ° C. Moreover, in this invention, by performing at 200 degreeC or more, crosslinkable groups (for example, a hydroxyl group, a methylol group, an isocyanate group) other than an epoxy group, an oxetane group, etc. can also be bridge | crosslinked, and a stronger crosslinked structure is formed. It becomes possible. Post-heating is performed in a short time, generally several seconds to several minutes. This step is usually referred to as a technique after baking after exposure.

Next, the photosensitive resin composition layer after (3) exposure ((4) post-heating) is developed with (5) an aqueous developer. By this development, the exposed portion of the photosensitive resin composition layer is developed with an aqueous developer, and the unexposed portion remains on the substrate, whereby a photosensitive resin composition layer having a desired shape (pattern) is formed.
Aqueous developers include inorganic alkalis (eg, potassium hydroxide, sodium hydroxide, aqueous ammonia), primary amines (eg, ethylamine, n-propylamine), secondary amines (eg, diethylamine, di-n-propyl). Amines), tertiary amines (eg triethylamine), alcohol amines (eg triethanolamine), quaternary ammonium salts (eg tetramethylammonium hydroxide, tetraethylammonium hydroxide), and alkaline solutions using mixtures thereof There is. The most preferred developer is one containing tetramethylammonium hydroxide. In addition, an appropriate amount of a surfactant may be added to the developer.
Development may also be performed by dipping, spraying, paddling, or other similar development methods.

  (5) After the development step, the photosensitive resin composition layer remaining on the substrate may be rinsed using deionized water in some cases.

Furthermore, after the (5) development step, the photosensitive resin composition layer remaining on the substrate is subjected to (6) full-surface exposure as necessary. The exposure energy for this overall exposure is preferably 100 to 1000 mJ / cm ² .
This (6) overall exposure is preferable because the transparency is improved when a cured film for a display device is formed.

  Next, (5) the photosensitive resin composition layer remaining on the substrate after the development step is subjected to (7) thermosetting treatment in order to obtain a final patterned cured film. This thermosetting is performed in order to form a cured film having high heat resistance, chemical resistance, and film strength. When a general photosensitive polyimide precursor composition is used, it has been heat-cured at a temperature of about 300 to 400 ° C. On the other hand, when the photosensitive resin composition of the present invention is heated to 150 ° C. or higher, a cured film having film properties equivalent to or higher than those of conventional photosensitive polyimide precursor compositions can be obtained. As for this heating, it is more preferable to heat to 180-250 degreeC, and it is especially preferable to heat to 200-240 degreeC. Moreover, in this invention, by performing at 200 degreeC or more, crosslinkable groups (for example, a hydroxyl group, a methylol group, an isocyanate group) other than an epoxy group, an oxetane group, etc. can also be bridge | crosslinked, and a stronger crosslinked structure is formed. It becomes possible.

By the photosensitive resin composition of the present invention, a cured film having excellent transparency and high transparency even when baked at high temperature can be obtained.
It can also be used as a dry etching resist.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a flattening film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Various known organic EL display devices and liquid crystal display devices can be used.

[Curing 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 suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.

[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 including the cured film of the present invention.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Various known organic EL display devices and liquid crystal display devices can be used.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device and the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
The liquid crystal display device that can be used by the liquid crystal display device of the present invention includes a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, and an OCB. (Optical Compensated Bend) method and the like.
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

FIG. 1 is a conceptual diagram illustrating an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

FIG. 2 is a conceptual cross-sectional view showing an example of the 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 the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type.

  Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) shown in FIG. 4A of 9793, and the bank layer (221) and the third interlayer insulating film (216b) shown in FIG. 10 of JP 2010-27591A. ), Second interlayer insulating film (125) and third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12), a pixel isolation insulating film (14), and the like.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

(Synthesis example)
<Synthesis of alkali-soluble resin: A-1>
As monomer components for forming the copolymer, 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%) and azobisisobutyronitrile (AIBN) (2.57 g) as a radical polymerization initiator were used in a solvent propylene glycol monomethyl ether acetate (PGMEA) (115 g). A-1 PGMEA solution (solid content concentration: 30% by mass) was obtained by carrying out a polymerization reaction at 4 ° C. for 4 hours.
The styrene conversion weight average molecular weight measured by GPC of the obtained A-1 was 15,000.

<Synthesis of alkali-soluble resin: A-2>
As monomer components for forming a copolymer, methacrylic acid 12.05 g (35 mol%), styrene 4.17 g (10 mol%), dicyclopentanyl methacrylate 13.22 g (15 mol%), 3-ethyl-3oxetanyl 29.48 g (40 mol%) of methacrylate was used, 2.57 g of azobisisobutyronitrile (AIBN) was used as a radical polymerization initiator, and these were obtained at 70 ° C. in 135 g of a solvent propylene glycol monomethyl ether acetate (PGMEA). A polymerization reaction was carried out for 4 hours to obtain a PGMEA solution of A-2 (solid content concentration: 30% by mass).
The styrene conversion weight average molecular weight measured by GPC of the obtained A-2 was 13,000.

<Preparation of photosensitive resin composition>
Alkali-soluble resin (component A), 1,2-quinonediazide compound (component B), component X, adhesion improver and surfactant in PGMEA so that the solid content ratio shown in the following table is obtained is a solid content concentration of 32% by mass. The mixture was dissolved and mixed, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of various examples and comparative examples. The compounding quantity of each component in the following table | surface is shown by the mass part.

The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
<B component>
B-1: TAS-200 (made by Toyo Gosei)

<X component>
C-7: Bis (triethoxysilylpropyl) disulfide, trade name Z-6920, manufactured by Toray Dow Corning Silicone Co. C-9: Bis (triethoxysilylpropyl) tetrasulfide, trade name KBE-864, manufactured by Shin-Etsu Chemical Co., Ltd.

<Comparison of X component>
R-1: 1,3-bis (triethoxysilyl) ethane, KBE-3026, manufactured by Shin-Etsu Chemical Co., Ltd. R-2: bis (2-benzamidophenyl) disulfide, Tokyo Chemical Industry Co., Ltd. R-3: dithiobisphenol, Tokyo Chemical Industry R-4: 2-hydroxyethyl disulfide, Wako Pure Chemical Industries, Ltd.

<Adhesion improver>
G-1: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Surfactant>
H-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)

  The following evaluation was performed about the obtained composition.

<Evaluation of sensitivity>
A glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin-coated and then 90 ° C./120 seconds. Pre-baking was performed on a hot plate to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed using a MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. through a predetermined mask set in a hole having a diameter of 5 μm. The exposed photosensitive resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. The optimum i-line exposure (Eopt) when resolving a 5 μm hole by these operations was taken as the sensitivity.
A: 80mJ / cm ² or more, 100 mJ / cm ² less B: 100mJ / cm ² or more, 160 mJ / cm ² less than C: 160mJ / cm ² or more, 250 mJ / cm ² less than D: 250mJ / cm ² or more

<Adhesion evaluation>
After each photosensitive resin composition is slit coated on a Mo (molybdenum) substrate, the solvent is removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 4.0 μm. did. The obtained photosensitive resin composition layer is subjected to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, this substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film. Using a cutter on the cured film, cuts were made at intervals of 1 mm vertically and horizontally, and a tape peeling test was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The smaller the numerical value, the higher the adhesion to the base substrate, and A or B is preferred.
A: The transferred area is less than 1% B: The transferred area is 1% or more and less than 5% C: The transferred area is 5% or more and less than 10% D: The transferred area is 10% or more

<Transparency evaluation>
A coating film having a thickness of 3.0 μm was formed on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)). Next, it exposed through the predetermined | prescribed mask using i line | wire stepper (Canon Co., Ltd. product FPA-3000i5 +). After liquid development with an alkaline developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C. for 65 seconds, the resultant was rinsed with ultrapure water for 1 minute. The developed coating film was irradiated with 300 mJ / cm ² light at a wavelength of 365 nm using an ultrahigh pressure mercury lamp, and then heated in an oven at 220 ° C. for 45 minutes. The transmittance of this 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, less than 95% C: 90% or more, less than 93% D: 85% or more, less than 90% E: less than 80%

<Evaluation of panel display aptitude>
In the active matrix liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a liquid crystal display device was obtained using the interlayer insulating film of the present invention. A driving voltage was applied to the obtained liquid crystal display device, and the presence or absence of crosstalk or afterimage was evaluated. If the insulating properties of the interlayer insulating film are inferior, display problems such as crosstalk and afterimages are likely to occur.
A: No crosstalk or afterimage occurs B: Crosstalk or afterimage occurs very rarely C: Crosstalk or afterimage occurs rarely D: Crosstalk or afterimage occurs occasionally E: Crosstalk or Afterimages occur frequently

  As is clear from the above results, it was found that the photosensitive resin composition of the present invention has high sensitivity, excellent adhesion to the substrate, and high transparency. Surprisingly, the panel display was excellent. On the other hand, when X component does not contain a sulfur atom (comparative example 2), it turns out that a sensitivity, transparency, and panel display suitability are inferior. On the other hand, when the X component does not contain a silicon atom (Comparative Examples 3 to 5), it was found that the panel display suitability is inferior in addition to sensitivity or adhesion. In particular, since Comparative Examples 2 to 5 tend to be inferior to Comparative Example 1 that does not include the X component, it can be seen that the technical significance of the photosensitive resin composition of the present invention is high.

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

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

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

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

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

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

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

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

1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

Claims (19)

(Component A) alkali-soluble resin,
(Component B) 1,2-quinonediazide compound, and (Component X) containing a compound represented by the following general formula (I) ,
A positive photosensitive resin composition, wherein the alkali-soluble resin is a copolymer comprising (a1) a repeating unit having an acid group and (a2) a repeating unit having a crosslinkable group .
(In general formula (I), R ^{1 to} R ⁶ each independently represents a hydrocarbon group or an alkoxy group, and L ¹ and L ² each independently represent an alkylene group, an arylene group, or a combination thereof. And n represents an integer of 2 to 4.) The positive photosensitive resin composition according to claim 1 , wherein the repeating unit (a1) is a repeating unit having a carboxyl group and / or a phenolic hydroxyl group. The said repeating unit (a1) is a repeating unit derived from methacrylic acid. A positive photosensitive resin composition. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the repeating unit (a2) is a repeating unit having an epoxy group and / or an oxetanyl group. The repeating unit (a2) is a repeating unit derived from glycidyl methacrylate. The positive photosensitive resin composition of any one of Claims 1-3. The alkali-soluble resin comprises (a1) a repeating unit having an acid group and (a2) a crosslinkable group As a repeating unit other than the repeating unit having a repeating unit containing an alicyclic structure The positive photosensitive resin composition of any one of Claims 1-5. The alkali-soluble resin has a content of repeating unit (a1) having an acid group of 3 to 45 mol. % Positive photosensitive resin composition of any one of Claims 1-6 which is%. The alkali-soluble resin has a content of repeating unit (a2) having a crosslinkable group of 5 to 50. The positive photosensitive resin composition of any one of Claims 1-7 which is mol%. The positive photosensitive resin composition of any one of Claims 1-8 whose compounding quantity of the said (component X) is 1-25 mass% in the total solid of a composition. The positive photosensitive resin composition according to any one of claims 1 to 9 , 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. object. The positive photosensitive resin according to any one of claims 1 to 10 , wherein L ¹ and L ² are each independently a group consisting of an alkylene group having 1 to 8 carbon atoms, a phenylene group, or a combination thereof. Composition. The positive photosensitive resin composition according to any one of claims 1 to 11 , wherein n is 3 or 4. (1) A step of applying the positive photosensitive resin composition according to any one of claims 1 to 12 on a substrate,
(2) a pre-baking step of baking the applied positive photosensitive resin composition;
(3) a step of exposing the baked positive photosensitive resin composition with actinic rays or radiation;
(4) a step of developing the exposed positive photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed positive photosensitive resin composition;
A method for forming a cured film comprising: The method for forming a cured film according to claim 13 , comprising: (6) a step of exposing the developed positive photosensitive resin composition to the entire surface after the developing step and before the post-baking step. The method for forming a cured film according to claim 13 or 14 , further comprising a step of performing dry etching on a substrate having a cured film obtained by thermosetting. The formation method of the cured film of any one of Claims 13-15 which performs the said thermosetting at 200 degreeC or more. A cured film obtained by curing the positive photosensitive resin composition according to claim 1 . The cured film of Claim 17 which is an interlayer insulation film. An organic EL display device or a liquid crystal display device having the cured film according to claim 17 .