KR20110001879A - Positive type photosensitive resin composition for interlayer insulating film, interlayer insulating film, organic el display device, and liquid crystal display device - Google Patents

Abstract

PURPOSE: A positive type photosensitive resin composition for an interlayer insulating film is provided to ensure high transparency and excellent insulation property when baked at a high temperature. CONSTITUTION: A positive type photosensitive resin composition for an interlayer insulating film comprises: (A) an alkali soluble resin including an acrylic repeating unit; (B) a 1,2-quinonediazide compound; and (C) a compound with at least two partial structures represented by chemical formula (I), which has 600-2000 of molecular weight. In chemical formula (I), R^1 and R^2 are independently show a methyl group or tert-butyl group, wherein at least one of R^1 and R^2 is a tert-butyl group; and R^3 is -O- or -NH-.

Description

POSITIVE TYPE PHOTOSENSITIVE RESIN COMPOSITION FOR INTERLAYER INSULATING FILM, INTERLAYER INSULATING FILM, ORGANIC EL DISPLAY DEVICE, AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a positive photosensitive resin composition for an interlayer insulating film, an interlayer insulating film using the positive photosensitive resin composition for an interlayer insulating film, an organic EL display device using the same, and a liquid crystal display device.

The organic EL display device, the liquid crystal display device, or the like is provided with a patterned interlayer insulating film. The photosensitive resin composition is widely used in the formation of this interlayer insulating film because the number of steps for obtaining the required pattern shape is small and sufficient flatness is obtained.

In addition to the physical properties of the cured film which is excellent in insulation, solvent resistance, heat resistance, and ITO sputterability, the interlayer insulating film in the said display apparatus is requesting high transparency. For this reason, the case where acrylic resin excellent in transparency is used as a film formation component is tried.

As a photosensitive resin composition for forming an interlayer insulation film, For example, the positive photosensitive resin composition containing the alkali-soluble acrylic polymer which has a side chain which has an unsaturated bond at the terminal, a 1, 2- quinonediazide compound, and a solvent is used. It is known (for example, see Japanese Patent Laid-Open No. 2008-256974).

Moreover, the photosensitive resin composition containing resin soluble in aqueous alkali solution which is a copolymer of unsaturated carboxylic acid or unsaturated carboxylic anhydride, a radically polymerizable compound which has an epoxy group, and another radically polymerizable compound, and a photosensitive acid generating compound is known (for example, See, for example, Japanese Patent No. 2961722).

However, when forming an insulating film by the said photosensitive resin composition, when exposed to high temperature at the time of a film-forming and a post process, there existed a problem that transmittance fell and sufficient transparency was not obtained. Moreover, since these acrylic interlayer insulation films contain many functional groups with high polarity, sufficient insulation may not be obtained in some cases.

The present invention is excellent in insulation and has high transparency even when baked at a high temperature, and the insulation and high transparency formed by using the positive photosensitive resin composition for an interlayer insulating film and the positive photosensitive resin composition for the interlayer insulating film. An object of the present invention is to provide an interlayer insulating film having a structure.

Further, another object of the present invention is to provide an organic EL display device having an interlayer insulating film having insulation and high transparency, and a liquid crystal display device.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, the compound which has a specific phenolic partial structure is used together with acrylic alkali-soluble resin, and the heat resistance transparency of a positive type interlayer insulation film improves, and the analogy of the formed interlayer insulation film It was found that the electrical conductivity was lowered and the present invention was completed.

That is, the said subject is solved by the structure of following <1>-<11>.

<1> Alkali-soluble resin containing the (A) acryl-type repeating unit, (B) 1, 2- quinonediazide compound, and (C) At least 2 partial structure represented by following General formula (I) in a molecule | numerator It is a positive photosensitive resin composition for interlayer insulation films containing the compound which has a molecular weight of 600-2000.

In said general formula (I), R <^1> and R <^2> represents a methyl group or tert- butyl group each independently, and at least ^{1 of} R <^1> and R <^2> is a tert- butyl group. R ³ represents -O- or -NH-.

<2> The compound which has at least two partial structure represented by said (C) general formula (I) in a molecule | numerator, and whose molecular weight is 600 or more and 2000 or less is the following compound (I-1), (I-2), and (I- Positive type photosensitive resin composition for interlayer insulation films as described in <1> which is a compound chosen from 3).

<3> Positive interlayer insulating film as described in <2> whose compound which has at least two partial structure represented by said (C) general formula (I) in a molecule | numerator, and whose molecular weight is 600 or more and 2000 or less is the following compound (I-1). Type photosensitive resin composition.

<4> Positive type photosensitive resin composition for interlayer insulation films in any one of <1>-<3> whose said (B) 1, 2-quinone diazide compound is a compound of the following structure.

In the above structure, the ratio (molar ratio) of H and 1,2-naphthoquinone diazide group in D is 50:50 to 1:99.

<5> <1>-<4> whose alkali-soluble resin containing the said (A) acryl-type repeating unit is alkali-soluble resin which has at least 1 sort (s) selected from the group which consists of an oxiranyl group and an oxetanyl group in a molecule | numerator. Positive type photosensitive resin composition for interlayer insulation films in any one of.

Positive type for interlayer insulation film as described in any one of <1>-<5> containing the crosslinking agent which has at least 1 group selected from the group which consists of a <6> (D-1) oxiranyl group and an oxetanyl group in a molecule | numerator. Photosensitive resin composition.

<7> Alkali-soluble resin containing the said (A) acryl-type repeating unit is alkali-soluble resin which neither an oxiranyl group nor an oxetanyl group has in a molecule | numerator, and (D-1) an oxiranyl group and an jade The positive type photosensitive resin composition for interlayer insulation films as described in <6> containing the crosslinking agent which has at least 1 group selected from the group which consists of a cetanyl group in a molecule | numerator.

<8> Positive type photosensitive resin composition for interlayer insulation films in any one of <1>-<5> containing the at least 1 sort (s) of crosslinking agent chosen from (D-2) melamine.

<9> The interlayer insulating film formed using the positive photosensitive resin composition for interlayer insulating films in any one of <1>-<8>.

<10> The organic electroluminescence display provided with the interlayer insulation film as described in <9>.

<11> The liquid crystal display device provided with the interlayer insulation film as described in <9>.

Advantageous Effects of Invention According to the present invention, the positive type photosensitive resin composition for an interlayer insulating film having excellent transparency even when baked at a high temperature, and the positive type photosensitive resin composition for forming the interlayer insulating film, and having high transparency An interlayer insulating film can be provided.

Moreover, according to this invention, the organic electroluminescence display provided with the interlayer insulation film which has insulation and high transparency, and a liquid crystal display can be provided.

1 is a cross-sectional view of an essential part of an organic EL display device using a TFT;

≪Positive type photosensitive resin composition for interlayer insulation film≫

EMBODIMENT OF THE INVENTION Hereinafter, the positive type photosensitive resin composition for interlayer insulation films of this invention is demonstrated in detail.

Positive type photosensitive resin composition (henceforth only a "photosensitive resin composition" hereafter) for the interlayer insulation film of this invention is alkali-soluble resin containing the (A) acryl-type repeating unit, (B) 1, 2-quinone A diazide compound and (C) have at least two partial structures represented by the following general formula (I) in a molecule | numerator, and are characterized by containing the compound whose molecular weight is 600 or more and 2000 or less.

In said general formula (I), R <^1> and R <^2> represents a methyl group or tert- butyl group each independently, and at least ^{1 of} R <^1> and R <^2> is a tert- butyl group. R ³ represents -O- or -NH-.

Hereinafter, the components (A) to (C) constituting the positive photosensitive resin composition for the interlayer insulating film will be described.

<Alkali-soluble resin containing the (A) acryl-type repeating unit>

The photosensitive resin composition of this invention contains alkali-soluble resin (Hereinafter, it may only call "alkali-soluble resin (A)") containing an acryl-type repeating unit as a polymerization component.

Alkali-soluble resin (A) in this invention is a polymer containing an acryl-type repeating unit, Although it does not specifically limit as long as it is resin which has alkali-soluble group in a molecule | numerator and is soluble in aqueous alkali solution, As an alkali-soluble group, it is a carboxyl group. Resin to which alkali solubility was given by having has been used suitably.

As for the ratio of the acryl-type repeating unit contained in alkali-soluble resin (A) of this invention, 20 mol%-100 mol% are preferable from a viewpoint that the pattern with high transmittance | permeability can be formed, and 35 mol%-100 mol% are More preferably, they are 50 mol%-100 mol% optimally.

Moreover, as alkali-soluble resin (A) of this invention, it is preferable to further have an alicyclic structure in a molecule | numerator from a viewpoint of the formed resin composition film | membrane high transmittance | permeability and low dielectric constant.

As the alicyclic structure, an alicyclic five-membered ring, an alicyclic six-membered ring, or an alicyclic structure in which two or more thereof are connected is preferable, and specifically, cyclohexyl, t-butylcyclohexyl, dicyclopentenyl, dicyclopentenyloxyethyl, Dicyclopentanyl, isobonyl, etc. are mentioned. Especially, cyclohexyl, dicyclopentenyl, dicyclopentenyloxyethyl, and dicyclopentanyl are preferable from the viewpoint of the heat resistance, insulation stability, and ITO sputterability of the film formed using the photosensitive resin composition.

The alkali-soluble resin (A) in the present invention is a copolymer containing a repeating unit (A1) having an alicyclic structure and a repeating unit (A2) having an alkali-soluble group (hereinafter, appropriately referred to as a specific copolymer (A)). Is preferred. This specific copolymer (A) may contain the repeating unit (A3) different from (A1) and (A2) shown below as needed.

Hereinafter, the repeating unit of (A1)-(A3) is demonstrated.

[Repeating Unit (A1) Having an Alicyclic Structure]

As a repeating unit (A1) which has alicyclic structure, the repeating unit derived from the monomer which has an alicyclic structure as mentioned above is mentioned.

Specific examples of the monomer having an alicyclic structure include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and (meth) acrylate. Dicyclopentanyl acrylate, isobornyl (meth) acrylate, and the like. Among them, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ( Dicyclopentanyl methacrylate is preferred.

Repeating unit (A1) which has alicyclic structure may be comprised individually by 1 type, and may be comprised by 2 or more types.

As for content of the repeating unit (A1) which has an alicyclic structure in the specific copolymer (A) in this invention, 5 mol%-60 mol% are preferable at the point of compatibility of various tolerances and developability, and 8 mol%- 55 mol% is more preferable, and 10 mol%-50 mol% are further more preferable.

[Repeating unit (A2) having an alkali soluble group]]

The specific copolymer (A) in this invention is a repeating unit (A2-1) which has a carboxyl group, and a repeating unit which has a carbon-containing unsaturated bond group and a carboxyl group from a viewpoint of the solubility improvement to the developing solution of the photosensitive resin composition. It includes either one of (A2-2).

-Repeating unit (A2-1) having a carboxyl group-

As a repeating unit (A2-1) which has a carboxyl group, the repeating unit derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in a molecule | numerator, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid, is mentioned, for example.

As unsaturated carboxylic acid used in order to obtain the repeating unit (A2-1) which has a carboxyl group, the thing quoted below is used.

That is, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example.

Moreover, as unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example.

Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the repeating unit (A2-1) which has a carboxyl group. Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, etc. are mentioned. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester of polyhydric carboxylic acid, for example, mono (succinate mono (2-acryloyloxyethyl)) and mono (2-methacryloyl) Oxyethyl), mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl), etc. are mentioned.

In addition, the unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the both terminal dicarboxy polymers, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. are mentioned. Can be.

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.

Especially, in order to form the repeating unit (A2-1) which has a carboxy group from developability viewpoint, it is preferable to use acrylic acid, methacrylic acid, or anhydride of unsaturated polyhydric carboxylic acid.

The repeating unit (A2-1) which has a carboxy group may be comprised individually by 1 type, and may be comprised by 2 or more types.

-Repeating unit (A2-2) having an unsaturated carbon group and a carboxyl group together;

The repeating unit (A2-2) having a carbon-to-carbon unsaturated bond group and a carboxyl group together is a repeating unit obtained by reacting a secondary hydroxyl group present in a repeating unit (A3-1) having an unsaturated carbon-to-carbon unsaturated bond group and an acid anhydride. It is preferable.

As an acid anhydride, a well-known thing can be used, Specifically, Dibasic acid anhydrides, such as maleic anhydride, a succinic anhydride, itaconic anhydride, a phthalic anhydride, tetrahydrophthalic anhydride, a hexahydrophthalic anhydride, a chloric anhydride; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride and biphenyltetracarboxylic anhydride. In these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from a developable viewpoint.

The reaction rate with respect to the secondary hydroxyl group of an acid anhydride is from a developable viewpoint, Preferably it is 10 mol%-100 mol%, More preferably, it is 30 mol%-100 mol%.

The repeating unit (A2) which has an alkali-soluble group may be comprised individually by 1 type of the repeating unit (A2-1) which has a carboxyl group, and is 1 type of the repeating unit (A2-2) which has an unsaturated bond group and a carboxyl group together. It may be comprised independently and may be comprised by mixing two types of these.

As for content of the repeating unit (A2) which has alkali-soluble group in the specific copolymer (A) in this invention, 1 mol%-50 mol% are preferable from a developable viewpoint, and 3 mol%-45 mol% are more Preferably, 5 mol%-40 mol% are more preferable. In addition, content of the repeating unit (A2) which has alkali-soluble group means here the total content of the repeating unit (A2-1) which has a carboxyl group, and the repeating unit (A2-2) which has an unsaturated bond group and a carboxyl group together. Turn on.

[Repeating unit (A3) other than (A1), (A2)]]

Specific copolymer (A) in this invention consists of a repeating unit (A3-1) which has an unsaturated carbon group between carbon atoms, an oxiranyl group, and an oxetanyl group as repeating units other than (A1) and (A2). The repeating unit (A3-2) which has at least 1 sort (s) of group chosen from the group, and the other repeating unit (A3-3) may be included.

-Repeating unit (A3-1) having an unsaturated bond group between carbons

As a repeating unit (A3-1) which has a carbon-to-carbon unsaturated bond group, the repeating unit derived from the monomer which has a carbon-to-carbon unsaturated bond group (polymerizable group) is mentioned. In particular, as the repeating unit (A3-1) having an unsaturated carbon-to-carbon bond, a repeating unit having a structure in which an epoxy ring in a compound containing an epoxy ring and an unsaturated carbon-to-carbon unsaturated bond group is added to a carboxyl group, or a carboxyl group and an unsaturated carbon-to-carbon bond group It is preferable that the carboxy group in the compound to contain is a repeating unit which has a structure which adds with an epoxy ring. More specifically, in the carboxyl group of the repeating unit (A2-1) which has a carboxy group mentioned above, the epoxy unit and the repeating unit which made the epoxy ring in the compound containing a carbon-containing unsaturated bond group react, or the monomer which has an epoxy ring mentioned later It is preferable that it is a repeating unit which made carboxyl groups, such as (meth) acrylic acid, and the carboxyl group of the compound containing a carbon-containing unsaturated bond group react with the epoxy ring in the derived repeating unit. By this reaction, a secondary hydroxyl group is introduced into the repeating unit (A3-1) having an unsaturated carbon to carbon bond.

As a compound containing an epoxy ring and a carbon-carbon unsaturated bond group, the compound which has 1 or more of an epoxy ring and a carbon-carbon unsaturated bond group may be sufficient, for example, glycidyl acrylate, glycidyl methacrylate, (3, 4- And compounds such as epoxycyclohexyl) methyl acrylate, (3,4-epoxycyclohexyl) methyl methacrylate and allyl glycidyl ether.

Among these, glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl acrylate, and (3,4-epoxycyclohexyl) methyl methacrylate are preferable, and glycidyl methacrylate is preferred. An acrylate, (3, 4- epoxycyclohexyl) methyl acrylate, (3, 4- epoxy cyclohexyl) methyl methacrylate is the most preferable from a solvent resistance and a heat resistance viewpoint.

The repeating unit (A3-1) which has a carbon-to-carbon unsaturated bond group may be comprised individually by 1 type, and may be comprised by 2 or more types.

As for content of the repeating unit (A3-1) which has an unsaturated bond group between carbons in the specific copolymer (A) in this invention, 0 mol%-60 mol% are preferable at the point of compatibility of various tolerances and developability, 0 mol%-55 mol% are more preferable, and 0 mol%-50 mol% are further more preferable.

-Repeating unit (A3-2) having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group-

As a repeating unit (A3-2) which has at least 1 sort (s) of group chosen from the group which consists of an oxiranyl group and an oxetanyl group, the repeating unit derived from an oxiranyl group containing unsaturated compound and an oxetanyl group containing unsaturated compound is mentioned. .

As an oxiranyl-group containing unsaturated compound, for example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, the glycine (alpha)-n-butyl acrylate Dill, acrylic acid-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-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methyl methacrylate, etc. are mentioned. Of these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3, 4-epoxycyclohexyl methyl methacrylate etc. are used preferably at the point which raises heat resistance and surface hardness of copolymerization reactivity and the obtained interlayer insulation film.

As an oxetanyl group containing unsaturated compound, the (meth) acrylic acid ester etc. which have an oxetanyl group are mentioned, for example.

As an oxetanyl group containing unsaturated compound, the (meth) acrylic acid ester etc. which have the oxetanyl group of Unexamined-Japanese-Patent No. 2001-330953 are mentioned, for example.

As such a compound, specifically, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl Process margin of the photosensitive resin composition which the 2-phenyl oxetane, 2- (methacryloyl oxymethyl) oxetane, 2- (methacryloyl oxymethyl) -4- trifluoromethyl oxetane etc. are obtained It is used suitably from the point which improves chemical resistance of this wide and obtained interlayer insulation film. These are used individually or in combination.

One type of repeating unit (A3-2) may be included and may be included 2 or more types. As for content of the repeating unit (A3-2) in the specific copolymer (A) in this invention, 0 mol%-50 mol% are preferable at the point of the various tolerance and transparency of the formed film, and 0 mol%-45 mol % Is more preferable, and 0 mol%-40 mol% are further more preferable.

Other repeating units (A3-3)

As another repeating unit (A3-3), it has a structure different from the repeating unit of (A1), (A2), (A3-1), and (A3-2). Although there is no restriction | limiting in particular as a repeating unit which may be contained in the specific copolymer (A), The repeating unit derived from a vinyl monomer, the repeating unit containing an aromatic ring structure, etc. are preferable.

By including the repeating unit derived from a vinyl monomer, the pattern formation property of a specific copolymer (A) may improve.

As a vinyl monomer which can form the repeating unit of (A3-3), it is (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid di, for example. Ester, (meth) acrylamide, vinyl ether, ester of vinyl alcohol, styrene, (meth) acrylonitrile, etc. are preferable.

As a specific example of such a vinyl monomer, the well-known compound contained in the said exemplary compounds is used suitably.

It is preferable that the specific copolymer (A) in this invention contains the repeating unit which has an aromatic ring structure from a viewpoint that the developability of the film pattern formed from the photosensitive resin composition becomes favorable.

It is preferable that the repeating unit which has an aromatic ring structure originates in the monomer shown below.

Namely, phenyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylic acid, benzyl (meth) acrylate, (meth) acrylate β-phenoxyethoxyethyl, (meth) acrylate nonylphenoxypolyethylene glycol (Meth) acrylic acid tribromophenyl, (meth) acrylic acid tribromophenyloxyethyl, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, Butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene, methyl vinylbenzoate protected with a group deprotectable by acidic substances (e.g. t-Boc, etc.) And (alpha) -methylstyrene, Among these, benzyl (meth) acrylic acid and styrene are preferable.

The other repeating unit (A3-3) may be comprised individually by 1 type, and may be comprised by 2 or more types.

As for content of the repeating unit of (A3-3) in the specific copolymer (A) in this invention, 0 mol%-50 mol% are preferable at the point of compatibility of various tolerances and developability, and 0 mol%-45 Mol% is more preferable, and 0 mol%-40 mol% are further more preferable.

As alkali-soluble resin (A) used by this invention, alkali-soluble resin which has at least 1 sort (s) of group chosen from the group which consists of an oxiranyl group and an oxetanyl group in a molecule | numerator is mentioned as a preferable thing. As a preferable specific example of such resin, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / 2-methylcyclohexyl acrylate / glycidyl methacrylate / N -(3,5-dimethyl-4-hydroxybenzyl) methacrylamide copolymer, methacrylic acid / tetrahydrofurfuryl methacrylate / glycidyl methacrylate / N-cyclohexyl maleimide / lauryl methacryl Rate / α-methyl-p-hydroxystyrene copolymer, styrene / methacrylic acid / glycidyl methacrylate / (3-ethyloxetan-3-yl) methacrylate / tricyclo [5.2.1.0 ^{2, 6} ] decane-8-ylmethacrylate copolymer, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / N-cyclohexylmaleimide / glycidyl methacrylate / styrene copolymer, methacrylate / 3,4-epoxycyclohexylmethyl methacrylate / styrene / tricyclo [5.2.1.0 ^2,6] decane-8-yl methacrylate copolymer And the like.

In the case of containing a crosslinking agent (D-1) which has at least 1 sort (s) of group chosen from the group which consists of an oxiranyl group and an oxetanyl group mentioned later as alkali-soluble resin (A) used by this invention, an oxiranyl group And it is also preferable to use alkali-soluble resin (A) which does not contain any of an oxetanyl group. Hereinafter, although such alkali-soluble resin (A) is illustrated, this invention is not limited to this.

Moreover, the weight average molecular weights of alkali-soluble resin illustrated below are 5000-80000.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of alkali-soluble resin (A) used by this invention becomes like this. Preferably it is 2 * 10 <^3> -1 * 10 <^5> , More preferably, it is 5 * 10 <^3> -. 5 × 10 ⁴ . When Mw is less than 2x10 <^3> , developing margin may become inadequate, the residual film ratio of a coating film obtained, etc. may fall, or the pattern shape, heat resistance, etc. of an interlayer insulation film obtained may fall, and 1x10 ⁵ If it exceeds, the sensitivity may decrease or the pattern shape may fall. In addition, the molecular weight distribution (hereinafter referred to as "Mw / Mn") which is the ratio of Mw and polystyrene conversion number average molecular weight (henceforth "Mn") becomes like this. Preferably it is 5.0 or less, More preferably, it is 3.0 or less. When Mw / Mn exceeds 5.0, the pattern shape of the obtained interlayer insulation film may fall. The positive type photosensitive resin composition for an interlayer insulating film containing the said alkali-soluble resin (A) can form a predetermined pattern shape easily, without developing a residual image, when developing.

It is preferable that it is 20 mass%-90 mass% with respect to the total solid of the photosensitive resin composition, and, as for content of alkali-soluble resin (A) in the photosensitive resin composition of this invention, it is more preferable that it is 25 mass%-85 mass%. It is more preferable that they are 30 mass%-80 mass%. If content is this range, the pattern formation property at the time of image development will become favorable.

<(B) 1, 2-quinone diazide compound>

The photosensitive resin composition of this invention contains the (B) 1, 2- quinone diazide compound. (B) 1, 2-quinone diazide compound in this invention is a compound which has a 1, 2- quinone diazide partial structure, and needs to have at least 1 1, 2- quinone diazide partial structure in a molecule | numerator. It is preferable to have two or more.

The (B) 1,2-quinone diazide compound is positive by improving alkali solubility of the photosensitive resin composition coating film by suppressing alkali solubility of the photosensitive resin composition coating film in an unexposed part, and generating carboxylic acid in an exposure part. It is possible to form the pattern of the mold.

The 1, 2- quinone diazide compound is obtained by condensation reaction of 1, 2- quinone diazide sulfonyl chloride, a hydroxy compound, an amino compound, etc. in presence of a dehydrochloric acid agent, for example.

As said 1, 2- quinone diazide sulfonyl chloride, a benzoquinone 1, 2- diazide- 4-sulfonyl chloride, a naphthoquinone 1, 2- diazide-5-sulfur, for example Phenyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride, etc. can be used, but in terms of sensitivity, the naphthoquinone-1,2-diazide-4-sulfonyl chloride Use is preferred.

Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2 , 3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,2' , 3'-pentahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2, 3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] indene, Tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl]- Ethylidene] bisphenol and the like can be used.

As said amino compound, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenyl ether, 4,4'- diamino diphenylmethane, 4,4'- diamino, for example Diphenylsulfone, 4,4'-diaminodiphenylsulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino4,4'-dihydroxybiphenyl, 4 , 4'-diamino3,3'-dihydroxybiphenyl, bis (3-amino4-hydroxyphenyl) propane, bis (4-amino3-hydroxyphenyl) propane, bis (3-amino4- Hydroxyphenyl) sulfone, bis (4-amino3-hydroxyphenyl) sulfone, bis (3-amino4-hydroxyphenyl) hexafluoropropane, bis (4-amino3-hydroxyphenyl) hexafluoropropane Etc. can be used.

In the synthesis of the 1,2-quinonediazide compound, the 1,2-quinonediazidesulfonyl chloride and the hydroxy compound and / or the amino compound are contained in 1 mol of the 1,2-quinonediazidesulfonyl chloride. It is preferable to mix | blend so that the sum total of a hydroxyl group and an amino group may be 0.5-1 equivalent. The preferable ratio of a dechlorinating agent and o-quinone diazide sulfonyl chloride is the range of 1 / 1-1 / 0.9. Preferable reaction temperature is 0-40 degreeC, and preferable reaction time is 1 to 24 hours.

As the reaction solvent, solvents such as dioxane, 1,3-dioxolane, acetone, methyl ethyl ketone, tetrahydrofuran, chloroform, N-methylpyrrolidone and γ-butyrolactone are used. Examples of the dechlorination agent include sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine, 4-dimethylaminopyridine, and the like.

As a 1, 2- quinonediazide compound, the compound which has the following structures is mentioned, for example.

In said structure, D is one group chosen from H or the group shown below.

However, in the structure, at least one D may be the quinone diazide group.

In this invention, the compound which has a 1, 2- naphthoquinone diazide group among a 1, 2- quinone diazide compound is preferable. Use of a compound having a 1,2-naphthoquinone diazide group results in high sensitivity and good developability.

Among the compounds having 1,2-naphthoquinonediazide groups, the compounds having the following structures are particularly sensitive, and thus can be preferably used.

Moreover, as a compound which has the most preferable 1,2-naphthoquinone diazide group, it is the following compound. As a ratio (molar ratio) of H and 1,2-naphthoquinone diazide group in D, it is preferable that they are 50: 50-1: 99 from a viewpoint of a sensitivity and transparency.

In the photosensitive resin composition of this invention, the compounding quantity of a 1, 2- quinonediazide compound makes a total amount of alkali-soluble resin (A) 100 from the point of the dissolution rate difference of an exposure part and an unexposed part, and the tolerance of a sensitivity. When it is mass part, 1 mass part-100 mass parts are preferable, and 3 mass parts-80 mass parts are more preferable.

As a 1, 2- quinonediazide compound, you may use individually by 1 type or in combination of 2 or more type. Moreover, you may use together with a photo-acid generator.

As a photo-acid generator, the well-known compound which generate | occur | produces an acid by irradiation of actinic light or radiation used for the photoinitiator of photocationic polymerization, the photoinitiator of radical photopolymerization, the photochromic agent of pigment | dye, photochromic agent, microresist, etc., or those A mixture can be selected suitably and used.

Specifically as a photo-acid generator, For example, a diazonium salt compound, a phosphonium salt compound, a sulfonium salt compound, an iodonium salt compound, an imide sulfonate compound, an oxime sulfonate compound, a diazo disulfone compound, a disulfone A compound and an o-nitrobenzyl sulfonate compound are mentioned.

As the photoacid generator, a compound having a strong pKa of 2 or less and generating sulfonic acid or an alkyl or arylcarboxylic acid substituted with an electron withdrawing group, or a disulfonylimide substituted with an electron withdrawing group in the same manner is preferable. Here, examples of the electron withdrawing group include haloalkyl groups such as halogen atoms such as F atoms, and trifluoromethyl groups, nitro groups, and cyano groups.

Moreover, as a photo-acid generator, the compound which introduce | transduced the group or compound which generate | occur | produces an acid by irradiation of actinic light or radiation, for example, US Patent No. 3,849,137 specification, German Patent No. 3914407. JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A 62-153853 And the compounds described in Japanese Patent Application Laid-Open No. 63-146029 and the like can also be used.

Moreover, as a photo-acid generator, the compound which generate | occur | produces an acid by the light as described in each specification, such as US patent 3,779,778, 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 the decomposition.

A sensitizer will absorb actinic light or a radiation and will be in an electron excited state. The sensitizer which has become an electron-excited state comes into contact with a sulfonium salt compound to produce an action such as electron transfer, energy transfer, and heat generation. Thereby, a polymerization initiator produces | generates a chemical change and decompose | disassembles and produces | generates a radical, an acid, or a base.

As an example of a preferable sensitizer, the compound which belongs to the following compounds, and has an absorption wavelength in 350 nm-450 nm region is mentioned.

That is, polynuclear aromatics (for example, pyrene, perylene, triphenylene, anthracene), xanthenes (for example, fluorescein, eosin, erythrosin, rhodamine B, rose bengal), and cyanines (for example For example, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue) , Acridines (e.g., acridine orange, chloroflavin, acriflavin), anthraquinones (e.g., anthraquinones), squariases (e.g., squalariums), coumarins ( For example, 7-diethylamino 4-methylcoumarin) can be mentioned.

Especially, as an sensitizer, anthracene derivative is especially preferable.

20-200 mass parts is preferable with respect to 100 mass parts of sulfonium salt compounds, and, as for the addition amount of a sensitizer, 30-150 mass parts is more preferable.

<(C) A compound having at least two partial structures represented by the general formula (I) in a molecule and having a molecular weight of 600 or more and 2000 or less>

In the positive photosensitive resin composition for an interlayer insulating film of the present invention, a compound having (C) at least two partial structures represented by the following general formula (I) in a molecule and having a molecular weight of 600 or more and 2000 or less (hereinafter, appropriately referred to as “a specific phenol-based Compound (C) ").

In said general formula (I), R <^1> and R <^2> represents a methyl group or tert- butyl group each independently, and at least ^{1 of} R <^1> and R <^2> is a tert- butyl group. R ³ represents -O- or -NH-.

R ¹ and R ² each independently represent a methyl group or tert-butyl group, and at least one of R ¹ and R ² is a tert-butyl group, but it is preferable that both of R ¹ and R ² are tert-butyl groups.

Moreover, R <^3> represents -O- or -NH- and it is preferable that it is -O-.

By containing a specific phenolic compound (C), coloring by the oxidation at the time of a baking process is reduced, the interlayer insulation film which has the outstanding transparency can be obtained, and the photosensitive resin composition of this invention which uses acrylic resin as a main component is used for it. The surprising effect of lowering the dielectric constant of the interlayer insulating film formed by these components is also expressed.

Although the specific phenolic compound (C) whose molecular weight is 600 or more and 2000 or less has two or more partial structures in a molecule | numerator represented by the said general formula (I) in a molecule | numerator, it is preferable that this partial structure contains two or more and 6 or less, More preferably, it is a compound containing in the range of two or more and four or less.

Examples of such a compound include tetrakis {methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate} methane and tetrakis {methylene-3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionate} methane, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1 -Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, N-N'hexane 1,6-diylbis [3- (3,5-di -tert-butyl-4-hydroxyphenylpropionamide)], N-N'octane 1,8-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], etc. Can be mentioned.

Although the molecular weight of the specific phenol type compound (C) used for this invention is 600 or more and 2000 or less, it is preferable that molecular weight is 700 or more from a viewpoint of the non acidity at the time of baking. Moreover, it is preferable that it is a monomolecular compound instead of the polymer (polymeric compound) containing the repeating unit which has a partial structure as mentioned above from the compatibility viewpoint of acrylic alkali-soluble resin (A) which concerns on this invention.

It is preferable from the viewpoint of transparency after baking that the specific phenol type compound (C) used for this invention contains the ester bond whose R <^3> is O. Since the specific phenol type compound which has an ester bond is excellent in the compatibility of acrylic alkali-soluble resin (A) which concerns on this invention, it is thought that it shows the outstanding transparency improvement effect.

Among these specific phenolic compounds, the following compounds (I-1), (I-2) and (I-3) are more preferable as specific phenolic compounds from the viewpoint of transparency after baking, and most preferably the following compounds (I-1).

A specific phenolic compound can also be obtained as a commercial item, For example, as said (I-1), the brand names Irganox 1010 (made by Chiba Japan), Adecastabe AO-60 (made by ADEKA), etc. are mentioned ( As the brand name of I-2), Smolizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Adecast Star AO-80 (manufactured by ADEKA), and the like are the brand name Irganox 1098 (manufactured by Chiba Japan). ), And the like.

Only 1 type may be used for the photosensitive resin composition of this invention, and a specific phenol type compound (C) may use 2 or more types together. It is preferable that content of a specific phenolic compound (C) is 0.1 mass%-6 mass% with respect to the total solid of the photosensitive resin composition, It is more preferable that it is 0.2 mass%-5 mass%, 0.5 mass%-4 Mass% is optimal. By making content into 0.1 mass% or more and 6 mass% or less, sufficient transparency of the formed film is obtained and sensitivity is expressed also at the time of pattern formation.

<Other additives>

The photosensitive resin composition of this invention may add antioxidant. As antioxidant which can be used for this invention, although phosphorus antioxidant, sulfur type antioxidant, etc. are mentioned, It is more preferable to use together with sulfur type antioxidant rather than phosphorus antioxidant. As an example of the sulfur type antioxidant which can be used together, a smear riser TPL-R (made by Sumitomo Gakuku Co., Ltd.), a smear riser TPM (made by Sumitomo Gagaku Co., Ltd.), a smear riser TPS (made by Sumitomo Gagaku Co., Ltd.), a Sumirai Low TP-D (manufactured by Sumitomo Gakuku Co., Ltd.), smililizer MB (manufactured by Sumitomo Gagaku Co., Ltd.), and the like. As content in the case of using a sulfur type antioxidant together, it is 0.1 mass%-5 mass% with respect to the total solid of the photosensitive resin composition normally, Preferably they are 0.2 mass%-4 mass%.

As the additives other than the antioxidant, various ultraviolet absorbers, metal deactivators, and the like described in "New Development of Polymer Additives (Daily Industries News)" may be added to the photosensitive resin composition of the present invention. Content of these additives should normally stay less than 5 mass% with respect to the total solid of the photosensitive resin composition, Preferably it is less than 3 mass%.

The photosensitive resin composition of this invention may contain the crosslinking agent further for the purpose of a curability improvement.

<Crosslinking agent having at least one group selected from the group consisting of (D-1) oxyranyl group and oxetanyl group>

The photosensitive resin composition of this invention may contain the crosslinking agent (D-1) which has at least 1 sort (s) of group chosen from the group which consists of an oxiranyl group and an oxetanyl group. In particular, when alkali-soluble resin (A) does not contain any of an oxiranyl group and an oxetanyl group, the crosslinking agent (D-1) which has at least 1 sort (s) of group chosen from the group which consists of an oxiranyl group and an oxetanyl group. Preference is given to using.

Examples of the crosslinking agent (D-1) include a copolymer having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group (hereinafter, may be described as a specific copolymer (D1)). have. It demonstrates in detail below.

As a specific copolymer (D1), what contains an alicyclic structure in the structure is preferable from a viewpoint that the transparency, developability, and insulation stability of the cured film formed using the photosensitive resin composition become favorable.

In the present invention, the specific copolymer (D1) includes a repeating unit (D1-1) having an alicyclic structure, and a repeating unit (D1-) having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group. It is preferable that it is a copolymer containing 2), and may contain (D1-3) other repeating units as needed. However, a specific copolymer (D1) does not contain a carboxy group in the structure. Moreover, it is preferable that a specific copolymer (D1) is an acryl-type epoxy copolymer from a viewpoint of transparency and insulation stability.

[Repeating unit (D1-1) having an alicyclic structure]

As a repeating unit (D1-1) which has an alicyclic structure, the repeating unit derived from the monomer which has an alicyclic structure as mentioned above is mentioned.

Specific examples of the monomer having an alicyclic structure include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and (meth) acrylate. Dicyclopentanyl acrylate, isobornyl (meth) acrylate, and the like. Among them, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ( Dicyclopentanyl methacrylate is preferred.

The repeating unit (D1-1) which has an alicyclic structure may be comprised individually by 1 type, and may be comprised by 2 or more types.

Content of the repeating unit (D1-1) which has alicyclic structure in the specific copolymer (D1) in this invention is 1 mol% from the point which is excellent in transparency and insulation stability of the cured film formed using the photosensitive resin composition. 80 mol% is preferable, 3 mol%-70 mol% are more preferable, and 5 mol%-60 mol% are further more preferable.

[Repeating unit (D1-2) having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group]

The repeating unit (D1-2) having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group is derived from a monomer having at least one group selected from the group consisting of an oxiranyl group and an oxetanyl group. Repeating units may be mentioned.

As a monomer which has an oxiranyl group, specifically, for example, glycidyl (meth) acrylate, (3, 4- epoxycyclohexyl) methyl (meth) acrylate, allyl glycidyl ether, 3, 4- Epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexyl-n-propyl (meth) acrylate, 3,4-epoxycyclohexyl-i-propyl (meth) acrylate, 1-vinyl-2, And compounds such as 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 and (3,4-epoxycyclohexyl) methyl (meth) acrylate are preferred from the viewpoint of solvent resistance and heat resistance.

As a monomer which has an oxetanyl group, the (meth) acrylic acid ester etc. which have an oxetanyl group in Unexamined-Japanese-Patent No. 2001-330953 are mentioned, for example.

As such a monomer, specifically, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl ) The process margin of the photosensitive resin composition from which 2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. are obtained It is wide and preferable at the point which raises the chemical resistance of the interlayer insulation film obtained.

The repeating unit (D1-2) which has at least 1 sort (s) of group chosen from the group which consists of an oxiranyl group and an oxetanyl group may be comprised individually by 1 type, and may be comprised by 2 or more types.

Content of the repeating unit (D1-2) which has at least 1 sort (s) of group chosen from the group which consists of an oxiranyl group and an oxetanyl group of the specific copolymer (D1) in this invention is formed using the photosensitive resin composition. From the point which is excellent in the solvent resistance and heat resistance of a cured film, 20 mol%-98 mol% are preferable, 30 mol%-95 mol% are more preferable, 40 mol%-90 mol% are further more preferable.

((D1-3) other repeating units)

The specific copolymer (D1) in the present invention may include other repeating units (D1-3). As this other repeating unit (D1-3), it is preferable that it is a repeating unit derived from a vinyl monomer.

As a vinyl monomer which can form another repeating unit (D13), it is (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, for example. And (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

As a specific example of such a vinyl monomer, the monomer quoted by the other repeating unit (A3-3) which can be contained in acrylic resin, for example is mentioned together.

Among these, (meth) acrylic acid ester or styrene is preferable. Most preferably, they are (meth) acrylic acid ester, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic-acid diethylene glycol monomethyl ether, and (meth) acrylic-acid diethylene glycol monoethyl 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 It is preferable from the viewpoint of transparency.

The other repeating unit (D1-3) may be comprised individually by 1 type, and may be comprised by 2 or more types.

Content of the other repeating unit (D1-3) in the specific copolymer (D1) in this invention is 0 mol%-50 from the point which is excellent in transparency and developability of the cured film formed using the photosensitive resin composition. Mol% is preferable, 3 mol%-40 mol% are more preferable, and 5 mol%-30 mol% are further more preferable.

When the specific copolymer (D1) as described above is polymerized, at least, a monomer capable of forming a repeating unit of (D1-1) and (D1-2) and, if necessary, a repeating unit of (D1-3). Can be synthesized by copolymerization.

Hereinafter, although the example of the specific copolymer (D1) which can be used suitably for this invention is mentioned, this invention is not limited to this.

Moreover, the weight average molecular weights of the compound illustrated below are 4000-41000.

Although there is no restriction | limiting in particular in the molecular weight of the specific copolymer (D1) used by this invention, From a viewpoint of an alkali dissolution rate, a film | membrane property, etc., as a weight average molecular weight, 1,000-300,000 are preferable, 2,000-200,000 are more preferable, 3,000-100,000 are especially preferable. In addition, this weight average molecular weight is the value measured by GPC method.

As a crosslinking agent in this invention, compounds other than the said specific copolymer (D1) can also be used. Examples of compounds other than the specific copolymers include ceoxide 2021P, copper 3000, epoxide GT401, EHPE3150 and EHPE3150E (above, manufactured by Daicel Chemical Industries, Ltd.).

The crosslinking agent in this invention may be used individually by 1 type, and may use 2 or more types together. As for the addition amount to the photosensitive resin composition of this invention of the crosslinking agent in this invention, when the total amount of alkali-soluble resin (A) mentioned above is 100 mass parts, 1 mass part-100 mass parts are preferable, and 3 mass parts-80 A mass part is more preferable. When addition amount exists in this range, it becomes the thing excellent in the solvent resistance, heat resistance, and insulation stability of the cured film formed using the photosensitive resin composition.

<(D-2) melamines>

(D-2) melamine is mentioned as another preferable example of the crosslinking agent in this invention. Melamine (D-2) used as a crosslinking agent is preferably a compound represented by the following general formula.

(Wherein, R ⁴ ~R ^9, which may be the same or different, represents a hydrogen atom or a -CH ₂ OR, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, except that one of R ⁴ ~R ⁹ will be -CH ₂ OR group)

As melamine represented by the said general formula, For example, hexamethylol melamine, hexabutyrolmelamine, the partial methylol-ized melamine and its alkylated substance, tetramethylol benzoguanamine, the partially methylolated benzoguanamine, its alkylated substance, etc. Can be mentioned.

These (D-2) melamines are available as a commercial item, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, Mitsui-Sinemid Co., Ltd.), Nikaraku Mx-750, -032, -706, -708, -40, -31, Nikaraku Ms- 11, Nikaraku Mw-30 (above, Sanwa Chemical Co., Ltd.) etc. can be used preferably.

When using these (D-2) melamines as a crosslinking agent, the addition amount is 1-100 weight part with respect to 100 weight part of (A) alkali-soluble resin, More preferably, it is 5-50 weight part. By adding in this range, preferable alkali solubility at the time of image development and the outstanding solvent resistance of the film | membrane after hardening are obtained.

The photosensitive resin composition of this invention heats (E) other than crosslinking agents, such as (A)-(C) which are the essential components mentioned above, a photoacid generator which is a preferable combined component, (D-1), (D-2), etc. Optional components such as a radical generator, (F) adhesion promoter, (G) surfactant, (H) thermosensitive acid generating compound, (I) polymerizable compound having at least one ethylenically unsaturated double bond, and (J) solvent You may contain it further according to the objective.

Hereinafter, arbitrary components are demonstrated.

<(E) Thermal radical generator>

The photosensitive resin composition of this invention may contain the (E) thermal radical generator.

As a thermal radical generating agent in this invention, what is generally known as a radical generating agent can be used. A thermal radical generating agent is a compound which generate | occur | produces a radical by the energy of heat, and starts and accelerates a polymerization reaction with polymeric compounds, such as alkali-soluble resin (A). By adding a thermal radical generating agent, the obtained cured film becomes stronger, and heat resistance and solvent resistance improve.

Hereinafter, although a thermal radical generating agent 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, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, and actives. Ester compounds, compounds having a carbon halogen bond, azo compounds, bibenzyl compounds and the like.

In the present invention, organic peroxides, azo compounds and bibenzyl compounds are more preferable, and bibenzyl compounds are particularly preferable from the viewpoints of heat resistance and solvent resistance of the obtained cured film.

Moreover, as a bibenzyl compound, the compound represented by following General formula (1) is preferable.

In General Formula (1), a plurality of R ^{3 's} each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom .

As the compound represented by the general formula (1), specifically, 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-tetraphenylsuccinate nitrile, dibenzyl, etc. are mentioned.

As (E) thermal radical generating agent used for this invention, Preferably, it is a compound of the range whose 100-hour half life temperature is 100 degreeC or more and 230 degrees C or less, More preferably, it is a compound of 120 degreeC or more and 220 degrees C or less.

When the 10-hour half-life temperature is in this temperature range, a cured film having excellent characteristics can be obtained.

The 10-hour half-life temperature of a thermal radical generating agent means the thing of the temperature which half amount of the compound to measure decomposes and generate | occur | produces a radical when it is left to stand for 10 hours under specific temperature.

As a compound of the range whose 10-hour half-life temperature is 100 degreeC or more and 230 degrees C or less, perbutyl A, perhexa 22, perbutyl Z, perhexa V, perbutyl P, by Nichi Oil Co., Ltd. among the said compounds, Percumyl D, perhexyl D, perhexa25B, perbutyl C, nofmer BC-90 (2,3-dimethyl-2,3-diphenylbutane), etc. are mentioned, and these are the heat | fever used for this invention. It is preferable as a radical generator.

Although the reason is not clear, the thermal radical generating agent which decomposes at higher temperature and generate | occur | produces a radical is preferable, and the heat resistance and solvent resistance of the obtained cured film become favorable.

The (E) thermal radical generating agent in this invention may be used individually by 1 type, and can also use 2 or more types together.

(E) When the amount of addition of the thermal radical generator to the photosensitive resin composition of the present invention is 100 parts by mass of the alkali-soluble resin (A), 0.1 parts by mass to 100 parts by mass is preferable, and more preferably 1 part by mass- It is most preferable from a viewpoint of a film physical property improvement that it is 50 mass parts and 5 mass parts-30 mass parts.

<(F) Adhesion Promoter>

In order to provide adhesiveness to a solid surface, you may add adhesion promoters, such as an organosilicon compound, a silane coupling agent, and a leveling agent, to the photosensitive resin composition of this invention as needed.

As these examples, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimeth Methoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxy Propyl trimethoxysilane, ureapropyl triethoxysilane, tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, etc. are mentioned.

When using an adhesion promoter for the photosensitive resin composition, 0.1-20 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (A), and 0.5-10 mass parts is more preferable.

<(G) surfactant>

In the photosensitive resin composition of this invention, in order to improve applicability | paintability, (G) surfactant can be contained. Here, as the (G) surfactant, a fluorine-based surfactant, a silicone-based surfactant, or a nonionic surfactant can be suitably used. For example, various surfactants described in JP 2001-330953 A can be used.

You may use these surfactant individually or in combination of 2 or more types.

In the photosensitive resin composition of this invention, these (G) surfactant becomes like this. Preferably it is 5 weight part or less, More preferably, it is 2 weight part or less with respect to 100 weight part of alkali-soluble resin (A). When the usage-amount of (G) surfactant exceeds 5 weight part, when forming a coating film on a board | substrate, film roughness of a coating film may arise easily.

<(H) Thermosensitive Acid Generating Compound>

The (H) thermosensitive acid generating compound can be used to further improve the heat resistance and hardness of the resulting interlayer insulating film. As an example, onium salt, such as a sulfonium salt, a benzothiazonium salt, an ammonium salt, a phosphonium salt, is mentioned, for example.

As an example of the said sulfonium salt, an alkyl sulfonium salt, benzyl sulfonium salt, a dibenzyl sulfonium salt, a substituted benzyl sulfonium salt, a benzothiazonium salt, etc. are mentioned, for example.

As the thermosensitive acid-producing compound, sulfonium salts or benzothiazonium salts are preferably used, and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4 -Acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate or 3-benzylbenzothiazolium Hexafluoroantimonate is preferably used.

As such a commercial item, Sanade SI-L85, the same SI-L110, the same SI-L145, the same SI-L150, the same SI-L160 (above, Sanshin Chemical Co., Ltd. make), etc. are mentioned, for example. Can be.

The use ratio of (H) component in the photosensitive resin composition of this invention becomes like this. Preferably it is 20 weight part or less, More preferably, it is 5 weight part or less with respect to 100 weight part of alkali-soluble resin (A). When the usage-amount of (H) component exceeds 20 weight part, a precipitate may precipitate in a coating film formation process, and may interfere with coating film formation.

<(I) polymerizable compound having at least one ethylenically unsaturated double bond>

As said (I) polymerizable compound which has at least 1 ethylenically unsaturated double bond (henceforth appropriately "polymerizable compound (I)"), for example, monofunctional (meth) acrylate and bifunctional (meth) ) Acrylate or (meth) acrylate more than trifunctional is mentioned suitably.

As said monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboroyl (meth) acrylate, 3-methoxybutyl (meth), for example Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned. As these commercial items, for example, Aronix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, and TC-120S (above, Nippon Nippon) Kayaku Co., Ltd., Biscot 158, East 2311 (above, Osaka Yukigagaku Kogyo Co., Ltd.), etc. are mentioned.

As said bifunctional (meth) acrylate, ethylene glycol (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 1, 9- nonane diol di (meth) acrylate, polypropylene glycol is mentioned, for example. Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, and the like. As these commercial items, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 ( Nippon Kayaku Co., Ltd. biscoat 260, copper 312, copper 335HP (above, Osaka Yuki Chemical Co., Ltd. product) etc. are mentioned.

As said trifunctional or more than (meth) acrylate, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a tri ((meth) acryloyloxyethyl) phosphate, a pentaerythritol, for example Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Examples of the commercially available product include Aronix M-309 and copper. M-400, M-405, M-450, M-7100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20 , East DPCA-30, East DPCA-60, East DPCA-120 (above, made by Nippon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Yuki) Kagaku Kogyo Co., Ltd.) etc. are mentioned.

Of these, trifunctional or higher (meth) acrylates are preferably used, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, or dipentaerythritol hexa (meth) acrylate are particularly preferred. desirable. These monofunctional, bifunctional or trifunctional or more (meth) acrylates are used individually or in combination.

The use rate of the polymeric compound (I) in the photosensitive resin composition of this invention is 50 weight part or less with respect to 100 weight part of alkali-soluble resin (A), More preferably, it is 30 weight part or less. 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. When this usage-amount exceeds 50 weight part, film roughness may arise at the process of forming the coating film of the photosensitive resin composition on a board | substrate.

<(J) solvent>

As a solvent used for manufacture of the photosensitive resin composition of this invention, alkali-soluble resin (A), (B) 1, 2- quinone diazide compound, (C) specific phenol type compound, and the other component mix | blended arbitrarily are uniform It is used so that it melt | dissolves easily and does not react with these components.

As such a solvent, what was illustrated as a solvent which can be used when manufacturing alkali-soluble resin (A) mentioned above is mentioned similarly.

Among them, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters or diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of coating 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, di Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxy propionate or ethyl ethoxypropionate can be used especially preferably.

Moreover, in order to raise the in-plane uniformity of a film thickness with the said solvent, you may use together a high boiling point solvent. As a high boiling point solvent which can be used together, it is N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpi, for example. Ralidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, male Diethyl acid, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among these, N-methylpyrrolidone, γ-butyrolactone or N, N-dimethylacetamide is preferable.

When using a high boiling point solvent together as a solvent for photosensitive resin composition manufacture of this invention, the usage-amount shall be 50 weight% or less with respect to solvent whole quantity, Preferably it is 40 weight% or less, More preferably, you may be 30 weight% or less. Can be. When the usage-amount of a high boiling point solvent exceeds this usage-amount, the film thickness uniformity, a sensitivity, and a residual film ratio of a coating film may fall.

When manufacturing the photosensitive resin composition of this invention as a solution state, although solid content concentration of components other than the solvent which occupies in a solution can be arbitrarily set according to a purpose of use, the value of a desired film thickness, etc., Preferably it is 5-50 weight%, More preferably, it is 10-40 weight%, More preferably, it is 12-35 weight%.

The composition solution thus prepared may be used for use after being filtered using a Millipore filter or the like having an opening having a pore size of about 0.2 μm.

`` Interlayer insulating film, organic EL display device, and liquid crystal display device ''

The interlayer insulating film of the present invention imparts energy to light to the coating film made of the positive type photosensitive resin composition for the interlayer insulating film of the present invention, improves developability of the energy-providing region, and removes the region by development. Preferably, it is formed by thermosetting.

Such an interlayer insulating film is excellent in transparency, heat resistance, and insulation, and is particularly effective for electronic devices. The electronic device referred to in the present invention means an organic EL display device and an electronic device for a liquid crystal display device, and the photosensitive resin composition of the present invention is particularly effective for this organic EL display device and an interlayer insulating film for a liquid crystal display device. To exert.

The photosensitive resin composition of this invention can be applied to the following pattern formation methods, and can form the interlayer insulation film of a desired shape.

[Pattern Forming Method]

As a method of forming a patterned cured film using the photosensitive resin composition of this invention, (1) the photosensitive resin composition of this invention is apply | coated on a suitable board | substrate, (2) this coated board | substrate is baked (prebaking), (3) exposure to actinic light or radiation, (4) post-heating as needed, (5) development with aqueous developer, (6) front-side exposure as needed, and (7) thermosetting (post-baking). The pattern formation method used is used. By using this pattern formation method, the cured film of a desired shape (pattern) can be formed on a board | substrate.

In addition, in the said pattern formation method, post-heating in (4) and front surface exposure in (6) may be performed as needed as needed.

Like the pattern formation method, after (1) the photosensitive resin composition of this invention is apply | coated on a semiconductor element or a glass substrate so that the thickness after hardening may become desired thickness (for example, 0.1-30 micrometers), By (2) prebaking, (3) exposure, (5) development, and (7) thermosetting, the patterned cured film for organic EL display devices or a liquid crystal display device can be formed.

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

The photosensitive resin composition of this invention is apply | coated on (1) suitable board | substrates.

The substrate may be selected according to the use of the cured film to be formed. For example, a semiconductor substrate or a ceramic substrate such as a silicon wafer, or a substrate made of glass, metal, or plastic is used. If a cured film is for semiconductor devices, it is common to use a silicon substrate, and if a cured film is for display devices, a glass substrate is used.

The coating method includes, but is not limited to, spray coating, spin coating, slit coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, dip coating and the like. .

By this (1) application | coating process, the photosensitive resin composition layer is formed on a board | substrate.

In order to evaporate the solvent remaining in the photosensitive resin composition layer after said (1) application | coating process, (2) prebaking is performed. This (2) prebaking is performed in the range of several minutes to 30 minutes at the temperature of 70 degreeC-130 degreeC.

Subsequently, exposure using actinic light or a radiation is performed to the photosensitive resin composition layer dried by prebaking (3) through the mask provided with the desired pattern. Energy exposure is generally ^{10mJ / cm 2 ~1000mJ / cm 2} , preferably from 20mJ / cm ² ~500mJ / cm ² energy. As the actinic ray or the radiation, X-rays, electron beams, ultraviolet rays, visible rays and 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). Moreover, exposure is also possible by a laser system, such as an ultraviolet light laser.

By this (3) exposure process, the area | region developed by the aqueous developing solution and the area | region which is not developed are formed in the photosensitive resin composition layer on a board | substrate. Since the photosensitive resin composition of this invention has a positive effect | action, it becomes an area | region where an exposure part is developed by aqueous developing solution.

(3) It is advantageous to heat (post-heat) the board | substrate exposed by actinic light or radiation to the temperature of (4) 70-130 degreeC. Post-heating is performed for a short time, generally from several seconds to several minutes. This process is usually called a post-exposure baking.

Next, the photosensitive resin composition layer after (3) exposure ((4) post-heating) is developed with (5) aqueous developing solution. By this development, the exposed part of the photosensitive resin composition layer is developed by the aqueous developing solution, and the unexposed part remains on a board | substrate, and the photosensitive resin composition layer of a desired shape (pattern) is formed.

The aqueous developer includes inorganic alkalis (e.g. potassium hydroxide, sodium hydroxide, aqueous ammonia), primary amines (e.g. ethylamine, n-propylamine), secondary amines (e.g. diethylamine, di -n-propylamine), tertiary amines (e.g. triethylamine), alcoholamines (e.g. triethanolamine), quaternary ammonium salts (e.g. tetramethylammonium hydroxide, tetraethylammonium hydrooxide) ) And alkaline solutions using mixtures thereof. Most preferable developer contains tetramethylammonium hydrooxide. In addition, an appropriate amount of surfactant may be added to the developing solution.

In addition, you may perform image development by dip, spray, paddling, or another image development method.

(5) After the development process, the photosensitive resin composition layer remaining on the substrate may be rinsed and washed with deionized water in some cases.

In addition, (5) after image development, the photosensitive resin composition layer which remains on a board | substrate is subjected to (6) front surface exposure as needed. It is preferable that the exposure energy of this whole surface exposure is energy of 100-1000mJ / cm <^2> .

When forming the cured film for display apparatuses by performing this (6) front surface exposure, since the transparency improves, it is preferable.

Subsequently, in order to obtain the final patterned cured film of the photosensitive resin composition layer which remains on a board | substrate after (5) developing processes, (7) thermosetting processes are performed. This thermosetting is performed in order to form the cured film with large heat resistance, chemical resistance, and film strength. When the general photosensitive polyimide precursor composition is used, it heat-hardens at the temperature of about 300-400 degreeC. On the other hand, the photosensitive resin composition of this invention is 150 degreeC-300 degreeC, More specifically, 160 degreeC-250 degreeC heating, the cured film which has film property equivalent to or more than the conventional photosensitive polyimide precursor composition is obtained.

By the photosensitive resin composition of this invention, the interlayer insulation film which is excellent in insulation and has high transparency also when baked at high temperature is obtained. Since the interlayer insulation film which uses the positive photosensitive resin composition of this invention has high transparency and there is no possibility of discoloration by heat, it is useful for the use of an organic EL display device or a liquid crystal display device.

The organic EL display device or liquid crystal display device of the present invention is not particularly limited except having a planarization film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL displays having various structures. A device and a liquid crystal display device are mentioned.

[Example]

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the exceeding well-known. In addition, "part" is a mass reference | standard unless there is particular notice.

Synthesis Example

<Alkali-soluble resin (A): Synthesis of binder C>

As a monomer component for forming the copolymer, 12.47 g of methacrylic acid (hereinafter referred to as MAA), 4.66 g of styrene (hereinafter referred to as St), and 16.25 g of dicyclopentanyl methacrylate (hereinafter referred to as DCM) Binder C 'solution, which is a precursor of binder C, by using 0.5 g of azobisisobutyronitrile (AIBN) as a radical polymerization initiator and polymerizing the mixture in 40.81 g of solvent propylene glycol monomethyl ether acetate (PGMEA). Got. Moreover, polymerization temperature was adjusted to 60 degreeC-100 degreeC.

11.61 g glycidyl methacrylate (GMA), 0.17 g acetylacetonate chromium, and 14.19 g PGMEA were added to the said binder C 'solution, and it was made to react, and PGMEA solution (solid content concentration: 45 mass%) of binder C was obtained. Moreover, reaction temperature was adjusted to 90 degreeC-120 degreeC.

The weight average molecular weight measured by GPC of obtained binder C was 30000.

<Alkali-soluble resin (A): Synthesis of Binder D>

After nitrogen-substituting the flask, 459.0 g of diethylene glycol dimethyl ether solutions in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved were charged. Subsequently, 22.5 g of styrene, 67.5 g of methacrylic acid, 45.0 g of dicyclopentanyl methacrylate, and 90.0 g of methacrylic acid were charged, and then stirring was gradually started. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 5 hours, followed by heating at 90 ° C. for 1 hour to terminate the polymerization.

Thereafter, the reaction product solution was added dropwise to a large amount of water to solidify the reaction product. After washing with water, this coagulated product was redissolved in 200 g of tetrahydrofuran and coagulated again in a large amount of water.

After performing this redissolve-solidification operation | movement three times in total, the obtained coagulated | cured material was vacuum-dried at 60 degreeC for 48 hours, and the target copolymer was obtained. Then, it was set as the copolymer solution using diethylene glycol ethyl methyl ether so that solid content concentration might be 30 weight%.

Comparative Alkali Soluble Resin: Synthesis of Binder E

8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene 40 parts, N-phenyl- (5-norbornene-2,3-dicarboxyimide) 60 Part, 2.8 parts of 1,5-hexadiene, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride 0.05 parts and diethylene glycol ethylmethyl 400 parts of ether was charged to the pressure-resistant glass reactor substituted by nitrogen, and the polymerization reaction was performed at 80 degreeC for 2 hours, stirring, and the solution of an alicyclic olefin polymer was obtained. The weight average molecular weight of the obtained alicyclic olefin polymer hydride was 4,330, the number average molecular weight was 2,600, and the hydrogenation rate was 99.9%. The solution of the alicyclic olefin polymer hydride was filtered through a fluorine resin filter having a pore diameter of 0.2 μm, and activated carbon was separated to obtain 476 parts of the alicyclic olefin polymer solution. Filtration was performed without standing. The alicyclic olefin polymer solution after filtration was concentrated with a rotary evaporator to obtain an alicyclic olefin polymer solution (2) having a solid content concentration of 35.0%.

<Linear epoxy copolymer (B): Synthesis of crosslinking agent 4>

As the monomer component for forming the linear epoxy copolymer, DCM (FA-513M, Hitachi Chemical Co., Ltd., 22.03 g), GMA (113.72 g), and HEMA (13.01 g) were used, and V-601 ( The PGMEA solution (Mw. 5000, solid content concentration: 30 mass%) of the crosslinking agent 4 was obtained by superposing | polymerizing-reacting these in the solvent PGMEA (347.0g) for 4 hours using Wakojunyaku make. Moreover, polymerization temperature was adjusted to the temperature of 90 degreeC.

The weight average molecular weight measured by GPC of the obtained crosslinking agent 4 was 5000.

(Comparative Example 1)

<Production of Photosensitive Resin Composition>

The following composition was melt | dissolved and mixed, and it filtered with the 0.2 micrometer polytetrafluoroethylene filter, and obtained the photosensitive resin composition of the comparative example 1.

Binder C solution obtained by the synthesis method described above (amount equivalent to 12.0 parts by solid content)

[(A) Alkali Soluble Resin]

5.0 parts of a photosensitizer (the following structure made by Toyosei Co., Ltd.)

[(B) quinonediazide compound]

Crosslinking agent 4 obtained by the synthesis method mentioned above (5.0 parts of solid content)

0.5 part of adhesion promoter (KBM-403 structure made by Shin-Etsu Chemical Co., Ltd.)

0.4 parts of thermal radical generator (Nichi Oil Nomer BC-90 structure)

Solvent (PGMEA) 77.1 parts

0.005 parts surfactant (DIC Megapack F172)

(Examples 1 to 10 and Comparative Examples 2 to 10)

The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 2 to 10 were prepared in the same manner as in Comparative Example 1, except that the amounts of each component of Comparative Example 1 were changed as shown in Tables 1 and 2 below. .

TABLE 1

TABLE 2

The detail of the photosensitizer, adhesion promoter (KBM-430), thermal radical generator (Nomer BC-90), specific phenolic compound (C), and crosslinking agent which were used in Table 1 and Table 2 is shown below. In addition, abbreviated-name other than the above-mentioned of the compound in a table | surface is as follows.

CHMA: cyclohexyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

BzMA: benzyl methacrylate

BTEAC: benzyltriethylammonium

EDM: diethylene glycol ethyl methyl ether

<Evaluation of transparency>

After coating each photosensitive resin composition on a glass substrate (Corning 1735, 0.7 mm thickness (made by Corning)) using a spinner, it prebaked on a hotplate for 2 minutes at 90 degreeC, and the photosensitive property of 3.0 micrometers in film thickness The resin composition layer was formed. The obtained photosensitive resin composition layer was exposed to a total irradiation amount of 300 mJ / cm ² (roughness: 20 mW / cm ² ) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation, and then the substrate was exposed to an oven. It heated at 230 degreeC for 1 hour, and obtained the cured film.

The light transmittance of the glass substrate which has this cured film was measured with the wavelength of the range of 400-800 nm using the spectrophotometer "150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.). Table 2 shows the values of the minimum light transmittance at that time. When this value is 92% or more, it can be said that transparency of a cured film is favorable.

<Evaluation of heat resistance transparency>

The substrate after the above-mentioned transparency evaluation was further heated in an oven at 230 ° C. for 2 hours, and then the light transmittance was measured using a spectrophotometer “150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.). Measured. Table 3 shows the values of the minimum light transmittance at that time. When this value is 81% or more, it can be said that the heat resistance transparency of a cured film is favorable.

[Table 3]

In Table 3, it turns out that the film | membrane formed by the photosensitive resin composition of the Example which added the specific phenolic compound (C) which concerns on this invention shows high transparency and heat resistance transparency. In addition, when a low molecular weight phenolic compound other than the specific phenolic compound (C) according to the present invention, a sulfur antioxidant, a phosphorus antioxidant and a hindered amine stabilizer are added (Comparative Examples 1 to 1) 7) and when the specific phenolic compound (C) is added to the alicyclic olefin polymer which is comparative alkali-soluble resin (comparative example 9), it turns out that outstanding transparency and heat resistance transparency are not obtained.

Evaluation of Insulation Stability

After applying the photosensitive resin composition on a bare wafer (N type low resistance) (manufactured by SUMCO) using a spinner, the photosensitive resin composition having a film thickness of 3.0 µm was prebaked on a hot plate at 90 ° C for 2 minutes. Formed a layer. The obtained photosensitive resin composition was exposed to a cumulative irradiation amount of 300 mJ / cm ² (roughness: 20 mW / cm ² ) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation, and the substrate was exposed to 1 at 230 ° C. in an oven. The cured film was obtained by heating for time.

About this cured film, the dielectric constant was measured at the measurement frequency of 1 MHz using CVmap92A (made by Four Dimensions Inc.). The results are shown in Table 4.

[Table 4]

From the result of Table 4, it turned out that in the photosensitive resin composition of this invention, relative dielectric constant falls compared with the case where a specific phenolic compound (C) is not added. In general, in an interlayer insulating film using an alkali-based alkali-soluble resin, the dielectric constant may increase, and the technique of the present invention which can lower the dielectric constant by 0.1 or more is very useful. In addition, when the alkali-soluble resin is changed to a known cyclic olefin resin by contrast between Comparative Example 9 and Comparative Example 10, even if the specific phenolic compound (C) according to the present invention is added, there is no decrease in the dielectric constant. It can be seen that.

Next, although the manufacturing method of the display apparatus of this invention is demonstrated taking the manufacturing method of an organic electroluminescent display as an example, this invention limits in particular except having a planarization film or an interlayer insulation film formed using the said photosensitive resin composition. Instead, various structures can be taken in the application to the liquid crystal display device.

Example 11

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

A bottom gate TFT 1 was formed on the glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed in a state of covering the TFT 1. Next, a contact hole (not shown here) is formed in the insulating film 3, and then a wiring 2 (1.0 μm in height) connected to the TFT 1 via this contact hole is placed on the insulating film 3. Formed. This wiring 2 is for connecting the organic EL element and the TFT 1 formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization layer 4 was formed on the insulating film 3 in a state of filling the unevenness by the wiring 2. Formation of the planarization film 4 on the insulating film 3 is carried out by spin-coating the photosensitive resin composition of Example 3 on a substrate, prebaking (120 ° C. × 2 minutes) on a hot plate, and then applying high pressure mercury or the like from the mask. After irradiating i line | wire (365 nm) to 100mJ / cm <^2> (roughness 20mW / cm <^2> ), it developed by alkaline aqueous solution, the pattern was formed, and it heat-processed for 30 minutes at 220 degreeC. The applicability | paintability at the time of apply | coating this photosensitive resin composition was favorable, and generation | occurrence | production of a wrinkle and a crack was not recognized by the cured film obtained after exposure, image development, and baking. In addition, the film thickness of the planarization film which produced 500 nm of average level | step differences of the wiring 2 was 2000 nm.

Next, the bottom emission type organic EL element was formed on the obtained planarization film 4. First, on the planarization film 4, the 1st electrode 5 which consists of ITO was connected to the wiring 2 through the contact hole 7, and was formed. Then, the resist was apply | coated and prebaked, and it exposed and developed through the mask of a desired pattern. Using this resist pattern as a mask, pattern processing was performed by wet etching using ITO etchant. Then, the resist pattern was stripped using the resist stripping solution (mixed liquid of monoethanolamine and DMSO). The 1st electrode obtained in this way is corresponded to the anode of organic electroluminescent element.

Next, the insulating layer 8 of the shape which covers the periphery of a 1st electrode was formed. The insulating film 8 was formed in the insulating layer by the method similar to the above using the photosensitive resin composition of Example 3. By providing this insulating layer, the short between the 1st electrode and the 2nd electrode formed in a later process can be prevented.

In addition, the hole transport layer, the organic light emitting layer, and the electron transport layer were sequentially deposited through a desired pattern mask in a vacuum vapor deposition apparatus. Next, the 2nd electrode which consists of Al was formed in the whole surface above a board | substrate. The obtained said board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix organic EL display device obtained by connecting a TFT 1 for driving this to each organic EL element was obtained. When voltage was applied through the drive circuit, it was found that the display was a good organic EL display device with good display characteristics.

Example 12

In the active matrix liquid crystal display device of FIGS. 1 and 2 of Patent No. 3332100, the interlayer insulating film 17 was formed as follows to obtain a liquid crystal display device of Example 12. FIG.

That is, using the photosensitive resin composition of Example 3, the interlayer insulating film 17 was formed by the method similar to the formation method of the planarization film 4 of the organic electroluminescent display in Example 11.

When the drive voltage was applied to the obtained liquid crystal display device, it showed that favorable display characteristics were shown and it was a highly reliable liquid crystal display device.

Claims (11)

(A) Alkali-soluble resin containing an acryl-type repeating unit, (B) 1, 2- quinonediazide compound, and (C) At least two partial structure represented by following General formula (I) in a molecule | numerator, molecular weight Positive type photosensitive resin composition for interlayer insulation films containing this compound which is 600 or more and 2000 or less.

In said general formula (I), R <^1> and R <^2> represents a methyl group or tert- butyl group each independently, and at least ^{1 of} R <^1> and R <^2> is a tert- butyl group. R ³ represents -O- or -NH-. The method of claim 1,
The compound which has at least two partial structure represented by said (C) general formula (I) in a molecule | numerator, and whose molecular weight is 600 or more and 2000 or less is the following compound (I-1), (I-2), and (I-3) Positive type photosensitive resin composition for interlayer insulation films which is a compound chosen.

The method of claim 2,
The positive photosensitive resin composition for interlayer insulation films whose compound which has at least two partial structure represented by said (C) general formula (I) in a molecule | numerator, and whose molecular weight is 600 or more and 2000 or less is following compound (I-1).

The method of claim 1,
Positive type photosensitive resin composition for interlayer insulation films whose said (B) 1, 2- quinonediazide compound is a compound of the following structure.

In the above structure, the ratio (molar ratio) of H and 1,2-naphthoquinone diazide group in D is 50:50 to 1:99. The method of claim 1,
Positive type photosensitive resin composition for interlayer insulation films whose alkali-soluble resin containing the said (A) acryl-type repeating unit is alkali-soluble resin which has at least 1 sort (s) selected from the group which consists of an oxiranyl group and an oxetanyl group in a molecule | numerator. The method of claim 1,
(D-1) Positive type photosensitive resin composition for interlayer insulation films containing the crosslinking agent which has at least 1 sort (s) of group chosen from the group which consists of an oxiranyl group and an oxetanyl group in a molecule | numerator. The method of claim 6,
Alkali-soluble resin containing the said (A) acryl-type repeating unit is alkali-soluble resin which neither an oxiranyl group nor an oxetanyl group has in a molecule | numerator, and (D-1) an oxiranyl group and an oxetanyl group Positive type photosensitive resin composition for interlayer insulation films containing the crosslinking agent which has at least 1 group selected from the group which consists of in a molecule | numerator. The method of claim 1,
(D-2) Positive type photosensitive resin composition for interlayer insulation films containing at least 1 sort (s) of crosslinking agent chosen from melamines. The interlayer insulation film which uses the positive photosensitive resin composition for interlayer insulation films of any one of Claims 1-8. An organic EL display device comprising the interlayer insulating film according to claim 9. The liquid crystal display device provided with the interlayer insulation film of Claim 9.

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