JP2022190942A - Positive photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition which is excellent in sensitivity while maintaining insulation property, and is colorless transparent.SOLUTION: A positive photosensitive resin composition contains (A) a resin which is at least one resin selected from the group consisting of a polybenzoxazole precursor having a carboxylic acid terminal or a phthalic acid terminal, and a hydroxyl group and carboxyl group-containing polyimide, and has a YI value when formed in a single resin film with a thickness of 20 μm of 2 or less, (B) a photoacid generator which has a naphthalimide skeleton or an imino group, and has no absorption band at a wavelength of 400 nm or more, and (C) a silane compound having at least one group selected from the group consisting of a carboxylic acid group, an acid anhydride group, a sulfonic acid group and an acrylic acid group, in the molecule.SELECTED DRAWING: None

Description

The present invention relates to a positive photosensitive resin composition.

Light-emitting diode (hereinafter sometimes abbreviated as LED) display devices are self-luminous, do not require a backlight, and can be made lighter and thinner, and are used in various display devices. .

An LED display element generally has a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate. It has a structure in which a plurality of functional layers (a hole injection layer, a hole transport layer, an electron transport layer, etc.) including a light emitting layer are laminated between them. Since the LED display element is self-luminous as described above, there are top emission type that emits light from the opposite side of the substrate and bottom emission type that emits light from the substrate side using a transparent substrate or electrode. can be selected. In recent years, a top-bottom emission type that can emit light from both sides has been studied. In order to form a bottom emission type or top/bottom emission type LED display device as described above, in addition to forming the substrate and the electrodes from a transparent material, the insulating layer and the planarizing layer are also formed from a transparent material. It is considered necessary.

By the way, polybenzoxazole resins and polyimide resins, which are excellent in heat resistance, electrical properties, mechanical properties, etc., are used for insulating layers and planarizing layers of LED display devices. Since fine patterning is required for the formation of such insulating layers and planarizing layers, positive photosensitive resin compositions have been used in which polybenzoxazole resins and polyimide resins are combined with diazoquinone compounds as photosensitive agents. (For example, Patent Document 1).

Japanese Patent Publication No. 1-46862

In the positive photosensitive resin composition as described above, even if the resin, which is the main component, is made colorless and transparent, the diazoquinone compound, which is a photosensitive agent, has absorption in the visible light region, so that a colorless and transparent insulating layer and a flattening layer are formed. It is not possible to form a layer, and it is necessary to use a photosensitizer instead of the diazoquinone compound. Photoacid generators such as sulfonium salt compounds are known as such photosensitizers, but it is necessary to increase the amount added in order to maintain the same photosensitivity characteristics (resolution during patterning) as those of diazoquinone compounds. .

On the other hand, a photoacid generator such as a sulfonium salt compound generates active species of a strong acid compared to a diazoquinone compound. Therefore, when the content in the photosensitive resin composition increases, the insulating properties of the cured product tend to decrease. . Therefore, in fields where insulation is required, such as electronic parts such as LED display devices, there are restrictions on the content of photoacid generators such as sulfonium salt compounds.

Therefore, the main object of the present invention is to provide a photosensitive resin composition suitable for forming a colorless and transparent insulating layer, a planarizing layer, etc., which is excellent in sensitivity while maintaining the insulating properties of the cured product. be.

The present inventors maintained the photosensitivity of the photosensitive resin composition by propagating the generated acid to the deep part of the photosensitive resin composition even if the amount of acid generated from the photoacid generator during exposure is small. I realized that it might be possible. As a result of further investigation, it was found that by using a specific photo-acid generator and a specific silane compound together, even a photo-acid generator that generates a strong acid can be used without increasing its content. It is possible to maintain photosensitivity and insulation equivalent to those of a photosensitive resin composition using a diazoquinone compound of No. 1, and to realize colorless and transparent. The present invention has been completed based on such findings. The gist of the present invention is as follows.

［６］ [１]～[５]のいずれか一項に記載のポジ型感光性樹脂組成物からなるパターン硬化膜。
［７］ [６]に記載のパターン硬化膜を備えた電子部品。 [1] (A) At least one resin selected from the group consisting of a carboxylic acid-terminated or phthalic acid-terminated polybenzoxazole precursor, and a hydroxyl group- and carboxyl group-containing polyimide, having a thickness of 20 μm a resin having a YI value of 2 or less when used as a single resin film;
(B) a photoacid generator having a naphthalimide skeleton or an imino group and having no absorption band at a wavelength of 400 nm or more;
(C) a silane compound having in its molecule at least one group selected from the group consisting of a carboxylic acid group, an acid anhydride group, a sulfonic acid group, and an acrylic acid group;
A positive photosensitive resin composition comprising:
[2] The positive photosensitive resin composition according to [1], wherein the (B) photoacid generator is contained in a proportion of 0.1 to 15 parts by mass with respect to 100 parts by mass of the (A) resin. thing.
[3] The positive photosensitive composition according to [1] or [2], wherein the (C) silane compound is contained in a proportion of 0.1 to 5 parts by mass with respect to 100 parts by mass of the (A) resin. Resin composition.
[4] The positive photosensitive resin composition according to any one of [1] to [3], further comprising (D) a thermal base generator.
[5] The positive photosensitive resin according to any one of [1] to [4], wherein the (B) photoacid generator is at least one selected from compounds represented by the following formulas: Composition.

[6] A pattern cured film made of the positive photosensitive resin composition according to any one of [1] to [5].
[7] An electronic component comprising the patterned cured film according to [6].

According to the present invention, a specific resin having a YI value of 2 or less when the resin alone film having a thickness of 20 μm is combined with a photoacid generator having a specific structure that does not have an absorption band at a wavelength of 400 nm or more and a specific By using a silane compound together, it is possible to realize a colorless and transparent photosensitive resin composition which is excellent in sensitivity while maintaining insulating properties.

Modes for carrying out the invention

The positive photosensitive resin composition according to the present invention includes a specific resin having a YI value of 2 or less when the resin alone film having a thickness of 20 μm is formed, and (B) a specific resin having no absorption band at a wavelength of 400 nm or more. It contains a structured photoacid generator and a specific silane compound as essential components. Each component constituting the positive photosensitive resin composition according to the present invention will be described below.

<(A) Component>
The positive photosensitive resin composition according to the present invention comprises (A) a resin component, (A1) a carboxylic acid-terminated or phthalic acid-terminated polybenzoxazole precursor, and (A2) a hydroxyl- and carboxyl-containing polyimide. at least one resin selected from the group consisting of

The (A1) polybenzoxazole precursor that can be used in the present invention is a polybenzoxazole precursor having a YI value of 2 or less when formed into a 20 μm-thick resin-only film and having a carboxylic acid terminal or a phthalic acid terminal. If so, conventionally known polybenzoxazole precursors can be used without limitation. In the present invention, the terminal of the polybenzoxazole precursor is carboxylic acid or phthalic acid, thereby improving the solubility during development. Moreover, (A1) the terminal of the polybenzoxazole precursor is preferably phthalamic acid. (B) The acid generated by the photoacid generator causes dehydration ring closure of the phthalamic acid when the resin is placed in an acidic environment, thereby further improving the insulating properties of the positive photosensitive resin composition.

(A1) The polybenzoxazole precursor can be obtained by reacting a dihydroxydiamine as an amine component and a dicarboxylic acid component such as a dicarboxylic acid dichloride, a dicarboxylic acid, or a dicarboxylic acid ester as an acid component.

（式中、Ｘは４価の有機基を示し、Ｙは２価の有機基を示す。ｎは２以上の整数であり、好ましくは１０～２００、より好ましくは２０～７０である。） (A1) The polybenzoxazole precursor is preferably a polyhydroxyamide, preferably a polyhydroxyamide having a repeating structure represented by the following general formula (1).

(Wherein, X represents a tetravalent organic group, Y represents a divalent organic group, n is an integer of 2 or more, preferably 10 to 200, more preferably 20 to 70.)

(A1) When synthesizing the polybenzoxazole precursor by the above synthesis method, in the general formula (1), X is the residue of the dihydroxydiamines, and Y is the residue of the dicarboxylic acid component. be.

Examples of the dihydroxydiamines having the repeating structure include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis(3-amino-4-hydroxy phenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3 -amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3 ,3-hexafluoropropane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene and the like. Among these, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3, 3,3-hexafluoropropane is preferred.

Examples of the dicarboxylic acid component having the repeating structure include isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, and 2,6-naphthalenedicarboxylic acid. , 4,4′-dicarboxybiphenyl, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl) Dicarboxylic acids having aromatic rings such as propane, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, oxalic acid, malonic acid, succinic acid, 1,2 -cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid and other aliphatic dicarboxylic acids. Among these, 4,4'-dicarboxydiphenyl ether is preferable from the viewpoint of obtaining a polybenzoxazole precursor having a small YI value and excellent transparency.

In the general formula (1), the tetravalent organic group represented by X may be either an aliphatic group or an aromatic group, but is preferably an aromatic group, and two hydroxy groups and two amino groups are aromatic at the ortho positions. It is more preferably located on the ring. The tetravalent aromatic group preferably has 6 to 30 carbon atoms, more preferably 6 to 24 carbon atoms. Specific examples of the tetravalent aromatic group include, but are not limited to, the groups shown below, and a known aromatic group that can be contained in the polybenzoxazole precursor is selected depending on the application. can do.

Among the above aromatic groups, the tetravalent aromatic group is preferably a group shown below from the viewpoint of obtaining a polybenzoxazole precursor having a small YI value and excellent transparency.

（式中、Ａは単結合、－ＣＨ_２－、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ_２－、－ＮＨＣＯ－、－Ｃ（ＣＦ_３）_２－、－Ｃ（ＣＨ_３）_２－からなる群から選択される２価の基を表す。） In general formula (1), the divalent organic group represented by Y may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and is bonded to the carbonyl in general formula (1) on the aromatic ring. It is more preferable to have The number of carbon atoms in the divalent aromatic group is preferably 6-30, more preferably 6-24. Specific examples of the divalent aromatic group include, but are not limited to, the groups shown below, and a known aromatic group contained in the polybenzoxazole precursor may be selected depending on the application. Just do it.

(wherein A is a single bond, -CH ₂ -, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ represents a divalent group selected from the group consisting of -.)

Among the above aromatic groups, the divalent organic group is preferably a group shown below from the viewpoint of obtaining a polybenzoxazole precursor having a small YI value and excellent transparency.

(A1) The polybenzoxazole precursor may contain two or more of the above polyhydroxyamide repeating structures. In addition, (A1) the polybenzoxazole precursor may contain a structure other than the repeating structure of polyhydroxyamide described above, and may contain, for example, a repeating structure of polyamic acid or a benzoxazole structure.

(A1) The number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 1,000 to 100,000, more preferably 5,000 to 50,000. Here, the number average molecular weight is a numerical value measured by gel permeation chromatography (GPC) and converted with standard polystyrene. The weight average molecular weight (Mw) of (A) the polybenzoxazole precursor is preferably 5,000 to 200,000, more preferably 10,000 to 100,000. Here, the weight average molecular weight is a numerical value measured by GPC and converted with standard polystyrene. Mw/Mn is preferably 1-5, more preferably 1-3.

(A1) Polybenzoxazole precursors may be used singly or in combination of two or more.

Polyamide (A2) that can be used in the present invention has a YI value of 2 or less when made into a 20 μm-thick resin-only film and contains hydroxyl groups and carboxyl groups. can be used. (A2) Polyimide also preferably has a phthalamic acid terminal as described above. (B) The acid generated by the photoacid generator causes dehydration ring closure of the phthalamic acid when the resin is placed in an acidic environment, thereby further improving the insulating properties of the positive photosensitive resin composition.

(A2) Polyimide is a polyimide in which the imidization rate of polyamic acid, which is a polyimide precursor, is 50% or more, contains hydroxyl groups and carboxyl groups in the structure, and can exhibit solubility in an alkaline aqueous solution. . Here, showing solubility in an alkaline aqueous solution means that a polyimide dry film having a thickness of 5 μm is soluble in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) at 21 to 25° C. within 450 seconds. say.

As shown in Reaction Scheme 1 below, polyimide is produced by a polycondensation reaction between a tetracarboxylic dianhydride and a diamine compound to produce a polyimide precursor, and a dehydration ring closure reaction of this precursor to form a polyimide. can be obtained by In this case, by using a diamine compound containing a hydroxyl group or a diamine compound containing a carboxyl group as the diamine compound, hydroxyl groups and carboxyl groups can be introduced into the polyimide.

Y in the polyimide in Reaction Scheme 1 corresponds to Y in the tetracarboxylic dianhydride (tetracarboxylic dianhydride residue), and X in the polyimide corresponds to X in the diamine compound (diamine compound residue). corresponds to The description regarding the tetracarboxylic dianhydride and the diamine compound below also applies to Y (tetracarboxylic dianhydride residue) and X (diamine compound residue) in the polyimide.

The tetracarboxylic dianhydride is not particularly limited, and may be either an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. Aromatic tetracarboxylic dianhydride may have one aromatic ring in one molecule, may have two or more aromatic rings, may have a condensed aromatic ring .

Examples of tetracarboxylic dianhydrides having one aromatic ring in one molecule include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

Tetracarboxylic dianhydrides having two or more independent aromatic rings in one molecule include, for example, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3- dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis(3, 4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(2,3 -dicarboxyphenyl)ether dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 4,4' -oxydiphthalic dianhydride, 4,4-(p-phenylenedioxy)diphthalic dianhydride, 4,4-(m-phenylenedioxy)diphthalic dianhydride, 2,2',6,6' -biphenyltetracarboxylic dianhydride, ethylene glycol bis-anhydro-trimellitate, and the like.

Tetracarboxylic dianhydrides having a condensed aromatic ring in one molecule include 1,2,5,6-naphthalenedicarboxylic dianhydride, 1,4,5,8-naphthalenedicarboxylic dianhydride, 2, 3,6,7-naphthalenedicarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7 , 8-phenanthrenetetracarboxylic dianhydride and the like.

The aliphatic tetracarboxylic dianhydride may be an alicyclic tetracarboxylic dianhydride or a chain aliphatic tetracarboxylic dianhydride.

Examples of alicyclic tetracarboxylic dianhydrides include 3,3′,4,4′-bicyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4 -cyclobutanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tricyclo[6.4.0.0(2 ,7)]dodecane-1,8:2,7-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,1′-bicyclohexane-3,3′,4 , 4′-tetracarboxylic dianhydride and the like.

Examples of chain aliphatic tetracarboxylic dianhydrides include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, and the like. is mentioned.

As the tetracarboxylic dianhydride, a silicone-based tetracarboxylic dianhydride such as 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane Anhydride (4,4'-(hexafluoroisopropylidene)-diphthalic dianhydride), 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexa Fluoropropane dianhydride, 2,2'-bis(trifluoromethyl)-4,4',5,5'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluorotrimethylene)diphthalic acid dianhydride anhydride, 4,4′-(octafluorotetramethylene)diphthalic dianhydride, 2,2′-bis(trifluoromethyl)-4,4′,5,5′-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluorotrimethylene)diphthalic dianhydride, 4,4'-(octafluorotetramethylene)diphthalic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1 , 1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) A tetracarboxylic dianhydride containing a fluorine atom such as -1,1,1,3,3,3-hexafluoropropane dianhydride can also be used.

Tetracarboxylic dianhydride, when made into a photosensitive resin composition, has an excellent balance between the solubility of the exposed area in an alkaline aqueous solution and the solubility resistance of the unexposed area, so that two or more fragrances are independent in one molecule. It is preferable to use a tetracarboxylic acid dianhydride having a ring. Among them, a tetracarboxylic acid having an ether bond is used because it has excellent optical transparency, improves photosensitivity, and has excellent mechanical properties as a pattern film. More preferred is 4,4′-oxydiphthalic dianhydride. In addition, 4,4'-(hexafluorotrimethylene)diphthalic dianhydride is preferable from the viewpoint of obtaining a polyimide having a small YI value and excellent transparency.

The tetracarboxylic dianhydrides may be used alone or in combination of two or more.

The hydroxyl-containing diamine compound may have one hydroxyl group or two or more hydroxyl groups in one molecule. The diamine compound having a hydroxyl group may be an aromatic diamine compound or an aliphatic diamine compound. A diamine compound having a hydroxyl group may contain a fluorine atom in the molecule.

Diamine compounds containing one hydroxyl group in one molecule include 2,4-diaminophenol and the like.

Diamine compounds containing two hydroxyl groups in one molecule include 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3 '-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybenzophenone, 2,2-bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis( 3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 9,9 '-bis(3-amino-4-hydroxyphenyl)fluorene and the like.

A diamine compound containing a hydroxyl group imparts solubility in an alkaline aqueous solution to the polyimide, and when it is made into a photosensitive resin composition, an excellent dissolution inhibition effect can be obtained by combining it with a photoacid generator. It is preferable to use a diamine compound containing two hydroxyl groups in one molecule, more preferably a diamine containing a fluorine group, and further 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. preferable.

A diamine compound containing a hydroxyl group may be used alone or in combination of two or more.

A diamine compound containing a carboxyl group may have one carboxyl group or two or more carboxyl groups in one molecule. The diamine compound having a carboxyl group may be an aromatic diamine compound or an aliphatic diamine compound.

Diamine compounds containing a carboxyl group include diaminobenzoic acid such as 3,5-diaminobenzoic acid, 3,3'-diamino-4,4'-dicarboxybiphenyl, 4,4'-diamino-2,2' , 5,5′-tetracarboxybiphenyl and other carboxybiphenyl compounds, 4,4′-diamino-3,3′-dicarboxydiphenylmethane, 3,3′-diamino-4,4′-dicarboxydiphenylmethane and other carboxydiphenyl alkanes, carboxydiphenyl ether compounds such as 4,4'-diamino-2,2',5,5'-tetracarboxydiphenyl ether, diphenyl sulfone compounds such as 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, Bis(hydroxyphenoxy)biphenyl compounds such as 2,2-bis[4-(4-amino-3-carboxyphenyl)phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl ] and bis[(carboxyphenoxy)phenyl]sulfone compounds such as sulfone.

A diamine compound containing a carboxyl group has a small YI value, from the viewpoint of a polyimide having excellent transparency, and from the viewpoint of the storage stability of the polyimide, a diamine containing one carboxyl group in one molecule is preferred, aromatic diamines are more preferred, and 3,5-diaminobenzoic acid is even more preferred.

A diamine compound containing a carboxyl group may be used alone or in combination of two or more.

A diamine compound containing neither a hydroxyl group nor a carboxyl group (hereinafter also referred to as "another diamine compound") may be used. Other diamine compounds may be aromatic diamine compounds or aliphatic diamine compounds. In this case, the aromatic diamine compound may have one aromatic ring in one molecule, may have two or more independent aromatic rings in one molecule, or may have condensed aromatic rings in one molecule. may have

Other diamine compounds having one aromatic ring in one molecule include, for example, 1,4-phenylenediamine, 1,2-phenylenediamine and 1,3-phenylenediamine.

Other diamine compounds having two or more independent aromatic rings in one molecule include, for example, 4,4'-(biphenyl-2,5-diylbisoxy)bisaniline, 4,4'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis(4-(4-aminophenoxy)phenyl)sulfone, 2,2- bis(4-(4-aminophenoxy)phenyl)propane, bis(4-(3-aminophenoxy)phenyl)sulfone, 1,3-bis(4-aminophenoxy)neopentane, 4,4'-diamino-3, 3'-dimethylbiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl (3,3'-dimethylbenzidine), 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino diphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, N-(4-aminophenoxy)-4-aminobenzamine, bis(3-aminophenyl) sulfone, norbornanediamine and the like. be done.

Other diamine compounds having a condensed aromatic ring in one molecule include 4,4′-(9-fluorenylidene)dianiline, 2,7-diaminofluorene, 1,5-diaminonaphthalene, 3,7-diamino-2, 8-dimethyldibenzothiophene 5,5-dioxide and the like.

Other diamine compounds other than the above include silicone diamine compounds, 4-fluoro-1,2-phenylenediamine, 4-fluoro-1,3-phenylenediamine, 3-trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,2-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2,2′-bis(trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diamino-2-(trifluoromethyl)diphenyl ether, 4,4'-diamino-2,2'-(trifluoromethyl)biphenyl, 4,4'-diamino -2-methyl-2'-trifluoromethylbiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-{4-amino-2-(trifluoromethylbiphenyl), fluoromethyl)phenoxy}phenyl]hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2 , 2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis{4-(4-aminophenoxy)-3,5-dibromophenyl } diamine compounds containing fluorine atoms such as hexafluoropropane, and polyether diamines such as polyoxyethylene diamine and polyoxypropylene diamine.

When using another diamine compound, the other diamine compound is preferably a diamine containing an ether bond from the viewpoint of the mechanical properties of the pattern film.

When other diamine compounds are used, the other diamine compounds may be used alone or in combination of two or more.

From the viewpoint of good pattern film resolution and stress relaxation of the pattern film, the total amount of the diamine compound containing a hydroxyl group and the diamine compound containing a carboxyl group in 100 mol% of the diamine compound is 0.1 mol%. The above is preferable, 1 mol % or more is more preferable, and 10 mol % or more is still more preferable. The upper limit of the sum of the hydroxyl-containing diamine compound and the carboxyl-containing diamine compound is not particularly limited, and may be 100 mol %, for example, 90 mol % or less.

Polyimide avoids dissolution and expansion of unexposed areas by the developer and ensures good sensitivity of the exposed areas and excellent solubility in the developer. : number of moles of the carboxyl group) is preferably 100:0.5 to 100:60, more preferably 100:5 to 100:40.

The number average molecular weight (Mn) of polyimide is preferably 5,000 or more, more preferably 8,000 or more, and preferably 100,000 or less, more preferably 50,000 or less. In the present specification, the number average molecular weight is a numerical value measured by (GPC) and converted with standard polystyrene.

The weight average molecular weight (Mw) of polyimide is preferably 10,000 or more, more preferably 16,000 or more, and preferably 200,000 or less, more preferably 180,000 or less. In the present specification, the weight average molecular weight is a numerical value measured by (GPC) and converted with standard polystyrene. Mw/Mn is preferably 1 or more, preferably 15 or less, and more preferably 13 or less.

Polyimide may be used individually by 1 type, or may be used in combination of 2 or more type.

A polyimide can be produced by producing a polyimide precursor from a tetracarboxylic dianhydride and a diamine compound and then imidizing it. A polyimide may be produced directly from a tetracarboxylic dianhydride and a diamine compound. The reaction conditions are not particularly limited and can be set as appropriate.

<(B) Photoacid Generator>
The positive photosensitive resin composition according to the present invention uses, as a photoacid generator, a photoacid generator having a naphthalimide skeleton or an imino group and having no absorption band at a wavelength of 400 nm or more. In conventional positive photosensitive resin compositions containing polybenzoxazole precursors and polyimides as resin components, diazoquinone compounds such as naphthoquinonediazide were used to impart excellent photosensitivity, but they are all colored. Therefore, even if a transparent resin was used, coloring was unavoidable. In addition, if a photoacid generator that is a strong acid is used to maintain photosensitivity, the insulation properties of the photosensitive resin composition decrease due to the influence of the acid. It can be said. However, when the content of the photoacid generator is small, naturally the photosensitivity (resolution) is lowered. In the present invention, a transparent strong acid photoacid generator having no absorption band in the visible light region is used to improve the colorless transparency of the photosensitive resin composition, and the content of the photoacid generator is reduced to provide insulation. While maintaining the properties, the photosensitivity (resolution) is also maintained by using it together with (C) a silane compound described later. In the present invention, "having no absorption band at a wavelength of 400 nm or more" means that, as a 0.001% propylene glycol monomethyl ether acetate (PGMEA) solution, the absorbance at a wavelength of 400 nm with an optical path length of 1 cm is 0.01 or less. means that

As the photoacid generator which has a naphthalimide skeleton or an imino group and does not have an absorption band at a wavelength of 400 nm or more, conventionally known ones can be used without limitation. In particular, from the viewpoint of transparency and photosensitivity of the photosensitive resin composition, compounds represented by the following formulas can be preferably used.

(B) The photoacid generator is preferably contained in a proportion of 0.1 to 15 parts by mass, more preferably 0.3 to 12 parts by mass, relative to 100 parts by mass of the resin (A). preferable.

<(C) Silane compound>
The positive photosensitive resin composition according to the present invention includes (B) the photoacid generator and (C) a carboxylic acid group, an acid anhydride group, a sulfonic acid group, and an acrylic acid group in the molecule. Included are silane compounds having at least one group selected from the group. (B) The photoacid generator generates cations upon irradiation with light. For example, the two types of photoacid generators described above generate protons and sulfonium anions by light irradiation. The protons sequentially propagate the acid through the functional groups of the (C) silane compound as shown in the scheme below. As a result, since the acid can be propagated to the deep part, it is considered that the photosensitivity can be maintained even when the content of the photoacid generator (B) is small.

As the silane compound (C), any one having the above-described functional group can be used without any particular limitation. Examples of silane compounds having a carboxylic acid group include the following compounds. In the formula, Me represents a methyl group and Et represents an ethyl group.

Silane compounds having an acid anhydride group include silane compounds having a succinic anhydride group, such as trimethoxysilylpropyl succinic anhydride, triethoxysilylpropyl succinic anhydride, methyldimethoxysilylpropyl succinic anhydride, methyl and diethoxysilylpropyl succinic anhydride.

On the other hand, a silane compound having a sulfonic acid group is hydrolyzed due to the high acidity of the sulfonic acid group, and can be obtained using a silane compound having a functional group that can be chemically converted to a sulfonic acid group. Specific examples include a silane compound having a sulfonate ester group that can be converted to a sulfonic acid group by hydrolysis, and a silane compound having a mercapto group and/or a sulfide group that can be converted to a sulfonic acid group by oxidation. Silane compounds having a mercapto group include, for example, 3-mercaptopropyltrimethoxysilane, 2-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane and the like. Examples of silane compounds having a sulfide group include bis(3-triethoxysilylpropyl)disulfide.

Silane compounds having acrylic acid groups include methacryloyl groups such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. and silane compounds having an acryloyl group such as 3-acryloxypropyltrimethoxysilane.

The above silane compounds may be used singly or in combination of two or more.

Moreover, the inclusion of these silane compounds can also improve the adhesion between the substrate (TFT substrate, etc.) and the cured film when the positive photosensitive resin composition is used as a patterned cured film.

(C) The silane compound is preferably contained in a proportion of 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the resin (A). .

In the present invention, (C) the silane compound may be used in combination with the above-described silane compound having a functional group and a basic silane compound. The combined use of the silane compound having a functional group and the basic silane compound can further improve the insulating properties of the positive photosensitive resin composition.

Basic silane compounds include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene)propylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

<Other ingredients>
The positive photosensitive resin composition according to the present invention may contain other components in addition to the components (A) to (C) described above. For example, (D) a thermal base generator may be further included in order to cope with a lower heat curing temperature. In the present invention, the term "thermal base generator" refers to a compound that generates a base upon heating. By containing a thermal base generator, the imidization of the positive photosensitive resin composition of the present invention can be further promoted.

As the thermal base generator (D), any compound that generates a base by heating as described above can be used without particular limitation. undecene-7 (DBU) or salts thereof (e.g., phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); 1,5-diazabicyclo[4.3.0]nonene- 5(DBN) or a salt thereof (e.g., phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt, etc.); benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl) tertiary amines such as phenol and N,N-dimethylcyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphines; phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; organic metal salts such as zinc octylate and tin octylate; and metal chelates. Among these, tetraphenylborate salts of 1,8-diazabicyclo[5.4.0]undecene-7 derivatives are particularly preferred.

When a thermal base generator is used, (D) the thermal base generator is preferably contained in a proportion of 0.01 to 20 parts by mass, preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the resin (A). More preferably, it is contained in a proportion of parts by mass.

Moreover, the positive photosensitive resin composition according to the present invention may further contain (E) a cross-linking agent. A cross-linking agent is an agent that can be cross-linked or polymerized by heating. The cross-linking agent reacts with the polybenzoxazole precursor or polybenzoxazole in the process of heat treatment after coating, exposure, and development, or the cross-linking agent itself polymerizes to reduce the residual film rate of the unexposed area. In addition, it is possible to prevent the development residue in the exposed portion and improve the patterning property.

The cross-linking agent is preferably a compound having a methylol group, an alkoxymethyl group, an epoxy group, an oxetanyl group or a vinyl ether group, a compound in which these groups are bonded to a benzene ring, and a methylol group and an alkoxymethyl group at the N-position. Group-substituted melamine resins or urea resins are more preferred.

Examples of cross-linking agents include the following.

Among the above, a cross-linking agent having a melamine structure is preferable from the viewpoint of improving patterning properties and improving chemical resistance.

A crosslinking agent may be used individually by 1 type, or may be used in combination of 2 or more type.

When a cross-linking agent is used, (E) the cross-linking agent is preferably contained in a proportion of 0.5 to 50 parts by mass, preferably 1 to 20 parts by mass, relative to 100 parts by mass of the resin (A). is more preferable.

Moreover, the positive photosensitive resin composition according to the present invention may contain (F) a solvent. The solvent is not particularly limited as long as it dissolves the above components. For example, N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, Tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, diethylene glycol monomethyl ether and the like. γ-butyrolactone is preferred in terms of solubility and workability.

A solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

When a solvent is used, the amount of the solvent can be selected according to the coating thickness, viscosity, and the like.

The positive photosensitive resin composition may contain components other than the above as long as the effects of the present invention are not impaired. For example, it can contain t-butyl catechols, which can reduce development residue (scum). In addition, silane coupling agents other than (C), adhesion improvers other than (D), surfactants, leveling agents, plasticizers, fine particles (organic fine particles such as polystyrene and polytetrafluoroethylene, colloidal silica, carbon, Inorganic fine particles such as layered silicate), coloring agents, fibers and the like can be contained.

The viscosity of the positive photosensitive resin composition is preferably 20 mPa·s or more, more preferably 200 mPa·s or more, and preferably 50 Pa·s or less, more preferably 10 Pa·s or less. As used herein, the viscosity is a numerical value measured at 25° C. with a cone-plate viscometer.

The positive photosensitive resin composition of the present invention may be applied to a film and then dried to form a dry film. A dry film is used by laminating a resin layer so as to be in contact with a substrate. The coating method is not particularly limited, and can be carried out using a blade coater, lip coater, comma coater, film coater, or the like. The coating thickness can be selected according to the coating method, viscosity and the like.

The film (carrier film) to which the positive photosensitive resin composition is applied is not particularly limited, and thermoplastic films can be used, including polyester films such as polyethylene terephthalate and polyimide films.

<Cured film>
A cured product can be obtained by curing the positive photosensitive resin composition or the resin layer of the dry film. A pattern film made of a cured product can be produced as follows.

First, a coating film is obtained by applying a positive photosensitive resin composition onto a substrate and drying it, or by transferring a resin layer from a dry film onto the substrate. The method of applying the positive photosensitive resin composition onto the substrate is not particularly limited. and an ink jet method. The method for drying the coating film is not particularly limited, and includes air drying, heat drying using an oven or a hot plate, vacuum drying, and the like.

The base material is not particularly limited, but when used in an LED display device, it is preferably a TFT substrate in which thin film transistors are formed on a base material such as glass or polyimide.

The coating is then exposed directly or through a patterned photomask. The light used for exposure is a light having a wavelength capable of activating the (B) photoacid generator and generating an acid. . Sensitizers may be used to adjust photosensitivity. The exposure device is not particularly limited, and includes a contact aligner, mirror projection, stepper, laser direct exposure device and the like.

After exposure, the coating film may be heated to ring-close part of the polybenzoxazole precursor (A1) in the unexposed area or the unclosed ring (amic acid) part of the polyimide (A2). In this case, the ring closure rate is preferably about 30%, for example, 10% or more and 40% or less. The heating time and heating temperature can be appropriately selected depending on the types of (A1) the polybenzoxazole precursor and (B) the photoacid generator, the coating thickness, and the like.

The coating can then be treated with a developer to remove the exposed portions of the coating to form a patterned film (uncured). The developing method is not particularly limited, and a known photoresist developing method can be used, and examples thereof include a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment.

The developer is not particularly limited, and inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia; organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine; Examples include aqueous solutions of quaternary ammonium salts such as butylammonium hydroxide. A water-soluble organic solvent such as methanol, ethanol, or isopropyl alcohol, or a surfactant may be added.

After that, the pattern film (uncured) may be washed with a rinse liquid. The rinse liquid is not particularly limited, and includes distilled water, methanol, ethanol, isopropyl alcohol, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The pattern film (uncured) is cured by heating to obtain a pattern film composed of a cured product. By heating, (A1) the polybenzoxazole precursor is ring-closed and converted to polybenzoxazole, or (A2) the unclosed ring (amic acid) portion of the polyimide is ring-closed. The heating conditions can be conditions that allow ring closure of the (A1) polybenzoxazole precursor and (A2) the unclosed ring (amic acid) portion of the polyimide. Heating for 5 minutes or more and 120 minutes or less is mentioned. The heating temperature is preferably 200° C. or higher and 300° C. or lower. The heating device is not particularly limited, and includes a hot plate, an oven, and a heating oven in which a temperature program can be set. The atmosphere (gas) during heating may be air or an inert gas such as nitrogen or argon.

<Application>
Applications of the positive photosensitive resin composition according to the present invention are not particularly limited. layer.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples. In the following description, "parts" and "%" are based on mass unless otherwise specified.

(A) Preparation of Resin Component The following four types of resin were prepared.
(1) Polybenzoxazole precursor (PBO1)
65 g of N-methylpyrrolidone (NMP) was added to a 300 mL flask and heated to 60°C. 9.9777 g (0.02724 mol) of powdered 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (6-FAP) was added and completely Further, 10 g of NMP was added, the flask was immersed in an ice bath, and the mixture was stirred until the temperature of the liquid became 10° C. or less.Next, powdery 4,4′-diphenyletherdicarboxylic acid chloride (DEDC) was A total of 8.80 g (0.02982 mol) was added in 1 g increments while maintaining the temperature of the liquid at 20° C. or less.After stirring was continued at room temperature for 6 hours, 0.32 g of ion-exchanged water was added, and the temperature was raised to 50° C. The mixture was stirred for 30 minutes while maintaining the temperature at 50° C. 141 g of methanol was added, and stirring was continued until the mixture became homogeneous. The precipitated solid was filtered using a filter cloth, and the recovered solid was added all at once to an 800 mL beaker containing 282 g of ion-exchanged water, stirred at room temperature for 30 minutes, and filtered to recover the solid. The entire amount of the obtained solid was added to a 300 mL beaker, and 206 g of propylene glycol 1-monomethyl ether (1-methoxy-propanol (PGM)) as a good solvent was added and stirred until completely dissolved.
The resulting solution was added to an 800 mL beaker containing 302 g of deionized water as a poor solvent and 0.0605 g of oxalic acid as an organic acid over 2 hours. The pH of the liquid in the beaker was below 3 before the addition of the solution.
After the addition, 0.183 g of oxalic acid was further added to the 800 mL beaker and allowed to stand for one day. The solid collected by filtration was dried under reduced pressure at 80° C. to obtain 16.5 g of polybenzoxazole precursor 1 (PBO1). The polystyrene equivalent molecular weight by GPC was Mn: 12,600 and Mw: 30,300.

(2) Polybenzoxazole precursor (PBO2)
65 g of NMP was added to a 300 mL flask and heated to 60°C. 10.931 g (0.02982 mol) of powdered 6-FAP was added and completely dissolved. Further, 10 g of NMP was added, the flask was immersed in an ice bath, and the liquid was stirred until the temperature became 10 ° C. or less. A total of 8.039 g (0.02724 mol) of powdered DEDC was added in 1 g increments while maintaining the temperature of the liquid at 20° C. or lower, and stirring was continued at room temperature for 6 hours. 0.8406 g (5.675 mmol) of acid was added, the temperature was raised to 50° C., and the temperature was maintained at 50° C. and stirred for 30 minutes.
After that, it was purified in the same manner as PBO1 to obtain 17.5 g of polybenzoxazole precursor 2 (PBO2). The polystyrene equivalent molecular weight by GPC was Mn: 12,200 and Mw: 31,000.

(3) Polyimide (PI1)
A 1000 mL three-necked flask equipped with a heater, a reflux vessel equipped with a triangular tube, a thermometer, and a stirrer was charged with 30 ethylene glycol bisanhydro trimellitate (Rikacid TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.). .19 g (0.0758 mol), 22.82 g (0.0758 mol) of 4,4′-oxydiphthalic dianhydride (ODPA), and 3.58 g (0.02357 mol) of 3,5-diaminobenzoic acid (DABz) , 34.52 g (0.0943 mol) of 6-FAP, 13.3 g (0.03032 mol) of polyoxypropylene diamine (manufactured by BASF, Baxxodur EC302), and 270 mL of γ-butyrolactone were added and stirred for 2 hours, and pyridine was added to the reaction solution. 7.27 g and 20 g of toluene were added. After stirring for 15 minutes under a nitrogen atmosphere, the heater temperature was set to 220° C. and stirring was continued for 10 minutes to confirm complete dissolution of the solid. Toluene, pyridine and water were then removed while stirring for 24 hours. Heating was stopped to obtain 90 g of alkali-soluble polyimide (PI1). Polystyrene equivalent molecular weights measured by GPC were Mn=12,000 and Mw=150,000.

(4) Polybenzoxazole precursor (PBO3)
17.5 g of polybenzoxazole precursor 3 (PBO3) was obtained in the same manner as PBO2, except that the terminal blocker was changed to 0.931 g (5.676 mmol) of 5-norbornene-2,3-dicarboxylic anhydride. Obtained. The polystyrene equivalent molecular weight by GPC was Mn: 12,200 and Mw: 31,000.

(B) Preparation of photoacid generator The following three kinds of photoacid generators were prepared.
(1) NIT (manufactured by Heraeus, compound of the following formula)

(2) PA-528 (manufactured by Heraeus, compound of the following formula)

(3) ILP-110 (manufactured by Heraeus, compound of the following formula)

(C) Preparation of Silane Compounds The following four types of silane compounds were prepared.
(1) SIT8192.6 (gelest) (manufactured by Azumax, compound of the following formula)

(2) SIT8189.8 (gelest) (manufactured by Azumax, compound of the following formula)

(3) SIT8378.3 (gelest) (manufactured by Azumax, compound of the following formula)

(4) SIP6723.7 (gelest) (manufactured by Azumax, compound of the following formula)

(D) Preparation of thermal base generator A tetraphenylborate salt of 1,8-diazabicyclo[5.4.0]undecene-7 derivative (U-CAT 5002, manufactured by San-Apro) was used.

<Preparation of positive photosensitive resin composition>
Each resin composition was prepared by mixing each component with a solvent (γ-butyrolactone) according to the composition shown in Table 1 below. The amount of the solvent was adjusted so that the solvent was 185 parts per 100 parts of the (A) resin.

<Evaluation of YI>
Each composition obtained as described above was applied to a glass substrate (AN-100) by spin coating, and then dried by heating on a hot plate at 100° C. for 5 minutes. Then, it was heated at 150° C. for 30 minutes and 230° C. for 60 minutes in an inert gas oven (oxygen concentration of 20 ppm or less) to obtain a cured film of 20 μm. The YI value of the obtained cured film was measured using a color difference meter. The evaluation criteria were as follows.
◎◎: 1 or less ◎: More than 1 to 2 or less ○: More than 2 to 3 or less ×: More than 3 The evaluation results were as shown in Table 1 below.

<Evaluation of Adhesion>
Each composition was applied to a glass substrate (AN-100) by spin coating, and then dried by heating on a hot plate at 100° C. for 5 minutes. Then, it was heated at 150° C. for 30 minutes and 230° C. for 60 minutes in an inert gas oven (oxygen concentration of 20 ppm or less) to obtain a cured film of 25 μm. The cured film was cut with a cutter knife to form 100 squares of 1 mm×1 mm. Using a high temperature and high humidity apparatus, it was allowed to stand at 120° C. and 100% relative humidity for 50 hours. A cellophane tape was pressed against the surface of the sample and peeled off at an angle of 90° to count the squares of the sample remaining on the substrate. The evaluation criteria were as follows.
A: 100 B: 90 or more and 99 or less C: Less than 90 The evaluation results were as shown in Table 1 below.

<Evaluation of sensitivity>
Each composition was applied to a glass substrate (AN-100) by spin coating and then dried by heating on a hot plate at 100° C. for 5 minutes to obtain a dry film of 10 μm.
A variable transmittance mask of 0% to 100% was placed on the dry film, and the cured film was irradiated with 1500 mJ/cm ² of i-line through the mask. Subsequently, it was developed with a 2.38% TMAH aqueous solution for 80 seconds to obtain a pattern film. The transmittance at which the substrate was developed was visually confirmed, and the minimum value was taken as the sensitivity. The evaluation criteria were as follows.
⊚: 200 mJ/cm ² or less ○: More than 200 J/cm ² and 1500 mJ/cm ² or less ×: More than 1500 mJ/cm ² XX: Undevelopable The evaluation results were as shown in Table 1 below.

<Evaluation of insulation>
(1) Production of Evaluation Substrate Photoresist (P-W1000T manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated on a silicon wafer carrying seed metals (Ti 50 nm, Cu 150 nm) by magnetron sputtering, and L/S = 5 µm/5 µm by exposure and development. The comb-tooth wiring was patterned. Wiring having a height of about 5 μm was formed by plating. After removing the photoresist, the seed metal was removed using an etchant (WLC-C2, WLC-T, manufactured by Mitsubishi Gas Chemical Co., Ltd.) to obtain an evaluation substrate.
(2) Production of Evaluation Sample Each composition was applied by spin coating onto the evaluation substrate obtained as described above, and cured at 220° C. for 1 hour to obtain a cured film laminate. Then, the electrode portion was opened by exposure and development to expose the copper interface. After that, electroless nickel-gold plating was performed to prepare a sample for evaluation.
(3) Evaluation method A banana plug was soldered onto the gold plating of the evaluation sample, and a highly accelerated life test device (HAST device: PC-304R9 manufactured by Hirayama Seisakusho) was used to test the test voltage at 60°C and 5V at 90% relative humidity. was applied, and the time during which the resistance value was 10 ⁷ Ω or more was measured. The insulation evaluation criteria were as follows.
A: 500 hours or more B: 300 hours or more and less than 500 hours C: Less than 300 hours The evaluation results were as shown in Table 1 below.

Claims (7)

(A) at least one resin selected from the group consisting of a carboxylic acid-terminated or phthalic acid-terminated polybenzoxazole precursor, and a hydroxyl group- and carboxyl group-containing polyimide, the resin alone having a thickness of 20 μm a resin having a YI value of 2 or less when formed into a film;
(B) a photoacid generator having a naphthalimide skeleton or an imino group and having no absorption band at a wavelength of 400 nm or more;
(C) a silane compound having in its molecule at least one group selected from the group consisting of a carboxylic acid group, an acid anhydride group, a sulfonic acid group, and an acrylic acid group;
A positive photosensitive resin composition comprising: 2. The positive photosensitive resin composition according to claim 1, wherein the photoacid generator (B) is contained in a proportion of 0.1 to 15 parts by mass with respect to 100 parts by mass of the resin (A). 3. The positive photosensitive resin composition according to claim 1, wherein the (C) silane compound is contained in a proportion of 0.1 to 5 parts by mass with respect to 100 parts by mass of the (A) resin. 4. The positive photosensitive resin composition according to any one of claims 1 to 3, further comprising (D) a thermal base generator. The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the (B) photoacid generator is at least one selected from compounds represented by the following formulae.

A pattern cured film comprising the positive photosensitive resin composition according to any one of claims 1 to 5. An electronic component comprising the patterned cured film according to claim 6 .