KR101882722B1 - Positive working photosensitive resin composition - Google Patents

Abstract

Thereby providing a positive-working photosensitive resin composition excellent in various performances. And a radiation-sensitive acid generator. 2. The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is an alkali-soluble resin.

Description

[0001] POSITIVE WORKING PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition, a method of forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device. More particularly, the present invention relates to a planarizing film for electronic components such as a liquid crystal display, an organic EL display, an integrated circuit element, and a solid-state imaging element, a positive photosensitive resin composition suitable for forming a protective film or an interlayer insulating film, and a method for forming a cured film using the same. will be.

In an electronic component such as a thin film transistor (hereinafter referred to as " TFT ") type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state image pickup element, an interlayer insulating film is generally formed to insulate wirings arranged in layers have. As a material for forming the interlayer insulating film, a photosensitive resin composition is widely used because it is preferable that the number of steps for obtaining a required pattern shape is small and sufficient flatness is required (Japanese Patent Laid-Open Publication No. 2001-354822 and Japanese Patent Laid- 343743).

Among the above electronic components, for example, a TFT type liquid crystal display element is manufactured by forming a transparent electrode film on the interlayer insulating film and forming a liquid crystal alignment film thereon. Therefore, in the process of forming the transparent electrode film, Or left in the stripping solution of the resist used for forming the pattern of the electrode, so that sufficient resistance to these is required.

On the other hand, as a highly sensitive photosensitive resin composition, an acrylic resist or an alicyclic olefin-based resist is known (JP-A-2010-181730, JP-A-2009-235414). Further, JP-A-2002-40649 is known as a negative-working photosensitive resin composition.

In recent years, TFT-type liquid crystal display devices are in the trend of large-screen, high-brightness, high-definition, high-speed response, thinning, and the composition for forming an interlayer insulating film used therein has high sensitivity. High performance is demanded in the high transmittance and the like.

As described above, when forming the interlayer insulating film from a photosensitive resin composition, a high sensitivity is required for the composition, and an interlayer insulating film formed from the interlayer insulating film is required to have various excellent performances such as low dielectric constant and high transmittance. No satisfactory photosensitive resin composition has heretofore been known.

The present invention has been made in view of the above circumstances. Accordingly, an object of the present invention is to provide a photosensitive resin composition which can obtain a cured film excellent in various performances and which is excellent in sensitivity, a cured film obtained by curing the photosensitive resin composition, a method of forming the same, and an organic EL display apparatus having the cured film And a liquid crystal display device.

Under such circumstances, the inventors of the present invention have conducted intensive studies and found that a positive-working photosensitive resin composition excellent in various performances can be provided by using an alkali-soluble resin containing a specific constituent unit as a resin component, thereby completing the present invention .

More specifically, the above-mentioned problem is solved by the following means <1>, preferably by <2> to <26>.

<1> A positive photosensitive resin composition comprising (A) an alkali-soluble resin containing a structural unit represented by the general formula (1) and (C) a radiation-sensitive acid generator.

In general formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 9 carbon atoms)

<2> The positive photosensitive resin composition according to <1>, which further satisfies the following (1) and / or (2).

(1) The alkali-soluble resin containing the structural unit represented by the general formula (1) (A) has an acid labile group.

(2) The positive photosensitive resin composition includes (B) a resin having an acid labile group.

&Lt; 3 > The positive photosensitive resin composition according to < 2 >, wherein the alkali-soluble resin containing an acid labile group is a resin containing an acid group and a crosslinking group.

(4) The positive photosensitive resin composition according to any one of (1) to (3), wherein the (C) radiation-sensitive acid generator is an oxime sulfonate compound.

<5> The positive resist composition according to any one of <2> to <4>, wherein the alkali-soluble resin containing an acid labile group is a positive resin which is an acid labile group which is an acid-labile group which generates a carboxyl group or a phenolic hydroxyl group Type photosensitive resin composition.

<6> The resin composition according to any one of <2> to <5>, wherein the alkali-soluble resin containing an acid labile group includes an acid labile group which is an acid- Wherein the positive photosensitive resin composition is a positive photosensitive resin composition.

<7> The positive photosensitive resin composition according to any one of <2> to <6>, wherein the alkali-soluble resin containing an acid labile group comprises at least one of the constituent units shown below.

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, R ² represents an alkyl group having 1 to 4 carbon atoms, N3 is an integer of 1 to 4, and n4 is an integer of 1 to 3,

<8> The positive resist composition according to any one of <2> to <7>, wherein the alkali-soluble resin containing an acid labile group includes a structural unit represented by the following general formula (2) or (3) A positive photosensitive resin composition.

<9> The positive photosensitive resin composition according to <8>, wherein the alkali-soluble resin containing an acid labile group includes a structural unit represented by the general formula (2).

<10> The positive photosensitive resin composition according to any one of <2> to <9>, wherein the alkali-soluble resin containing an acid labile group is a resin comprising a crosslinking group containing an oxetane group and / Composition.

<11> The positive resist composition according to any one of <2> to <10>, which further comprises (A) an alkali-soluble resin containing a constituent unit represented by formula (1) By weight based on the total weight of the positive photosensitive resin composition.

<12> The resin composition according to <11>, wherein the alkali-soluble resin (B) containing an acid labile group is (a) an unsaturated carboxylic acid, (b) a radically polymerizable compound containing an oxetane or an epoxy group, and (c) And a radically polymerizable compound containing a group represented by the following formula

<13> The resin composition according to <11>, wherein the alkali-soluble resin (B) containing an acid labile group contains (a) an unsaturated carboxylic acid, (b) a radically polymerizable compound containing an oxetane group, and (c) And a radical polymerizable compound.

<14> A positive photosensitive resin composition according to any one of <1> to <13>, wherein the alkali-soluble resin (A) comprises a structural unit further comprising an acid group.

<15> A positive photosensitive resin composition according to any one of <1> to <14>, wherein the alkali-soluble resin (A) further comprises a structural unit derived from styrene.

<16> The resin composition according to any one of <2> to <15>, wherein the main component of the solid component is a resin component, and the resin component further comprises (A) an alkali-soluble resin containing a structural unit represented by the general formula (1) B) an alkali-soluble resin containing an acid labile group, and (C) a radiation-sensitive acid generator in an amount of 0.1 to 10% based on the total solid content.

<17> A positive photosensitive resin composition according to any one of <1> to <16>, further comprising (D) a crosslinking agent.

(17) The positive resist composition as described in any one of (17) to (17), wherein the main component of the solid component is a resin component, and the resin component further comprises (A) an alkali-soluble resin containing a structural unit represented by the general formula (C) a radiation-sensitive acid generator in an amount of 0.1 to 10% based on the total solid content, and (D) a crosslinking agent in a range of 1 to 40% based on the total solid content.

<19> The positive photosensitive resin composition according to any one of <2> to <18>, wherein the alkali-soluble resin (B) comprises an acid labile group in a proportion of 10 to 97% by weight of the total resin component.

<20> The resin composition according to any one of <2> to <18>, further comprising (B) a resin (B ') other than the alkali-soluble resin containing an acid labile group, By weight based on the total weight of the positive photosensitive resin composition.

<21> A cured film obtained by applying the positive photosensitive resin composition described in any one of <1> to <20> on a substrate and curing the composition by light and / or heat.

<22> A cured film formed by applying the positive-working photosensitive resin composition described in any one of <1> to <20> on a substrate, exposing it to light without exposure to heat, and further heating it.

<23> An interlayer insulating film using the cured film according to <21> or <22>.

<24> A liquid crystal display device or an organic EL display device comprising the interlayer insulating film according to <23>.

<25>

(1) a step of applying the photosensitive resin composition described in any one of < 1 > to < 20 >

(2) a step of removing the solvent from the applied photosensitive resin composition,

(3) a step of exposing with active radiation,

(4) a step of developing with an aqueous developer, and

(5) A method of forming a cured film including a step of thermally curing.

<26> The method of forming a cured film according to <25>, which comprises a step of performing front exposure before a step of thermal curing after the developing step.

(Effects of the Invention)

According to the present invention, a positive-working photosensitive resin composition excellent in various performances can be obtained.

Fig. 1 shows a configuration diagram of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.
2 is a conceptual diagram showing an example of the configuration of a liquid crystal display device. Sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, &quot; ~ &quot; is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

The organic EL device in the present invention refers to an organic electroluminescence device.

Further, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

In the present invention, the term &quot; alkali solubility &quot; means that a solution of the compound (resin) is applied on a substrate and the film (thickness: 3 mu m) of the compound (resin) formed by heating at 90 DEG C for 2 minutes Means that the dissolution rate in 0.4% tetramethylammonium hydroxide aqueous solution is 0.01 占 퐉 / second or more. "Alkali insoluble" means that a compound (resin) solution is applied onto a substrate and heated at 90 占 폚 for 2 minutes to form a compound (Resin) film (thickness 3 占 퐉) at a temperature of 23 占 폚 in a 0.4% tetramethylammonium hydroxide aqueous solution is less than 0.01 占 퐉 / second.

The positive photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin containing a structural unit represented by the general formula (1) and (C) a radiation-sensitive acid generator. By such a constitution, various performances of the positive photosensitive resin composition can be dramatically improved.

In general formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 9 carbon atoms)

The resin used in the present invention is characterized by containing a constituent unit represented by the general formula (1), but it is preferable that the resin has an acid labile group. The acid labile group may be contained in the alkali-soluble resin containing the constituent unit represented by the general formula (1), or may be contained in an alkali-soluble resin different from the above-mentioned alkali-soluble resin. Further, it is more preferable to have an acid group and / or a crosslinkable group. It may contain other constitutional units. In the present invention, these groups or constitutional units may be contained in only one kind of resin or may be contained in one kind or two or more kinds of two kinds or more kinds of resins. Hereinafter, embodiments of the resin used in the present invention will be described. However, it goes without saying that the resin used in the present invention is not limited to these.

(Embodiment 1)

(A) A form in which an alkali-soluble resin containing a constituent unit represented by the general formula (1) (hereinafter sometimes referred to as "(A) resin") further comprises an acid labile group.

(Embodiment 2)

(A) A form in which the resin further comprises an acid labile group and a crosslinking group.

(Embodiment 3)

(A) A form in which the resin further comprises an acid labile group and an acid group.

(Fourth Embodiment)

(A) A form in which the resin further comprises an acid labile group, a crosslinking group and an acid group.

(Embodiment 5)

In any one of Embodiments 1 to 4, the resin (A) further comprises another structural unit.

(Embodiment 6)

(A) an alkali-soluble resin containing a structural unit represented by the general formula (1); and a form in which the resin other than the resin (A) contains an acid labile group. In this case, the resin containing an acid labile group may be referred to as &quot; (B) resin &quot; hereinafter.

(Seventh Embodiment)

(A) a resin and (B) a resin, and (B) the resin comprises an acid labile group and a crosslinking group.

(Embodiment 8)

(A) a resin and (B) a resin, and (B) the resin comprises an acid labile group and an acid group.

(Embodiment 9)

(A) a resin and (B) a resin, and (B) the resin comprises an acid labile group, a crosslinkable group and an acid group.

(Embodiment 10)

In any one of Embodiments 6 to 9, (A) the resin further comprises an acid group.

(Embodiment 11)

In any one of Embodiments 6 to 10, the resin (A) or the resin (B) further comprises another structural unit.

(Embodiment 12)

In the eleventh embodiment, the resin (A) comprises a structural unit derived from styrene, and the resin (B) comprises a structural unit derived from (meth) acrylic acid.

In the above embodiment, each of the resin (A) and the resin (B) may be one kind or two or more kinds.

The structural unit represented by the general formula (1)

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. R ² represents an alkyl group having 1 to 9 carbon atoms, preferably an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 2 to 6 carbon atoms. The alkyl group may be either a linear or branched alkyl group.

The constituent unit represented by the general formula (1) is preferably contained in a proportion of 1 to 50 mol% of the resin (A), more preferably in a proportion of 10 to 40 mol%, more preferably 30 mol% desirable.

Mountain instability

The resin of the present invention preferably contains an acid labile group. By including an acid labile group, the alkali solubility can be increased. The acid labile group contained in the present invention means a functional group capable of decomposing in the presence of an acid, preferably an acid-dissociable group which generates a carboxyl group or a phenolic hydroxyl group by the action of an acid.

More specifically, it is preferable that the resin used in the present invention contains a constituent unit derived from a monomer containing an acid labile group. Such a constituent unit is usually formed by using a constituent unit derived from a monomer having an acid-dissociable group which generates a carboxyl group or a phenolic hydroxyl group by the action of an acid.

(a1-1) a structural unit derived from a monomer having an acid-dissociable group which generates a carboxyl group by the action of an acid

(a1-1-1) a structural unit derived from a monomer having a carboxyl group

Examples of the monomer having a carboxyl group include monomers derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid.

As the unsaturated carboxylic acid to be used for obtaining a constituent unit derived from a monomer having a carboxyl group, those listed below are used. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid used for obtaining a constituent unit derived from a monomer having a carboxyl group may be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polycarboxylic acid, for example, mono (2-acryloyloxyethyl) succinate, mono Mono (2-acryloyloxyethyl) phthalate mono (2-methacryloyloxyethyl), and the like.

The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have.

Examples of the unsaturated carboxylic acid include acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene. Among them, from the viewpoint of developability, it is preferable to use acrylic acid, methacrylic acid or anhydride of unsaturated polycarboxylic acid in order to form a constituent unit derived from a monomer having a carboxyl group, and it is more preferable to use acrylic acid or methacrylic acid desirable.

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

(a1-1-2) a structural unit derived from a monomer having both an ethylenic unsaturated group and an acid anhydride residue

The constituent unit (a1-2) derived from a monomer having both an ethylenic unsaturated group and an acid anhydride moiety is a unit derived from a monomer obtained by reacting a hydroxyl group and an acid anhydride in a constituent unit derived from a monomer having an ethylenic unsaturated group .

As the acid anhydride, known ones can be used, and specific examples include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and anhydrous chloridic acid; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. Of these, phthalic anhydride, tetrahydrophthalic anhydride or succinic anhydride are preferable from the viewpoint of developability.

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

(a1-1-3) a structural unit derived from a monomer having an acid-dissociable group which generates a carboxyl group by the action of an acid

The constituent unit derived from a monomer having an acid-dissociable group which generates a carboxyl group by the action of an acid is preferably a constituent unit described in the above (a1-1-1) and the above-mentioned (a1-1-2) Is a structural unit derived from a monomer having a moiety protected by an acid-decomposable group.

As the acid-decomposable group, a known acid-decomposable group in the positive resist for KrF and the positive resist for ArF can be used, and there is no particular limitation. Conventional acid-decomposable groups include groups which are relatively easily decomposed by an acid (e.g., acetal-based functional groups such as tetrahydropyranyl groups) or groups which are relatively difficult to decompose by an acid (e.g., tert- Butyl-based functional groups such as butyl carbonate groups) are known.

Among these acid-decomposable groups, a carboxyl group is a structural unit derived from a monomer having a residue protected by acetal or a carboxyl group having a residue protected by a ketal, and the basic physical properties of the resist, particularly the sensitivity and pattern shape, From the viewpoint of storage stability of the resin composition. Among the acid-decomposable groups, from the viewpoint of sensitivity, it is more preferable that the carboxyl group is a residue protected by an acetal or ketal represented by the following formula (a1-1). When the carboxyl group is a residue protected by an acetal or a ketal represented by the following formula (a1-1), the moiety has a structure of - (C═O) -O-CR ¹ R ² (OR ³ ) as a whole .

(Formula (a1-1) of R ¹ and R ² represents a hydrogen atom or an alkyl group, each independently, except for the stage R ¹ and R ² together are a hydrogen atom. R ³ represents an alkyl group. R ^1, or R ² and R ³ may be connected to form a cyclic ether)

In formula (a1-1), R ¹ to R ³ each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be any of linear, branched and cyclic. Wherein both of R ¹ and R ² do not represent a hydrogen atom, and R ¹ and R ² At least one of them represents an alkyl group.

When R ¹ , R ² and R ³ in the formula (a1-1) represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

The straight chain or branched chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec- Butyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobonyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When R ¹ , R ² , and R ³ have a haloalkyl group as a substituent, R ¹ , R ² , and R ³ have an aralkyl group when they have an aryl group as a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group, an alpha -methylphenyl group, a naphthyl group, etc., Examples of the alkyl group as a whole, that is, an aralkyl group include benzyl group,? -Methylbenzyl group, phenethyl group, naphthylmethyl group and the like.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or ethoxy group.

When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent. When the alkyl group is a straight chain or branched chain alkyl group, the cycloalkyl group may have 3 to 12 carbon atoms And may have a cycloalkyl group. These substituents may be further substituted by the above substituents.

When R ¹ , R ² and R ³ in the formula (a1-1) represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms may be preferably exemplified. As the aryl group, for example, a phenyl group, a tolyl group, a silyl group, a cumenyl group, a 1-naphthyl group and the like can be mentioned.

Further, R ¹ , R ² and R ³ may combine with each other to form a ring by combining with the carbon atoms to which they are bonded. Examples of the ring structure in the case where R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, And examples thereof include a t-butyl group and a tetrahydropyranyl group.

In formula (a1-1), it is preferable that either R ¹ or R ² is a hydrogen atom or a methyl group.

The radically polymerizable monomer used for forming the structural unit derived from the monomer having a moiety represented by the formula (a1-1) may be commercially available or synthesized by a known method. For example, it can be synthesized by reacting (meth) acrylic acid with vinyl ether in the presence of an acid catalyst as shown below.

R ¹¹ represents a hydrogen atom or an alkyl group, and the alkyl group is the same as the alkyl group represented by R ¹ to R ³ in formula (a1-1). As R ^{11, a} hydrogen atom or a methyl group is preferable.

R ¹² and R ¹³ is ^{-CH (R 12) (R 13} ) R ² is as a synonym in the formula (a1-1), R ¹⁴ is R ¹ and consent of the formula (a), R ¹⁵ Is the same as R &lt; ³ &gt; in the formula (a1-1), and the preferable ranges thereof are also the same.

The above-mentioned synthesis may be carried out by previously copolymerizing (meth) acrylic acid with other monomers and then reacting with vinyl ether in the presence of an acid catalyst.

Examples of the structural unit containing an acid-dissociable group which generates a carboxyl group by the action of an acid used in the present invention include the following ones.

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, R ² represents an alkyl group having 1 to 4 carbon atoms, N3 is an integer of 1 to 4, and n4 is an integer of 1 to 3,

R ¹ each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

L ¹ represents a carbonyl group or a phenylene group, and a carbonyl group is more preferable. R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

n1, n2, n3 and n4 are each preferably 0.

Among them, particularly (1), (2), (5) or (7) is preferable, (2) or (7) is more preferable and (7) is particularly preferable.

Preferable specific examples of the structural unit (a1-1) derived from a monomer having an acid-dissociable group which generates a carboxyl group by the action of an acid include structural units derived from the following monomers. R represents a hydrogen atom or a methyl group, and a methyl group is more preferable.

In the present invention, it is particularly preferable that the alkali-soluble resin containing an acid labile group contains a structural unit represented by the following general formula (2) or (3).

(a1-2) a structural unit derived from a monomer having an acid-dissociable group which generates a phenolic hydroxyl group by the action of an acid

(a1-2-1) a structural unit derived from a monomer having a phenolic hydroxyl group

Examples of the structural unit derived from a monomer having a phenolic hydroxyl group include a structural unit derived from a hydroxystyrene monomer and a structural unit derived from a monomer in a novolac resin. Among these structural units,? -Methylhydroxystyrene Is preferred from the viewpoint of transparency. Among the constituent units derived from the monomer having a phenolic hydroxyl group, a constituent unit derived from a monomer represented by the formula (a1-2) is preferable from the viewpoints of transparency and sensitivity.

(Wherein R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents a single bond or a linking group, R ²² represents a halogen atom or an alkyl group, a represents an integer of 1 to 5, b represents And a + b is not more than 5. When two or more R ²² are present, these R ²² may be the same or different and may be the same.)

In the formula (a1-2), R ²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.

R ²¹ represents a single bond or a divalent linking group. In the case of a single bond, it is preferable since the sensitivity can be improved and the transparency of the cured film can be improved. Examples of the divalent linking group of R ²¹ include an alkylene group and specific examples of R ²¹ is an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, Pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among them, R ²¹ is preferably a single bond, a methylene group or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

Although a represents an integer of 1 to 5, a is preferably 1 or 2, and more preferably a is 1, from the viewpoint of the effects of the present invention and ease of production.

It is preferable that the bonding position of the hydroxyl group in the benzene ring is bonded to the 4-position when the carbon atom bonded to R ²¹ is the reference (1-position).

R ²² is a halogen atom or a straight or branched alkyl group having 1 to 5 carbon atoms. Specific examples include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- butyl group, a pentyl group, an isopentyl group and a neopentyl group . Among them, chlorine atom, bromine atom, methyl group or ethyl group is preferable from the viewpoint of easy production.

B represents 0 or an integer of 1 to 4;

Among the structural units derived from the monomer having a phenolic hydroxyl group, when R ^{21 in} the formula (a1-2) is not an alkylene group, a structural unit derived from a monomer represented by the formula (a1-2 ') has transparency and sensitivity From the viewpoint of viewability. As the linking group for R ²¹ , an alkyleneoxycarbonyl group and the like can be preferably exemplified (from the side of the main chain of the copolymer) in addition to the alkylene group. In this case, the constituent unit derived from the monomer having a phenolic hydroxyl group is preferably represented by the following formula -2 ').

(Wherein R ³⁰ is the same as R ²⁰ in formula (a1-2), R ³² is the same as R ²² in formula (a1-2), and a and b are as defined in formula (a1-2), and the preferable range is the same)

In the formula (a1-2 '), R ³³ represents a divalent linking group, and an alkylene group can be preferably exemplified. The alkylene group may be either linear or branched and preferably has 2 to 6 carbon atoms. Examples of the alkylene group include an ethylene group, a propylene group, an isopropylene group, an n-butylene group, a tert-butylene group, a pentylene group, , Neopentylene group, hexylene group, and the like. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Among them, R ³³ is preferably an ethylene group, a propylene group or a 2-hydroxypropylene group from the viewpoint of sensitivity.

(a1-2-2) a structural unit derived from a monomer having an acid-dissociable group which generates a phenolic hydroxyl group by the action of an acid

The constituent unit derived from a monomer having an acid-dissociable group which generates a phenolic hydroxyl group by the action of an acid includes (a1-2-1) a phenolic hydroxyl group of a constituent unit derived from a monomer having a phenolic hydroxyl group, Is a structural unit derived from a monomer having a moiety protected by an acid-decomposable group. As the acid-decomposable group, known ones can be used as described above, and they are not particularly limited. Among the acid-decomposable groups, a phenolic hydroxyl group is a constituent unit derived from a monomer protected by an acetal or a monomer having a phenolic hydroxyl group protected by a ketal, and the basic physical properties of the resist, particularly the sensitivity and pattern shape, From the viewpoints of storage stability and formability of contact holes. Among the acid-decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is a residue protected by an acetal or ketal represented by the formula (a1-1). Further, when the phenolic hydroxyl group is a residue protected by an acetal or ketal represented by the formula (a1-1), the residue has a structure of -Ar-O-CR ¹ R ² (OR ³ ) as a whole. AR represents an arylene group.

Preferred examples of the acetal ester structure of the phenolic hydroxyl group are R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group, and R ³ = benzyl group.

Examples of the radical polymerizable monomer used for forming a constituent unit derived from a monomer having a phenolic hydroxyl group-containing moiety protected by an acetal or ketal include 1-alkoxyalkyl protected hydroxystyrene, hydroxystyrene Alkoxyalkyl protecting group of? -Methyl-hydroxystyrene, a tetrahydropyranyl protecting group of? -Methyl-hydroxystyrene, a 1-alkoxy-protecting group of 4-hydroxyphenyl methacrylate, Alkyl protecting group, a tetrahydropyranyl protecting group of 4-hydroxyphenyl methacrylate, a 1-alkoxyalkyl protective group of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, a 4-hydroxybenzoic acid Alkoxyalkyl protected derivatives of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 4-hydroxybenzoic acid (2-methoxybenzoic acid) Methacryloyl Oxyethyl) ester, a 1-alkoxyalkyl protected product of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, a 4-hydroxybenzoic acid (3-methacryloyloxypropyl) Alkoxyalkyl protected derivatives of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxyphenyl) Hydroxy-2-hydroxypropyl) ester, and the like.

Among them, a 1-alkoxyalkyl protected product of 4-hydroxyphenylmethacrylate, a tetrahydropyranyl protected product of 4-hydroxyphenylmethacrylate, a 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester (2-methacryloyloxyethyl) ester of 4-hydroxybenzoic acid (1-methacryloyloxyethyl) ester, a tetrahydrofuranyl protected derivative of 4-hydroxybenzoic acid Alkoxyalkyl protecting group, a tetrahydropyranyl protecting group of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, a 1-alkoxy (meth) acryloyloxy group of 4-hydroxybenzoic acid Alkyl protecting group, a tetrahydropyranyl protecting group of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) Alkoxyalkyl protecting group of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hy Tetrahydropyranyl protecting group of a hydroxypropyl ester) is preferable from the viewpoint of transparency.

Specific examples of the acetal protecting group and the ketal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include 1-ethoxyethyl, 1-methoxyethyl, 1-n-butoxyethyl, Ethylhexyloxy group, 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1- Benzyloxyethyl group, and the like, which may be used alone or in combination of two or more.

The radically polymerizable monomer that can be used for forming the structural unit (a1) derived from the monomer may be a commercially available one, or a compound synthesized by a known method may be used. For example, a compound having a phenolic hydroxyl group can be synthesized by reacting with a vinyl ether in the presence of an acid catalyst. The above-mentioned synthesis may be carried out by previously copolymerizing a monomer having a phenolic hydroxyl group with other monomers, and then reacting with a vinyl ether in the presence of an acid catalyst.

Specific preferred examples of the structural unit (a1-2) derived from a monomer include structural units derived from the following monomers, but the present invention is not limited thereto.

When the resin (A) used in the present invention contains an acid labile group, the content of the constituent units derived from these monomers is preferably from 3 to 70 mol%, more preferably from 5 to 60 mol% , More preferably from 10 to 50 mol%.

When the resin (B) used in the present invention contains an acid labile group, the content of the acid labile group-containing structural unit is preferably from 3 to 90 mol%, more preferably from 20 to 90 mol% , And still more preferably from 30 to 85 mol%.

The acid labile group which is an acid labile group which generates a carboxyl group or a phenolic hydroxyl group by the action of an acid is preferably an acid labile group which is an acid labile group which generates a carboxyl group by at least the action of an acid. Particularly, it is preferable to use an acid labile group which is an acid-labile group which generates a carboxyl group by the action of an acid, and to use a carboxyl group as an acid group described later, because the effect of the present invention is more effectively exhibited.

Crosslinkable group

The alkali-soluble resin used in the present invention preferably includes a crosslinkable group. Resistance to processing solutions such as ITO sputtering resistance, peeling solution and etching solution tends to be improved with respect to the cured film formed by including the crosslinkable group. As the crosslinkable group, an oxetane group, an epoxy group, a methacryloyl group, and an acryloyl group are exemplified, and an oxetane group and / or an epoxy group are preferable.

In the present invention, usually, a structural unit including a crosslinking group is put into a resin using such a monomer having a crosslinkable group.

The constituent unit containing a crosslinkable group is preferably from 10 to 70 mol%, more preferably from 20 to 60 mol%, still more preferably from 30 to 55 mol%, of the constituent units of the total components of the resin components.

The structural unit containing a crosslinkable group used in the present invention is more preferably a structural unit derived from (meth) acrylic acid and / or an ester thereof. Further, it may contain a structural unit other than the structural unit derived from (meth) acrylic acid and / or an ester thereof, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound.

And more preferably a structural unit represented by the following general formula.

(Wherein R ¹ is a hydrogen atom or a methyl group, L ¹ is a single bond or a divalent linking group, and C is a crosslinkable group)

R ¹ represents a hydrogen atom or a methyl group, and a methyl group is preferable. L ¹ is a single bond or a divalent linking group, preferably a phenylene group, an ester group or an amide group, and more preferably an ester group. C is a crosslinkable group, and an oxetane group or an epoxy group is preferable.

Season

The alkali-soluble resin used in the present invention preferably includes an acid group. By including an acid group, it is easy to dissolve in an alkaline developing solution, so that the effect of the present invention can be exerted more effectively. The acid group in the present invention means a proton dissociable group having a pKa smaller than 7. The acid group is usually put into the resin as a constituent unit containing an acid group by using a monomer capable of forming an acid group. The inclusion of such a structural unit containing an acid group in the resin tends to increase the alkali solubility. In particular, when the positive photosensitive resin composition of the present invention contains, in addition to the resin (A), an alkali-soluble resin (B) separately containing an acid labile group, the resin (A) and the alkali- It is preferable to include a constitutional unit containing the acid group. By such a constitution, it becomes easy to dissolve uniformly in an alkaline developer.

Examples of the acid group used in the present invention include those derived from a carboxylic acid group, those derived from a hydroxy group, those derived from a sulfonamide group, those derived from a 1,3-diketone group, and the like. Derived and / or derived from a hydroxy group.

The constituent unit containing an acid group used in the present invention is more preferably a constituent unit derived from (meth) acrylic acid and / or an ester thereof. Further, it may contain a structural unit other than the structural unit derived from (meth) acrylic acid and / or an ester thereof, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound.

And more preferably a structural unit represented by the following general formula.

(Wherein R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a single bond or a divalent linking group, and A represents an acid group)

R ¹ represents a hydrogen atom or a methyl group, and a methyl group is preferable. L ¹ is a single bond or a divalent linking group, preferably a single bond, an alkylene group or an arylene group, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms, or a phenylene group. A is an acid group, and a hydroxyl group and a carboxylic acid group are preferable, and a carboxylic acid group is more preferable.

Specific examples of the monomer containing an acid group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Among them, acrylic acid and methacrylic acid are preferable.

The unit constituting the acid group is preferably from 1 to 50 mol%, more preferably from 5 to 40 mol%, and still more preferably from 5 to 30 mol% of the constituent unit constituting the whole resin component.

The constituent unit containing an acid group is more preferably from 1 to 20 mol%, more preferably from 5 to 10 mol% in the resin (A) in the case that the resin (A) has an acid labile group. On the other hand, in the case where the resin (A) does not contain an acid labile group, that is, in the case of the form containing the resin (B), the content of the constituent unit containing the acid group in the resin (A) is preferably 1 to 50 mol% And more preferably 10 to 30 mol%. The content of the constituent unit containing an acid group in the resin (B) is preferably from 1 to 30 mol%, more preferably from 5 to 10 mol%.

Other building blocks

The component A may further contain other structural units within the range not hindering the effect of the present invention.

The other structural unit is preferably a structural unit derived from at least one member selected from the group consisting of p-hydroxystyrene,? -Methyl-p-hydroxystyrene, styrene and? -Methylstyrene.

Preferable examples of the structural unit may include a structural unit derived from at least one member selected from the group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene and N-substituted maleimide.

(Meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl, (meth) acrylic acid (Meth) acrylates containing an alicyclic structure such as isobornyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate or hydrophobic monomers such as styrene are preferable. From the viewpoint of sensitivity, 2-hydroxyethyl (meth) acrylate and N-substituted maleimide are preferable. Of these, (meth) acrylic acid esters having an alicyclic structure are more preferable. From the viewpoint of etching resistance, styrenes such as styrene and? -Methylstyrene are preferable.

These other structural units may be used alone or in combination of two or more.

The resin (A) and the resin (B) are preferably addition-polymerizable resins, and each of the constituent units derived from (meth) acrylic acid and / or the esters thereof, the constituent units derived from styrene and the constituent units derived from a vinyl compound And at least one kind selected from the group consisting of

(Meth) acrylic acid and / or an ester thereof, the sensitivity can be further improved and the transparency can be further improved. By including a constituent unit derived from styrene, the dry etching rate can be further lowered and the relative dielectric constant (K value) can be further lowered.

In the case where the (A) resin contains an acid labile group, the constitutional unit derived from (meth) acrylic acid and / or the ester thereof preferably accounts for 50 to 100 mol%, more preferably 60 to 95 mol% desirable.

On the other hand, in the case where the resin (A) does not contain an acid labile group, that is, the resin (A) in the form containing the resin (B), the resin preferably accounts for 70 to 20 mol% To 30 mol%, and the constitutional unit derived from (meth) acrylic acid and / or the ester thereof preferably accounts for 30 to 80 mol%, more preferably 40 to 70 mol% . In this case, the constituent unit derived from (meth) acrylic acid and / or the ester thereof in the resin (B) preferably accounts for 50 to 100 mol%, more preferably 80 to 95 mol%.

In particular, the resin (B) is preferably a resin obtained by copolymerizing (a) an unsaturated carboxylic acid, (b) a radically polymerizable compound containing oxetane or an epoxy group, and (c) a radically polymerizable compound containing an acid labile group , more preferably a resin obtained by copolymerizing (a) an unsaturated carboxylic acid, (b) a radically polymerizable compound containing an oxetane group, and (c) a radically polymerizable compound containing an acid labile group. Particularly, it is more preferable that the components other than these components are 2 mass% of the total.

The molecular weight of the resin (A) and the resin (B) can be suitably determined, but in the case of the resin (A) containing an acid labile group, the weight average molecular weight is preferably 3000 to 30000 and more preferably 6000 to 20000. On the other hand, in the case where the resin (A) does not contain an acid labile group, that is, the resin (A) containing the resin (B), the weight average molecular weight of the resin is preferably 5000 to 20,000, more preferably 6,000 to 15,000 , And the weight average molecular weight of the resin (B) is preferably from 5,000 to 30,000, more preferably from 6,000 to 20,000.

(B ') other than the resin (A) and the resin (B)

The positive photosensitive resin composition of the present invention may contain the resin (B ') other than the resin (A) and the resin (B). The resin (B ') preferably has any one of the structural units listed in the crosslinkable group, the acid group or other structural units, and preferably has at least an acid group.

As such a resin (B '), a resin having a carboxyl group in the side chain is preferable. For example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Application Laid-open No. 59-53836, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, which are described in each publication of JP-A No. 59-71048, , Acidic anhydride added to a polymer having a hydroxyl group, and the like, and a polymer having a (meth) acryloyl group in its side chain is also preferable.

(Meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A No. 7-140654, 2-hydroxy-3-phenoxypropyl acrylate Methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, Methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, styrene / methacrylic acid / dicyclopentyl methacrylate / glycidyl methacrylate copolymer described in JP-A-5-165214 And the like.

In addition, Japanese Patent Application Laid-Open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224 A publicly known polymer compound described in Japanese Patent Application Laid-Open Nos. 2000-56118, 2003-233179, and 2009-52020 can be used.

These other resins (B ') may contain only one kind or two or more kinds thereof.

In the positive photosensitive resin composition of the present invention, the main component of the solid content is usually a resin component. In the present invention, it is preferable that 70% by weight or more of the solid content is a resin component, more preferably 80% by weight or more of the solid content is a resin component, and 90% And is preferably a resin component.

In the present invention, when an alkali-soluble resin (B) containing an acid labile group is used, it is preferably contained in a proportion of 10 to 97% by weight, more preferably 15 to 95% by weight, More preferably 90% by weight.

In the present invention, when the resin (B ') is used, it is preferably contained in a proportion of 3 to 70% by weight, more preferably 5 to 65% by weight, and more preferably 10 to 60% Is more preferable.

(C) a radiation-sensitive acid generator

The photosensitive resin composition of the present invention comprises (C) a radiation-sensitive acid generator. The radiation-sensitive acid generator used in the present invention is preferably a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but the chemical structure thereof is not particularly limited. In addition, for a radiation-sensitive acid generator that does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid upon exposure to an actinic ray having a wavelength of 300 nm or more by being used in combination with a sensitizer can be preferably used in combination with a sensitizer . As the radiation-sensitive acid generator used in the present invention, a radiation-sensitive acid generator that generates an acid with a pKa of 4 or less is preferable, and a radiation-sensitive acid generator that generates an acid with a pKa of 3 or less is more preferable.

Examples of the radiation sensitive acid generators include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds, naphthoquinone di And a zid compound. Among them, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These radiation-sensitive acid generators may be used alone or in combination of two or more.

Specific examples thereof include the following.

2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine as the trichloromethyl-s- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy- Bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine or 2- (4-methoxynaphthyl) s-triazine, 2- [ ) -Bis (4,6-trichloromethyl) -s-triazine;

As the diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfonate, 4-methoxyphenyl phenyl iodonium trifluoromethane sulfonate, 4-methoxyphenylphenyliodonium tri (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecarboxy) phenyl iodide Phenyl hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetradecarboxy) phenyliodonium-p-toluenesulfonate and the like;

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfone 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate; and the like;

Quaternary ammonium salts such as tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate , Benzyldimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate and the like;

Diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and the like;

As the imidosulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] hepto-5-endocarboximide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfonate, N- Hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimide propanesulfonate and the like;

The following compounds as oxime sulfonate compounds.

As the compound having an oxime sulfonate compound, that is, an oxime sulfonate moiety, a compound including an oxime sulfonate moiety represented by formula (b1) can be preferably exemplified.

(In the formula (b1), R ⁵ represents an alkyl group or an aryl group)

The alkyl group in R &lt; ⁵ &gt; may be linear, branched or cyclic. The permissible substituents are described below.

As the alkyl group for R ⁵ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ⁵ is preferably an aryl group having ⁶ to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a cycloalkyl group Etc.).

As the aryl group for R ^5, an aryl group having ⁶ to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R &lt; ⁵ &gt; may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

The oximesulfonate compound represented by the formula (b1) is particularly preferably an oximesulfonate compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5) Do.

(Formula (OS-3) ~ formula (OS-5) of the R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ² are, each independently, a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ Each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents an integer of 0 to 6 Lt; / RTI &

The alkyl group, aryl group or heteroaryl group in R ¹ in the above formulas (OS-3) to (OS-5) may have a substituent.

The alkyl group in R ¹ in formulas (OS-3) to (OS-5) is preferably an alkyl group having 1 to 3 total carbon atoms which may have a substituent.

Examples of the substituent which the alkyl group in R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- , n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl and benzyl groups.

The aryl group in R ¹ in formulas (OS-3) to (OS-5) is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the aryl group in R ¹ may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, sulfonic acid groups, , And an alkoxysulfonyl group.

Examples of the aryl group for R ¹ include a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group and p-phenoxyphenyl group.

The heteroaryl group in R ¹ in formulas (OS-3) to (OS-5) is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the heteroaryl group in R ¹ may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, An alkoxy group, an alkoxy group, an alkoxy group,

The heteroaryl group in R ¹ in the above formulas (OS-3) to (OS-5) may be a heterocyclic group in which at least one of the rings is a heteroaromatic ring, for example, a heterocyclic aromatic ring and a benzene ring may be coordinated.

Examples of the heteroaryl group for R ¹ include a ring selected from the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring and a benzoimidazole ring which may have a substituent And a group excluding one hydrogen atom from the group represented by R &lt; 1 &gt;

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

One or two of R ² present in at least two of the compounds in the above formulas (OS-3) to (OS-5) are preferably an alkyl group, an aryl group or a halogen atom, and one of R ² is an alkyl group, And it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

The alkyl group or aryl group in R ² of the above formulas (OS-3) to (OS-5) may have a substituent. Examples of the substituent which the alkyl group or aryl group in R ² may have include the same groups as the substituent which the alkyl group or aryl group in R ¹ may have.

The alkyl group in R ² is preferably an alkyl group having 1 to 12 carbon atoms in total which may have a substituent and more preferably an alkyl group having 1 to 6 total carbon atoms which may have a substituent.

Examples of the alkyl group for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, , A methoxymethyl group and a benzyl group are preferable and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s- , an n-propyl group, an n-butyl group, and an n-hexyl group are more preferable, and a methyl group is preferable.

The aryl group in R ² is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

Specific examples of the aryl group for R ² include a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group and a p-phenoxyphenyl group.

Examples of the halogen atom in R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of these, a chlorine atom and a bromine atom are preferable.

In the formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.

In the formulas (OS-3) to (OS-5), the ring containing X as reduction is a 5-membered ring or a 6-membered ring.

In the formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1. When X is S, n is preferably 2. [

The alkyl group and alkyloxy group in R ⁶ of the above formulas (OS-3) to (OS-5) may have a substituent.

The alkyl group in R ⁶ in formulas (OS-3) to (OS-5) is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the alkyl group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

Examples of the alkyl group for R ⁶ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- , n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl and benzyl groups are preferred.

The alkyloxy group in R ⁶ in the formulas (OS-3) to (OS-5) is preferably an alkyloxy group having 1 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the alkyloxy group of R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

The alkyloxy group in R ⁶ is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group or an ethoxyethyloxy group.

Examples of the aminosulfonyl group for R ⁶ in the formulas (OS-3) to (OS-5) include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group and an aminosulfonyl group .

Examples of the alkoxysulfonyl group represented by R ⁶ in formulas (OS-3) to (OS-5) include methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group and butyloxysulfonyl group.

In the formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, .

It is particularly preferable that the compound containing an oxime sulfonate residue represented by the above formula (b1) is an oxime sulfonate compound represented by any one of the following formulas (OS-6) to (OS-11).

(In the formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, , A halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ represents a hydrogen atom or a methyl group )

Expression (OS-6) ~ R ¹ in (OS-11) is R ¹ and agreed in the formula (OS-3) ~ (OS -5), preferable form is also the same.

R ⁷ in the formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

R ⁸ in formulas (OS-6) to (OS-11) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, And is preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group. R ⁹ in formulas (OS-8) and (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R ¹⁰ in the formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

In addition, in the oxime sulfonate compound, any of the three-dimensional structure (E, Z) of oxime may be a mixture.

Specific examples of the oxime sulfonate compound represented by the above formulas (OS-3) to (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.

The compound containing an oxime sulfonate residue represented by the formula (b1) is preferably a compound represented by the formula (OS-1).

(Wherein R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group; R ² represents an alkyl group or an aryl group)

X is ^{-O-, -S-, -NH-, -NR 5} -, -CH 2 -, -CR 6 H- or -CR ⁶ R ⁷ - represents a, R ⁵ ~R ⁷ represents an alkyl group or an aryl group .

R ²¹ to R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring.

As R ²¹ to R ²⁴ , a hydrogen atom, a halogen atom and an alkyl group are preferable, and at least two of R ²¹ to R ²⁴ may be bonded to each other to form an aryl group. Among them, a form in which all of R ²¹ to R ²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

All of the functional groups may have a substituent.

The compound represented by the above formula (OS-1) is more preferably a compound represented by the following formula (OS-2).

R ¹ , R ² and R ²¹ to R ²⁴ in the formula (OS-2) are the same as those in the formula (OS-1), and preferable examples are also the same.

Among them, the form in which R ^{1 in the} formulas (OS-1) and (OS-2) is more preferably a cyano group or an aryl group is more preferable and R ¹ is a cyano group, Naphthyl group is most preferable.

In addition, in the oxime sulfonate compound, the stereostructure (E, Z, etc.) of oxime or benzothiazole ring may be either one or a mixture thereof.

Specific examples (Exemplary Compounds b-1 to b-34) of a compound represented by the formula (OS-1) which can be preferably used in the present invention are shown below, but the present invention is not limited thereto. Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

Of these compounds, b-9, b-16, b-31 and b-33 are preferred from the viewpoint of compatibility between sensitivity and stability.

The compound containing an oxime sulfonate residue represented by the formula (b1) may be an oxime sulfonate compound represented by the following formula (b2).

(In the formula (b2), R ⁵ represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m represents an integer of 0 to 3, and when m is 2 or 3, May be different)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.

The halogen atom as X is preferably a chlorine atom or a fluorine atom.

m is preferably 0 or 1.

M in the formula (b2) is 1, X is a methyl group, X is a substituted position in an ortho position, R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonobonylmethyl group, p-toluyl group is particularly preferable.

The compound containing an oxime sulfonate group represented by formula (b1) may be an oxime sulfonate compound represented by formula (b3).

(Wherein (b3) of the R ⁵ is R ⁵ as agreed in the formula (b1), X 'is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, cyano or nitro groups And L represents an integer of 0 to 5)

The R ⁵ in the formula (b3) is preferably a methyl group, an ethyl group, a n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro- A n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.

X 'is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.

L is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by formula (b3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) benzyl Benzyl cyanide, α - [(methylsulfonyloxyimino) -4-methoxyphenyl] acetyl chloride, and the like. Α - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α - [(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, Butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, and? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

Specific examples of the preferable oxime sulfonate compound include the following compounds (i) to (vii), and they may be used singly or in combination of two or more. The compounds (i) to (vii) are commercially available. It may also be used in combination with other types of (C) radiation-sensitive acid generators.

Examples of the quinone diazide compound include an o-quinone diazide compound (1,2-quinone diazide compound) and a p-quinone diazide compound (1,4-quinone diazide compound). Among them, a 1,2-quinonediazide compound is preferable and a 1,2-naphthoquinone diazide compound is particularly preferable from the viewpoints of sensitivity and developability.

The 1,2-quinonediazide compound is obtained, for example, by condensation reaction of a 1,2-quinonediazide sulfonyl chloride with a hydroxy compound, an amino compound or the like in the presence of a dehydrochloric acid agent.

Examples of the 1,2-quinonediazide compounds include 1,2-benzoquinone diazidesulfonic acid esters, 1,2-naphthoquinone diazidesulfonic acid esters, 1,2-benzoquinone diazidesulfonic acid amides, 1,2- Naphthoquinone diazidesulfonic acid amide and the like. Specifically, see J. Kosar, "Light-Sensitive Systems", pp. 399-352 (1965), John Wiley & Sons New York, WS De Forest "Photoresist" 50 (1975), McGraw-Hill, New York), JP-A-2004-170566, JP-A-2002-40653, JP-A-2002-351068, and JP-A-2004-4233 And a 1,2-quinonediazide compound described in JP-A-2004-271975. It is also preferable that they are described in paragraphs 0066 to 0081 of Japanese Patent Application Laid-Open No. 2008-224970.

Of the compounds having a 1,2-naphthoquinone diazide group, compounds having the following structures can be preferably used since they have particularly high sensitivity.

The most preferable 1,2-naphthoquinonediazide group-containing compound is the following compound. The ratio (molar ratio) of H to 1,2-naphthoquinone diazide group in D is preferably 50:50 to 1:99 from the viewpoints of sensitivity and transparency.

In the photosensitive resin composition of the present invention, the (C) radiation-sensitive acid generator is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the resin component. In particular, it is preferable that (C) the radiation-sensitive acid generator is contained in the range of 0.1 to 10% with respect to the total solid content.

(D) Crosslinking agent

The photosensitive resin composition of the present invention preferably contains (D) a crosslinking agent, if necessary. As the (D) crosslinking agent, for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule, a crosslinking agent containing an alkoxymethyl group, and a compound having at least one ethylenically unsaturated double bond may be added. In the photosensitive resin composition of the present invention, the crosslinking agent (D) is preferably used in an amount of 1 to 40 parts by weight based on 100 parts by weight of the resin component. In particular, it is preferable that the crosslinking agent (D) is contained in an amount of 1 to 40% relative to the total solid content.

By adding the crosslinking agent (D), the cured film can be made into a stronger film. As the crosslinking agent, the following may be added.

&Lt; Compounds having two or more epoxy groups in the molecule &

Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, aliphatic epoxy resin, .

These are available as commercial products. Examples of the bisphenol A epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Mitsubishi Kagaku Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 JER4005, JER4007, JER4010 (manufactured by Mitsubishi Chemical Corporation), EPICLON 830, EPICLON 835 (manufactured by DIC Corporation), and the like, as the bisphenol F type epoxy resin, JER152, JER157, JER157S65, and JER157S70 (manufactured by Mitsubishi Chemical Corp.), EPICLON (trade name, manufactured by Mitsubishi Kagaku K.K.), and the like are used as the phenol novolak type epoxy resin, EPICLON N-770, EPICLON N-770 and EPICLON N-775 (manufactured by DIC Corporation), and EPICLON N-660, EPICLON N-665 and EPICLON N-740 as cresol novolak type epoxy resins, EPICLON N-690, EPICLON N-690 and EPICLON N-695 (manufactured by DIC Corporation) and EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) Epoxy resins include JERYX4000, JERYX4000H, J Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, EP-4085S and EP-4088S (manufactured by ADEKA Corporation), Celloxide 2021P and JERYL6121H (manufactured by Mitsubishi Kagaku K.K.) EPOLEAD PB 3600, PB 4700 (manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, Copper 212, Copper 212L, Copper 214L, Copper 216L, 311, 314, 321, 321L, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 810, 811, 850, DLC-203, DLC-204, DLC-205, DLC-205, DLC-205, DLC-205, DLC-204, DLC- 206, DLC-301, DLC-402 (by Nagase Chemtech), YH-300, YH-301, YH-302, YH-315, YH-324 and YH-325 . In addition, ADEKARESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000 and EPPN- , EPPN-502 (manufactured by ADEKA Corporation), JER1031S, JER1032H60, JER604, and JER630. These may be used alone or in combination of two or more.

Of these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin and biphenyl type epoxy resin. Particularly, bisphenol A type epoxy resin, phenol novolak type epoxy resin, aliphatic epoxy resin and biphenyl type epoxy resin are preferable.

&Lt; Compounds having two or more oxetanyl groups in the molecule >

Specific examples of the compound having two or more oxetanyl groups in the molecule include OXT-121, OXT-221, OX-SQ and PNOX (manufactured by DOA GOSEI CO., LTD.).

The amount of the compound having an epoxy group or oxetanyl group added to the photosensitive resin composition is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the total amount of the resin components.

&Lt; Crosslinking agent containing alkoxymethyl group >

As the crosslinking agent containing an alkoxymethyl group, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. These are obtained by respectively converting methylol group of methylolated melamine, methylolated benzoguanamine, methylated glycoluril or methylol group into alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group and the like can be mentioned, but a methoxymethyl group is particularly preferable from the viewpoint of an outgassing amount . Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable crosslinking compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.

These alkoxymethyl group-containing crosslinking agents are commercially available, for example, from Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 , 1174, UFR65, 300 (manufactured by Mitsui Cyanamid Co., Ltd.), Nigalak MX-750, -032, -706, -708, -40, -31, -270, -280, Carlack MS-11, NIKALAK MW-30HM, -100 LM, -390 (manufactured by Sanwa Chemical Co., Ltd.), and the like can be preferably used.

When the crosslinking agent containing an alkoxymethyl group is used in the photosensitive resin composition of the present invention, the amount of the crosslinking agent containing an alkoxymethyl group is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the resin component. Addition in this range provides the desired alkali solubility at the time of development and excellent solvent resistance of the film after curing.

&Lt; Compounds having at least one ethylenically unsaturated double bond >

As the compound having at least one ethylenic unsaturated double bond, a (meth) acrylate compound such as monofunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional or more (meth) acrylate can be preferably used .

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobonyl (meth) acrylate, 3-methoxybutyl - (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, and the like.

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, and bisphenoxyethanol fluorene diacrylate.

(Meth) acrylate, tri (meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

These compounds having at least one ethylenic unsaturated double bond among them may be used alone or in combination of two or more.

The proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the resin component. By including a compound having at least one ethylenically unsaturated double bond in such a ratio, heat resistance and surface hardness of the insulating film obtained from the photosensitive resin composition of the present invention can be improved. When a compound having at least one ethylenically unsaturated double bond is added, it is preferable to add (J) a thermal radical generator.

(E) Solvent

The photosensitive resin composition of the present invention usually contains (E) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential component, the preferable component, and the optional component are dissolved in the (E) solvent.

As the solvent (E) used in the photosensitive resin composition of the present invention, known solvents can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers , Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, di Propylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like.

As the (E) solvent used in the photosensitive resin composition of the present invention, for example,

(E-1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

(E-2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dipropyl ether;

(E-3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate and ethylene glycol monobutyl ether acetate;

(E-4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

(E-5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

(E-6) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate;

(E-7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;

(E-8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate;

(E-9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;

(E-10) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate;

(E-11) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate and isoamyl lactate;

(E-12) A compound represented by the following general formula (1), wherein n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetic acid, ethyl propionate, isopropyl propionate, , Aliphatic carboxylic acid esters such as isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate;

(E-13) ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxybutyl acetate, , 3-methyl-3-methoxybutylbutylate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate;

(E-14) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone;

(E-15) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone;

(E-16)? -Butyrolactone, and the like.

If necessary, these solvents may contain propylene carbonate, propylene glycol diacetate, ethyl diglycol acetate, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, diethyl oxalate, diethyl maleate, ethylene carbonate, And a solvent such as propylene carbonate may be further added. These solvents may be used alone or in combination of two or more. The solvent usable in the present invention is preferably used alone or in combination of two or more, more preferably two solvents in combination, and the use of propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers in combination More preferable.

The amount of the solvent (E) contained in the photosensitive resin composition of the present invention is preferably from 50 to 3,000 parts by weight, more preferably from 100 to 2,000 parts by weight, further preferably from 150 to 1,500 parts by weight, per 100 parts by weight of the resin component Do.

(A) an alkali-soluble resin containing a structural unit represented by the general formula (1) in an amount of 1 to 70% by weight based on the total solid content of the positive photosensitive resin composition when the resin does not contain an acid labile group (B) an alkali-soluble resin containing an acid labile group in an amount of 30 to 99%, and (C) a radiation-sensitive acid generator in an amount of 0.1 to 10% However, the total amount does not exceed 100%). (A) an alkali-soluble resin containing a constituent unit represented by the general formula (1) in an amount of 1 to 50% based on the total solid content of the positive-working photosensitive resin composition, and (B) (C) a radiation-sensitive acid generator in an amount of 0.1 to 10%, and (D) a crosslinking agent in a range of 1 to 40%, wherein the alkali-soluble resin is contained in an amount of 50 to 98% (However, the total content does not exceed 100%).

The positive photosensitive resin composition of the present invention may further contain additives such as adhesion improvers, basic compounds, surfactants, plasticizers and heat radical generators, antioxidants, thermal acid generators, ultraviolet absorbers, thickeners and organic or inorganic precipitation inhibitors Of known additives can be added.

(F) Adhesion improver

The photosensitive resin composition of the present invention may contain (F) an adhesion improver. The adhesion improver (F) that can be used in the photosensitive resin composition of the present invention improves the adhesion of an inorganic substance as a base material, for example, a silicone compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, . Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the (F) adhesion improver used in the present invention is for the purpose of modifying the interface, and is not particularly limited and known ones can be used.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltriacoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? - Silane, and vinyltrialkoxysilane. Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is more preferable. These may be used alone or in combination of two or more. These are effective in improving the adhesion with the substrate and also in adjusting the taper angle with the substrate.

The amount of the (F) adhesion improver in the photosensitive resin composition of the present invention is preferably from 0.1 to 20 parts by weight, more preferably from 0.5 to 10 parts by weight, per 100 parts by weight of the resin component.

(G) Basic compound

The photosensitive resin composition of the present invention may contain (G) a basic compound. As the basic compound (G), any of those used as a chemically amplified resist can be arbitrarily selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Amine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

Examples of the heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N- But are not limited to, dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, , Pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] Diazabicyclo [5.3.0] -7-undecene, and the like.

Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide and tetra-n-hexylammonium hydroxide.

Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate and tetra-n-butylammonium benzoate.

In the present invention, a compound represented by the formula (g1) may also be used as a basic compound. By using the compound represented by the formula (g1), low dielectric constant and high substrate adhesion can be achieved.

(G1)

(In the formula (g1), R ¹ and R ² each independently represent an alkyl group which may have 1 to 10 carbon atoms which may be branched, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent or a morpholino group. ³ represents an oxygen atom or a sulfur atom, and A represents a divalent linking group)

R ¹ is preferably an aryl group which may have a substituent, a cycloalkyl group which may have a substituent or a morpholino group, more preferably a morpholino group.

When R ¹ is an aryl group, a phenyl group and a naphthyl group may be exemplified, and a phenyl group is more preferable. The aryl group may have a substituent, but preferably has no substituent.

When R ¹ is a cycloalkyl group, a 5-membered or 6-membered cycloalkyl group is preferred, and a 6-membered cycloalkyl group is more preferred. The cycloalkyl group may have a substituent, but preferably has no substituent.

R ² is preferably an alkyl group which may have 1 to 10 carbon atoms which may be branched, an aryl group which may have a substituent, or a cycloalkyl group which may have a substituent.

When R ² is an alkyl group, an alkyl group having 1 to 8 carbon atoms is preferred.

When R ² is an aryl group, a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable. The aryl group may have a substituent, but preferably has no substituent.

When R ² is a cycloalkyl group, a 5-membered or 6-membered cycloalkyl group is preferable, and a 6-membered cycloalkyl group is more preferred. The cycloalkyl group may have a substituent, but preferably has no substituent.

A represents a divalent linking group and includes an alkylene group (e.g., a methylene group, an ethylene group, a propylene group and the like), a cycloalkylene group (e.g. a cyclohexylene group and a cyclopentylene group), an arylene group Phenylene group, 1,4-phenylene group, naphthylene group, etc.), an ether group, a carbonyl group, an ester group, an amide group, or a combination thereof) , An alkylene group, an ether group, or a combination thereof.

The compound represented by the formula (g1) is preferably a compound represented by the formula (g2).

(G2)

(In the formula (g2), R ¹ and R ² each independently represent an alkyl group which may be branched, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent or a morpholino group. Represents a divalent linking group)

R ^1, R ^2, A is R ^1, R ^2, A and agreement in the formula (g1), respectively, is a preferred range consent.

The compound represented by the formula (g1) is more preferably a compound represented by the formula (g3).

(G3)

(In the formula (g3), A represents a divalent linking group)

A agrees with A in the above formula (g1), and the preferable range is also agreement.

The basic compounds usable in the present invention may be used singly or in combination of two or more kinds.

The amount of the basic compound (G) contained in the photosensitive resin composition of the present invention is preferably 0.001 to 2.50 parts by weight, more preferably 0.005 to 2 parts by weight, per 100 parts by weight of the resin component. 00 parts by weight.

(H) Surfactant

The photosensitive resin composition of the present invention may contain (H) a surfactant. As the surfactant (H), any of anionic, cationic, nonionic or amphoteric surfactants may be used, but preferred surfactants are nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicones, and fluorine surfactants. (Trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by JEMCO), Megapack (manufactured by DIC) (Manufactured by Sumitomo Sri M Co., Ltd.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), and PolyFox (manufactured by OMNOVA). Further, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography when the surfactant contains the constituent unit A and the constituent unit B represented by the following formula (1) and tetrahydrofuran (THF) (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

(Wherein R ¹ and R ³ each independently represents a hydrogen atom or a methyl group, R ² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴ represents a hydrogen atom or a C1- P represents an integer of not less than 10% by weight and not more than 80% by weight, and q represents an amount of not less than 20% by weight 90% by weight or less, r is an integer of 1 or more and 18 or less, and n is an integer of 1 or more and 10 or less)

It is preferable that L is a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, more preferably an alkyl group having 2 or 3 carbon atoms Do. The sum (p + q) of p and q is preferably p + q = 100, i.e., 100% by weight.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

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

The amount of the surfactant (H) added to the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, further preferably 0.01 to 1 part by weight, based on 100 parts by weight of the resin component Do.

(I) a plasticizer

The photosensitive resin composition of the present invention may contain (I) a plasticizer. (I) plasticizers include, for example, dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.

The amount of the plasticizer (I) added to the photosensitive resin composition of the present invention is preferably from 0.1 to 30 parts by weight, more preferably from 1 to 10 parts by weight, based on 100 parts by weight of the resin component.

(J) Thermal radical generator

The photosensitive resin composition of the present invention may contain (J) a thermal radical generator, and when it contains an ethylenically unsaturated compound such as a compound having at least one ethylenically unsaturated double bond, (J) a thermal radical generator . As the thermal radical generator in the present invention, a known thermal radical generator may be used.

The thermal radical generator is a compound that generates radicals by thermal energy to initiate or promote the polymerization reaction of the polymerizable compound. The cured film obtained by adding the heat radical generator may become more tough, and the heat resistance and solvent resistance may be improved.

Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, , An azo-based compound, and a non-benzyl compound. The heat radical generator (J) may be used alone or in combination of two or more.

The amount of the heat radical generator (J) to be added to the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer (A) And most preferably 0.5 to 10 parts by weight.

(K) Antioxidant

The photosensitive resin composition of the present invention may contain (K) an antioxidant. (K) antioxidant may include a known antioxidant. (K) the addition of an antioxidant can prevent coloration of the cured film or reduce the film thickness reduction due to decomposition and has an advantage of excellent heat-resistant transparency. Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite, sulfite, thiosulfate, hydroxylamine And derivatives thereof. Among them, a phenolic antioxidant is particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used singly or in combination of two or more.

Examples of commercially available phenolic antioxidants include adecastab AO-60, adecastab AO-80 (manufactured by ADEKA), and Irganox 1098 (manufactured by Chiba Japan Co., Ltd.).

The content of the antioxidant (K) is preferably 0.1 to 6% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.5 to 4% by mass based on the total solid content of the photosensitive resin composition. With this range, sufficient transparency of the film formed can be obtained, and sensitivity at the time of pattern formation becomes good.

Various ultraviolet absorbers, metal deactivators, and the like described in "New Developments of Polymer Additives " (Japan Daily Newspaper) may be added to the photosensitive resin composition of the present invention as additives other than the antioxidant.

<Increase / decrease>

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with (C) a radiation-sensitive acid generator in order to accelerate the decomposition thereof. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer in the electron-excited state comes into contact with the photoacid generator to generate electron movement, energy transfer, heat generation, and the like. As a result, the photoacid generator causes a chemical change and decomposes to generate an acid. Examples of preferable sensitizers include compounds having an absorption wavelength in any one of the wavelength ranges of 350 nm to 450 nm belonging to the following compounds.

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Xanthone, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, and the like), xanthone (for example, Oxanols, thiazides, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, (Such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, acridine, acridine), acridine (for example, thionine, methylene blue, toluidine blue) Butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squaryliums (for example, squalium), styryls, (For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins Methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-pne).

Of these sensitizers, polynuclear aromatic compounds, acridones, styryls, base styryls and coumarins are preferable, and polynuclear aromatic compounds are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

(Method of forming a cured film)

Next, a method of forming the cured film of the present invention will be described.

The method for forming a cured film of the present invention includes the following steps (1) to (5).

(1) a step of applying the photosensitive resin composition of the present invention onto a substrate

(2) a step of removing the solvent from the applied photosensitive resin composition

(3) a step of exposing by an actinic ray

(4) Step of developing with aqueous developer

(5) Heat curing step (post baking step)

Each step will be described below in order.

(1), the photosensitive resin composition of the present invention is applied (usually applied) to a substrate to form a wet film containing a solvent.

In the solvent removing step (2), the solvent is removed from the applied film by depressurization (vacuum pressure) and / or heating to form a dried film on the substrate.

(3), an actinic ray having a wavelength of 300 nm or more and 450 nm or less is irradiated to the obtained coating film. In this step (B), the photoacid generator is decomposed to generate acid. The acid-decomposable group contained in the (A) copolymer is hydrolyzed by the catalytic action of the generated acid to form a carboxyl group or a phenolic hydroxyl group.

Post exposure baking (Post Exposure Bake) (hereinafter, also referred to as &quot; PEB &quot;) can be performed as needed in order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated. PEB can promote the generation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group.

The acid decomposable group in the structural unit derived from the monomer represented by the formula (a1-1) in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to form a carboxyl group or Since a phenolic hydroxyl group is generated, a positive image can be formed by development without necessarily performing PEB. In addition, PEB at a relatively low temperature may promote the hydrolysis of the acid-decomposable group without causing a crosslinking reaction. The temperature at which PEB is carried out is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 80 占 폚.

In the developing step of (4), the liberated copolymer having a carboxyl group or a phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing the exposed region including a resin composition having a carboxyl group or a phenolic hydroxyl group which is easily dissolved in an alkaline developer.

(A1) by pyrolyzing the acid-decomposable group in the constituent unit (a1) to produce a carboxyl group or a phenolic hydroxyl group by heating the positive image obtained in the step of post baking of the structural unit (5) have. The heating is preferably performed at a high temperature of 150 ° C or higher, more preferably 180 ° C to 250 ° C, and particularly preferably 200 ° C to 250 ° C. The heating time can be suitably set according to the heating temperature and the like, but it is preferably within the range of 10 to 90 minutes.

When a step of irradiating the development pattern with an actinic ray, preferably ultraviolet light, to the development pattern before the postbaking process is added, the crosslinking reaction can be promoted by the acid generated by the actinic ray irradiation.

Next, a method for forming a cured film using the photosensitive resin composition of the present invention will be described in detail.

&Lt; Preparation method of photosensitive resin composition >

Various components are mixed in a predetermined ratio and by an arbitrary method, and the mixture is stirred and dissolved to prepare a photosensitive resin composition. For example, it is also possible to prepare a solution in which each component is dissolved in advance in the (E) solvent, and then mix them in a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be used after being filtered using a filter having a pore size of 0.2 mu m or the like.

<Application Process and Solvent Removal Process>

A desired dry film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking). As the substrate, for example, a glass plate in which a polarizing plate, a black matrix layer and a color filter layer, if necessary, and a transparent electroconductive circuit layer are further formed in the production of a liquid crystal display element can be exemplified. The method of application to the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, and a spin coating method can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. If it is manufactured by a large-sized substrate, it is preferable because productivity is high. Here, a large substrate refers to a substrate having a size of 1 m or more on each side.

The heating conditions in the solvent removal step (2) are those in which the acid decomposable group is decomposed in the constituent unit (a1) in the resin component in the unexposed portion so that the resin component is not soluble in the alkali developing solution. But it is preferably about 80 to 130 DEG C for about 30 to 120 seconds.

&Lt; Exposure step and development step (pattern formation method) >

In the exposure step, the substrate on which the coating film is formed is irradiated with an actinic ray through a mask having a predetermined pattern. After the exposure process, a heating process (PEB) is carried out if necessary. In the development process, an exposure pattern is formed by removing the exposure area using an alkaline developer.

(436 nm), i-line (365 nm), h-line (405 nm), and the like can be used for the exposure by the active light beam. ) Can be preferably used as the active light ray having a wavelength of 300 nm or more and 450 nm or less. If necessary, the irradiation light may be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

The developing solution used in the developing step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate or the like can be used. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkaline solution may be used as a developer.

The pH of the developing solution is preferably 10.0 to 14.0.

The development time is preferably 30 to 180 seconds, and the developing method may be any of a puddle method and a dipping method. After the development, washing with water for 30 to 90 seconds is carried out to form a desired pattern.

&Lt; Middle bake process (shape control) >

It is also possible to control the shape of the pattern corresponding to the unexposed area obtained by the development by adding baking at a lower temperature than the post-baking before the post-baking step described below. The middle baking is usually performed at a lower temperature than post baking, for example, at 70 to 130 캜 for 1 to 10 minutes in a hot plate and for 5 to 20 minutes in an oven by using a heating apparatus such as a hot plate or an oven, The heat curing reaction in the post baking can be suppressed, and the pattern shape can be brought close to the rectangular shape.

&Lt; Post baking step (crosslinking step) >

For example, 180 to 250 캜 for a predetermined time, for example, 5 to 60 minutes on a hot plate, using a heating apparatus such as a hot plate or an oven for a pattern corresponding to the unexposed region obtained by development And an oven for 30 to 90 minutes to decompose the acid-decomposable group in the resin component to generate a carboxyl group or a phenolic hydroxyl group to react with the crosslinkable group in the constituent unit (a2) Or an interlayer insulating film can be formed. In addition, transparency can be improved by performing the heat treatment in a nitrogen atmosphere. Further, the substrate on which the pattern has been formed is re-exposed to the substrate on which the pattern is formed prior to the heat treatment, and post-baked (re-exposure / post-baking) is performed to activate the crosslinking step by generating an acid from the component (B) present in the unexposed portion It is preferable to function as a catalyst.

That is, it is preferable that the method of forming a cured film of the present invention includes a re-exposure step of re-exposing by the actinic ray between the developing step and the post-baking step. The exposure in the re-exposure step may be carried out by the same means as in the exposure step, but in the re-exposure step, it is preferable to perform the entire exposure on the side of the substrate on which the film is formed by the photosensitive resin composition of the present invention.

The preferable exposure amount of the re-exposure process is 100 to 1,000 mJ / cm &lt; 2 &gt;.

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent transparency can be obtained even when the insulating resin is baked at a high temperature. The interlayer insulating film formed using the photosensitive resin composition of the present invention has high transparency and is excellent in physical properties of a cured film, and thus is useful for an organic EL display device and a liquid crystal display device.

The organic EL display device and the liquid crystal display device of the present invention are not particularly limited except for having a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention and various known organic EL display devices having various structures Or a liquid crystal display device.

In addition, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned applications and can be used for various purposes. For example, in addition to a planarizing film and an interlayer insulating film, a protective film for a color filter, a spacer for maintaining a thickness of a liquid crystal layer in a liquid crystal display device constantly, and a microlens provided on a color filter in a solid- .

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

A bottom gate type TFT 1 is formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ is formed in a state of covering the TFT 1. A wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 after forming a contact hole (not shown) in the insulating film 3 here. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or the subsequent steps and the TFT 1. [

The planarization layer 4 is formed on the insulating film 3 in a state in which the irregularities due to the wirings 2 are buried in order to planarize the irregularities due to the formation of the wirings 2.

On the planarizing film 4, a bottom-emission organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarization film 4 by being connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.

An insulating film 8 is formed so as to cover the periphery of the first electrode 5. By forming the insulating film 8, a short circuit is prevented between the first electrode 5 and the second electrode formed in a subsequent step can do.

Although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited by evaporation through a desired pattern mask. Next, a second electrode made of Al is formed on the entire surface above the substrate, And an ultraviolet curing type epoxy resin, thereby forming an active matrix type organic EL display device in which the TFT 1 for driving each organic EL element is connected.

Fig. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. Fig. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel is composed of a TFT corresponding to all pixels arranged between two glass substrates 14, (16) are disposed on the substrate. An ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17 in each element formed on the glass substrate. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of a liquid crystal 20 and a black matrix are arranged is provided.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

(Synthesis Example 1 of Binder)

Diethylene glycol ethyl methyl ether (HiSolve EDM, manufactured by Tohoku Kagaku Kogyo Co., Ltd., 45 g) as a solvent was placed in a three-necked flask, and the temperature was raised to 90 占 폚 under a nitrogen atmosphere. (MMA, 3.27 g, manufactured by Wako Pure Chemical Industries, Ltd.), 2-tetrahydrofuranyl methacrylate (MATHF, synthesis product, 22.17 g) and hydroxyethyl methacrylate (HEMA, (OXE-30, manufactured by Osaka Organic Chemical Industry Co., Ltd., 20.26 g) and n-butoxymethylacrylamide (NBMA, Tokyo Kasegai Co., And 7.3 g of dimethyl 2,2'-azobis (2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd., 8 mol% based on the monomer) as a polymerization initiator were dissolved, . After completion of dropwise addition, stirring was continued for 2 hours. V-601 (1.84 g, 2 mol% based on the monomer) was further added to the solution, and the reaction was terminated by further stirring for 2 hours. Thereby obtaining a binder S-1. The weight average molecular weight was 12,000.

S-2 to S-4 were synthesized in the same manner except that the kinds of monomers and the like were changed as shown in the following table.

The units of the monomer components in the above table are expressed as mol%. The initiator is represented by mol% based on 100 mol% of the monomer component. The solid content concentration is represented by monomer weight / (monomer weight + solvent weight) x 100 (unit: wt%). The reaction temperature when V-601 was used as an initiator was 90 DEG C and the reaction temperature when V-65 was used was 70 DEG C (the same applies to the following tables).

In the table, PHS represents p-hydroxystyrene (synthetic), MAEVE represents 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), GMA represents glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Styrene (manufactured by Wako Pure Chemical Industries, Ltd.), V-65 represents 2,2'-azobis (2,4-diaminobiphenyl) Dimethyl valeronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.).

(Synthesis Example 2 of binder)

A high-solved DEM (35.7 g) as a solvent was placed in a three-necked flask, and the temperature was raised to 90 占 폚 under a nitrogen atmosphere. MMA (12.65 g), HEMA (11.05 g), St (5.20 g), NBMA (12.5 g), V-601 (3.47 g, 8 mol% based on the monomer) was dissolved and added dropwise over 2 hours. After completion of dropwise addition, stirring was continued for 2 hours. V-601 (1.84 g, 2 mol% based on the monomer) was further added to the solution, and the reaction was terminated by further stirring for 2 hours. Thus, a binder A-1 was obtained. The weight average molecular weight was 12,000. Similarly, A-2 to A-21 were synthesized. The monomer species used, solvents, etc. are shown in the following table.

In the table, EHMA represents 2-ethylhexyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), MMAm represents methoxymethylacrylamide (manufactured by MRC Unitech), PGMEA represents methoxypropyl acetate (manufactured by Showa Denko) . The? -Methylstyrene dimer is Wako Junyaku Co., and the dodecyl mercaptan is Wako Junyaku Co., Ltd.

(Synthesis Example 3 of Binder)

PGMEA (35.7 g) was placed in a three-necked flask, and the temperature was raised to 90 占 폚 under a nitrogen atmosphere. To the solution was dissolved MAA (1.72 g), MAEVE (12.65 g), OXE-30 (11.05 g), HEMA (5.20 g), V- 65 (3.47 g, 3 mol% based on monomer) in PGMEA And the mixture was added dropwise over 2 hours. After completion of dropwise addition, the reaction was terminated by stirring for 2 hours. Thereby obtaining a binder B-1. The weight average molecular weight was 15,000.

Similarly, B-2 to B-18 and B'-1 to 3 were synthesized. The monomer species used and the solvent are shown in the following table.

In the table, t-BuMA represents tert-butyl methacrylate (Wako Pure Chemical Industries), DCPM represents dicyclopentyl methacrylate (FA-513M, manufactured by Hitachi Kasei Kogyo), StOEVE represents 4- Methoxyethyloxy) styrene (the same applies to the following table).

(Synthesis Example 1 of Comparative Binder)

PGMEA (35.7 g) was placed in a three-necked flask, and the temperature was raised to 70 占 폚 in a nitrogen atmosphere. To this solution was dissolved MAA (1.03 g), MAEVE (12.65 g), OXE-30 (12.52 g), HEMA (5.20 g), V-65 (3.47 g, 7 mol% based on monomer) And added. After completion of dropwise addition, the mixture was stirred for 4 hours to complete the reaction. Thereby obtaining a binder R-1. The weight average molecular weight was 10,000.

Similarly, R-2 was synthesized. The monomer species used and the solvent are shown in the following table.

(Synthesis Example 2 of Comparative Binder)

A PHS / t-BuMA / BnMA polymer (R-3) (A-1 described in JP-A-2010-181730) was obtained by the method described in JP-A-2010-181730.

(Synthesis Example 3 of Comparative Binder)

Butyl ester / bicyclo (2.2.1) hept-5-ene-2-methylbenzoate (molar ratio: 50/50) of norbornene was replaced by R-4 .

Synthesis of 2-tetrahydrofuranyl methacrylate (MATHF)

Methacrylic acid (86 g, 1 mol) was cooled to 15 DEG C and camphorsulfonic acid (4.6 g, 0.02 mol) was added. 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise to the solution. After stirring for 1 hour, a saturated aqueous solution of sodium hydrogencarbonate (500 ml) was added. The mixture was extracted with ethyl acetate (500 ml) and dried over magnesium sulfate. The insoluble material was filtered off and concentrated under reduced pressure at 40 ° C or lower. The water was distilled under reduced pressure to obtain 125 g of MATHF having a boiling point (bp.) Of 54 to 56 캜 / 3.5 mmHg as a colorless oil (yield: 80%).

Synthesis of StOEVE

Was synthesized according to the synthesis of MATHF.

P-1: Synthesis of oxime sulfonate of the following structure

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 ml), and the mixture was heated to 40 캜 for reaction for 2 hours. 4N HCl aqueous solution (60 ml) was added dropwise to the reaction solution under ice-cooling, and ethyl acetate (50 ml) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour. 2N HCl aqueous solution (60 ml) was added to separate the organic layer. The organic layer was concentrated and the crystals were dissolved in diisopropyl ether Slurry, filtered, and dried to obtain a ketone compound (6.5 g). Acetic acid (7.3 g) and a 50% by weight hydroxylamine aqueous solution (8.0 g) were added to the suspension of the resulting ketone compound (3.0 g) and methanol (30 ml), and the mixture was heated to reflux. After cooling, water (50 ml) was added, and the precipitated crystals were filtered, washed with cold methanol and dried to obtain an oxime compound (2.4 g).

The obtained oxime compound (1.8 g) was dissolved in acetone (20 ml), and triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling and the temperature was raised to room temperature and reacted for 1 hour. Water (50 ml) was added to the reaction solution, and the precipitated crystals were filtered and then slurry was rinsed with methanol (20 ml), followed by filtration and drying to obtain B10 (2.3 g).

In addition, ¹ H-NMR spectrum of B10 (300㎒, CDCl ₃₎ is δ = 8.3 (d, 1H) , 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

P-3: Synthesis of sulfonium salt of the following structure

Triphenylsulfonium bromide (34.3 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in methanol (200 ml). An aqueous solution of paratoluenesulfonic acid dihydrate (20.8 g) dissolved in water (100 ml) was added dropwise to the solution over 30 minutes. The precipitated crystals were filtered, and slurry was carried out with methanol / water = 50/50 (50 ml), followed by filtration and drying to obtain 30.3 g of P-3.

&Lt; Adjustment of Photosensitive Resin Composition of Examples and Comparative Examples >

The following components were mixed and adjusted to methyl ethyl diglycol (MEDG) so that the solid content concentration became 20% by weight. And filtered using a polytetrafluoroethylene filter of 0.2 mu m to prepare a positive photosensitive resin composition. The blending ratio of the binder in the table indicates the weight ratio.

The abbreviations of various additives in the above table are as follows.

P-1: An oxime sulfonate of the following structure (synthetic product)

P-2: oxime sulfonate (PAI-101, manufactured by Midori Kagaku Kogyo Co., Ltd.) having the following structure:

P-3: Sulfonium salt of the following structure (synthesized product)

NQD: Orsonophthoquinone diazide (manufactured by Toyo Kasei Kogyo Co., Ltd.)

S-1: Dibutoxyanthracene of the following structure (manufactured by Kawasaki Chemical Industry Co., Ltd.)

JER: Epoxy crosslinking agent (JER150S70, Mitsubishi Kagaku Co.)

JER2: Epoxy crosslinking agent (JER1031S, Mitsubishi Kagaku Co.)

EX: Epoxy crosslinking agent (Denacol EX-321L, manufactured by Nagase Chemtex)

MX: Methoxymethyl cross-linking agent (Nigalak MX-270, manufactured by Sanwa Chemical Co., Ltd.)

F-1:? -Glycidoxypropyltrialkoxysilane

G-1: 2,4,5-triphenylimidazole

G-2: 1,5-diazabicyclo [4.3.0] -5-nonene

G-3: Compound represented by (g4)

(G4)

W-1: Megapack F-554 (DIC)

W-2: FTX-218G (manufactured by NEOS)

In the above formula, Ts represents a p-toluenesulfonyl group, and TsO- represents a p-toluenesulfonic acid anion.

<Evaluation>

The obtained composition was evaluated as follows.

<Transmittance>

A coating film having a film thickness of 3.0 mu m was formed on a glass substrate. Subsequently, exposure was performed through a predetermined mask using an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.). Puddle development with an alkaline developer (2.38 wt% tetramethylammonium hydroxide aqueous solution) at 23 DEG C for 65 seconds, followed by rinsing with ultrapure water for 1 minute. The coated film after development was irradiated with light of 300 mJ / cm 2 at a wavelength of 365 nm using an ultra-high pressure mercury lamp, and then heated in an oven at 220 캜 for 45 minutes. The transmittance of the cured film was measured at a wavelength of 400 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). The lowest transmittance is shown in the table (fresh transparency).

Further, it was heated in an oven at 230 DEG C for 2 hours. The transmittance of this cured film was similarly measured (heat-permeability).

<Sensitivity>

The photosensitive resin composition of the present invention was slit-coated on a silicon wafer having a silicon oxide film, followed by vacuum drying to form a coating film having a thickness of 3 m.

Subsequently, exposure was performed through a predetermined mask using an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.). Puddle development with an alkaline developer (2.38 wt% tetramethylammonium hydroxide aqueous solution) at 23 DEG C for 65 seconds, followed by rinsing with ultrapure water for 1 minute. With these operations, the optimal exposure amount when the line-and-space of 5 占 퐉 was resolved 1: 1 was taken as sensitivity. From the viewpoint of productivity, the optimum exposure dose is preferably 50 mJ / cm 2 or less, and more preferably 20 mJ / cm 2 or less.

&Lt; Residual film ratio at the time of development >

Further, the film thickness of the unexposed portion after development was measured, and the ratio of the film thickness after coating (unexposed film thickness after development / film thickness after coating x 100 (%)) was evaluated to evaluate the residual film ratio at the time of development.

<Relative dielectric constant>

A slurry of a photosensitive resin composition solution was applied to a bare wafer (N type low resistance) (manufactured by SUMCO), and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a photosensitive resin composition layer having a film thickness of 3.0 mu m. The resultant photosensitive resin composition was exposed to light with a cumulative irradiation dose of 300 mJ / cm 2 (illuminance: 20 mW / cm 2) with a PLA-501F exposure device (ultra-high pressure mercury lamp) manufactured by Canon Inc. and the substrate was heated in an oven at 220 ° C for 1 hour A cured film was obtained.

The relative dielectric constant of this cured film was measured at a measurement frequency of 1 MHz using CVmap92A (manufactured by Four Dimensions Inc.). When this value is small, the relative dielectric constant of the cured film can be said to be good.

&Lt; Dry etching resistance >

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then the solvent was removed by heating on a hot plate at 90 DEG C for 120 seconds to obtain a photosensitive resin composition layer .

The resultant photosensitive resin composition layer was exposed with a PLA-501F exposure apparatus (ultrahigh pressure mercury lamp) manufactured by Canon Inc. so that the cumulative irradiation dose was 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) Lt; 0 &gt; C for 1 hour to obtain a cured film. The cured film was subjected to etching under the conditions of a dry etching apparatus "CDE-80N (Shibaura Mechatronics, Ltd.)", an etching gas of CF ₄ 50 ml / min, O ₂ 10 ml / min, Dry etching was performed. The etching rate was calculated from the film reduction amount. The smaller the numerical value, the higher the dry etching resistance.

<Evaluation of Transparent Electrode Sputter Resistance>

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then the solvent was removed by heating on a hot plate at 90 DEG C for 120 seconds to obtain a photosensitive resin composition layer .

The resultant photosensitive resin composition layer was exposed with a PLA-501F exposure apparatus (ultrahigh pressure mercury lamp) manufactured by Canon Inc. so that the cumulative irradiation dose was 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) Lt; 0 &gt; C for 1 hour to obtain a cured film.

On this cured film, ITO was formed as a transparent electrode by sputtering (ULVAC, SIH-3030, sputtering temperature: 250 캜). The surface of the cured film after the sputtering was observed with an optical microscope (500 times). No wrinkles or slight wrinkles, but OK and OK were indicated as OK and NG, respectively.

<Taper angle>

A coating film having a film thickness of 3.0 mu m was formed on a glass substrate. Then, using an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.), an optimum exposure dose was exposed through a predetermined mask in a pattern having a drain pattern of a diameter of 10 mu m corresponding to the contact hole. The obtained pattern was cut vertically, and the angle with the substrate was calculated from the optical photograph.

<Swelling rate>

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then the solvent was removed by heating on a hot plate at 90 DEG C for 120 seconds to obtain a photosensitive resin composition layer .

The resultant photosensitive resin composition layer was exposed with a PLA-501F exposure apparatus (ultrahigh pressure mercury lamp) manufactured by Canon Inc. so that the cumulative irradiation dose was 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) Lt; 0 &gt; C for 1 hour to obtain a cured film.

The cured film was immersed in a mixed solution of monoethanolamine / dimethyl sulfoxide = 30/70 for 6 minutes, and the film was drained to wipe off the liquid on the surface, and the film thickness was immediately measured. The ratio of the film thickness before immersion and the film thickness after immersion was expressed as a percentage.

Swelling rate (%) = film thickness after immersion (占 퐉) / film thickness before immersion (占 퐉) 占 100

<Overall evaluation>

The above evaluation was synthesized and evaluated in five steps. 1 is the best. The practical level is 3 or more. The above results are summarized in the following table.

As is clear from the above table, it was found that a positive-type photosensitive resin composition excellent in various performances was obtained by using a polymer having a constituent unit represented by the general formula (1) in the positive-type photosensitive resin composition. Incorporation of the oxymethylene structure into the constituent unit of the resin component not only makes it possible to improve the dry etching resistance and the K value, but also a positive photosensitive resin composition of particularly high sensitivity can be obtained. Further, the photosensitive resin composition of the present invention can improve the peeling liquid resistance, and it is also important that the taper angle of the pattern can be improved.

(Example 110)

Using the compositions of Examples 1 to 98, a coating film having a film thickness of 3.0 占 퐉 was formed on a glass substrate. Subsequently, using an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.), an optimum exposure dose was exposed through a predetermined mask in a pattern having a recessed pattern with a diameter of 10 mu m corresponding to the contact hole. After development, the wafer was calcined at 90 to 130 캜 using an oven (referred to as middle baking), and post baking was performed in an oven at 230 캜 for one hour. The obtained pattern was vertically cut and the angle with the substrate was calculated from the optical photograph. The results are shown in the following table, and it was possible to achieve a high taper angle by performing the middle baking.

(Example 111)

Using the photosensitive resin composition of Example 6, evaluation was carried out in the same manner as in Example 6 using an ultrahigh pressure mercury lamp and using a UV-LED light source exposing machine. Results The same results as in Example 6 were obtained.

(Example 112)

Sensitivity and evaluation were carried out in the same manner as in the evaluation of the sensitivity of the photosensitive resin composition of Example 6 except that the substrate was changed from a silicon wafer to a glass substrate using the photosensitive resin composition of Example 6. Results The same results as in Example 6 were obtained.

(Example 113)

A photosensitive resin composition was prepared in the same manner as in Example 6 except that the photosensitive resin composition of Example 6 was used and the exposure machine was changed from an exposure machine manufactured by Canon Inc. to a FX-803M (gh-Line stepper) Sensitivity and evaluation were performed similarly to the evaluation. As a result, the same result as in Example 6 was obtained.

(Example 114)

As in the evaluation of the sensitivity to the photosensitive resin composition of Example 6 except that the photosensitive resin composition of Example 6 was used and the exposure machine was changed from an exposure device manufactured by Canon Inc. to a 355 nm laser exposure device and 355 nm laser exposure was carried out And sensitivity and evaluation were performed. As a result, the same result as in Example 6 was obtained.

As the 355 nm laser exposure device, "EGIS" (wavelength: 355 nm, pulse width 6 nsec) manufactured by V Technology Co., Ltd. was used and the exposure amount was measured using "PE10B-V2" manufactured by OPHIR.

As described above, it can be seen that the photosensitive resin composition of the examples shows excellent sensitivity irrespective of whether the substrate or the exposure machine is used.

(Example 115)

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

A bottom gate type TFT 1 was formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ was formed in a state of covering the TFT 1. Subsequently, a contact hole (not shown) was formed in the insulating film 3, and a connection wiring 2 (height 1.0 mu m) was formed on the insulating film 3 through the contact hole. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or the subsequent steps and the TFT 1. [

The planarization layer 4 was formed on the insulating film 3 in a state in which the irregularities due to the wirings 2 were filled in order to planarize the irregularities due to the formation of the wirings 2. The formation of the planarization film 4 on the insulating film 3 was performed by spin-coating the photosensitive resin composition of Example 18 on a substrate, pre-baking (90 占 폚 for 2 minutes) on a hot plate, , I-line (365 nm) was irradiated at 45 mJ / cm 2 (illumination: 20 mW / cm 2) and then developed with an aqueous alkaline solution to form a pattern and subjected to heat treatment at 230 ° C. for 60 minutes. The coating properties when the photosensitive resin composition was applied were good, and no wrinkles or cracks were observed in the cured films obtained after exposure, development and firing. The average step of the wiring 2 was 500 nm, and the thickness of the planarization film 4 was 2,000 nm.

Subsequently, a bottom-emission type organic EL device was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through the contact hole 7. Thereafter, the resist was coated and prebaked, exposed through a mask of a desired pattern, and developed. And patterning was carried out by wet etching using this resist pattern as a mask in ITO etchant. Then, the resist pattern was peeled off using a resist stripping solution (a mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The thus obtained first electrode 5 corresponds to the anode of the organic EL element.

Then, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. An insulating film 8 was formed in the same manner as above using the photosensitive resin composition of Example 7 as the insulating film. By forming this insulating film, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in a subsequent step.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially evaporated through a desired pattern mask in a vacuum vapor deposition apparatus. Then, a second electrode made of Al was formed on the entire upper surface of the substrate. The obtained substrate was taken out from the evaporator, and sealed by attaching it using a sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix type organic EL display device in which TFTs 1 for driving the organic EL elements are connected to each organic EL element was obtained. As a result of applying a voltage through the driving circuit, it was found that the organic EL display device exhibits good display characteristics and is highly reliable.

(Example 116)

An organic EL device was prepared in the same manner as in Example 115 except that the photosensitive resin composition of Example 6 was replaced with the photosensitive resin composition of Example 1. [ The organic EL display device exhibits good display characteristics and is highly reliable.

(Example 117)

An organic EL device was produced in the same manner as in Example 115 except that the photosensitive resin composition of Example 32 was replaced with the photosensitive resin composition of Example 32. [ The organic EL display device exhibits good display characteristics and is highly reliable.

(Example 118)

A cured film 17 was formed as an interlayer insulating film in an active matrix type liquid crystal display device described in Figs. 1 and 2 of Japanese Patent No. 3321003 as follows to obtain a liquid crystal display device of Example 118. [

That is, the cured film 17 was formed as an interlayer insulating film in the same manner as the method for forming the planarization film 4 of the organic EL display device in Example 115, using the photosensitive resin composition of Example 6.

As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited good display characteristics and was highly reliable.

(Example 119)

A liquid crystal display device was manufactured in the same manner as in Example 118 except that the photosensitive resin composition of Example 6 was replaced with the photosensitive resin composition of Example 1. The liquid crystal display device exhibits good display characteristics and is a highly reliable liquid crystal display device.

(Example 120)

A liquid crystal display was manufactured in the same manner as in Example 118 except that the photosensitive resin composition of Example 32 was replaced with the photosensitive resin composition of Example 32. The liquid crystal display device exhibits good display characteristics and is a highly reliable liquid crystal display device.

Claims (27)

(A) an alkali-soluble resin containing a structural unit represented by the general formula (1) and (C) a radiation-sensitive acid generator,
(1) and / or (2) below, wherein the positive photosensitive resin composition further comprises:
[(1) The alkali-soluble resin containing the structural unit represented by the general formula (1) in the above (A) has an acid labile group.
(2) The positive photosensitive resin composition includes (B) an alkali-soluble resin containing an acid labile group.
Wherein the alkali-soluble resin comprising (A) the constituent unit represented by the general formula (1) and / or the acid labile group (B) is at least one selected from oxetane groups, epoxy groups, methacryloyl groups, A structural unit comprising at least one crosslinkable group selected from a diaryl group,
Wherein the positive photosensitive resin composition further comprises a resin (B ') other than the alkali-soluble resin comprising the alkali-soluble resin (A) containing the structural unit represented by the general formula (1) and the acid-labile group (B) , And the structural unit (B ') comprises a structural unit comprising at least one crosslinkable group selected from an oxetane group, an epoxy group, a methacryloyl group, and an acryloyl group.
In general formula (1)

[Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 9 carbon atoms] The method according to claim 1,
Wherein the alkali-soluble resin (A) comprising an alkali-soluble resin containing a structural unit represented by the general formula (1) and / or the acid-labile group (B) is a resin containing an acid group, Composition. delete 3. The method according to claim 1 or 2,
Wherein the (C) radiation-sensitive acid generator is an oxime sulfonate compound. 3. The method of claim 2,
Wherein the alkali-soluble resin containing an acid labile group is a resin containing an acid labile group which is an acid-dissociable group that generates a carboxyl group or a phenolic hydroxyl group by the action of an acid. 3. The method of claim 2,
Wherein the alkali-soluble resin containing an acid labile group is a resin comprising an acid labile group which is an acid-dissociable group which generates a carboxyl group or a phenolic hydroxyl group by an action of an acid group and a acid group which are carboxyl groups. 3. The method of claim 2,
Wherein the acid-labile group-containing alkali-soluble resin comprises at least one of the constituent units shown below.

[Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ² represents an alkyl group having 1 to 4 carbon atoms. n1 and n2 are integers of 1 to 5, n3 is an integer of 1 to 4, and n4 is an integer of 1 to 3, 3. The method of claim 2,
Wherein the acid-labile group-containing alkali-soluble resin comprises a constitutional unit represented by the following general formula (2) or (3).

9. The method of claim 8,
Wherein the acid-labile group-containing alkali-soluble resin comprises a structural unit represented by the general formula (2). 3. The method of claim 2,
Wherein the acid-labile group-containing alkali-soluble resin is a resin comprising a crosslinking group containing an oxetane group and / or an epoxy group. 3. The method of claim 2,
A positive photosensitive resin composition comprising the alkali-soluble resin (A) containing a structural unit represented by the general formula (1) and the alkali-soluble resin containing the acid-labile group (B). 12. The method of claim 11,
The alkali-soluble resin (B) containing an acid labile group may be prepared by copolymerizing a radically polymerizable compound containing (a) an unsaturated carboxylic acid, (b) a radically polymerizable compound containing oxetane or an epoxy group, and (c) Wherein the positive photosensitive resin composition is a resin. 12. The method of claim 11,
The alkali-soluble resin (B) containing an acid labile group is a resin obtained by copolymerizing (a) an unsaturated carboxylic acid, (b) a radically polymerizable compound containing an oxetane group, and (c) a radically polymerizable compound containing an acid labile group Wherein the positive photosensitive resin composition is a positive photosensitive resin composition. 3. The method according to claim 1 or 2,
Wherein the alkali-soluble resin (A) is a polymer further comprising a structural unit containing an acid group. 3. The method according to claim 1 or 2,
Wherein the alkali-soluble resin (A) is a polymer further comprising a structural unit derived from styrene. 3. The method of claim 2,
(A) an alkali-soluble resin containing a structural unit represented by the general formula (1) and an alkali-soluble resin containing the acid-labile group (B) as the resin component, wherein the main component of the solid component is a resin component, (C) a radiation-sensitive acid generator in an amount of 0.1 to 10% based on the total solid content. 3. The method according to claim 1 or 2,
(D) a cross-linking agent. 18. The method of claim 17,
(A) an alkali-soluble resin containing a structural unit represented by the general formula (1) and an alkali-soluble resin containing the acid-labile group (B) as the resin component, wherein the main component of the solid component is a resin component, (C) a radiation-sensitive acid generator in an amount of 0.1 to 10% based on the total solid content, and (D) a crosslinking agent in an amount of 1 to 40% based on the total solid content. 3. The method of claim 2,
Wherein the alkali-soluble resin (B) comprises an acid labile group in an amount of 10 to 97% by weight of the total resin component. 3. The method of claim 2,
(B ') resin other than the alkali-soluble resin (B) containing an acid labile group, and the resin (B') is contained in a proportion of 3 to 70% by weight of the total resin component. Type photosensitive resin composition. A cured film characterized by applying the positive photosensitive resin composition according to any one of claims 1 to 3 on a substrate and curing it by light and / or heat. A cured film formed by applying the positive-working photosensitive resin composition according to claim 1 or 2 onto a substrate, exposing the exposed positive-working photosensitive resin composition to light without exposure to heat, and further heating it. An interlayer insulating film characterized by using the cured film according to claim 21. 23. A liquid crystal display device comprising the interlayer insulating film according to claim 23. (1) a step of applying the positive photosensitive resin composition described in (1) or (2) on a substrate, (2) a step of removing the solvent from the applied positive photosensitive resin composition, (3) , (4) a step of developing with an aqueous developer, and (5) a step of thermosetting. 26. The method of claim 25,
And a step of performing a front exposure before the step of thermal curing after the developing step. An organic EL display device comprising the interlayer insulating film according to claim 23.

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