KR20150003138A - Photosensitive curable resin composition, cured film and method for the cured film - Google Patents

Abstract

The present invention has the purpose to provide a photosensitive resin composition, which has a high sensitivity, an excellent storage stability, and an excellent reliability of an obtained cured film (in particular, chemical resistance), and a large exposure margin or development margin when manufacturing a cured film. As a means to achieve the purpose, provided is a photosensitive resin composition, which comprises (A) a polymer component including a repeat unit originated from a monomer having a carboxyl group protected with an acid labile group, and/or a repeat unit originated from a monomer having a phenolic hydroxide group protected by an acid labile group (a1), and a repeat unit (a2) having a cross linking group, in the identical polymer and/or different polymers; (B) a compound having an oxime sulfonate residue group represented by general formula (b1); and (C) a solvent, wherein the solvent includes at least one solvent having a boiling point less than 180°C, and at least one solvent having a boiling point of 180°C or higher, and (the sum amount of the solvent having a boiling point less than 180°C):(the sum amount of the solvent having a boiling point of 180°C or higher) is 99:1-50:50 in mass conversion.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a cured film, and a method of manufacturing the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition, a cured film and a method for producing the same. Further, the present invention relates to an organic EL display device using the cured film, and an electronic device such as a liquid crystal display device. More particularly, the present invention relates to a positive type photosensitive resin composition suitable for forming a planarizing film, a protective film or an interlayer insulating film of an electronic component such as an organic EL display device, a liquid crystal display device, an integrated circuit device, And a method for producing a cured film.

In an organic EL display device, a liquid crystal display device, or the like, a patterned interlayer insulating film is provided so as to insulate between wirings generally arranged in layers. In order to form this interlayer insulating film, it is preferable that the number of steps for obtaining a necessary pattern shape is small and furthermore, it is desired to have sufficient flatness, and thus a photosensitive resin composition is widely used.

In the patterned interlayer insulating film and the planarizing film using the photosensitive resin composition as described above, a highly reliable curing film such as a film having excellent transparency and excellent resistance to solvent resistance and sputtered indium tin oxide (ITO) .

Further, in recent years, high resolution of a photosensitive resin composition has been required in order to make display characteristics of an organic EL display device and a liquid crystal display device high definition.

As the photosensitive resin composition, those disclosed in Japanese Patent Application Laid-Open No. 2004-264623 are known. In addition, a solvent for use in a photosensitive resin composition has been extensively studied so far, and for example, a chemically amplified positive resist composition capable of forming a resist pattern having a large residual ratio of unexposed portions has been proposed (see, for example, Japanese Patent Laid-Open No. 2001 -56558).

However, the inventors of the present invention have studied the Japanese Unexamined Patent Application Publication Nos. 2004-264623 and 2001-56558, and have found that these compositions have high sensitivity, excellent storage stability, and reliability (particularly, chemical resistance) And it was found that the photosensitive resin composition was not a wide exposure margin or a developing margin at the time of producing a cured film. Further, when ITO is provided on the surface of the photosensitive composition by sputtering or the like, resistance to such is also required. The object of the present invention is to provide a cured film which has high sensitivity, excellent storage stability, excellent reliability (particularly, chemical resistance) of the obtained cured film, broad exposure margin and development margin at the time of producing a cured film, And a photosensitive resin composition excellent in sputter resistance. It is also an object of the present invention to provide a photosensitive resin composition having resistance to ITO by sputtering or the like (hereinafter sometimes referred to as " ITO sputter resistance ").

Under these circumstances, the inventors of the present invention have conducted an intensive study. As a result of intensive studies, it has been found that a photosensitive resin composition containing 6 as a solvent component, a solvent having a boiling point of less than 180 캜 and a solvent having a boiling point of 180 캜 or higher, (The total amount of the solvent having a boiling point of 180 DEG C or higher) is in the range of 99: 1 to 50:50, the above problems can be solved.

Specifically, it is preferable to use the means described in <2> to <6>, <8> and <10> described below by means of the following <1>, <7>, <9> , The above problem has been achieved.

(1) A resin composition comprising (A) a repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group and / or a repeating unit (a1) derived from a monomer having a phenolic hydroxyl group protected with an acid- a2) in the same polymer and / or different polymer,

(B) a compound containing an oxime sulfonate residue represented by the following general formula (b1), and

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

(C) at least one kind of solvent having a boiling point of less than 180 deg. C and at least one kind of solvent having a boiling point of 180 deg. C or more as the above-mentioned solvent, : A total amount of the solvent having a boiling point of 180 占 폚 or more) is 99: 1 to 50:50 in terms of mass.

<2> The photosensitive resin composition according to <1>, wherein the partition coefficient (Log P) of the solvent having a boiling point of 180 ° C or higher is in a range of -0.5 to 1.0.

(3) The oxime sulfonate compound according to any one of (1) to (3), wherein the compound (B) is a compound containing an oxime sulfonate residue represented by the following general formula (OS-3), OS- Lt; 1 &gt; or &lt; 2 &gt;.

(In the general formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom , R ⁶ each independently represents 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, Represents an integer of 6.)

(In the general 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, X may be the same or different.)

The repeating unit (a2) derived from the monomer having a crosslinking group is preferably a repeating unit (a2) containing at least one member selected from the group consisting of a cyclic ether residue of a 3-membered ring and / or a 4-membered ring, The photosensitive resin composition according to any one of < 1 > to < 3 >.

<5> The photosensitive resin composition according to any one of <1> to <4>, further comprising (E) an epoxy resin.

&Lt; 6 > The photosensitive resin composition according to any one of < 1 > to < 5 >, which is a chemically amplified positive photosensitive resin composition.

(7) A process for producing a photosensitive resin composition, comprising the steps of (1) applying the photosensitive resin composition described in any one of (1) to (6)

(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 a developer, and

(5) A method of forming a cured film, which comprises a step of thermally curing.

<8> The method for forming a cured film according to <7>, which comprises a step of exposing the entire surface after the developing step and before the step of heat curing.

<9> A cured film formed by the forming method described in <7> or <8>.

<10> The cured film according to <9>, which is an interlayer insulating film.

<11> An organic EL display device or liquid crystal display device comprising the cured film according to <9> or <10>.

According to the present invention, there is provided a photosensitive resin composition which has high sensitivity, excellent storage stability, excellent reliability (particularly, chemical resistance) of the obtained cured film, broad exposure margin and development margin at the time of producing a cured film, and excellent resistance to ITO sputtering .

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. In the present specification, "a group" such as an alkyl group may or may not have a substituent unless otherwise specified. In the case of a group having a limited number of carbon atoms, the number of carbon atoms means the number including the carbon number of the substituent. The organic EL element means an organic electroluminescence element.

The photosensitive resin composition of the present invention comprises (A) a repeating unit derived from a monomer having a carboxyl group protected with an acid decomposable group and / or a repeating unit (a1) derived from a monomer having a phenolic hydroxyl group protected with an acid decomposable group, (B) a compound containing an oxime sulfonate residue represented by the following general formula (b1), and (C) a solvent, wherein the solvent is at least one selected from the group consisting of (A total amount of the solvent having a boiling point of 180 DEG C or higher) and a solvent having a boiling point of 180 DEG C or higher and a solvent having a boiling point of 180 DEG C or higher, 1 to 50:50.

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

By such a constitution, a photosensitive resin composition excellent in sensitivity, storage stability, solvent resistance, and exposure margin can be obtained.

Such a photosensitive resin composition is post-baked to some extent with a solvent remaining in the film, so that the crosslinking reaction is more likely to be promoted, and a dense film can be formed, thereby improving the resistance to ITO sputtering.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

(A) Polymer

(1) a polymer having (a1) a structural unit having an acid group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group, and (2) (A2) a polymer having a structural unit having a crosslinkable group and a polymer having a structural unit having a residue protected with an acid-decomposable group. It may contain other polymers. The polymer component (A) (hereinafter sometimes referred to as "component (A)") in the present invention may contain, in addition to the above (1) and / or (2) Quot; polymer &quot;

The component (A) may contain other monomer unit (a3) in addition to the monomer unit (a1) and the monomer unit (a2).

In the present invention, among repeating units derived from a monomer having a carboxyl group protected by an acid-decomposable group and repeating units derived from a monomer having a phenolic hydroxyl group protected with an acid-decomposable group, a repeating unit derived from a monomer having a carboxyl group protected with an acid- Do.

It is preferable that the (A) copolymer is a resin that is alkali-insoluble and becomes alkali-soluble when the acid-decomposable group of the monomer unit (a1) is decomposed. Herein, the acid-decomposable group means a functional group capable of decomposing in the presence of an acid. That is, in the repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group, the repeating unit derived from a monomer having a phenolic hydroxyl group protected by an acid and capable of forming a carboxyl group by decomposition of a protecting group and protected with an acid- By decomposing the protecting group by an acid, it is possible to generate a phenolic hydroxyl group. Here, in the present invention, "alkali solubility" means that the coating solution (thickness 3 μm) of the compound (resin) formed by heating the solution of the compound (resin) on a substrate at 90 ° C. for 2 minutes at 23 ° C. Means that the dissolution rate in the 0.4% aqueous solution of tetramethylammonium hydroxide in the aqueous solution is 0.01 탆 / second or more. "Alkali insoluble" means that the solution of the compound (resin) is coated on the substrate and heated at 90 캜 for 2 minutes Means that the dissolution rate of the coating film (thickness 3 占 퐉) of the compound (resin) to be formed in an aqueous 0.4% tetramethylammonium hydroxide solution at 23 占 폚 is less than 0.01 占 퐉 / second.

The above-mentioned (A) copolymer does not exclude the introduction of an acidic group, as long as the whole of the copolymer (A) is kept insoluble in alkali, but the other carboxyl group, A monomer unit or the like.

The (A) copolymer is preferably a polymer of addition polymerization type and is a polymer containing, as a main component, a monomer unit derived from (meth) acrylic acid and / or an ester thereof. Furthermore, within the scope of not deviating from the spirit of the present invention, it is also possible to use monomer units other than the monomer units derived from (meth) acrylic acid and / or esters thereof, for example, monomer units derived from styrene, monomers derived from vinyl compounds Unit or the like.

The (A) copolymer preferably contains monomer units derived from (meth) acrylic acid and / or esters thereof in an amount of 50 mol% or more relative to all monomer units in the polymer, more preferably 90 mol% or more (Meth) acrylic acid and / or an ester thereof. It is particularly preferable that the polymer is a polymer comprising only monomer units derived from (meth) acrylic acid and / or an ester thereof.

Further, the "monomer unit derived from (meth) acrylic acid and / or its ester" is also referred to as "acrylic monomer unit". Further, "(meth) acrylic acid" means "methacrylic acid and / or acrylic acid".

Hereinafter, the monomer unit (a1) and the monomer unit (a2) will be respectively described.

(a1) a repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group, or a repeating unit derived from a monomer having a phenolic hydroxyl group protected with an acid-

The component (A) has a repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group or a repeating unit derived from a monomer having a phenolic hydroxyl group protected with an acid-decomposable group. By having the monomer unit (a1) as the component (A), a highly sensitive photosensitive resin composition can be obtained.

(a1-1) a repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group

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

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

As the unsaturated carboxylic acid to be used for obtaining the monomer unit having a carboxyl group, the following can be used. 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 monomer unit 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 polyvalent carboxylic acid, and examples thereof include monosaccharide mono (2-acryloyloxyethyl), succinic acid mono Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like.

Further, the unsaturated polycarboxylic acid may be mono (meth) acrylate of the both terminal dicarboxylic polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate and the like .

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, in order to form a monomer unit having a carboxyl group, it is preferable to use acrylic acid, methacrylic acid, or an anhydride of an unsaturated polycarboxylic acid, and more preferably use acrylic acid or methacrylic acid .

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

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

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

As the acid anhydride, known dicarboxylic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and anhydride anhydride; Acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and biphenyltetracarboxylic 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 repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group

The repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group is preferably a repeating unit derived from the above-mentioned (a1-1-1), the carboxyl group described in the above (a1-1-2) &Lt; / RTI &gt;

As the acid decomposable group, there can be used any known acid decomposable group in the positive resist for KrF and the positive resist for ArF, and there is no particular limitation. Conventionally, examples of the acid decomposable group include groups which are relatively easily decomposable by an acid (for example, an acetal functional group such as a tetrahydropyranyl group) or groups which are relatively difficult to decompose by an acid (for example, a t- t-butyl functional group such as t-butyl carbonate group) are known.

Among these acid decomposable groups, it is preferable that the carboxyl group is a monomer unit having an acetal-protected residue or a carboxyl group-having a carboxylate-protected residue, and the basic properties of the resist, particularly the sensitivity and pattern shape, the formation of contact holes, It is preferable from the viewpoint of stability. Among the acid decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxy group is an acetal or ketal-protected residue represented by the following formula (a1-1). When the carboxy group is an acetal or ketal-protected residue represented by the following formula (a1-1), the moiety has a structure of - (C═O) -O-CR ¹ R ² (OR ³ ) have.

(In formula (a1-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, provided that when R ¹ and R ² are both hydrogen atoms, R ³ represents an alkyl group, R ¹ or R &lt; ² &gt; and R &lt; ³ &gt; may be connected to form a cyclic ether.

In formula (a1-1), R ¹ to R ³ each independently represent 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 at least one of R ¹ and R ² represents an alkyl group.

In formula (a1-1), when R ¹ , R ² and R ³ represent an alkyl group, the alkyl group may be 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 thereof 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 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 isobornyl 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 are a haloalkyl group, and when they have an aryl group as a substituent, R ¹ , R ² and R ³ are an aralkyl group when they have a halogen atom 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 6 to 12 carbon atoms. Specific examples thereof include a phenyl group, an? -Methylphenyl group, a naphthyl group and the like, Examples of the alkyl group as a whole, that is, the aralkyl group, include a benzyl group, an a-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

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 an ethoxy group.

When the alkyl group is a cyclic alkyl group, the cyclic alkyl 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, And may have 3 to 12 cyclic alkyl groups.

These substituents may be further substituted by the above substituents.

In formula (a1-1), R ¹ and R ² And R ³ represents 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 can be preferably exemplified. As the aryl group, for example, a phenyl group, a tolyl group, a cumenyl group, a 1-naphthyl group and the like can be mentioned.

Further, R ¹ , R ² and R ³ may be bonded to each other to form a ring with the carbon atom to which they are bonded. Examples of the ring structure when 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, An adamantyl 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 monomer unit having a moiety represented by the formula (a1-1) may be a commercially available product, or a product synthesized by a known method may be used. For example, by reacting (meth) acrylic acid with a 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 are -CH (R ¹² ) (R ¹³ ), synonymous with R ² in formula (a1-1), R ¹⁴ is the same as R ¹ in formula (a) , R &lt; ¹⁵ &gt; is the same as R &lt; ³ &gt; in formula (a1-1)

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.

In the present invention, the following monomer unit (a1-1) is a preferable example.

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

Each R ¹ 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 all hydrogen atoms.

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

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

As preferable specific examples of the monomer-derived repeating unit (a1-1) having a carboxyl group protected with an acid-decomposable group, the following monomer units can be exemplified. R represents a hydrogen atom or a methyl group.

(a1-2) a repeating unit derived from a monomer having a phenolic hydroxyl group protected with an acid-decomposable group

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

Examples of the monomer unit having a phenolic hydroxyl group include a hydroxystyrene-based monomer unit and a monomer unit in a novolak-based resin. Of these, monomer units derived from -methylhydroxystyrene are preferred from the viewpoint of transparency . Among the monomer units having a phenolic hydroxyl group, the monomer units represented by the formula (a1-2) are preferred from the viewpoints of transparency and sensitivity.

(In the formula (a1-2), 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 Is an integer of 0 to 4, and a + b is not more than 5. When two or more R ²² are present, these R ²² may be mutually the same or may be the same.)

In 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 single-crystal combination, it is preferable since sensitivity can be improved and 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.

A is an integer of 1 to 5, but a is preferably 1 or 2, and more preferably a is 1, from the viewpoint of the effects of the present invention and from the viewpoint of easy 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 thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a 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 in view of easiness of production.

B represents 0 or an integer of 1 to 4;

Among the monomer units having a phenolic hydroxyl group, when R ²¹ in the formula (a1-2) is not an alkylene group, the monomer unit represented by the formula (a1-2 ') is more preferred in terms of transparency and sensitivity Do. As the linking group for R ²¹ , an alkyleneoxycarbonyl group and the like can be preferably exemplified (from the side of the main chain (main chain) of the copolymer) in addition to the alkylene group. In this case, the monomer unit having a phenolic hydroxyl group is preferably Is preferably represented by the formula (a1-2 ').

(In formula (a1-2 '), 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 and a and b in a1-2), respectively.

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, and examples thereof 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 repeating unit derived from a monomer having a phenolic hydroxyl group protected with an acid-decomposable group

The repeating unit derived from a monomer having a phenolic hydroxyl group protected with an acid-decomposable group is preferably a repeating unit derived from a monomer (a1-2-1) in which the phenolic hydroxyl group of the monomer unit having a phenolic hydroxyl group is a residue protected by an acid- &Lt; / RTI &gt; As the acid decomposable group, known ones can be used as described above, and there is no particular limitation. Among the acid decomposable groups, it is preferred that the phenolic hydroxyl group is a monomer unit having an acetal-protected residue or a phenolic hydroxyl group-having a ketal-protected residue, and the basic properties of the resist, particularly the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, In view of the formation of contact holes. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the formula (a1-1). Further, when the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the formula (a1-1), the residues have a structure of -Ar-O-CR ¹ R ² (OR ³ ) as a whole. Ar represents an arylene group.

Preferable 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 radically polymerizable monomer used for forming a monomer unit having a phenolic hydroxyl group having an acetal or ketal protected moiety include a 1-alkoxyalkyl protected product of hydroxystyrene, a tetrahydrofuran of hydroxystyrene Alkoxyalkyl protecting group of? -Methyl-hydroxystyrene, a tetrahydropyranyl protecting group of? -Methyl-hydroxystyrene, a 1-alkoxyalkyl protective group of 4-hydroxyphenyl methacrylate, Hydroxyphenyl methacrylate, 1-alkoxyalkyl protected derivatives of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, 4-hydroxybenzoic acid (1-methacryloyl (2-methacryloyloxyethyl) ester, 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 4-hydroxybenzoic acid Oxyethyl) ester Alkoxyalkyl protected form of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, tetrahydrofuran of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, Alkoxyalkyl protected derivatives of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxy- Tetrahydrofuranyl protected form of hydroxypropyl ester).

Among them, a 1-alkoxyalkyl protected form of 4-hydroxyphenyl methacrylate, a tetrahydropyranyl protected form of 4-hydroxyphenyl methacrylate, a protected form of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) (2-methacryloyloxyethyl) ester of 4-hydroxybenzoic acid (1-methacryloyloxyethyl) ester, a protected tetrahydrothiopyranyl derivative of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester of a 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, a tetrahydrothiopyranyl protected derivative of a 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, a tetrahydropyranyl protected derivative of 4-hydroxybenzoic acid Alkoxyalkyl protecting group of 4-hydroxybenzoic acid (3-methacryloyloxy-2-hy Tetrahydrothiopyranyl protecting group of the ester is preferable from the viewpoint of transparency.

Specific examples of the acetal protecting group and ketal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, , 1-cyclohexyloxyethyl group, 1- (2-cyclohexyloxy) ethyl group, 1- (2-ethylhexyloxy) , 1-benzyloxyethyl group, etc. These may be used alone or in combination of two or more.

The radically polymerizable monomer used for forming the monomer unit (a1) may be a commercially available product, or a product synthesized by a known method may be used. For example, by reacting a compound having a phenolic hydroxyl group 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 another monomer, and then reacting with a vinyl ether in the presence of an acid catalyst.

Specific preferred examples of the monomer unit (a1-2) include the following monomer units.

The content of the monomer unit (a1) among the monomer units constituting the component (A) is preferably from 3 to 70 mol%, more preferably from 5 to 60 mol%, from the viewpoint of sensitivity, , And more preferably 10 to 50 mol%.

The repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group is characterized in that it is faster than a repeating unit derived from a monomer having a phenolic hydroxyl group protected with an acid-decomposable group. Therefore, when a rapid development is desired, a monomer-derived repeating unit having a carboxyl group protected with an acid-decomposable group is preferable. Conversely, when it is desired to slow the development, it is preferable to use a monomer-derived repeating unit having a phenolic hydroxyl group protected with an acid-decomposable group.

(a2) a monomer unit having a crosslinking group

The component (A) has a monomer unit (a2) having a crosslinking group. The crosslinking group is not particularly limited as long as it is a group causing a curing reaction by a heat treatment. Preferable examples of the monomer unit having a crosslinking group include a monomer unit containing at least one member selected from the group consisting of a cyclic ether residue of a 3-membered ring and / or a 4-membered ring, and an ethylenic unsaturated group. More specifically, the following can be mentioned.

(a2-1) a monomer unit having a cyclic ether residue of a 3-membered ring and / or a 4-membered ring

The above (A) copolymer preferably contains a monomer unit (monomer unit (a2-1)) having a cyclic ether residue of a 3-membered ring and / or a 4-membered ring. The cyclic ether residue of the three-membered ring is also referred to as an epoxy group, and the cyclic ether residue of the four-membered ring is also referred to as an oxetanyl group. The monomer unit (a2-1) having an epoxy group and / or an oxetanyl group is preferably a monomer unit having an alicyclic epoxy group and / or an oxetanyl group, and more preferably a monomer unit having an oxetanyl group.

The monomer unit having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one monomer unit, and may contain at least one epoxy group and at least one oxetanyl group, two or more epoxy groups, May have two or more oxetanyl groups, and it is not particularly limited, but it is preferable that the epoxy group and / or oxetanyl group in total have 1 to 3, and it is more preferable that the epoxy group and / or oxetanyl group has 1 or 2 in total More preferably one having an epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the monomer unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Dicumyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, Heptyl,? -Ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- vinylbenzyl glycidyl ether, paragraphs of Japanese Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton described in Nos. 0031 to 0035, and the like.

Specific examples of the radically polymerizable monomer used to form the monomer unit having an oxetanyl group include (meth) acrylic esters having an oxetanyl group described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953 .

As specific examples of the radically polymerizable monomer used for forming the monomer unit having an epoxy group and / or an oxetanyl group, a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure are preferable.

Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and oxetanyls described in paragraphs 0011 to 0016 of JP-A No. 2001-330953 (Meth) acrylic acid ester having an oxetanyl group as described in paragraphs 0011 to 001 of Japanese Patent Application Laid-Open No. 2001-330953. Among these, preferred are acrylic esters such as 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethacrylate, acrylic acid (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetan-3-yl) methyl. These monomer units may be used alone or in combination of two or more.

It is preferable that the monomer unit (a2-1) has a residue selected from the group consisting of the following formulas (a2-1-1) and (a2-1-2).

The fact that the monomer unit (a2-1) has any of the three residues represented by the above formula (a2-1-1) means that from the structure represented by the formula (a2-1-1), one or more hydrogen atoms It means that you have a period to exclude.

It is more preferable that the monomer unit (a2-1) has a 3,4-epoxycyclohexyl group, a 2,3-epoxycyclohexyl group and a 2,3-epoxycyclopentyl group.

(Wherein R ^1b and R ^6b each independently represents a hydrogen atom or an alkyl group, and R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b , R ^10b Each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group.

In the formula (a2-1-2), R ^1b and R ^6b each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms Hereinafter also referred to as &quot; lower alkyl group &quot;).

R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, more preferably a fluorine atom and a chlorine atom, and more preferably a fluorine atom.

The alkyl group may be straight chain, branched chain or cyclic, and may have a substituent. The straight-chain or branched-chain alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. The cyclic alkyl group preferably has 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and more preferably 5 to 7 carbon atoms. The straight chain or branched chain alkyl group may be substituted with a cyclic alkyl group, and the cyclic alkyl group may be substituted with a straight chain and / or branched chain alkyl group.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.

The alkyl group and the aryl group may further have a substituent. Examples of the substituent which the alkyl group may have include a halogen atom and an aryl group. Examples of the substituent which the aryl group may have include a halogen atom and an alkyl group.

Of these, R ^2b , R ^3b , R ^4b , R ^5b , R ^7b , R ^8b , R ^9b and R ^10b are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, More preferably a perfluoroalkyl group having 1 to 4 carbon atoms.

As the group having a residue represented by the above formula (a2-1-2), a (3-ethyloxetan-3-yl) methyl group can be preferably exemplified.

As specific preferred examples of the monomer unit (a2-1), the following monomer units can be exemplified. R represents a hydrogen atom or a methyl group.

In the present invention, from the viewpoint of curing sensitivity, an oxetanyl group is preferable among the cyclic ether residue of three-membered ring and four-membered ring. In the present invention, from the viewpoint of transmittance (transparency), alicyclic epoxy groups and oxetanyl groups are preferred. In the present invention, as the cyclic ether residue of a 3-membered ring and a 4-membered ring, an alicyclic epoxy group and an oxetanyl group are preferable, and an oxetanyl group is particularly preferable.

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

Copolymer used in the present invention, -NH-CH ₂ -OR is also preferred structural units (a2-2) having a group represented by (R is an alkyl group of 1 to 20 carbon atoms). By having the structural unit (a2-2), the curing reaction can be caused by a gentle heat treatment, and a cured film excellent in various characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched or cyclic alkyl groups, but is preferably a linear or branched alkyl group. The structural unit (a2) is more preferably a structural unit having a group represented by the following general formula (a2-20).

In general formula (a2-20)

(In the general formula (a2-20), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms.)

R ² is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched or cyclic alkyl groups, but is preferably a linear or branched alkyl group.

Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, an i-butyl group, an n-butyl group and a methyl group are preferable.

(a2-3) a monomer unit having an ethylenic unsaturated group

One monomer unit (a2) having a crosslinking group includes a monomer unit (a2-3) having an ethylenically unsaturated group (hereinafter also referred to as "monomer unit (a2-3)"). The monomer unit (a2-3) having an ethylenically unsaturated group is preferably a monomer unit having an ethylenically unsaturated group in its side chain, more preferably a monomer unit having an ethylenically unsaturated group at the end and having a side chain of 3 to 16 carbon atoms , And a monomer unit having a side chain represented by the formula (a2-3-1) is more preferable.

(In the formula (a2-3-1), R ¹ represents a divalent linking group having 1 to 13 carbon atoms, and R ³ represents a hydrogen atom or a methyl group.)

R ¹ is a divalent linking group having 1 to 13 carbon atoms which contains an alkenyl group, an arylene group, or a combination thereof, and may contain a bond such as an ester bond, an ether bond, an amide bond, a urethane bond, or the like. The alkenyl group may also be a cyclic alkenyl group. The divalent linking group may have a substituent such as a hydroxy group or a carboxy group at an arbitrary position. Specific examples of R ¹ include divalent linking groups represented by formulas (A-1) to (A-10).

Of the side chains represented by the formula (a2-3-1), aliphatic side chains are preferred. Among the side chains having a linking group represented by the formula (a2-3-1), a side chain having an acryloyl group or a methacryloyl group at the end is more preferable.

The ethylenic unsaturated group contained in the side chain represented by the formula (a2-3-1) is preferably contained in an amount of 1 mole relative to 150 to 2000 g of the polymer (A), more preferably 1 mole It is more preferable that it is contained.

The method for obtaining the monomer unit (a2-3) having a side chain represented by the formula (a2-3-1) is not particularly limited, and for example, a method of polymerizing a polymer having a specific functional group by a polymerization method such as radical polymerization in advance (A2-3) can be obtained by reacting a compound having an ethylenic unsaturated group at the terminal and a group (hereinafter referred to as a specific compound) reacting with the specific functional group.

Examples of the specific functional group include a carboxyl group, an epoxy group, a hydroxyl group, an amino group having an active hydrogen, a phenolic hydroxyl group, and an isocyanate group. Monomers having specific functional groups for synthesizing a polymer having a specific functional group will be described later.

Examples of the combination of the specific functional group and the group that reacts with the specific functional group possessed by the specific compound include a combination of a carboxyl group and an epoxy group, a combination of a carboxyl group and an oxetanyl group, a combination of a hydroxy group and an isocyanate group, a combination of a phenolic hydroxyl group and an epoxy group, A combination of an isocyanate group, a combination of an amino group and an isocyanate group, and a combination of a hydroxy group and an acid chloride.

Examples of the specific compound include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, isocyanate ethyl methacrylate, isocyanate Ethyl acrylate, methacrylic chloride, acryl chloride, methacrylic acid, and acrylic acid.

Preferred examples of the combination of the specific functional group and the specific compound include a combination of a carboxyl group as a specific functional group and glycidyl methacrylate as a specific compound and a combination of a hydroxy group as a specific functional group and isocyanate ethyl methacrylate as a specific compound.

In the present invention, the monomer unit (a2-3) is preferably a monomer unit represented by the formula (a2-3-2).

(Formula (a2-3-2) of, R ¹ and R ¹ are the same also accept a preferable range in the formula ^{(a2-3-1). R 2, R} 3 are, each independently, a hydrogen atom or a methyl group, respectively .)

Specific examples of the monomer having a specific functional group required for obtaining a polymer having a specific functional group include, but are not limited to, the following.

Examples of the monomer having a carboxyl group include mono (2- (acryloyloxy) ethyl) phthalate, N- ( (Carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 5-hexene, 1,7-oxadiene monoepoxide, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl acrylate.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate , 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone (Ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyl acrylate, 2-acryloyloxyethyl acrylate, 2- (acryloyloxy) ethyl ester, caprolactone 2- Hydroxy-norbornene-2-carboxyl-6-lactone, 5-methacryloyloxy-6-hydroxy norbornene-2-carboxyl- have.

Examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide and N- (hydroxyphenyl) maleimide .

Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloyl isocyanate, and m-tetramethyl xylene isocyanate.

Further, in the present invention, in the case of obtaining a polymer having a specific functional group, it is preferable to use a monomer having a specific functional group as described above and (a1) a repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group, A monomer which is a repeating unit derived from a monomer having a hydroxyl group is used in combination. Monomers other than the above-mentioned (a1) and (a2) which are other monomer units (a3) may be used in combination.

The method for obtaining the polymer having a specific functional group to be used in the present invention is not particularly limited. For example, in a solvent in which a monomer having a specific functional group, a monomer other than the monomer, and a polymerization initiator, Followed by a polymerization reaction at a temperature. The solvent to be used at that time is not particularly limited as long as it dissolves the monomer constituting the polymer having a specific functional group and the polymer having a specific functional group. Specific examples thereof include the solvents described in the solvent (C) described later. The polymer having the specific functional group thus obtained is usually in the state of a solution dissolved in a solvent.

Subsequently, the obtained polymer having a specific functional group is allowed to react with a specific compound to obtain a monomer unit (a2-3) having an ethylenic unsaturated group at the end of the side chain. Then, usually, a solution of a polymer having a specific functional group is provided in the reaction. For example, glycidyl methacrylate is reacted with a solution of an acrylic polymer having a carboxyl group at a temperature of 80 ° C to 150 ° C in the presence of a catalyst such as benzyltriethylammonium chloride to form a monomer unit (a2-3) Can be obtained.

In addition to using the above-mentioned polymer reaction for forming the monomer unit (a2-3), aryl methacrylate, allylacrylate and the like may be used as the radical polymerizable monomer. These monomer units may be used alone or in combination of two or more.

In the present invention, the monomer unit (a2) preferably contains the monomer unit (a2-1).

The content of the monomer unit (a2) among the monomer units constituting the component (A) is preferably from 5 to 60 mol%, more preferably from 10 to 55 mol%, and most preferably from 20 to 20 mol%, from the viewpoints of various resistance and transparency of the formed film. To 50 mol% is more preferable. Within the above range, the transparency of the cured film obtained from the photosensitive resin composition and the ITO sputter resistance are improved.

Preferred embodiments of the <<< constituent unit (a2) >>>

When the polymer containing the constituent unit (a2) does not substantially contain the constituent unit (a1), the constituent unit (a2) accounts for from 5 to 90 mol% of the polymer containing the constituent unit (a2) , More preferably from 20 to 80 mol%.

When the polymer containing the structural unit (a2) contains the structural unit (a1), the structural unit (a2) is a polymer containing the structural unit (a1) and the structural unit (a2) But is preferably 3 to 70 mol%, more preferably 10 to 60 mol% from the viewpoint of resistance.

In the present invention, it is preferable to contain the structural unit (a2) in an amount of 3 to 70 mol%, preferably 10 to 60 mol%, of the total structural units of the component (A) desirable.

Within the above range, the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition are improved.

(a3) Other monomer units

In the present invention, the component (A) may have other monomer units (a3) except for the monomer units (a1) and (a2). Examples of the monomer which is the other monomer unit (a3) include styrene, alkyl (meth) acrylate, cyclic alkyl (meth) acrylate, aryl (meth) acrylate, unsaturated dicarboxylic acid diester, An unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride, and other unsaturated compounds.

Specific examples include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, vinylbenzoate, ethyl vinylbenzoate, (Meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, isopropyl (meth) acrylate, Acrylate, 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl methacrylate, acrylonitrile and the like. In addition, the compounds described in paragraphs 0021 to 0024 of Japanese Patent Application Laid-Open No. 2004-264623 can be mentioned. Among them, a group in which a group reacting with the monomer unit (a2) or a separately added crosslinking agent is generated by the (final) heating treatment is preferable from the viewpoint of film strength. Specifically, a tertiary alkyl (meth) acrylate ester is preferable, and tert-butyl (meth) acrylate is more preferable. The monomers to be the monomer unit (a3) may be used alone or in combination of two or more.

The (A) copolymer preferably contains 1 to 15 mol% of a monomer unit having an unprotected carboxyl group or a monomer unit having an unprotected phenolic hydroxyl group, from the viewpoint of sensitivity.

The molecular weight of the (A) copolymer is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000, in terms of polystyrene reduced weight average molecular weight. Within the above range, the sensitivity and ITO sputter resistance are better.

The photosensitive resin composition of the present invention preferably contains the copolymer component (A) in a proportion of 80 wt% or more. The (A) copolymer may contain only one kind, or may contain two or more kinds. In the present invention, two or more kinds are preferable. By using two or more of them, the solvent resistance tends to be further improved.

Various methods are also known for the method of synthesizing the component (A). For example, a radical polymerization method using a radical polymerization monomer containing at least a radically polymerizable monomer used for forming the monomer unit represented by the above-mentioned (a1) Can be synthesized by polymerization of a monomeric monomer mixture in an organic solvent using a radical polymerization initiator.

(B)

In the present invention, an oxime sulfonate compound represented by the following formula (b1) is contained. In the present invention, when a solvent having a boiling point of less than 180 deg. C and a solvent having a boiling point of 180 deg. C or more are used and oxime sulfonate is used as the solvent, high sensitivity, excellent chemical resistance, and storage stability It becomes possible to provide an excellent photosensitive composition.

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

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 cyclic alkyl group (such as a 7-dimethyl-2-oxonorbornyl group) , Preferably a bicycloalkyl group, or the like).

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 ⁵ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

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

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ² each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ¹ represents an alkyl group, an aryl group or a heteroaryl group, 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 0 to 6 Represents an integer.)

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

Of the above formulas (OS-3) to (OS-5), the alkyl group for R ¹ is preferably an alkyl group having 1 to 30 carbon atoms in total 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-butyl group, , n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl, phenoxyethyl, methylthioethyl, phenylthioethyl, ethoxycarbonylethyl, phenoxyl A cyclopropylmethyl group, a cyclopropylmethyl group, a cyclopropylmethyl group, a cyclohexylmethyl group,

Of these, preferred are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- An n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

Of the above-mentioned formulas (OS-3) to (OS-5), the aryl group for R ¹ 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, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, Thiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group.

Among them, a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group and p-phenoxyphenyl group are preferable.

Among the above-mentioned formulas (OS-3) to (OS-5), the heteroaryl group for R ¹ 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 a halogen atom, alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, sulfonic acid group, An alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group,

Of the above-mentioned formulas (OS-3) to (OS-5), at least one of the heteroaryl groups in R ^{1 may} be a heteroaromatic ring, for example, a heterocyclic aromatic ring and a benzene ring may be condensed.

Examples of the heteroaryl group for R ¹ include a group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophen ring, a benzothiazole ring, and a benzoimidazole ring which may have a substituent And a group excluding one hydrogen atom from the selected ring.

Of the above 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.

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

Among the above-mentioned formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ² may have a substituent.

Examples of the substituent which the alkyl group or aryl group in R ² may have include the same group as the substituent that 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 carbon atoms in total which may have a substituent.

Specific 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- N-hexyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, perfluorohexyl group, chloromethyl group, bromomethyl group, methoxymethyl group, benzyl group, A phenylthioethyl group, an ethoxycarbonylethyl group, a phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group.

Among them, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s- , A benzyl group is preferable and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Propyl group, n-butyl group and n-hexyl group are more preferable, and methyl group is particularly preferable.

The aryl group in R ² is preferably an aryl group having a total of 6 to 30 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, Phenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group.

Among them, a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group and a p-phenoxyphenyl group are preferable.

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.

Of the above 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 a 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 2 desirable.

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

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyl group for R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms in total 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, benzyl, phenoxyethyl, methylthioethyl, phenylthioethyl, ethoxycarbonylethyl, phenoxyl A cyclopropylmethyl group, a cyclopropylmethyl group, a cyclopropylmethyl group, a cyclohexylmethyl group,

Of these, preferred are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- An n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyloxy group for R ⁶ 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 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 alkyloxy group for R ⁶ include a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, an ethoxyethyloxy group, a methylthioethyloxy group, a phenyl A thioethyloxy group, an ethoxycarbonylethyloxy group, a phenoxycarbonylethyloxy group, and a dimethylaminocarbonylethyloxy group.

Of these, methyloxy, ethyloxy, butyloxy, hexyloxy, phenoxyethyloxy, trichloromethyloxy or ethoxyethyloxy groups are preferred.

Of the above-mentioned formulas (OS-3) to (OS-5), examples of the aminosulfonyl group in R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group and an aminosulfonyl group have.

Of the above-mentioned formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ⁶ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group and a butyloxycarbonyl 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, Do.

The compound containing the oxime sulfonate compound represented by the formula (b1) is particularly preferably an oxime sulfonate compound represented by any 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 and R ⁸ represents a hydrogen atom, 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, a halogen atom, a chlorine atom, Lt; / RTI &gt;

Expression (OS-6) ~ R ¹ in (OS-11) is R ¹ and agreed in the formula (OS-3) ~ (OS -5), as a preferred aspect.

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 the oxime sulfonate compound, any of the three-dimensional structures (E, Z) of oxime may be a mixture or a mixture thereof.

Specific examples of the oxime sulfonate compounds 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 the oxime sulfonate compound 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 is an alkyl group, or , And 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 are bonded to each other to form an aryl group. Among them, the case where all of R ²¹ to R ²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

Each of the functional groups described above may further have a substituent.

The compound represented by the above formula (OS-1) is 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 preferred examples are also the same.

Among them, R ¹ in the formulas (OS-1) and (OS-2) is preferably a cyano group or an aryl group, more preferably represented by the formula (OS-2), R ¹ is a cyano group, Most preferred are the sun or the naphthyl group.

In the oxime sulfonate compound, the stereostructure (E, Z, etc.) of oxime or benzothiazole ring may be either or both of them.

Specific examples (Exemplary Compounds b-1 to b-34) of a compound represented by the formula (OS-1) that can be 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.

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

It is also preferable that the compound containing the oxime sulfonate compound represented by the formula (b1) is 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, X may be the same or 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.

In the formula (b2), m 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-oxonorbornylmethyl group , Or a p-toluyl group is particularly preferable.

The compound containing an oxime sulfonate compound represented by the formula (b1) is also preferably an oxime sulfonate compound represented by the formula (b3).

(Wherein R ^B1 represents an alkyl group, an alkoxy group, or a halogen atom, and R ^B2 represents an alkyl group or an aryl group.)

R ^B1 is preferably an alkoxy group, more preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.

R ^B2 is preferably an alkyl group and is preferably a methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro- a n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group.

Specific examples of preferred oxime sulfonate compounds 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 (B) photoacid generators.

In the photosensitive resin composition of the present invention, the oxime sulfonate compound (B) is preferably used in an amount of from 0.1 to 100 parts by weight based on 100 parts by weight of the total resin component (preferably a solid component, more preferably the above (A) 10 parts by mass, and more preferably 0.5 to 10 parts by mass.

(C) Solvent

In the present invention, at least one solvent contains a solvent having a boiling point of less than 180 占 폚 and at least one solvent having a boiling point of 180 占 폚 or higher. The total amount of the solvent (the total amount of the solvent having a boiling point of less than 180 캜) (the total amount of the solvent having a boiling point of 180 캜 or more) is 99: 1 to 50:50, preferably 99: 1 to 70:30, Is blended in a ratio of 99: 1 to 90: 10, and most preferably 99: 1 to 95: 5.

In particular, when the ratio of the solvent (the total amount of the solvent having a boiling point of less than 180 캜) to the total amount of the solvent (the total amount of the solvent having a boiling point of 180 캜 or more) is in the range of 99: 1 to 90:10, the effect of preventing the coating property of the photosensitive resin composition from being deteriorated have.

By employing a compound containing the oxime sulfonate moiety represented by the general formula (b1) as the photoacid generator by using two or more kinds of such solvents, it is possible to provide a photosensitive composition which is excellent in sensitivity, storage stability, solvent resistance, An excellent photosensitive resin composition can be obtained. Particularly, it is very unexpected that the effect is exhibited in combination with the photoacid generator.

(Solvent having a boiling point lower than 180 deg. C)

In the present invention, the solvent having a boiling point of less than 180 캜 preferably has a boiling point of 120 to 179 캜, more preferably 130 to 178 캜, and even more preferably 140 to 178 캜.

In the present invention, the solvent having a boiling point of less than 180 占 폚 may be one kind or two or more types. In the case of two or more types, the boiling point of each component may be less than 180 占 폚.

As the solvent having a boiling point lower than 180 ° C, a known solvent can be used. Specific 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, dipropylene Glycol monoalkyl ether acetates, esters, ketones, amides, lactones and the like having a boiling point of less than 180 ° C can be widely employed.

Preferred are propylene glycol monomethyl ether acetate (PGMEA), diethylene glycol ethyl methyl ether (hyposorb EDM) and ethyl 3-ethoxypropionate.

The solvent having a boiling point of less than 180 占 폚 preferably has a distribution coefficient LogP of -0.5 to 1.0, more preferably -0.3 to 0.8. By setting such a range, the compatibility with the polymer becomes better, and the resistance to ITO sputtering tends to be further improved.

In this specification, the partition coefficient (LogP) represents the octanol-water partition coefficient. The octanol-water partition coefficient (LogP value) can be measured by a flask permeation method generally described in JIS Japan Industrial Standard Z7260-107 (2000). In addition, the octanol-water partition coefficient (LogP value) can be estimated by computational chemical methods or empirical methods instead of actual measurements. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Broto's fragmentation method (Eur. J. Med. Chem., Chim. Theor., 19, 71 (1984)). In the present invention, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is used.

The CLogP value is a value obtained by calculating the common logarithm LogP of the partition coefficient P of 1-octanol and water. Although known methods and software for the calculation of the CLogP value can be used, the present invention uses the CLOGP program embedded in the system of Cambridge Soft Corporation: Chem Draw Pro.

Whether or not the value of LogP of any compound differs depending on the measurement method or the calculation method is within the scope of the present invention is determined by the Crippen's fragmentation method.

(Solvent (auxiliary solvent) having a boiling point of 180 DEG C or higher)

In the present invention, the solvent having an abnormality of 180 占 폚 or higher (hereinafter also referred to as an auxiliary solvent) preferably has a boiling point of 180 to 260 占 폚, more preferably 180 to 250 占 폚, further preferably 180 to 240 占 폚 Do.

In the present invention, the solvent having a boiling point of 180 ° C or higher may be one kind or two or more types. In the case of two or more types, the boiling point of each component may be 180 캜 or higher.

(EC, 261 占 폚), propylene carbonate (PC, 240 占 폚) (all Kanto Kagaku), dipropylene glycol methyl ether (DPM, 190 占 폚), tripropylene glycol methyl ether (DPNB, 229 占 폚), tripropylene glycol n-butyl ether (TPNB, 274 占 폚), dipentaerythritol n-butyl ether Propylene glycol diethylacetate (PGDA, 190 占 폚), 1,3-butylene glycol diacetate (1,3-BGDA, 232 占 폚), 1,4-butanediol diacetate (1,4-BDDA, 220 占 폚), 1,6-hexane diol diacetate (1,6-HDDA, 260 占 폚), dipropylene glycol methyl n-propyl ether (DPMNP, 203 占 폚), ethylene glycol monobutyl Diethyleneglycol monoethyl ether (EDG, 202 占 폚), diethylene glycol monoethyl ether acetate (EDGAC, 217 占 폚), diethylene glycol (DRA-150, 260 占 폚), ethyl lactate (ELA, 181 占 폚), 1,3-butylene glycol 1,3-BGDA, PGDA and PC are preferable, and ELA, 1, 2, 3, 4, 5 and 6 are preferable, and diethylene glycol methyl n-butyl ether (DPMNB, 216 캜) 3-BGDA, PGDA and PC are more preferable.

In the present invention, the solvent having a boiling point of 180 캜 or higher is preferably -0.5 to 1.0 in terms of the partition coefficient (Log P) in view of storage stability, and more preferably -0.3 to 0.8. Among them, ethylene carbonate (EC, 0.3), propylene carbonate (PC, 0.62) (all Kanto Kagaku Co.), propylene glycol diacetate (PGDA, -0.23), 1,3-butylene glycol diacetate BGDA, 0.09), diethylene glycol monoethyl ether acetate (EDGAC, -0.02), and lactic acid ethyl acetate (ELA, 0.32) (available from Daicel Chemical Industries, Ltd.).

The content of the solvent (C) in the photosensitive resin composition of the present invention is preferably 100 to 1,000 parts by weight per 100 parts by weight of the resin component, the total amount of the solvent having a boiling point of 180 캜 or more and the solvent having a boiling point of less than 180 캜 More preferably 150 to 900 parts by weight, and still more preferably 200 to 800 parts by weight.

The crosslinking agent

The photosensitive resin composition of the present invention contains a crosslinking agent, if necessary. As the crosslinking agent, for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond may be added as described below. By adding a crosslinking agent, 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 and aliphatic epoxy resin.

These are available as commercial products. Examples of the bisphenol A type epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 JER4005, JER4007, and JER4010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (manufactured by DIC Corporation), and the like as the bisphenol F type epoxy resin, JER152, JER154, JER157S65, and JER157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) as the phenol novolak type epoxy resin, and LCE-21, RE-602S (manufactured by Nihon Kayaku Co., EPICLON N-760, EPICLON N-770, EPICLON N-770 and EPICLON N-775 (manufactured by DIC Corporation) as the cresol novolak type epoxy resin, EPICLON N-670, EPICLON N-670, EPICLON N-680, EPICLON N-690, EPICLON N-690 and EPICLON N-695 (manufactured by DIC Corporation) , Aliphatic epoxy resins include ADEKA RESIN EP-4080S, copper EP04085S, EP-4088S (manufactured by ADEKA), Suloxide 2021P, Suloxide 2081, Suloxide 2083, Suloxide 2085, EHPE3150, EPOLEAD PB 3600 and PB 4700 Manufactured by Kagaku Kogyo Co., Ltd.) and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- -501, and EPPN-502 (manufactured by ADEKA Co., Ltd.). 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 and cresol novolak type epoxy resin. Particularly preferred are bisphenol A type epoxy resins, phenol novolak type epoxy resins and aliphatic epoxy resins.

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

As specific examples of the compound having two or more oxetanyl groups in the molecule, OXT-121, OXT-221, OX-SQ and PNOX (manufactured by Dowa Kosei K.K.) may be used.

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.

<Crosslinking agent containing alkoxymethyl group>

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. These can be obtained by converting methylol melamine, methylol benzoguanamine, methylol glycoluryl, or the methylol group of the methylol moiety into an alkoxymethyl group, respectively. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of generated outgas, in particular, a methoxymethyl group desirable. Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable crosslinking compounds, and from the viewpoint of transparency, alkoxymethylated glycoluril is particularly preferable.

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.), NIKARAKU MX-750, -032, -706, -708, -40, -31, -270, -280, -290, NIKARAKU MS-11, NIKARAKU MW-30HM, -100 LM, -390 (manufactured by SANWA CHEMICAL CO., LTD.) And the like can be preferably used.

When an alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the amount of the alkoxymethyl group-containing crosslinking agent to be added 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. By adding it in this range, favorable alkali solubility at the time of development and excellent solvent resistance of the film after curing can be obtained.

&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 higher functional (meth) have.

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

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

Examples of trifunctional or higher (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (Meth) 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 singly or in combination of two or more kinds.

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 containing a compound having at least one ethylenically unsaturated double bond in such a ratio, the 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.

Increase / decrease agent

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with a radiation-sensitive acid generator in order to promote its decomposition. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer brought into 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 decomposes by chemical change and generates acid. Examples of preferred sensitizers include compounds having an absorption wavelength in any of the wavelength ranges from 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- Xanthones such as xanthone, thioxanthone, dimethylthioxanthone, and diethylthioxanthone), xanthan derivatives such as xanthone (e.g., fluorene, eosin, erythrosine, rhodamine B and rose bengal) (Such as thiocarbocyanine, oxacarbocyanine), melocyanines (e.g., melocyanine, carbomeroxy), rhodacyanines, oxonols, thiazines (Such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, 10-butyl-2-chloro-thiophene, (Such as anthraquinone), squaryliums (e.g., squalium), styryls, (For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, , 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-pne).

Among 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.

Adhesion improver

The photosensitive resin composition of the present invention may contain a silane coupling agent as an adhesion improver. The silane coupling agent that can be used in the photosensitive resin composition of the present invention is a silane coupling agent that improves the adhesion of an inorganic substance to be a base material, for example, a silicon compound such as silicon, silicon oxide, silicon nitride, or the like, metal such as gold, / RTI &gt;

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -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 for improving the adhesion with the substrate, and are also effective for adjusting the taper angle with the substrate.

The content of the silane coupling agent in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the resin component.

Surfactants

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

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 Co., Ltd.), Megapack (Manufactured by Asahi Glass Co., Ltd.), and PolyFox (OMNOVA SHUSHE), and the like.

The surfactant preferably has a 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 are each independently a hydrogen atom or a methyl group, R ² is a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴ is a hydrogen atom or a C1- P represents an alkylene group having 3 to 6 carbon atoms, p and q each represent a weight percentage representing a polymerization ratio, p represents a value of 10 wt% or more and 80 wt% or less, q represents a weight % Or more and 90% or less by weight, 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 from the viewpoint of compatibility and wettability to the surface to be coated, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 2 or 3 carbon atoms is more preferable Do. It is preferable that the sum (p + q) of p and q is p + q = 100, that is, 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, and more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the resin component More preferable.

Thermal radical generator

The photosensitive resin composition of the present invention may contain a thermal radical generator. As the thermal radical generator in the present invention, a known thermal radical generator may be used.

The thermal radical generator is a compound which generates radicals by the energy of heat and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the resulting cured film becomes stronger, and 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, A compound having a bond, an azo compound, a bibenzyl compound, and the like. One kind of thermal radical generator may be used alone, or two or more kinds of thermal radical generators may be used in combination.

The addition amount of the heat radical generator in 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, most preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer Do.

Antioxidant

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant may be contained. Addition of an antioxidant has the advantage of being able to prevent the cured film from being colored or to reduce the film thickness reduction due to decomposition and also to have 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 salts, sulfites, thiosulfates, hydroxyl Amine derivatives and the like. Among them, a phenol-based antioxidant is particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used alone or in combination of two or more.

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

The content of the antioxidant 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. Within this range, sufficient transparency of the formed film can be obtained and the sensitivity at the time of pattern formation becomes good.

As the additives other than the antioxidant, various ultraviolet absorbers, metal deactivators, and the like described in &quot; New developments of the polymer additive &quot; (Ilgan Kogyo Shimbun) may be added to the photosensitive resin composition of the present invention.

Basic compound

The photosensitive resin composition of the present invention may contain a basic compound. As the basic compound, any of those used in the chemically amplified resist can be 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- Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

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

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl- Benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy 4-methyl morpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1, 2-diazabicyclo [4.3.0] -naphthalene, pyrazine, pyridazine, pyridine, pyrrolidine, piperidine, piperazine, morpholine, , 8-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.

The basic compounds which can be used in the present invention may be used singly or in combination of two or more kinds. However, two or more basic compounds are preferably used together, and more preferably two kinds of basic compounds are used. It is more preferable to use them in combination.

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.2 part by weight, per 100 parts by weight of the resin component.

(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 is characterized by including 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 developer

(5) Heat curing step (post baking step)

Each step will be described below in order.

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

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

(3), an active 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. By the catalytic action of the generated acid, the acid-decomposable group contained in the (A) copolymer is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.

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

The acid-decomposable group in the monomer unit 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 upon exposure to form a carboxyl group or a phenolic hydroxyl group A positive image can be formed by development without necessarily performing PEB.

Further, by performing PEB at a relatively low temperature, the hydrolysis of the acid decomposable group can be promoted 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.

(4), an aqueous developer, for example, a copolymer having a liberated carboxyl group or a phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing the exposed region containing a resin composition having a carboxyl group or a phenolic hydroxyl group which is easily dissolved in an alkaline developer.

(A2) by thermal decomposition of an acid-decomposable group in the monomer unit (a1) by heating the obtained positive image in a post-baking step of the monomer unit (5) to form a cured film can do. This heating is preferably carried out 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 appropriately set depending on the heating temperature and the like, but is preferably within a range of 10 to 90 minutes.

When a step of irradiating an entire surface of the development pattern with an actinic ray, preferably ultraviolet light, is performed before the post-baking step, the cross-linking reaction can be promoted by an acid generated by actinic light 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 in any manner, 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 solvent (C), 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 diameter of 0.2 mu m or the like.

<Application Process and Solvent Removal Process>

The 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). Examples of the above substrate include a polarizing plate and a glass plate provided with a black matrix layer and a color filter layer as necessary and provided with a transparent conductive circuit layer in the production of a liquid crystal display element. The application method to the substrate is not particularly limited, and for example, a slit coating method, a spraying 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. When manufactured from a large-sized substrate, productivity is high and preferable. 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 decomposes in the monomer unit (a1) in the resin component in the unexposed portion and the resin component is not soluble in the alkali developing solution. But it is preferably about 80 to 130 占 폚 for about 30 to 120 seconds.

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

In the exposure step, a mask having a predetermined pattern is interposed between the substrate provided with the coating film and the active ray is irradiated. After the exposure process, a heating process (PEB) is carried out if necessary, and in the development process, an exposed area is removed by using an alkaline developer to form an image pattern.

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

It is preferable that a developer to be used in the developing process 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 developing time is preferably 30 to 180 seconds, and the developing method may be any of a liquid method, a dipping method and the like. After the development, a desired pattern can be formed by performing an aqueous (water) cleaning for 30 to 90 seconds.

&Lt; Post baking step (crosslinking step) >

The pattern corresponding to the unexposed area obtained by the development is heated at a predetermined temperature, for example, 180 to 250 占 폚, for a predetermined time, for example, 5 to 5 minutes on a hot plate, using a heating apparatus such as a hot plate or an oven. (A2) by dissolving an acid-decomposable group in the resin component to generate a carboxyl group or a phenolic hydroxyl group by performing heat treatment for 30 minutes to 60 minutes in an oven for 30 to 90 minutes to cause crosslinking reaction with the crosslinkable group in the monomer unit , Hardness, and the like can be formed. Further, when the heat treatment is performed, transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

Prior to the heat treatment, an acid is generated from the component (B) present in the unexposed portion by post-baking (re-exposure / post-baking) after re-exposure to the substrate on which the pattern is formed by an actinic ray , And to function as a catalyst promoting the crosslinking process.

That is, the method of forming a cured film of the present invention preferably 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 performed 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 where 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;.

The photosensitive resin composition of the present invention can provide an interlayer insulating film having high transparency 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 is useful for an organic EL display device or a liquid crystal display device because it has high transparency and excellent physical properties of a cured film.

The organic EL display device and the liquid crystal display device of the present invention are not particularly limited except that they have a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention and may be various known organic EL displays Device or a liquid crystal display device.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned use, and can be used for various purposes. For example, in addition to a planarizing film or an interlayer insulating film, a protective film for a color filter, a spacer for keeping the thickness of the liquid crystal layer in a liquid crystal display device constant, a micro lens 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 so as to cover the TFT 1. A wiring 2 (height 1.0 mu m) connected to the TFT 1 via the contact hole is formed on the insulating film 3 after forming a contact hole (not shown) in the insulating film 3 . The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or in a subsequent step to the TFT 1. [

The planarization layer 4 is formed on the insulating film 3 so as to fill the irregularities formed by the wirings 2 in order to planarize the irregularities formed by the formation of the wirings 2.

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

The insulating film 8 is formed so as to cover the periphery of the first electrode 5. By providing the insulating film 8, the first electrode 5 and the second electrode Can be prevented.

Although not shown in Fig. 1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially evaporated and deposited via a desired pattern mask. Then, a second electrode made of Al is formed on the entire upper surface of the substrate, An organic EL display device of an active matrix type in which an encapsulating glass plate and an ultraviolet curing type epoxy resin are used to bond them to each other and the TFTs 1 for driving the organic EL elements are connected, Can be obtained.

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 a liquid crystal display panel in which all of the two glass substrates 14 and 15 that are stuck Elements of the TFT 16 corresponding to the pixel are disposed. In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of the liquid crystal 20 and a black matrix are arranged is provided.

Example

EXAMPLES Next, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" are by weight.

In the present embodiment, the following symbols each represent the following compounds.

V-65: 2,2'-azobis (2,4-dimethylvaleronitrile)

GMA: glycidyl methacrylate

MAA: methacrylic acid

MMA: methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

NBMA: n-butoxymethyl acrylamide (Tokyo Kasei now)

HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko)

MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

OXE-30: Methacrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

M100: 3,4-epoxycyclohexylmethacrylate (manufactured by Daicel Chemical Industries, Ltd.)

CHOEMA: 1- (cyclohexyloxy) ethyl methacrylate

MATHF: tetrahydrofuran-2-yl methacrylate

Ph-1: alpha -methylhydroxystyrene

P-Ph-1: 1-ethoxyethyl protected form of? -Methylhydroxystyrene

St: Styrene

&Lt; Synthesis of MATHF (tetrahydrofuran-2-yl methacrylate)

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, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure at 40 ° C or lower. The yellow oily matter was distilled under reduced pressure to obtain 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg as a colorless oil (Yield: 80%).

&Lt; CHOEMA (Synthesis of 1- (cyclohexyloxy) ethyl methacrylate)

CHOEMA was synthesized in the same manner as in the synthesis of MAEVE.

<Synthesis of P-Ph-1 (1-ethoxyethyl protected product of? -Methylhydroxystyrene)

P-Ph-1 was obtained by reacting Ph-1 with ethyl vinyl ether under an acid catalyst to obtain P-Ph-1 as an ethyl acetal protecting agent for a phenolic hydroxyl group.

&Lt; Synthesis of Polymer A-1 &

Polymer A-1 corresponding to component A of the present invention was synthesized as follows.

(1 molar equivalent) of methacrylic acid was added dropwise to 144.2 parts (2 molar equivalents) of ethyl vinyl ether while 0.5 part of phenothiazine was added and the reaction system was cooled to 10 DEG C or lower. The mixture was then stirred at room temperature (25 DEG C) for 4 hours Lt; / RTI &gt; 5.0 parts of p-toluenesulfonic acid pyridinium was added, and the mixture was stirred at room temperature for 2 hours and allowed to stand at room temperature overnight. 5 parts of sodium hydrogencarbonate and 5 parts of sodium sulfate were added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated under reduced pressure at 40 ° C or lower. The yellow oil was distilled under reduced pressure to obtain a boiling point (bp) of 43 To obtain 134.0 parts of 1-ethoxyethyl methacrylate as a colorless oil at ~ 45 占 폚 / 7 mm Hg fraction.

The obtained methacrylic acid 1-ethoxyethyl (63.28 parts (0.4 molar equivalent)), GMA (42.65 parts (0.3 molar equivalent)), MAA (8.61 parts (0.1 molar equivalent) ) And PGMEA (110.8 parts) was heated to 70 占 폚 under a nitrogen stream. While stirring the mixed solution, a mixed solution of a radical polymerization initiator V-65 (4 parts by Wako Pure Chemical Industries, Ltd.) and PGMEA (100.0 parts) was added dropwise over 2.5 hours. After completion of the dropwise addition, PGMEA solution (solid concentration: 40%) of polymer A-1 was obtained by reacting at 70 DEG C for 4 hours.

The polymer A-1 thus obtained had a weight average molecular weight of 15,000 as measured by gel permeation chromatography (GPC).

<Synthesis of Polymers A-2 to A-10 and A-12 to A-21>

Polymers A-2 to A-10 and A-12 to A-21 were synthesized in the same manner as in the synthesis of Polymer A-1, except that the respective monomers used and the amounts used were changed as shown in Table 1 . The solvent used for the synthesis of A-10 was replaced with diethylene glycol ethyl methyl ether (trade name: Hyosorb EDM, manufactured by Tohoku Kagaku Kogyo K.K.) and ethyl 3-ethoxypropionate Except that the catalyst was changed to A-14 and A-15, respectively. Their weight average molecular weights were the same as those of A-10.

&Lt; Synthesis of Polymer A-11 >

In a three-necked flask, diethylene glycol ethyl methyl ether (trade name: Hyosorb EDM, manufactured by Toho Chemical Industry Co., Ltd., 35.7 g) was added as a solvent and the temperature was raised to 90 占 폚 in a nitrogen atmosphere. To the solution was added MAA (3.48 g, manufactured by Wako Pure Chemical Industries, Ltd.), MMA (0.43 g), HEMA (0.55 g), St (12.64 g), NBMA (2-methylpropionate, 3.47 g, manufactured by Wako Pure Chemical Industries, Ltd., 8 mol% based on the monomer) was added dropwise over 2 hours. After completion of dropwise addition, stirring was continued for 2 hours. g, and 2 mol% based on the monomer) were further added and stirred for 2 hours to terminate the reaction, whereby a binder A-11 was obtained.

[Table 1]

Details of the abbreviations used for the compounds used in Examples and Comparative Examples are as follows.

B-1: CGI-1397 (compound having the structure shown below, manufactured by Chiba Specialty Chemicals)

B-2:? - (p-toluenesulfonyloxyimino) phenylacetonitrile (synthesis method is shown below)

B-3: Compound having the structure shown below (synthesis method is shown below)

B-4: Triphenylsulfonium nonafluorobutanesulfonate

B-5: Compound having the structure shown below (NAI-101, Midori Kagaku Co., Ltd.)

C-1: Lactic acid ethyl acetate (ELA, manufactured by Daicel Chemical Industries, Ltd., boiling point 181 캜, LogP = 0.32)

C-2: 1,3-butylene glycol diacetate (1,3-BGDA, manufactured by Daicel Chemical Industries, Ltd., boiling point 232 ° C, LogP = 0.09)

C-3: Propylene glycol diacetate (PGDA, manufactured by Daicel Chemical Industries, Ltd., boiling point 190 占 폚, LogP = -0.23)

C-4: propylene carbonate (PC, Kanto Kagaku Co., boiling point 240 ° C, LogP = 0.62)

C-5: 1,6-hexanediol diacetate (1,6-HDDA, manufactured by Daicel Chemical Industries, Ltd., boiling point 260 ° C, LogP = 1.06)

C-6: A compound having the structure shown below (LogP = -0.51, manufactured by Tokyo Chemical Industry Co., Ltd.)

C-7: Tripropylene glycol n-butyl ether (TPNB, manufactured by Daicel Chemical Industries, Ltd., boiling point: 274 ° C, LogP = 1.46)

L-1: DBA (9,10-dibutoxyanthracene, structure shown below, manufactured by Kawasaki Chemical Industry Co., Ltd.)

E-1: JER157S65 (phenol novolak type epoxy resin, Japan Epoxy Resin Co., Ltd.)

E-2: JER828 (bisphenol A type epoxy resin, Japan Epoxy Resin Co., Ltd.)

G-1: KBM-403 (3-glycidoxypropyltrimethoxysilane, structure shown below, manufactured by Shin-Etsu Chemical Co., Ltd.)

H-1: 1,5-diazabicyclo [4.3.0] -5-nonene (available from Tokyo Gagai)

H-2: Triphenylimidazole (companion Tokyo)

H-3: A compound having the structure shown below

I-1: W-3 (structure shown below, made by DIC)

Bu in the above formula represents a butyl group.

[Synthesis of B-2]

Α- (p-toluenesulfonyloxyimino) phenylacetonitrile was synthesized according to the method described in paragraph 0108 of Japanese Patent Application No. 2002-528451.

[Synthesis of B-3]

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 캜 for reaction for 2 hours. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, 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 占 폚 for 1 hour. 2N HCl aqueous solution (60 mL) was added thereto to separate the liquid. The organic layer was concentrated, and crystals were dissolved in diisopropyl ether The residue was 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 resulting suspension of the ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, 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 resulting 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 mixture was heated 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 with methanol (20 mL), followed by filtration and drying to obtain B-7 (2.3 g).

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

(Example 1)

Each component was dissolved and mixed so that the following composition 1 was obtained, and the solution was filtered through a polytetrafluoroethylene filter having a diameter of 0.2 탆 to obtain a photosensitive resin composition of Example 1.

<Composition 1>

(A) Copolymer: PGMEA solution of polymer A-1 (solid content 40%) 100.0 parts in solid content

(B) Photoacid generator: 2.0 parts of B-1 shown above

(L) sensitizer: 2.0 parts of L-1 shown above

(C) Solvent: Lactic acid ethyl acetate (ELA) 3.0 parts

(E) Crosslinking agent: 2.0 parts of E-1 shown above

(G) Adhesion improving agent: 0.5 parts of G-1 shown above

(H) Basic compound: 0.1 part of H-1 shown above

(H) Basic compound: 0.01 part of H-2 shown above

(I) Surfactant: 0.02 part of I-1 shown above

(Examples and Comparative Examples)

The respective compounds used in Example 1 were dissolved and mixed in the same amounts as in Example 1, except that the compounds described in the following table were changed, and photosensitive resin compositions of Examples and Comparative Examples were prepared. In addition, in Examples 44 to 47, in addition to the compounds described in Table 3 below, the amount of the auxiliary solvent was further added in an amount twice that of Example 1 to adjust the photosensitive resin composition. Other than that, the compounds were changed as shown in the following Table 3 and evaluated.

In Comparative Example 5, the composition described in Example 1 of Japanese Patent Application Laid-Open No. 5-165214 was used. In Comparative Example 6, the composition described in Example 1 of Japanese Patent Application Laid-Open No. 2004-264623 was used. In Comparative Example 7, the composition described in Japanese Patent Laid-Open No. 2001-056558 was used. In Comparative Example 8, the composition described in Example 1 of Japanese Patent Application Laid-Open No. 2005-301210 was used.

The following evaluations were performed on the photosensitive resin compositions of the examples and comparative examples obtained as described above.

&Lt; Evaluation of sensitivity &

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

Subsequently, the obtained photosensitive resin composition layer was exposed using a PLA-501F Exposure Machine (ultra-high pressure mercury lamp) manufactured by Canon Inc. via a predetermined mask. Then, the exposed photosensitive resin composition layer was developed in an alkaline developer (0.4 wt% tetramethylammonium hydroxide aqueous solution) at 23 DEG C / 60 seconds, and rinsed with ultrapure water for 20 seconds.

With these operations, the optimum i-line exposure amount (Eopt) at the time of resolving the line-and-space of 10 mu m at a ratio of 1: 1 was taken as the sensitivity. The evaluation criteria are as follows. Quot; 1 &quot; and &quot; 2 &quot; The results are shown in the following table.

1: Eopt is less than 40 mJ / cm 2

2: Eopt less than 40mJ / cm2 and less than 60mJ / cm2

3: Eopt is 60mJ / cm2 or more and less than 80mJ / cm2

4: Eopt more than 80mJ / ㎠

<Evaluation of Storage Stability>

The sensitivity immediately after the adjustment of the photosensitive resin composition was evaluated by the same method as described above to obtain the initial sensitivity. Sensitivity was measured when the same composition was stored at 30 DEG C for one week and when it was stored for two weeks, and the relative value of how much the composition was changed from the initial sensitivity was evaluated in three steps. Quot; 1 &quot; and &quot; 2 &quot; The results are shown in the following table.

1: Sensitivity change less than 5%

2: Sensitivity change from 5% to less than 10%

3: Sensitivity change from 10% to less than 15%

4: 15% or more change in sensitivity

&Lt; Evaluation of solvent resistance &

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (Corning Co.)), 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 obtained photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) with a PLA-501F exposure device (ultra high pressure mercury lamp) manufactured by Canon Inc., At 230 占 폚 for 1 hour to obtain a cured film.

The film thickness (T ¹ ) of the obtained cured film was measured. Then, the cured film was immersed 20 minutes while controlling the temperature of dimethyl sulfoxide a substrate formed of a 70 ℃, the cured film and measure the film thickness (t ¹⁾ after immersion, the film thickness change ratio by an immersion {| t ¹ -T ¹ | / T ¹ } × 100 [%]. The results are shown in the following table.

When the value of the film thickness change rate is less than 1% (that is, when the results of criteria 1 to 3 are obtained), the cured film has good solvent resistance.

1: The value of the film thickness change ratio was less than 0.2%

2: The value of the film thickness change rate is 0.2% or more and less than 0.5%

3: value of film thickness change rate is 0.5% or more and less than 1%

4: value of the film thickness change ratio is 1% or more

&Lt; Evaluation of exposure margin &

(Line width) of the post-development 5 占 퐉 line-and-space pattern in the case where the exposure amount was increased or decreased (占 1.25 and 占 0.75) when exposure was performed at an exposure amount (illumination: 20 mW / I evaluated the change. The results are shown in the following table. When the line width variation is less than 0.5 mu m, that is, when the variation is less than the evaluation &quot; 2 &quot;, the exposure margin is good. The results are shown in the following table.

1: Line width change is less than 0.3 탆

2: Line width change is 0.3 탆 or more and less than 0.5 탆

3: Line width change is not less than 0.5 탆 and less than 0.7 탆

4: Line width change of 0.7 탆 or more

<Evaluation of Developing Margin>

(Line width) of the developed 5 占 퐉 line and space pattern when the developing time was increased or decreased (占 1.25 and 占 0.75) when exposure was performed at an exposure amount (illuminance: 20 mW / cm2, i line) The line width change was evaluated. The results are shown in the following table. When the line width variation is less than 0.5 mu m, that is, when the variation is less than the evaluation &quot; 2 &quot;, the exposure margin is good. The results are shown in the following table.

1: Line width change is less than 0.3 탆

2: Line width change is 0.3 탆 or more and less than 0.5 탆

3: Line width change is not less than 0.5 탆 and less than 0.7 탆

4: Line width change of 0.7 탆 or more

<Evaluation of ITO aptitude>

A cured film having a film thickness of 3.0 占 퐉 was formed on a glass substrate (Corning 1737, 0.7 mm thick (Corning Co.)) as in the evaluation of the solvent resistance. On this cured film, an ITO transparent electrode was formed by sputtering (ULVAC SHARE, SIH-3030, sputtering temperature: 200 캜). The surface of the cured film after the sputtering was observed with an optical microscope (500 times) and evaluated from the following viewpoints.

1: No wrinkles on the surface of the cured film

2: Wrinkles are slightly formed on the surface of the cured film

3: There is significant wrinkle on the surface of the cured film

4: Occurrence of crack

When a remarkable wrinkle or crack is observed on the surface of the cured film after the ITO transparent electrode is formed by sputtering, the transmittance of the cured film is lowered, which is undesirable. That is, &quot; 1 &quot; and &quot; 2 &quot;

[Table 2]

[Table 3]

As is apparent from the above table, when the composition of the present invention was used, it was found that the composition was excellent in sensitivity, storage stability, solvent resistance and exposure margin.

When the distribution coefficient of the auxiliary solvent is less than -0.5, the storage stability tends to be slightly inferior to that of the best embodiment (Example 50). When the auxiliary solvent has a partition coefficient of less than -0.5, the ITO sputter resistance (Example 49). &Lt; tb &gt; &lt; TABLE &gt;

It was also found that the solvent resistance tends to be slightly lower than that of the best example (Example 51) when using an auxiliary solvent having a higher boiling point (for example, a boiling point of 270 占 폚 or more) .

On the other hand, even when an imide sulfonate compound having an approximate structure of a compound containing an oxime sulfonate residue represented by the general formula (b1) is used (Comparative Example 4), the effect of the present invention is not exhibited at all Could know.

In addition, it was found that the ITO sputter resistance was further improved by blending two kinds of main solvents.

Further, it was found that when the two components were blended as the copolymer, the solvent resistance tended to be further improved.

(Example 68)

Using the photosensitive resin composition of Example 1, evaluation was carried out in the same manner as in Example 1 using a UV-LED light source exposing apparatus instead of an ultra-high pressure mercury lamp. As a result, the same results as in Example 1 were obtained.

(Example 69)

Sensitivity and evaluation were performed in the same manner as in the evaluation of the sensitivity of the photosensitive resin composition of Example 21 except that the substrate was changed from a glass substrate to a silicon wafer using the photosensitive resin composition of Example 21. [ As a result, the same results as in Example 21 were obtained.

(Example 70)

The photosensitive resin composition of Example 11 was obtained in the same manner as in Example 11 except that the photosensitive resin composition of Example 11 was used and the exposure machine was changed from an exposure machine manufactured by Canon Inc. to FX-803M (gh-Line stepper) The sensitivity was evaluated in the same manner as in the evaluation of the sensitivity. As a result, the same result as in Example 11 was obtained.

(Example 71)

The sensitivity to the photosensitive resin composition of Example 11, except that the photosensitive resin composition of Example 11 was used to change the exposure machine from an exposure device manufactured by Canon Inc. to a 355 nm laser exposure device and to perform 355 nm laser exposure , The sensitivity was evaluated. As a result, the same result as in Example 11 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" OPHIR SHARSE.

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

(Example 72)

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 so as to cover the TFT 1. Subsequently, a contact hole (not shown) is formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 via the contact hole is formed on the insulating film 3 . This wiring 2 is for connecting the organic EL element formed between the TFTs 1 or a later step to the TFT 1. [

In order to planarize the irregularities formed by the formation of the wirings 2, the planarization layer 4 was formed on the insulating film 3 in a state in which irregularities by the wirings 2 were filled. The planarizing film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 31 on the substrate, prebaking (90 占 폚 for 2 minutes) on a hot plate, using a high-pressure mercury lamp on the mask , Irradiated with i-line (365 nm) at 45 mJ / cm 2 (illuminance: 20 mW / cm 2), developed with an aqueous alkaline solution to form a pattern, and subjected to heat treatment at 230 ° C for 60 minutes. The coating properties upon application of the photosensitive resin composition were satisfactory, and wrinkles and cracks were not observed in the cured films obtained after exposure, development and firing. The average step difference of the wiring 2 was 500 nm, and the film thickness of the prepared 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 being connected to the wiring 2 through the contact hole 7. Thereafter, the resist was applied and prebaked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was carried out by wet etching using ITO etchant. Thereafter, the resist pattern was peeled off using a resist stripping solution (a mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained 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. As the insulating film, the insulating film 8 was formed using the photosensitive resin composition of Example 31 in the same manner as described above. By providing this insulating film, a short circuit can be prevented between the first electrode 5 and the second electrode formed in the subsequent step.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially vapor-deposited in a vacuum deposition apparatus through a desired pattern mask. Subsequently, 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 bonding using a sealing glass plate and an ultraviolet curable epoxy resin.

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

(Example 73)

An organic EL device was prepared in the same manner as in Example 72 except that the photosensitive resin composition of Example 31 was replaced with the photosensitive resin composition of Example 41. [ Exhibited good display characteristics, indicating that the organic EL display device is highly reliable.

(Example 74)

An organic EL device was produced in the same manner as in Example 72 except that the photosensitive resin composition of Example 31 was replaced with the photosensitive resin composition of Example 51. [ Exhibited good display characteristics, indicating that the organic EL display device is highly reliable.

(Example 75)

In the active matrix type liquid crystal display device shown in Figs. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 as an interlayer insulating film was formed as follows to obtain a liquid crystal display device of Example 75. Fig.

That is, the photosensitive resin composition of Example 46 was used to form a cured film 17 as an interlayer insulating film in the same manner as the method of forming the planarization film 4 of the organic EL display device in the above-mentioned Example 72. [

When the driving voltage was applied to the obtained liquid crystal display device, good display characteristics were exhibited and it was found that the liquid crystal display device was highly reliable.

(Example 76)

A liquid crystal display device was manufactured in the same manner as in Example 75 except that the photosensitive resin composition of Example 46 was replaced with the photosensitive resin composition of Example 56. And exhibited good display characteristics, indicating that the liquid crystal display device is highly reliable.

(Example 77)

A liquid crystal display was manufactured in the same manner as in Example 75 except that the photosensitive resin composition of Example 46 was replaced with the photosensitive resin composition of Example 66. [ And exhibited good display characteristics, indicating that the liquid crystal display device is highly reliable.

1: TFT (thin film transistor) 2: wiring
3: insulating film 4: planarization film
5: first electrode 6: glass substrate
7: Contact hole 8: Insulating film
10: liquid crystal display device 12: backlight unit
14, 15: glass substrate 16: TFT
17: cured film 18: contact hole
19: ITO transparent electrode 20: liquid crystal
22: Color filter

Claims (18)

(A) a repeating unit derived from a monomer having a carboxyl group protected with an acid-decomposable group and / or a repeating unit (a1) derived from a monomer having a phenolic hydroxyl group protected with an acid-decomposable group and a crosslinking group- , Polymer components contained in the same polymer and / or different polymers,
(B) a compound containing an oxime sulfonate residue represented by the following general formula (b1), and

(In the general formula (b1), R ⁵ represents an alkyl group or an aryl group.)
(C) at least one kind of solvent having a boiling point of less than 180 deg. C and at least one kind of solvent having a boiling point of 180 deg. C or more as the above-mentioned solvent, : A total amount of the solvent having a boiling point of 180 占 폚 or higher) is 99: 1 to 50:50 in terms of mass. The method according to claim 1,
And the partition coefficient (Log P) of the solvent having a boiling point of 180 캜 or higher is in a range of -0.5 to 1.0. 3. The method according to claim 1 or 2,
The compound containing the oxime sulfonate residue (B) is selected from the group consisting of the following general formula (OS-3), general formula (OS-4), general formula (OS-5), and general formula (b2) By weight based on the total weight of the photosensitive resin composition.

(In the general formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom , R ⁶ each independently represents 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, Represents an integer of 6.)

(In the general 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, X may be the same or different.) 3. The method according to claim 1 or 2,
(A2) derived from a monomer having a crosslinking group contains at least one member selected from the group consisting of a cyclic ether residue of a 3-membered ring and / or a 4-membered ring, and an ethylenic unsaturated group. 3. The method according to claim 1 or 2,
(E) an epoxy resin. 3. The method according to claim 1 or 2,
The compound containing the oxime sulfonate residue (B) is selected from the group consisting of the following general formula (OS-3), general formula (OS-4), general formula (OS-5), and general formula (b2) (A2) derived from a monomer having a crosslinking group contains at least one member selected from the group consisting of a cyclic ether residue of a 3-membered ring and / or a 4-membered ring, and an ethylenic unsaturated group Sensitive resin composition.

(In the general formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom , R ⁶ each independently represents 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, Represents an integer of 6.)

(In the general 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, X may be the same or different.) 3. The method according to claim 1 or 2,
The compound containing the oxime sulfonate residue (B) is selected from the group consisting of the following general formula (OS-3), general formula (OS-4), general formula (OS-5), and general formula (b2) , And further contains an epoxy resin (E).

(In the general formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom , R ⁶ each independently represents 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, Represents an integer of 6.)

(In the general 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, X may be the same or different.) 3. The method according to claim 1 or 2,
The compound containing the oxime sulfonate residue (B) is selected from the group consisting of the following general formula (OS-3), general formula (OS-4), general formula (OS-5), and general formula (b2) (A2) derived from a monomer having a crosslinking group contains at least one member selected from the group consisting of a cyclic ether residue of a 3-membered ring and / or a 4-membered ring, and an ethylenic unsaturated group , And (E) an epoxy resin.

(In the general formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom , R ⁶ each independently represents 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, Represents an integer of 6.)

(In the general 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, X may be the same or different.) 3. The method according to claim 1 or 2,
Wherein the repeating unit (a2) derived from a monomer having a crosslinking group contains at least one member selected from the group consisting of a cyclic ether residue of a 3-membered ring and / or a 4-membered ring, and an ethylenic unsaturated group, By weight. 3. The method according to claim 1 or 2,
Wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition. (1) a step of applying the photosensitive resin composition described in any one of claims 1 or 2 on a substrate,
(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 a developer, and
(5) A method of forming a cured film, which comprises a step of thermally curing. 12. The method of claim 11,
A step of exposing the entire surface after the developing step and before the step of heat curing. A cured film formed by the method for forming a cured film according to claim 11. A cured film formed by the method for forming a cured film according to claim 12. 14. The method of claim 13,
A cured film which is an interlayer insulating film. 15. The method of claim 14,
A cured film which is an interlayer insulating film.  An organic EL display device or liquid crystal display device comprising the cured film according to claim 13. An organic EL display device or liquid crystal display device comprising the cured film according to claim 14.

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