KR101932449B1 - Positive-type photosensitive resin composition, method of producing cured film, cured film, liquid crystal display device, and organic electroluminescent display device - Google Patents

Abstract

Which is high in sensitivity, high in resistance to peeling liquid and NMP, good in adhesion to a transparent electrode film or metal, excellent in dry etching resistance, and capable of obtaining a cured film hard to cause display failure even in a display device To provide a resin composition. (Component A) a polymer component comprising a polymer which satisfies at least one of (1) and (2), (1) a polymer component comprising (a1) a structural unit having an acid group protected with an acid- (A2) a polymer having a structural unit having a crosslinkable group, (component C) a photoacid generator and (component D) a polymer having a structural unit having an acid- ) Solvent. ≪ / RTI >

Description

TECHNICAL FIELD [0001] The present invention relates to a positive type photosensitive resin composition, a method of forming a cured film, a cured film, a liquid crystal display, and an organic EL display device }

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

In an electronic component such as a thin film transistor (hereinafter referred to as "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state image pickup element, an interlayer insulating film is formed . As a material for forming the interlayer insulating film, a photosensitive resin composition is widely used because it is preferable that the number of steps for obtaining a required pattern shape is small and that it has sufficient flatness.

Among the above electronic components, for example, a TFT type liquid crystal display element has a structure in which a transparent electrode film (ITO) is formed on the interlayer insulating film, a wiring made of metal such as molybdenum (Mo) or titanium (Ti) (Mainly monoethanolamine (MEA)) or a liquid crystal alignment film (liquid crystal alignment film) which is exposed to high temperature conditions in the process of forming a transparent electrode film or used for pattern formation of an electrode since the liquid crystal alignment film is formed through the process of forming a liquid crystal alignment film Methylpyrrolidone (NMP) used in the process of the present invention. Further, since the interlayer insulating film is sometimes subjected to a dry etching process, sufficient resistance to dry etching is also required.

Japanese Patent Application Laid-Open No. 2009-258722 discloses a resin composition which contains a specific acrylic acid-based constituent unit which generates a carboxyl group by decomposition of a dissociable group and is alkali-insoluble or alkali-insoluble and which becomes alkali-soluble when the acid- , A resin containing a constituent unit derived from an epoxy group-containing radically polymerizable monomer, a compound having two or more epoxy groups in the molecule (excluding the above resin containing a constituent unit comprising an epoxy group-containing radically polymerizable compound) A positive photosensitive resin composition containing a compound capable of generating an acid upon irradiation with an actinic ray of 300 nm or more has been proposed.

Further, in the pamphlet of International Publication No. 2009/136647, a positive photosensitive resin composition containing an alkali-soluble resin (A), a photosensitizer (B) and a specific silicon compound (C) has been proposed.

However, the photosensitive resin composition proposed in Japanese Patent Application Laid-Open Nos. 2009-258722 and 2009/136647 discloses a resist stripping liquid (mainly monoethanolamine (MEA)) used after forming an interlayer insulating film, It has been required to improve the resistance to NMP (N-methylpyrrolidone) and the display problem in the liquid crystal display device because the resistance to dry etching is not high.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to solve the following problems.

That is, a problem to be solved by the present invention is to provide a positive photosensitive resin composition capable of obtaining a cured film having high resistance to resist stripping liquid and NMP, excellent dry etching resistance, A cured film obtained by curing a photosensitive resin composition, a method of forming the cured film, and an organic EL display device and a liquid crystal display device provided with the cured film.

Under such circumstances, the present inventors have conducted intensive studies and found that the above problems can be solved by using a silicon compound having a specific structure. This is because, in a chemically amplified resist having a crosslinkable group, the alkoxysilyl compound effectively functions as a curing agent to bond with a crosslinkable group or a deprotected acid group. More specifically, the above problems are solved by the following means <1> or <16>, more preferably by the following means <2> to <16>.

&Lt; 1 > (Component A) A polymer component comprising a polymer satisfying at least one of the following (1) and (2)

(1) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group,

(2) a polymer having (a1) a polymer having a structural unit having a group protected with an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group,

(Component C) photoacid generator, and

(Component D) solvent, and further comprises

(Component X) A positive-working photosensitive resin composition characterized by containing a silicon compound having two or more hydrolyzable silyl groups and / or silanol groups represented by formula (X1) in one molecule.

(Wherein at least one of R ^X1 to R ^X3 is a hydrolyzable group selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group and an isopropenoxy group or And the remaining R ^X1 to R ^X3 each independently represent a hydrogen atom, a halogen atom or a monovalent organic substituent group.

&^Lt; 2 &^gt; The positive photosensitive resin composition according to &^lt; ¹ &^gt;, wherein at least two of R ^X1 to R ^X3 in the structural unit (X1) is an alkoxy group.

<3> The positive photosensitive resin composition according to <1> or <2>, wherein the content of the component X is 0.1% by weight or more based on the sum of the components excluding the solvent of the resin composition.

&Lt; 4 > The positive photosensitive resin composition according to any one of < 1 > to < 3 >, wherein the structural unit (a1) is a structural unit having a carboxyl group protected by an acetal or ketal moiety.

<5> The positive photosensitive resin composition according to any one of <1> to <4>, wherein the structural unit (a1) is a structural unit represented by formula (a1-1).

(Wherein R ¹ and R ² each represents a hydrogen atom, an alkyl group or an aryl group, and either one of the at least R ¹ and R ² alkyl group or aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group)

<6> The positive photosensitive resin composition according to any one of <1> to <5>, wherein at least two of R ^X1 to R ^X3 in the structural unit (X1) are a methoxy group or an ethoxy group.

<7> The positive photosensitive resin composition according to any one of <1> to <6>, wherein the structural unit (a2) is a structural unit having at least one kind selected from an epoxy group and an oxetanyl group.

<8><1> to <7> according to any one of, the content W _A and W _B weight ratio of the content of the component B in component _{A W A / W B = 98} / 2~20 / 80 in positive photosensitive Resin composition.

<9> A positive photosensitive resin composition according to any one of <1> to <8>, wherein the component C is an oxime sulfonate compound having at least one of oximesulfonate moieties represented by formula (c0).

(10) A process for producing a positive photosensitive resin composition, comprising the steps of: applying a positive photosensitive resin composition according to any one of < 1 > to &

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

(3) a step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray,

(4) a step of developing the exposed photosensitive resin composition by an aqueous developer, and

(5) A post-baking step of thermally curing the developed photosensitive resin composition.

<11> The method for forming a cured film according to <10>, wherein the step of exposing the photosensitive resin composition developed before the post-baking step after the development step.

<12> The method for forming a cured film according to <10> or <11>, further comprising a step of performing dry etching on the substrate having the cured film obtained by thermal curing.

<13> A cured film formed by the method for forming a cured film according to any one of <10> to <12>.

<14> The cured film as an interlayer insulating film according to <13>.

<15> An organic EL display device or liquid crystal display device comprising the cured film according to <13> or <14>.

<16> A chemical-resistance improving agent for a positive-working photosensitive resin composition, which contains a silicon compound having two or more hydrolyzable silyl groups and / or silanol groups represented by formula (X1) in one molecule.

(Wherein at least one of R ^X1 to R ^X3 is a hydrolyzable group selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group and an isopropenoxy group or And the remaining R ^X1 to R ^X3 each independently represent a hydrogen atom, a halogen atom or a monovalent organic substituent group.

(Effects of the Invention)

According to the present invention, it is possible to provide a positive photosensitive resin composition which is high in resistance to MEA and NMP, excellent in dry etching resistance, and capable of obtaining a cured film hardly causing display problems even in a display device, Film, a method of forming the same, and an organic EL display device and a liquid crystal display device provided with the cured film.

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 present invention will be described in detail.

The description of "lower limit to upper limit" in the specification indicates "lower limit and higher limit," and the description of "upper limit to lower limit" indicates "upper limit or lower limit." That is, a numerical range including an upper limit and a lower limit.

Component (C), photoacid generator or the like "may be simply referred to as" component C "or the like, and" (a1) a structural unit having a residue protected by an acid-decomposable group " .

When both or either of "acrylate" and "methacrylate" is referred to, the term "(meth) acrylate" and the term "acrylate" Quot ;, respectively.

(Positive photosensitive resin composition)

The positive photosensitive resin composition of the present invention (hereinafter, simply referred to as &quot; photosensitive resin composition &quot;) comprises (component A) a polymer component comprising a polymer satisfying at least one of the following (1)

(1) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group,

(A2) a copolymer having a structural unit having a crosslinkable group and (a2) a copolymer having a structural unit having a crosslinkable group, (a2) a copolymer having a structural unit having an acid group decomposable group, (C) a photoacid generator, (D) a solvent, and (C) a silicon compound having two or more hydrolyzable silyl groups and / or silanol groups represented by formula (X1) in one molecule.

Further, it is preferable that the photosensitive resin composition of the present invention does not have a constituent unit having an acid-decomposable group-protected moiety and at least a copolymer having a constituent unit having an acid group and a constituent unit having a crosslinkable group.

The photosensitive resin composition of the present invention contains a specific resin (component A), a photoacid generator and a specific silicon compound, and thus has a high resistance to a peeling liquid, particularly a peeling liquid containing monoethanolamine or NMP, It is possible to form a cured film which is excellent in dry etching resistance and hardly causes display problems even in a display device.

Further, the photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

Further, the photosensitive resin composition of the present invention can be preferably used as a positive photosensitive resin composition for a dry etching resist.

The notation in which the substituent and the non-substituent are not described in the notation of the group (atomic group) in the present specification includes not only a substituent but also a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The method for introducing the structural unit contained in the copolymer such as the component A used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and these monomers are copolymerized. In the polymer reaction method, a necessary functional group is introduced into the constituent unit by using a reactive group contained in the constituent unit of the copolymer obtained after the polymerization reaction. Examples of the functional group include a protecting group for protecting an acid group such as a carboxyl group or a phenolic hydroxyl group and decomposing in the presence of strong acid to liberate them, a crosslinking group such as an epoxy group or an oxetanyl group, an alkaline group such as a phenolic hydroxyl group or a carboxyl group And a soluble group (acid group).

<(A) Polymer Component>

The composition of the present invention comprises (1) a polymer having (a1) a constituent unit having an acid group protected by an acid-decomposable group and (a2) a constituent unit having a crosslinkable group, and (2) A polymer having a structural unit having a group protected with a group and (a2) a polymer having a structural unit having a crosslinkable group. In addition, polymers other than these may be contained. The polymer component (A) (hereinafter, also referred to as "component (A)") in the present invention may contain, in addition to the above-mentioned (1) and / or (2) Quot; means that a polymer is included.

The component (A) is preferably an addition polymerization type resin, more preferably a polymer comprising a constituent unit derived from (meth) acrylic acid and / or an ester thereof. Further, it may contain a structural unit other than the structural unit derived from (meth) acrylic acid and / or an ester thereof, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound.

The "structural unit derived from methacrylic acid and / or ester thereof" is also referred to as "acrylic structural unit". Further, "(meth) acrylic acid" means "methacrylic acid and / or acrylic acid".

<< Constituent unit (a1) >>

Component A has at least (a1) a structural unit having a group whose acid group is protected with an acid-decomposable group. The component (A) has the constituent unit (a1), so that a photosensitive resin composition having extremely high sensitivity can be obtained.

In the present invention, the "group protected with an acid-decomposable group" can be any group known as an acid group and an acid decomposable group, and is not particularly limited. Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group. Examples of the acid decomposable group include groups which are relatively easily decomposed by an acid (for example, an ester structure of a group represented by the formula (A1) described later, an acetal group such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group (For example, a tertiary alkyl group such as a tert-butyl ester group, or a tertiary alkylcarbonate group such as a tert-butylcarbonate group) may be used.

(a1) The constituent unit in which the acid group has a group protected with an acid-decomposable group is preferably a constituent unit having a protected carboxyl group protected with an acid-decomposable group or a constituent unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.

Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order.

<<< (a1-1) Structural unit having a protected carboxyl group protected with an acid-decomposable group >>>

The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit having a carboxyl group of a carboxyl group-containing structural unit protected by an acid-decomposable group described below in detail.

The above-mentioned structural unit having a carboxyl group which can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is not particularly limited and known structural units can be used. (A1-1-1) 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 or an unsaturated tricarboxylic acid, (A1-1-2) having a structure derived from an unsaturated group and an acid anhydride.

(A1-1-1) a constituent unit derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule and (a1-1-2) a constituent unit derived from an ethylenic unsaturated group and an acid anhydride And the constitutional unit having a structure derived from the same will be described in order.

<<<< (a1-1-1) Constituent units derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, etc. >>>>

As the constituent unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule, those listed below are used as the unsaturated carboxylic acid used in the present invention. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl Hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic 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 to obtain the structural 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 polycarboxylic acid, for example, mono (2-acryloyloxyethyl) succinate, mono Mono (2-acryloyloxyethyl) phthalate mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have. Examples of the unsaturated carboxylic acid include acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene.

Among them, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule from the viewpoint of developability, acrylic acid, methacrylic acid, 2- (meth) acryloyl (Meth) acryloyloxyethyl-phthalic acid or anhydride of an unsaturated polycarboxylic acid, and the like, and acrylic acid, methacrylic acid, methacrylic acid, It is more preferable to use acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid.

The structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone, or may be composed of two or more kinds.

<<<< (a1-1-2) Constituent units having a structure derived from an ethylenic unsaturated group and an acid anhydride together >>>>

The structural unit (a1-1-2) having both the ethylenic unsaturated group and the structure derived from an acid anhydride is preferably a unit derived from a monomer obtained by reacting a hydroxyl group and an acid anhydride which are present in the structural unit having an ethylenic unsaturated group.

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

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

<<<< Acid decomposable group which can be used in the structural unit (a1-1) >>>>

As the acid decomposable group that can be used for the structural unit (a1-1) having a protected carboxyl group protected with the acid decomposable group, the acid decomposable group may be used.

Among these acid decomposable groups, the carboxyl group is preferably a protected carboxyl group protected in the form of an acetal from the viewpoints of the basic physical properties of the photosensitive resin composition, in particular, from the viewpoints of sensitivity and pattern shape, formation of contact holes, and storage stability of the photosensitive resin composition. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the carboxyl group is a protected carboxyl group protected in the form of acetal represented by the following general formula (a1-10). When the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10), the protected carboxyl group as a whole has a structure of - (C═O) -O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) .

The general formula (a1-10)

(Formula (a1-10) of R ¹⁰¹ and R ¹⁰² represents a hydrogen atom or an alkyl group, each independently, other than the R-stage ¹⁰¹ and, if R ¹⁰² is a hydrogen atom together. R ¹⁰³ represents an alkyl group. R ^101, or R ¹⁰² and R ¹⁰³ may be connected to form a cyclic ether)

In the general formula (a1-10), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of linear, branched and cyclic. Wherein no work is both of R ¹⁰¹ and R ¹⁰² represent a hydrogen atom, at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

When R ¹⁰¹ , R ¹⁰² and R ^{103 in} the general formula (a1-10) represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

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

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

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When R ¹⁰¹ , R ¹⁰² and R ¹⁰³ have a halogen atom as a substituent, they are a haloalkyl group, and when they have an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are aralkyl groups.

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

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

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

When the alkyl group is a cyclic alkyl group, the cyclic alkyl group may have a linear or branched alkyl group having from 1 to 10 carbon atoms as a substituent. When the alkyl group is a straight chain or branched chain alkyl group, And may have up to 12 cyclic alkyl groups.

These substituents may be further substituted by the above substituents.

When R ¹⁰¹ , R ¹⁰² and R ^{103 in} the general formula (a1-10) represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms may be preferably exemplified. As the aryl group, for example, a phenyl group, a trityl group, a cumenyl group, a 1-naphthyl group and the like can be mentioned.

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may combine with each other to form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ^103, or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, And examples thereof include a t-butyl group and a tetrahydropyranyl group.

In the general formula (a1-10), it is preferable that one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

The radically polymerizable monomer used for forming the structural unit having a protective carboxyl group represented by the general formula (a1-10) may be a commercially available one, or a compound synthesized by a known method may be used. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of Japanese Patent Laid-Open Publication No. 2011-221494.

The first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit represented by the following general formula.

(Wherein R ¹ and R ² each represents a hydrogen atom, an alkyl group or an aryl group, and either one of the at least R ¹ and R ² alkyl group or aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group)

When R ¹ and R ² are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 alkyl groups.

X represents a single bond or an arylene group, with a single bond being preferred.

A second preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit represented by the following general formula:

(Wherein R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

R ¹²¹ is preferably a hydrogen atom or a methyl group.

L ¹ is preferably a carbonyl group.

R ¹²² to R ¹²⁸ are preferably a hydrogen atom.

Preferable specific examples of the structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

<<< (a1-2) Protecting Protected by Acid-Decomposable Group Constituent with a phenolic hydroxyl group >>>

The structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a structural unit having a phenolic hydroxyl group and a structural unit having a protected phenolic hydroxyl group by an acid-decomposable group described in detail below.

<<<< (a1-2-1) Constituent with phenolic hydroxyl group >>>>

Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a constitutional unit in a novolak-based resin. Among them, a structural unit derived from hydroxystyrene or? -Methylhydroxystyrene has a sensitivity . The structural unit represented by the following general formula (a1-20) as a structural unit having a phenolic hydroxyl group is also preferable from the viewpoint of sensitivity.

In general formula (a1-20)

(In the general formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, R ²²² represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms , a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is not more than 5. When two or more R ²²² are present, these R ²²² may be the same or different,

In the general formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.

R ²²¹ represents a single bond or a divalent linking group. In the case of a single bond, the sensitivity can be improved and the transparency of the cured film can be further improved. Examples of the divalent linking group of R ²²¹ include alkylene groups and specific examples of R ²²¹ 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 &lt; ²²¹ &gt; is preferably a single bond, a methylene group or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Although a represents an integer of 1 to 5, a is preferably 1 or 2, and more preferably a is 1, from the viewpoint of the effects of the present invention and ease of production.

It is preferable that the bonding position of the hydroxyl group in the benzene ring is bonded to the 4-position when the carbon atom bonded to R ²²¹ is the reference (1 position).

R ²²² is a halogen atom or a straight or branched alkyl group having 1 to 5 carbon atoms. Specific examples include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- butyl group, a pentyl group, an isopentyl group and a neopentyl group . Among them, chlorine atom, bromine atom, methyl group or ethyl group is preferable from the viewpoint of easy production.

B represents 0 or an integer of 1 to 4;

<<<< Acid decomposable group which can be used in the structural unit (a1-2) >>>>

The acid decomposable group which can be used for the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group is preferably an acid decomposable group which can be used for the structural unit (a1-1) having a protected carboxyl group protected with the acid- As with the acid-decomposable group, known ones can be used, and they are not particularly limited. Among the acid decomposable groups, structural units having a protected phenolic hydroxyl group protected by an acetal are preferable from the viewpoints of the basic physical properties of the photosensitive resin composition, particularly the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, and the formability of the contact hole. Among the acid decomposable groups, from the viewpoint of sensitivity, the phenolic hydroxyl group is more preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the above general formula (a1-10). When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10), the total of the protected phenolic hydroxyl groups is -Ar-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) Structure. Ar represents an arylene group.

Preferable examples of the acetal ester structure of the phenolic hydroxyl group include R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, R ¹⁰¹ = R ¹⁰² = methyl group, and R ¹⁰³ = benzyl group.

Examples of the radically polymerizable monomers used for forming the structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include those described in Japanese Patent Laid-Open Publication No. 2011-215590 .

Of these, a 1-alkoxyalkyl protected derivative of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protected derivative of 4-hydroxyphenyl methacrylate are preferred from the viewpoint of transparency.

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

The radically polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group may be a commercially available one, or a known one may be used. For example, a compound having a phenolic hydroxyl group can be synthesized by reacting with a vinyl ether in the presence of an acid catalyst. The above-mentioned synthesis may be carried out by previously copolymerizing a monomer having a phenolic hydroxyl group with other monomers, and then reacting with a vinyl ether in the presence of an acid catalyst.

Specific preferred examples of the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group include the following structural units, but the present invention is not limited thereto.

<<< Preferred Embodiment of Constituent Unit (a1) >>>

When the polymer containing the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is preferably 20 to 100 mol%, more preferably 30 To 90 mol% is more preferable.

When the polymer containing the constituent unit (a1) contains the following constituent unit (a2), the constituent unit (a1) is a polymer containing the constituent unit (a1) and the constituent unit (a2) To 70 mol%, and more preferably 10 mol% to 60 mol%. In particular, when the acid-decomposable group usable in the structural unit (a1) is a structural unit having a carboxyl group protected in the form of an acetal in the form of an acetal, it is preferably 20 to 50 mol%.

The structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is characterized in that the phenomenon is faster than that of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid decomposable group. Therefore, when a rapid development is desired, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferable. On the contrary, when it is desired to slow the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

<< (a2) Structural unit having a crosslinkable group >>

(A) has a structural unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group which causes a curing reaction by a heat treatment. Preferred examples of the structural unit having a crosslinkable group include at least one group selected from the group consisting of an epoxy group, an oxetanyl group, a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) and an ethylenic unsaturated group , And is preferably at least one selected from the group consisting of an epoxy group, oxetanyl group and -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). Among them, the photosensitive resin composition of the present invention preferably contains the constituent unit in which the component (A) contains at least one of an epoxy group and an oxetanyl group. More specifically, the following can be mentioned.

<<< (a2-1) Constituent Unit Having an Epoxy Group and / or an Oxetanyl Group >>>

The polymer (A) preferably contains a structural unit (structural unit (a2-1)) having an epoxy group and / or oxetanyl group. The cyclic ether group of the 3-membered ring is also called an epoxy group, and the cyclic ether group of the 4-membered ring is also called an oxetanyl group.

The structural unit (a2-1) having an epoxy group and / or an oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may contain at least one epoxy group and at least one oxetanyl group, Or more oxetanyl group, and it is not particularly limited, but it is preferable to have 1 to 3 epoxy groups and / or oxetanyl groups in total, and it is preferable to have one or two epoxy groups and / or oxetanyl groups in total More preferably one having an epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate , glycidyl? -n-butyl acrylate,? -epoxybutyl acrylate,? -epoxybutyl methacrylate,? -epoxycyclohexylmethyl acrylate, Epoxycyclohexylmethyl, 3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Japanese Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton as described in paragraphs [0031] to [00300] of WO 00/1995, the contents of which are incorporated herein by reference.

Specific examples of the radical polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meth) acrylate esters having an oxetanyl group as described in paragraphs 0011 to 001 of JP-A No. 2001-330953 , The contents of which are incorporated herein by reference.

Specific examples of the radically polymerizable monomer used for forming the above-mentioned structural unit (a2-1) having an epoxy group and / or oxetanyl group are monomers containing a methacrylic acid ester structure and monomers containing an acrylic ester structure Do.

Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl. These constituent units may be used singly or in combination of two or more.

Preferable specific examples of the above-mentioned structural unit (a2-1) having an epoxy group and / or an oxetanyl group include the following constitutional units. R represents a hydrogen atom or a methyl group.

<<< (a2-2) Structural unit having an ethylenic unsaturated group >>>

(A2-2) having an ethylenic unsaturated group as one of the structural unit (a2) having a crosslinkable group (hereinafter also referred to as &quot; structural unit (a2-2) &quot;). The structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenic unsaturated group in its side chain, more preferably a structural unit having an ethylenic unsaturated group at its terminal and having 3 to 16 carbon atoms, A structural unit having a side chain represented by the following general formula (a2-2-1) is more preferable.

(A2-2-1)

(In the general formula (a2-2-1), R ³⁰¹ represents a divalent linking group having 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and * represents a linking group to the main chain of the structural unit (a2) Lt; / RTI &gt;

R ³⁰¹ is a divalent linking group having 1 to 13 carbon atoms, which may contain an alkenyl group, an arylene group, or a combination thereof, and may include a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond. The divalent linking group may have a substituent such as a hydroxyl group or a carboxyl group at an arbitrary position. Specific examples of R ³⁰¹ include the following divalent linking groups.

Among the side chains represented by the general formula (a2-2-1), aliphatic side chains including the divalent linking group represented by R ³⁰¹ are preferable.

Others (a2-2) With regard to the constituent unit having an ethylenic unsaturated group, the description of paragraphs 0072 to 0090 of Japanese Patent Laid-Open Publication No. 2011-215580 may be taken into consideration, and the contents thereof are included in the specification of the present invention.

<<< (a2-3) Structural unit having a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) >>>

Polymer used in the present invention are also preferred structural units (a2-3) having a group represented by -NH-CH ₂ -OR (R is alkyl group having 1 to 20 carbon atoms). By having the structural unit (a2-3), a curing reaction can be caused by a satisfactory heat treatment, and a cured film having excellent properties 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 (a2-30).

(A2-30)

(In the general formula (a2-30), 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.

<<< Preferred Embodiment of Constituent Unit (a2) >>>

When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) is preferably 5 to 90 mol%, more preferably 20 To 80 mol% is more preferable.

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

In the present invention, regardless of the embodiment, the content of the structural unit (a2) in the total structural units of the component (A) is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.

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

<< (a3) Other building blocks >>

In the present invention, the component (A) may contain, in addition to the above structural units (a1) and / or (a2), the other structural units (a3). These constituent units may contain the polymer components (1) and / or (2). In addition, apart from the polymer component (1) or (2), a polymer component having substantially no structural units (a1) and (a2) and having another structural unit (a3) may be contained. When the polymer component (1) or (2) contains a polymer component substantially not containing (a1) and (a2) and having another constituent unit (a3), the blending amount of the polymer component is preferably 60 By mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less.

The monomer to be the other constituent unit (a3) is not particularly limited and includes, for example, styrenes, alkyl (meth) acrylates, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters , Unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds can be mentioned. Further, as described later, it may have a structural unit having an acid group. The monomers to be the other constituent unit (a3) may be used alone or in combination of two or more.

Preferred embodiments of the polymer component of the present invention are described below, but the present invention is not limited thereto.

(First Embodiment)

An embodiment wherein the polymer component (1) further comprises one or more other structural units (a3).

(Second Embodiment)

(A1) an embodiment wherein the polymer having a constituent unit having a group in which an acid group is protected with an acid-decomposable group further comprises one or more other constituent units (a3) of the polymer constituent (2).

(Third Embodiment)

An embodiment in which the polymer (a2) having a structural unit having a crosslinkable group in the polymer component (2) further comprises one or more other structural units (a3).

(Fourth Embodiment)

An embodiment wherein any one of the first to third embodiments includes a structural unit containing at least an acid group as the other structural unit (a3).

(Fifth Embodiment)

An embodiment having a polymer which does not substantially contain (a1) and (a2) and which further comprises another structural unit (a3) apart from the polymer component (1) or (2).

(Sixth Embodiment)

An embodiment comprising at least polymer component (2).

(Seventh Embodiment)

An embodiment comprising two or more combinations of the first to sixth embodiments.

(Eighth embodiment)

An embodiment comprising a polymer having at least an acid group-containing constituent unit as the other constituent unit (a3) separately from the polymerizable component (1) or (2).

(Ninth embodiment)

An embodiment including a copolymer having a structural unit having at least an acid group and a structural unit having a crosslinkable group as the other structural unit (a3) separately from the polymerizable component (1) or (2).

(Tenth Embodiment)

In the embodiment 8 or 9, the acid group is a structural unit having a carboxyl group and / or a phenolic hydroxyl group.

Specific examples of the structural unit (a3) include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile and ethylene glycol monoacetoacetate monomethacrylate Unit. In addition, the compounds described in paragraphs 0021 to 0024 of Japanese Patent Application Laid-Open No. 2004-264623 can be mentioned.

Further, as the other structural unit (a3), a styrene group or a group having an alicyclic cyclic skeleton is preferable from the viewpoint of electrical characteristics. Specific examples include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl Methacrylate, and the like.

In addition, as the other structural unit (a3), a (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and n-butyl (meth) acrylate. More preferred is methyl (meth) acrylate. The content of the structural unit (a3) among the constituent units constituting the polymer (A) is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less. The lower limit value may be 0 mol%, but may be, for example, 1 mol% or more, and may be 5 mol% or more. Within the range of the above-mentioned numerical values, the properties of the cured film obtained from the photosensitive resin composition are improved.

  As the other structural unit (a3), it is preferable to include an acid group. By including an acid group, it is easy to dissolve in an alkaline developing solution, and the effect of the present invention is more effectively exhibited. The acid group in the invention means a proton dissociable group having a pKa smaller than 7. The acid group is included in the polymer as a constituent unit containing an acid group by using a monomer capable of forming an acid group. By incorporating such a structural unit containing an acid group into the polymer, it tends to be easily dissolved in the alkaline developer.

Examples of the acid group used in the present invention include those derived from a carboxylic acid group, those derived from a sulfonamide group, those derived from a phosphonic acid group, those derived from a sulfonic acid group, those derived from a phenolic hydroxyl group, A sulfonylimide group, and the like, and those derived from a carboxylic acid group and / or derived from a phenolic hydroxyl group are preferable.

Examples of the radical polymerizable monomer used for forming the constituent unit having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; And unsaturated carboxylic acids such as dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid.

Examples of the radical polymerizable monomer used for forming the structural unit having a carboxylic acid anhydride residue include maleic anhydride, itaconic anhydride, and the like.

Examples of the radically polymerizable monomer used for forming the constituent unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene,? -Methyl-p-hydroxystyrene, and the like disclosed in JP-A-2008-40183 Hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxybenzoic acid derivatives such as 4- An addition reaction product of a hydroxybenzoic acid and glycidyl acrylate, and the like.

Of these, methacrylic acid, acrylic acid, compounds described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, 4-hydroxy Addition reaction products of benzoic acid and glycidyl methacrylate, and addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable, and compounds described in paragraphs 0011 to 001 of Japanese Patent Application Laid-Open No. 2008-40183, The addition reaction product of 4-hydroxybenzoic acid derivative, 4-hydroxybenzoic acid and glycidyl methacrylate, the addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate, as described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, , A structural unit derived from at least one member selected from the group consisting of acrylic acid, methacrylic acid, p-hydroxystyrene and? -Methyl-p-hydroxystyrene More preferably a structural unit derived from acrylic acid or methacrylic acid, and particularly preferably a structural unit derived from methacrylic acid. These constituent units may be used singly or in combination of two or more.

Specific preferred examples of the structural unit (b1) include the following structural units.

The constituent unit containing an acid group is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 5 to 40 mol%, and particularly preferably from 5 to 30 mol%, of the constituent units of the whole polymer component , And particularly preferably from 5 to 20 mol%.

In the present invention, as the polymer which does not substantially contain (a1) and (a2) and other structural unit (a3), a resin having a carboxyl group in the side chain is preferable apart from the polymer component (1) or (2). For example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Application Laid-open No. 59-53836, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, which are described in each publication of JP-A No. 59-71048, , Acidic anhydride added to a polymer having a hydroxyl group, and the like, and a polymer having a (meth) acryloyl group in its side chain is also preferable.

(Meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (Meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / Benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl Methacrylate / methacrylic acid copolymer, and the like.

In addition, Japanese Patent Application Laid-Open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224 Publicly known polymer compounds described in JP-A-2000-56118, JP-A-2003-233179, and JP-A-2009-52020 can be used, and the contents thereof are included in the specification of the present invention.

These polymers may be contained in one kind alone or in two or more kinds.

As these polymers, commercially available polymers such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (manufactured by Sartomer), ArUFON UC-3000, ArUFON UC-3510, ArUFON UC- UF-3910, ArUFON UC-3920, ArUFON UC-3080 (manufactured by Dojo Kosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 (manufactured by BASF).

When styrene such as styrene or? -Methylstyrene is used as the other structural unit (a3), it is preferable to further include a structural unit represented by the following formula (b3-1). R ⁴ is preferably a hydrogen atom.

(Wherein R ⁴ represents a hydrogen atom or a methyl group)

Examples of the structural unit (b3) include structural units derived from at least one member selected from the group consisting of (meth) acrylic acid esters, styrenes and N-substituted maleimides, and (meth) acrylic acid esters And structural units derived from at least one member selected from the group consisting of styrenes.

Among them, examples of the radically polymerizable monomer used for forming the structural unit (b3) include (meth) acrylic esters having an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl acrylate, Methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and styrene can be preferably exemplified, and methyl (meth) acrylate, 2-hydroxyethyl methacrylate and styrene are more preferable. (Meth) acrylate is more preferable, and methyl methacrylate is particularly preferably exemplified.

<< (A) Molecular weight of polymer >>

The molecular weight of the polymer (A) is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of polystyrene reduced weight average molecular weight. Within the above range of the numerical value, the property is good. The ratio (number of dispersions) of the number average molecular weight to the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< (A) Method of producing polymer >>

Further, although various methods are known for the synthesis of the component (A), for example, at least the radically polymerizable (meth) acrylic polymer containing a radically polymerizable monomer used for forming the constituent unit represented by the above (a1) Can be synthesized by polymerization of a monomer mixture using a radical polymerization initiator in an organic solvent. It may also be synthesized by a so-called polymer reaction.

The photosensitive resin composition of the present invention preferably contains the component (A) in an amount of 50 to 99.9 parts by mass based on 100 parts by mass of the total solid content, more preferably 70 to 98 parts by mass.

&Lt; Component (X) >

The silicon compound used in the present invention is characterized by having two or more hydrolyzable silyl groups and / or silanol groups represented by the following formula (X1) in one molecule.

(Wherein at least one of R ^X1 to R ^X3 is a hydrolyzable group selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group and an isopropenoxy group or And the remaining R ^X1 to R ^X3 each independently represent a hydrogen atom, a halogen atom or a monovalent organic substituent group.

At least one of R ^X1 to R ^X3 in the formula (X1) is a hydrolyzable group selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group and an isopropenoxy group Lt; / RTI &gt; Each of R ^X1 to R ^X3 independently represents a hydrogen atom, a halogen atom or a monovalent organic substituent group (for example, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or an aralkyl group).

As the hydrolyzable group bonded to the silicon atom in the formula (X1), an alkoxy group and a halogen atom are particularly preferable, and an alkoxy group is more preferable.

The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, still more preferably an alkoxy group having 1 to 5 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms And a methoxy group or an ethoxy group is particularly preferable.

As the halogen atom, there can be mentioned F atom, Cl atom, Br atom and I atom. From the viewpoint of easiness of synthesis and stability, preferred is a Cl atom and a Br atom. More preferably, .

The component X has two or more groups represented by the formula (X1). That is, a compound having two or more silicon atoms bonded with a hydrolysable group in the molecule is preferably used. The number of silicon atoms bonded to the hydrolyzable group contained in Component A is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2 or 3.

By having at least two constituent components (X1), it can function as a cross-linking agent in the cured film to improve the resistance to peeling liquid and solvent of the cured film.

The hydrolyzable group may be bonded to one silicon atom in a range of 1 to 4, and the total number of hydrolyzable groups in the formula (X1) is preferably in a range of 2 or 3, and three hydrolyzable groups It is particularly preferable that they are combined. When two or more hydrolysable groups are bonded to a silicon atom, they may be the same or different.

Examples of the preferable alkoxy group as the hydrolyzable group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group, a phenoxy group and a benzyloxy group. A plurality of these alkoxy groups may be used in combination, or a plurality of different alkoxy groups may be used in combination.

Examples of the alkoxysilyl group bonded with an alkoxy group include trialkoxysilyl groups such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group; Dialkoxymonoalkylsilyl groups such as a dimethoxymethylsilyl group and a diethoxymethylsilyl group; And monoalkoxydialkylsilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl group.

Component X may contain a sulfur atom, an ester bond, a urethane bond, an ether bond, a urea bond or an imino group. Among them, the component X preferably contains a sulfur atom from the viewpoint of crosslinkability, and further contains an ester bond, an urethane bond or an ether bond (particularly an ether bond contained in the oxyalkylene group) which is easily decomposed into alkaline water . Component X containing a sulfur atom may function as a vulcanizing agent to promote the reaction (crosslinking) of the cured film. The component X in the present invention is preferably a compound having no ethylenic unsaturated bond. The component X preferably has only a hydrolyzable silyl group and / or a silanol group as a polymerizable group.

The component X in the present invention is a compound in which a plurality of groups represented by the above formula (X1) are bonded through a divalent linking group. From the viewpoint of the effect, such a divalent linking group includes a sulfide group (-S-) , An imino group (-N (R) -) or a urethane bond (-OCON (R) - or N (R) COO-). R represents a hydrogen atom or a substituent. As the substituent in R, an alkyl group, an aryl group, an alkenyl group, an alkynyl group or an aralkyl group can be exemplified.

The method for synthesizing the component X is not particularly limited and can be synthesized by a known method. As an example, a typical synthesis method of component X including a linking group having the above specific structure is shown.

<Method for synthesizing a compound having a sulfide group as a linking group and having a hydrolyzable silyl group and / or a silanol group>

A method for synthesizing a component X having a sulfide group as a linking group (hereinafter referred to as "sulfide linkage group-containing component X" as appropriate) is not particularly limited, but specific examples thereof include reaction of a component X having a halogenated hydrocarbon group with an alkali sulfide, , Reaction of component X having a mercapto group with component X having a halogenated hydrocarbon group, reaction of a component X having a halogenated hydrocarbon group with mercaptans, reaction of a component X having an ethylenically unsaturated bond, A reaction of component X having an ethylenically unsaturated bond and a component X having a mercapto group, a reaction of a component X having a mercapto group and a compound having an ethylenically unsaturated bond, a component having a ketone group and a mercapto group Reaction of X with a component X having a diazonium salt and a mercapto group, reaction of an oxirane with a component X having a mercapto group, A reaction between a component X having a mercapto group and a component X having an oxyl group, a reaction between a mercapto group and a component X having an oxyl group, and a reaction of a component X having a mercapto group with aziridines.

<Method for synthesizing a compound having an imino group as a linking group and having a hydrolyzable silyl group and / or a silanol group>

The method for synthesizing a component X having an imino group as a linking group (hereinafter referred to as "imino linking group-containing component X" as appropriate) is not particularly limited. For example, the reaction between a component X having an amino group and a halogenated hydrocarbon, The reaction of component X having a hydrocarbon group, the reaction of component X having an halogenated hydrocarbon group with an amine, the reaction of component X having an amino group with an oxirane, the reaction of component X having an amino group with component X having an oxyl group, Reaction of X with aziridines with component X having an amino group, reaction of component X having an ethylenically unsaturated bond with amines, reaction of component X having an ethylenically unsaturated bond with component X having an amino group, reaction of an ethylenically unsaturated bond And a component X having an amino group, a reaction between a compound having an acetylenic unsaturated bond and Reaction of component X having an amino group, reaction of component X having an imatinib unsaturated bond with an organic alkali metal compound, reaction of component X having an imatinib unsaturated bond with an organic alkaline earth metal compound, and reaction of component X having a carbonyl compound and an amino group Can be exemplified.

<Synthesis method of a compound having a urethane bond (ureylene group) as a linking group and having a hydrolyzable silyl group and / or a silanol group>

A method for synthesizing a component X having a ureylene group as a linking group (hereinafter referred to as "ureylene linkage-containing component X" as appropriate) is not particularly limited, but specifically, for example, a reaction between an amino group-containing component X and an isocyanate, For example, the reaction of component X having isocyanate and isocyanate and reaction of component X having amines and isocyanate can be exemplified.

Specific examples of the component X include 1,2-bis (triethoxysilyl) ethane, 1,4-bis (trimethoxysilyl) butane, 1-methyldimethoxysilyl- Bis (trimethoxysilyl) pentane, 1-methyldimethoxysilyl-5-trimethoxysilylpentane, 1,1-bis (trimethoxysilyl) pentane, Bis (trimethoxysilyl) pentane, 1,5-bis (trimethoxysilyl) hexane, 1,5-bis (trimethoxysilyl) pentane, (Trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 2,5-bis (trimethoxysilyl) hexane, Bis (trimethoxysilyl) octane, 2,7-bis (trimethoxysilyl) heptane, 1,8-bis (Methoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, 2,7-bis (trimethoxysilyl) (Trimethoxy Vinyl trichlorosilane, 1,3-bis (trichlorosilane) propane, 1,3-bis (tribromosilane) propane, vinyltrimethoxysilane, vinyltriethoxysilane, , 4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Methacryl Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltriethoxysilane,? -Methacryloxypropyltriethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane, -Aminopropyltrimethoxysilane, N- (β-aminoethyl) - γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) Aminoethyl) -? - aminopropyltriethoxysilane,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane , N-phenyl- gamma -aminopropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, dimethoxy-3-mercaptopropyl (2-aminoethylthioethyl) diethoxymethylsilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, dimethyl Bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, 1,4-bis (triethoxysilyl) Benzene, bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) Bis (trimethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) urea,? -Chloropropyltrimethoxysilane,? -Triethoxysilylpropylmethacrylate,? - In-laid propyltriethoxysilane and the like can be mentioned silane, trimethyl silanol, diphenyl silane diol, triphenyl silanol.

In addition, the compounds shown below are preferred, but the present invention is not limited to these compounds.

Wherein R and R &lt; ¹ &gt; each represent a partial structure selected from the following structures. When a plurality of R and R &lt; ¹ &gt; exist in the molecule, they may be the same or different, and the synthetic aptitude is preferably the same.

Component X can be obtained by appropriately synthesizing, but it is preferable to use commercially available component X from the viewpoint of cost. Examples of the component X include commercially available products such as silane products and silane coupling agents commercially available from Shin-Etsu Chemical Co., Ltd., Toray, Dow Corning Co., Ltd., Momentive Performance Materials Co., Ltd., , These commercial products may be appropriately selected and used according to the purpose in the resin composition of the present invention.

As the component X in the present invention, a partial hydrolysis condensation product obtained by using one species of a compound having a hydrolyzable silyl group and / or a silanol group or a partial hydrolysis condensation product obtained by using two or more species can be used. Hereinafter, these compounds are sometimes referred to as "partial (co) hydrolysis-condensation products".

Of the silane compounds as the partial (co) hydrolytic condensation product precursors, silane compounds having a substituent selected from a methyl group and a phenyl group as a substituent on silicon are preferable from the viewpoints of versatility, cost, and compatibility of the film. Specific examples thereof include methyltrimethoxy Silane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane are exemplified as preferable precursors.

In this case, the partial (co) hydrolysis-condensation product is preferably a dimer of a silane compound as described above (which is obtained by dissolving 2 moles of water in 2 moles of silane compound and desorbing 2 moles of alcohol to form a disiloxane unit) Preferably 2 to 50 moles, more preferably 2 to 30 moles, and it is also possible to use a partially hydrolyzed condensate containing two or more silane compounds as raw materials.

The partially hydrolyzed condensate may be a commercially available silicone alkoxy oligomer (for example, commercially available from Shin-Etsu Chemical Co., Ltd.) and may be hydrolyzed A product prepared by reacting less than the equivalent amount of the hydrolyzate with respect to the silane compound and then removing by-products such as alcohol and hydrochloric acid may be used. In the production, when the alkoxysilanes or acyloxysilanes as described above are used as the hydrolyzable silane compounds of the starting materials to be precursors, for example, acids such as hydrochloric acid and sulfuric acid, alkali metals or alkaline earth metals such as sodium hydroxide and potassium hydroxide Hydroxides of metals, alkaline organic substances such as triethylamine, and the like may be partially hydrolyzed and condensed as a reaction catalyst, and when produced directly from chlorosilanes, hydrochloric acid by-produced may be used as a catalyst to react with water and alcohol.

(Trialkoxysilyl) alkane is more preferable, and bis- (3-trimethoxysilyl) silane is more preferred from the viewpoints of excellent curability, adhesiveness, heat-resistant color stability, excellent balance between transparency and adhesive strength, Bis (trimethoxysilyl) heptane, 1,8-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) (Methoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane, and more preferably at least one member selected from the group consisting of 1,6-bis Trimethoxysilyl) hexane, and bis- (3-trimethoxysilylpropyl) amine are more preferable.

The X component used in the present invention is preferably a silicon compound represented by the formula (X2).

(Wherein X represents a group represented by the formula (X1), a represents an integer of 2 or more, and Ro represents a linking group having an a value)

X in the formula (X2) is in agreement with the group represented by the formula (X1), and the preferable range is also synonymous.

In the formula (X2), a is preferably 2 to 4, more preferably 2 or 3.

The compound represented by the formula (X2) is more preferably a compound represented by the following formula (X3).

(Wherein X represents the formula (X1), a represents an integer of 2 or more, and n represents an integer of 1 to 5. Roo represents a single bond or a linking group of an a value)

X in the formula (X3) is in agreement with the group represented by the formula (X1), and the preferable range is also synonymous.

In the formula (X3), a is preferably 2 to 4, more preferably 2 or 3, and particularly preferably 2.

In formula (X3), Roo represents a single bond and -CR ₂ - (R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), -S-, -CO-, -O-,

Or a combination of two or more thereof.

In the formula (X3), Roo is more preferably a single bond and -CR ₂ - (R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), -S-, -CO-, -O-, or a combination thereof Group, more preferably a single bond, -CH ₂ -, -S-, or a combination thereof.

In the formula (X3), n is preferably an integer of 1 to 3, more preferably 1 or 2.

The molecular weight of the silicon compound used in the present invention is preferably 100 to 1500, more preferably 250 to 1100.

In the present invention, silicon compounds described in formulas (S-1) to (S-17) are particularly preferably employed.

The component X may be used alone or in combination of two or more.

The amount of the component X in the present invention is preferably 0.1% by weight or more, more preferably 0.5% by weight or more based on the total amount of the components excluding the solvent of the resin composition, from the viewpoints of the curability, the adhesiveness, the heat resistant coloration stability, More preferable. The upper limit value is not particularly determined, but is preferably 10% by weight or less, and more preferably 5% by weight or less.

(Component C)

The photosensitive resin composition of the present invention (component C) contains a photoacid generator.

The component C is preferably a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but is not limited to the chemical structure thereof. Also, for a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid in response to an actinic ray having a wavelength of 300 nm or more by being used in combination with a sensitizer can be preferably used in combination with a sensitizer.

As the component C, a photoacid generator that generates an acid with a pKa of 4 or less is preferable, and a photoacid generator that generates an acid with a pKa of 3 or less is more preferable.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidazolone compounds and oxime sulfonate compounds. Among them, it is preferable to use an oxime sulfonate compound from the viewpoint of high sensitivity. These photoacid generators may be used alone or in combination of two or more. Specific examples thereof include photoacid generators described in paragraphs 0029 to 534 of JP-A-2004-264623, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoro And the like are preferably used.

The photosensitive resin composition of the present invention preferably contains an oxime sulfonate compound having at least one oxime sulfonate residue represented by the following formula (c0) as the (C) photoacid generator. In addition, the broken line indicates a bonding position with another chemical structure.

The oxime sulfonate compound having at least one of the oxime sulfonate moieties represented by the formula (c0) is preferably a compound represented by the following formula (c1).

(In the formula (c1), R ⁵ and R ⁶ each independently represent a monovalent organic group, R ⁵ and R ⁶ may be connected to form a ring, and R ⁷ represents an alkyl group or an aryl group)

In formula (c1), R ⁵ represents an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, a 2-thienyl group, Four alkoxy groups or cyano groups. When R ⁵ is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups may be substituted with a substituent selected from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, .

In formula (c1), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl, dialkylamino, morpholino or cyano group which may be substituted with W. R ⁶ and R ⁵ may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or the 6-membered ring may be bonded to a benzene ring which may have 1 or 2 arbitrary substituents.

In formula (c1), R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. The alkyl group may be a cyclic alkyl group. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms .

The alkyl group having 1 to 6 carbon atoms represented by R ⁵ may be a linear or branched alkyl group and includes, for example, methyl, ethyl, propyl, isopropyl, n-butyl, , n-pentyl group, isoamyl group, n-hexyl group or 2-ethylbutyl group.

Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ⁵ include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group and a 2-bromopropyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ⁵ include methoxy group and ethoxy group.

When R ⁵ represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups may be substituted with a halogen atom (e.g., a chlorine atom, a bromine atom or an iodine atom), a hydroxyl group, an alkyl group having 1 to 4 carbon atoms (Such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl) Propoxy group, i-propoxy group, n-butoxy group) and nitro group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁶ include methyl, ethyl, n-propyl, i-propyl, n-butyl, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, a n-decyl group and the like.

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁶ include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, A n-decyloxy group, and the like.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁶ include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, - Amyl group.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ⁶ include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, Perfluoro-n-amyloxy group, and the like.

Specific examples of the phenyl group which may be substituted with W represented by R ⁶ include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, Propyl) phenyl group, p- (n-butyl) phenyl group, p- (i- butyl) phenyl group, (o-amyl) phenyl group, o- methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (T-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-butoxy) phenyl group, Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, A dichlorophenyl group, a 2,4,6-tribromophenyl group, A 2,4,6-trifluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentafluorophenyl group, and a p-biphenylyl group.

Specific examples of the naphthyl group which may be substituted with W represented by R ⁶ include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl Methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

Specific examples of the anthranyl group which may be substituted with W represented by R ⁶ include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl- Methyl-1-anthranyl, 7-methyl-1-anthranyl, 8-methyl-1-anthranyl, Anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group, , 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group and 10-methyl-2-anthranyl group.

Examples of the dialkylamino group represented by R ⁶ include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group and a diphenylamino group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁷ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i- an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, a n-decyl group and the like.

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁷ include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, A n-decyloxy group, and the like.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁷ include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, - Amyl group.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ⁷ include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, Perfluoro-n-amyloxy group, and the like.

Specific examples of the phenyl group which may be substituted with W represented by R ⁷ include an o-tolyl group, a m-tolyl group, a p-tolyl group, an o-ethylphenyl group, Propyl) phenyl group, p- (n-butyl) phenyl group, p- (i- butyl) phenyl group, (o-amyl) phenyl group, o- methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (T-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-butoxy) phenyl group, Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, Dichlorophenyl group, 2,4,6-tribromophenyl group, 2, A 4,6-trifluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentafluorophenyl group, and a p-biphenylyl group.

Specific examples of the naphthyl group which may be substituted with W represented by R ⁷ include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl Methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

Specific examples of the anthranyl group which may be substituted with W represented by R ⁷ include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl- Methyl-1-anthranyl, 7-methyl-1-anthranyl, 8-methyl-1-anthranyl, Anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group, , 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group and 10-methyl-2-anthranyl group.

Specific examples of the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the alkoxy halide having 1 to 5 carbon atoms represented by W include R ⁶ or R ⁷ As exemplified as specific examples of the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the halogenated alkoxy group having 1 to 5 carbon atoms, .

R ⁶ and R ⁵ may combine with each other to form a 5-membered or 6-membered ring.

When R ⁶ and R ⁵ are bonded to each other to form a 5-membered ring or a 6-membered ring, examples of the 5-membered or 6-membered ring include a carbocyclic group and a heterocyclic ring, and examples thereof include cyclopentane, cyclohexane, cycloheptane, , Furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazin ring. The 5-membered or 6-membered ring may be bonded to a benzene ring which may have an arbitrary substituent. Examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene or thioxanthene ring system . The 5-membered or 6-membered ring may contain a carbonyl group, and examples thereof include cyclohexadieneone, naphthalenone and anthrone ring systems.

One preferred embodiment of the compound represented by the formula (c1) is a compound represented by the following formula (c1-1). The compound represented by the formula (c1-1) is a compound in which R ⁶ and R ⁵ in the formula (c1) are bonded to form a 5-membered ring.

(Formula (c1-1) of R ⁷ is R ⁷ and the consent of the formula (c1), X is an alkyl group, an alkoxy group or a halogen atom, t represents an integer of 0~3, t is 2 or 3, the plural Xs may be the same or different)

As the alkyl group represented by X, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable.

As the alkoxy group represented by X, a straight chain or branched chain alkoxy group having 1 to 4 carbon atoms is preferable.

The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

t is preferably 0 or 1.

In the formula (c1-1), t is 1, X is a methyl group, X is a substituted position in an ortho position, R ⁷ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A norbornylmethyl group or a p-tolyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by formula (c1-1) include the following compounds (i), (ii), (iii) and (iv) Or two or more of them may be used in combination. The compounds (i) to (iv) are commercially available.

It may also be used in combination with other types of photoacid generators.

As a preferred embodiment of the compound represented by the formula (c1)

R ⁵ represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group or an anthranyl group;

R ⁶ represents a cyano group;

R ⁷ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group , A naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms , A halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

The compound represented by the formula (c1) is also preferably a compound represented by the following formula (c1-2).

In formula (c1-2), R ⁸ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group, and L represents an integer of 0 to 5. R ⁷ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group , A naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms , A halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

Examples of R ⁷ in the formula (c1-2) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro- A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a p-

The halogen atom represented by R ⁸ is preferably a fluorine atom, a chlorine atom or a bromine atom.

The alkyl group having 1 to 4 carbon atoms represented by R ⁸ is preferably a methyl group or an ethyl group.

As the alkoxy group having 1 to 4 carbon atoms represented by R ⁸ , a methoxy group or an ethoxy group is preferable.

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

Formula (c1) the compound represented by the formula (c1-2) as a preferred embodiment of the compounds included in the compound represented by formula (c1) of the R ⁵ represents a phenyl group or a 4-methoxyphenyl group as in, R ⁶ is cyano And R ⁷ represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 4-tyl group.

Specific preferred examples of the compound represented by formula (c1-2) among the compounds represented by formula (c1) are shown below, but the present invention is not limited thereto.

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = methyl group)

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = ethyl group)

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-propyl group)

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-butyl group), and an α- (n-butylsulfonyloxyimino) benzyl cyanide

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = 4-triyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = methyl group)

methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = ethyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = n-propyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = n-butyl group)

methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = 4-trilyl group)

Examples of the compound having at least one oximesulfonate residue represented by the formula (c0) include oximesulfonate represented by the following formula (OS-3), formula (OS-4) Compound.

(In the formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and the plural R ^{2 s} present independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ present 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, 6 &lt; / RTI &gt;

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

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

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

The heteroaryl group represented by R ¹ in the above formulas (OS-3) to (OS-5) is preferably a heteroaryl group having 4 to 30 total carbon atoms, which may have a substituent, and is preferably at least one heteroaryl group For example, a complex aromatic ring and a benzene ring may be coordinated.

Examples of the substituent which the alkyl group, aryl group or heteroaryl group represented by 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 have.

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

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

The alkyl group or aryl group represented by R ² in formulas (OS-3) to (OS-5) may have a substituent.

Examples of the substituent which the alkyl group or aryl group represented by R ² may have include the same groups as the substituent which the alkyl group or aryl group in R ¹ may have.

The alkyl group represented by R ² in the formulas (OS-3) to (OS-5) is preferably an alkyl group having 1 to 12 carbon atoms in total which may have a substituent, and an alkyl group having 1 to 6 carbon atoms Is more preferable.

The alkyl group represented by R ² is preferably a methyl group, ethyl group, n-propyl group, n-butyl group or n-hexyl group, more preferably a methyl group.

The aryl group represented by R ² in the formulas (OS-3) to (OS-5) is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

As the aryl group represented by R ² , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group or p-phenoxyphenyl group is preferable.

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

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

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

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

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

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

Examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group and an aminosulfonyl group.

Examples of the alkoxysulfonyl group represented by R ⁶ include methoxysulfonyl group, ethoxysulfonyl group, propyloxysulfonyl group and butyloxysulfonyl group.

Examples of the substituent which the alkyl group or alkyloxy group represented by 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.

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, .

The compound represented by the formula (OS-3) is particularly preferably a compound represented by the following formula (OS-6), formula (OS-10) or formula (OS- 4) is particularly preferably a compound represented by the following formula (OS-7), and the compound represented by the above formula (OS-5) is preferably a compound represented by the following formula (OS- Is particularly preferable.

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

The expression (OS-6) ~ R ¹ in (OS-11) is R ¹ and agreed in the formula (OS-3) ~ (OS -5), a preferred embodiment versa.

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

R ⁸ in the formulas (OS-6) to (OS-11) is 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, More preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group, and is particularly preferably an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group .

R ⁹ in the 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 formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

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

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

As another preferred embodiment of the oxime sulfonate compound having at least one oxime sulfonate residue represented by the above formula (c0), those described in paragraphs 0117 to 1199 of Japanese Patent Laid-Open Publication No. 209719 .

It is preferable that the photosensitive resin composition of the present invention does not contain a 1,2-quinonediazide compound as a photoacid generator (component C) sensitive to an actinic ray. This is because the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less, and the sensitivity is lower than that of the oxime sulfonate compound.

On the contrary, since the oxime sulfonate compound acts as a catalyst against the deprotection of an acidic group protected by an acid generated by an actinic ray, an acid generated by the action of one photon contributes to many deprotection reactions, The yield is greater than 1, for example, a large value such as a power of 10, and it is presumed that high sensitivity is obtained as a result of so-called chemical amplification.

The content of the photoacid generator (component C) in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the content of the components A and B .

(Component D) Solvent

The photosensitive resin composition of the present invention preferably contains a (component D) solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which each component of the present invention is dissolved in a solvent (component D).

As the solvent used in the photosensitive resin composition of the present invention, a known solvent can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol Propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol mono Alkyl ether acetates, esters, ketones, amides, lactones, and the like. Examples of the solvent used in the photosensitive resin composition of the present invention include the solvent described in paragraph 0074 of JP-A No. 2009-258722.

Of these solvents, diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are particularly preferred.

These solvents may be used alone or in combination of two or more. The solvent usable in the present invention is preferably used alone or in combination of two or more, more preferably two solvents in combination, and the use of propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers in combination More preferable.

The content of the component D in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, and still more preferably 150 to 1,500 parts by weight based on 100 parts by weight of the component A.

The content of the solvent (component D) in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, and more preferably 150 to 1,500 parts by weight per 100 parts by weight of the total content of component A and component B. By weight is more preferable.

<Other ingredients>

The photosensitive resin composition of the present invention may contain other components.

As the other components, the photosensitive resin composition of the present invention preferably contains a photosensitizer from the viewpoint of sensitivity, and preferably contains a basic compound from the viewpoint of liquid storage stability, and preferably contains a crosslinking agent And from the viewpoint of substrate adhesion, it is preferable to contain an adhesion improver. From the viewpoint of coatability, it is preferable to contain a surfactant.

Hereinafter, other components that can be contained in the photosensitive resin composition of the present invention will be described.

[Photosensitizer]

The photosensitive resin composition of the present invention preferably contains a photosensitizer.

It is effective for improving exposure sensitivity by containing a photosensitizer, and is particularly effective when the exposure light source is a g- and h-line mixed line.

As the photosensitizer, an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a basestyryl derivative, and a distyrylbenzene derivative are preferable.

Examples of the anthracene derivative include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9- hydroxymethylanthracene, 9-bromoanthracene, 9,10-dibromoanthracene, 2-ethyl anthracene, and 9,10-dimethoxy anthracene are preferable.

As the acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.

As the thioxanthone derivative, thioxanthone, diethyl thioxanthone, 1-chloro-4-propanedioxanthone and 2-chlorothioxanthone are preferable.

As coumarin derivatives, coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.

Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole and 2- (4-dimethylaminostyryl) naphthothiazole .

Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene and di (3,4,5-trimethoxystyryl) benzene.

Among these, anthracene derivatives are preferable, and 9,10-dialkoxyanthracene (having 1 to 6 carbon atoms in the alkoxy group) is more preferable.

Specific examples of the photosensitizer include the following. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

The content of the photosensitizer in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight based on 100 parts by weight of the total content of Component A and Component B. When the content of the photosensitizer is 0.1 parts by weight or more, desired sensitivity is easily obtained. When the content is 10 parts by weight or less, transparency of the coating film is easily ensured.

[Basic compound]

The photosensitive resin composition of the present invention preferably contains a basic compound from the viewpoint of liquid storage stability.

As the basic compound, any of those used in the chemically amplified resist can be arbitrarily selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

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

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

Examples of the heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N- But are not limited to, dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, , 4-methylmorpholine, N-cyclohexyl-N '- [2- (4-morpholinyl) ethyl) piperidine, piperidine, piperidine, piperazine, morpholine, Thiourea, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-undecene.

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, but two or more kinds thereof are preferably used in combination, more preferably two kinds of them, and two kinds of heterocyclic amines Is more preferable.

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 0.002 to 0.2 part by weight based on 100 parts by weight of the total content of component A and component B.

[Crosslinking agent]

The photosensitive resin composition of the present invention preferably contains a crosslinking agent if necessary. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made into a stronger film.

As the crosslinking agent, for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, or a compound having at least one ethylenically unsaturated double bond may be added.

Of these crosslinking agents, compounds having two or more epoxy groups or oxetanyl groups in the molecule are preferable, and epoxy resins are particularly preferable.

The amount of the crosslinking agent to be added in the photosensitive resin composition of the present invention is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 44 parts by weight, and still more preferably 3 to 40 parts by weight relative to the total solid content of the photosensitive resin composition. Addition in this range provides a cured film excellent in mechanical strength and solvent resistance.

- a compound having two or more epoxy groups or oxetanyl 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, aliphatic epoxy resin and the like.

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, aliphatic epoxy resin and the like.

These are available as commercial products and include those described in paragraphs 0051 to 0053 of Japanese Patent Application Laid-Open No. 2009-258722 such as JER150S65 and JER1031S (all manufactured by Mitsubishi Kagaku Co., Ltd.). These may be used alone or in combination of two or more.

Of these, epoxy resins are preferable, and bisphenol A type epoxy resins, bisphenol F type epoxy resins and phenol novolak type epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferable.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aromoxetane OXT-121, OXT-221, OX-SQ and PNOX (manufactured by DOA KOSEI CO., LTD.) Can be used.

The oxetanyl group-containing compound is preferably used alone or in combination with a compound containing an epoxy group.

Among them, the amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to be added to the photosensitive resin composition of the present invention is preferably 1 to 50 parts by weight, more preferably 3 to 5 parts by weight, based on 100 parts by weight of the total content of component A and component B, To 30 parts by weight is more preferable.

- a compound having an alkoxymethyl group-containing crosslinking agent or at least one ethylenically unsaturated double bond -

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. As the compound having at least one ethylenic unsaturated double bond, a (meth) acrylate compound such as monofunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional or more functional (meth) .

Specific examples of the alkoxymethyl group-containing crosslinking agent or the compound having at least one ethylenically unsaturated double bond include those described in paragraphs 0093 to 0100 of JP-A No. 2011-170305, and the preferable range of the addition amount and the combination is the same .

[Adhesion improver]

The photosensitive resin composition of the present invention preferably contains an adhesion improver from the viewpoint of substrate adhesion.

The adhesion improver that can be used in the photosensitive resin composition of the present invention is an adhesion improver that can be used as a substrate, and can be formed by a method of reacting an inorganic substance to be a substrate, such as silicon, silicon oxide, silicon nitride, Thereby improving the adhesion of the insulating film. Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improver used in the present invention is for the purpose of modifying the interface, and a known silane coupling agent can be used without particular limitation.

Among them, a silane coupling agent can be preferably exemplified. However, the silane coupling agent of the present invention refers to a compound having one hydrolyzable silyl group or silanol group in one molecule, and the silicon compound corresponding to component X is not included in the silane coupling agent of the present invention.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacrylate Acryloxypropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? - , And vinyltrialkoxysilane.

Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is more preferable.

These may be used alone or in combination of two or more. These are effective in improving the adhesion with the substrate and also in adjusting the taper angle with the substrate.

The content of the adhesion improver 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 total content of Component A and Component B. [

[Surfactants]

The photosensitive resin composition of the present invention preferably contains a surfactant from the viewpoint of coatability.

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but preferred surfactants are nonionic surfactants.

Examples of the nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine series, and silicone surfactants.

It is more preferable that the photosensitive resin composition of the present invention contains a fluorine-based surfactant and / or a silicon-based surfactant as a surfactant.

Examples of the fluorinated surfactants and silicone surfactants include those disclosed in Japanese Patent Application Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, Japanese Patent Laid-Open Nos. 63-34540, 7-230165, 8-62834, 9-54432, 9-5988, 2001-330953 A surfactant described in each publication, or a commercially available surfactant may be used.

(Commercially available from Shin-Akita Kasei Co., Ltd.), Fluorad FC430 and 431 (manufactured by Sumitomo 3M Ltd.), Megafac F171 and F173 , F176, F189, R08 (manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105 and 106 (manufactured by Asahi Glass Co., Ltd.), PolyFox series (manufactured by OMNOVA ), And silicone surfactants. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

Further, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography when the surfactant contains the constituent unit A and the constituent unit B represented by the following formula (1) and tetrahydrofuran (THF) (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

(Wherein R ¹ and R ³ each independently represents a hydrogen atom or a methyl group, R ² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴ represents a hydrogen atom or an alkylene group having 1 to 4 carbon atoms P represents an integer of not less than 10% by weight and not more than 80% by weight, q represents an integer of not less than 10% by weight, and L represents an alkylene group of 3 to 6 carbon atoms, p and q are weight percentages indicating a polymerization ratio, R represents an integer of 1 or more and 18 or less, and n represents 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 of 1 to 4 carbon atoms and is preferably an alkyl group of 1 to 3 carbon atoms in view of compatibility and wettability to a surface to be coated, Lt; / RTI &gt; alkyl groups are more preferred.

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 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 even more preferably 0.01 to 1 part by weight based on 100 parts by weight of the total content of Component A and Component B Is more preferable.

<Others>

Other components such as a plasticizer, a heat radical generator, a thermal acid generator, an acid proliferator, a development promoter, and an antioxidant may be added to the photosensitive resin composition of the present invention. As for these components, for example, those disclosed in Japanese Patent Application Laid-Open No. 2009-98616, Japanese Patent Laid-Open No. 2009-244801, and other known ones can be used. Various ultraviolet absorbers, metal deactivators, and the like described in &quot; New developments of high molecular additive &quot; (Nikkan Kogyo Shinbun Co., Ltd.) may be added to the photosensitive resin composition of the present invention.

(Method of forming a cured film)

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

The method of forming the cured film of the present invention is not particularly limited, except that the positive photosensitive resin composition of the present invention is used, but preferably includes the following steps (1) to (5).

(1) a step of applying the positive 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 the photosensitive resin composition from which the solvent has been removed by an actinic ray

(4) a step of developing the exposed photosensitive resin composition with an aqueous developer

(5) a post-baking step of thermally curing the developed photosensitive resin composition

In the method for forming a cured film of the present invention, the developing step (4) may be performed without performing the heat treatment after the exposure in the above exposure step.

The method may further include a step of exposing the developed photosensitive resin composition to the whole before the post-baking step.

It is preferable that the method for forming a cured film of the present invention further includes (6) a dry etching process for performing dry etching on a substrate having a cured film obtained by thermal curing.

Each step will be described below in order.

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

In the solvent removal step of (2), it is preferable that the solvent is removed from the coated film by reduced pressure (vacuum) and / or heating to form a dried coating film on the substrate.

It is preferable to irradiate the obtained coating film with an actinic ray having a wavelength of 300 nm or more and 450 nm or less. In this process, a specific acid generator decomposes to generate acid. The acid-decomposable group in the constituent unit (a1) contained in the component A is decomposed by the catalytic action of the generated acid to generate an acid group.

In order to accelerate the decomposition reaction in the region where the acid catalyst is generated, Post Exposure Bake (hereinafter, also referred to as &quot; PEB &quot;) may be performed as needed. PEB can promote the generation of an acid group from the acid decomposable group.

The acid decomposable group in the structural unit (a1) in the specific resin is low in the activation energy of the acid decomposition and is easily decomposed by an acid derived from the photoacid generator due to exposure to generate an acid group. Therefore, it is preferable to carry out the above-described development step without performing the heat treatment after the exposure step. More specifically, it is preferable to form a positive image by performing development in the developing step 4) without performing PEB after the exposure step of (3).

Further, by conducting PEB at a relatively low temperature, decomposition 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 90 占 폚.

It is preferable to develop the component A having a free acid group and the component B having an acid group by using an alkaline developing solution in the developing step of the step (4). A positive image can be formed by removing the exposed region including the photosensitive resin composition having an acid group which is easily dissolved in an alkaline developing solution.

For example, by heating the positive image obtained in the step of post baking of the structural unit (5), for example, an acid group generated by thermal decomposition of an acid-decomposable group in the structural unit (a1) (b2) with a crosslinkable group to form a cured film. The heating is preferably performed at a high temperature of 150 ° C or higher, more preferably 180 ° C to 250 ° C, and particularly preferably 200 ° C to 250 ° C. The heating time can be suitably set according to the heating temperature and the like, but it is preferably within the range of 10 to 90 minutes.

The cured film obtained from the photosensitive resin composition of the present invention can be preferably used as a dry etching resist.

A dry etching process such as ashing, plasma etching, or ozone etching can be performed as the etching process when the cured film obtained by thermal curing by the post baking process of the substrate 5 is used as a dry etching resist.

In the dry etching process of the step (6), a reactive gas etching process for etching the substrate in the reaction gas, a reactive ion etching (RIE) process for ionizing and radicalizing the reactive gas by plasma, Etching treatment may be exemplified. These gas species and etching methods may be appropriately selected depending on the material to be dry-etched, the desired speed and accuracy, and the like. As a device for performing dry etching, a known device can be used.

In addition, it is preferable that the step of exposing the developed photosensitive resin composition to a post-baking step includes a step of exposing the entire surface of the photosensitive resin composition to a total exposure. When the step of irradiating the pattern of the developed photosensitive resin composition with actinic light, preferably ultraviolet light, Can accelerate the crosslinking reaction.

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

[Method for preparing photosensitive resin composition]

If necessary, the specific resin and the essential component of the acid generator are mixed with a solvent in a predetermined ratio and optionally by stirring, and dissolved to prepare a photosensitive resin composition. For example, a photosensitive resin composition may be prepared by preparing a solution prepared by dissolving a specific resin or acid generator in each solvent in advance, and then mixing them in a predetermined ratio. The solution of the photosensitive resin composition prepared as described above may be used after being filtered using a filter having a pore diameter of 0.1 mu m or the like.

<Coating Process and Solvent Removal Process>

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

(2) The heating conditions in the solvent removal step are those in which the acid-decomposable group is decomposed in the constituent unit (a1) in the component A in the unexposed portion and the component A is not soluble in the alkali developer, But it is preferably about 70 to 120 DEG C for about 30 to about 300 seconds.

<Exposure Step>

(3) In the exposure step, the substrate on which the dry film of the photosensitive resin composition is formed is irradiated with a predetermined pattern of actinic rays. The exposure may be performed through a mask, or a predetermined pattern may be directly drawn. An active ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. After the exposure process, PEB may be performed if necessary.

A low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a laser generator, an LED light source, and the like can be used for exposure by an actinic ray.

When a mercury lamp is commonly used, an actinic ray having a wavelength of g-line (436 nm), i-line (365 nm), h-line (405 nm) or the like can be preferably used. The mercury lamp is preferable in that it is suitable for exposure of a large area as compared with a laser.

When a laser is used, 343 nm and 355 nm are preferably used for the solid (YAG) laser and 351 nm (XeF) for the excimer laser, and 375 nm and 405 nm are more preferably used for the semiconductor laser. Of these, 355 nm and 405 nm are more preferable from the standpoints of stability and cost. The laser can be irradiated to the coating film once or plural times. The specific examples and preferred ranges of the energy density, the pulse width, the laser frequency, the exposure apparatus, and the filter are those described in paragraphs 0098 to 0100 of Japanese Patent Application Laid-Open No. 183398/1999.

<Development Process>

(4) In the developing process, a basic developer is used to remove the exposed area to form an image pattern. Examples of the basic compound used in the developer 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 cholinehydroxide; 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 developer is not particularly limited as far as development is feasible, but it 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 puddle method, a dipping method, and a shower method. After the development, washing with water for 10 to 90 seconds is carried out to form a desired pattern.

&Lt; Post baking step (crosslinking step) >

For example, 180 to 250 캜 for a predetermined time, for example, 5 to 60 minutes on a hot plate, using a heating apparatus such as a hot plate or an oven for a pattern corresponding to the unexposed region obtained by development , And an oven for 30 to 90 minutes to decompose the acid-decomposable group in the specific resin to generate a carboxyl group and / or a phenolic hydroxyl group to react with the crosslinkable group as an epoxy group and / or an oxetanyl group in the specific resin, Hardness and the like can be formed. In addition, transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

Further, the substrate on which the pattern has been formed is re-exposed to the substrate by the action of an actinic ray and then post-baked (re-exposure / post-baking) to generate an acid from the acid generator (B) As a catalyst.

That is, the method of forming a cured film in the present invention preferably includes a step of re-exposure by an actinic ray between a developing step and a post-baking step.

The exposure in the re-exposure step may be carried out by the same means as in the exposure step, but in the re-exposure step, it is preferable to perform the entire exposure on the side of the substrate on which the film is formed by the photosensitive resin composition of the present invention. The preferable exposure amount of the re-exposure process is 100 to 1,000 mJ / cm &lt; 2 &gt;.

<Dry Etching Process>

The dry etching step in the present invention is a step of performing dry etching on a substrate having a cured film obtained by thermosetting in the post baking step. The cured film obtained from the photosensitive resin composition of the present invention is excellent in dry etching resistance, so that the film reduction amount is small even when exposed to dry etching conditions.

Examples of the feed-lye etching material usable in the present invention include silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, - tin oxide coated glass; Metal, semiconductor, any substrate containing patterning regions of insulating material, and the like, but are not limited thereto.

The generation method of the plasma is not particularly limited, and both the decompression plasma method and the atmospheric plasma method can be applied.

Further, plasma etching, for example, helium, argon, krypton, an inert gas, O ₂ is selected from xenon _{into, CF 4, C 2 F 4} , N 2, CO 2, SF 6, CHF 3 of at least O, N, F or Cl may be preferably used.

In the dry etching step, for example, in the case of a silicon-based layer such as SiN _x or SiO ₂ , it is preferable to use a fluorine-based reaction gas such as O ₂ and CF ₄ or SiF ₆ .

The substrate in the dry etching step and the substrate in the coating step may be the same or different. For example, the substrate in the coating step may be a virtual substrate, and the cured film may be transferred to another substrate until the dry etching step.

The cured film obtained by curing the photosensitive resin composition of the present invention is also preferably used as a sacrifice layer for etching treatment such as dry etching or wet etching. When the cured film is peeled off after the etching treatment, a dry plasma Peeling can be performed by a known wet process such as a process or an alkali chemical treatment. Since the cured film of the present invention is cured through the baking process, peeling by the dry plasma process is particularly preferable.

Even when used as a flat resist as an etching resist, oxygen plasma treatment is preferably used, but it is also possible to peel off the resist by heat treatment with a chemical solution.

The cured film obtained by curing the photosensitive resin composition of the present invention can be particularly preferably used as a dry etching resist.

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention and can be preferably used as an interlayer insulating film. It is preferable that the cured film of the present invention is a cured film obtained by the method of forming a cured film of the present invention.

With the photosensitive resin composition of the present invention, a cured film having a high sensitivity, suppressing the occurrence of residues during development, and having a surface with excellent smoothness is obtained, and the cured film is useful as an interlayer insulating film. Further, the interlayer insulating film formed using the photosensitive resin composition of the present invention has high transparency, can form a pattern of a good shape, and has excellent smoothness on the surface thereof. Therefore, the use of the organic EL display device or the liquid crystal display device useful.

The organic EL display device or liquid crystal display device to which the photosensitive resin composition of the present invention can be applied is not particularly limited except that the cured film formed by using the photosensitive resin composition of the present invention is used as a planarizing film, a protective film, or an interlayer insulating film , And various known organic EL display devices and liquid crystal display devices having various structures.

For example, specific examples of the TFT (Thin-Film Transistor) included in the organic EL display device and the liquid crystal display device of the present invention include an amorphous silicon TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention has excellent electrical characteristics, it can be preferably used in combination with these TFTs.

As a liquid crystal display device capable of adopting the liquid crystal display device of the present invention, there are TN (Twisted Nematic), VA (Virtual Alignment), IPS (In-Place-Switching), FFS (Optical Compensated Bend) method.

Specific examples of the alignment method of the liquid crystal alignment film that can take the liquid crystal display of the present invention include a rubbing alignment method and a photo alignment method. It may also be polymer-oriented supported by PSA (Polymer Sustained Alignment) technology described in Japanese Patent Application Laid-Open No. 2003-149647 or Japanese Patent Application Laid-Open No. 2011-257734.

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, a protective film, an interlayer insulating film, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state image pickup device, Can be suitably used for resist for dry etching.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a structural conceptual diagram showing an example of an organic EL display device using the photosensitive resin composition of the present invention. Fig. 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 through the contact hole is formed on the insulating film 3 after forming a contact hole (not shown) in the insulating film 3 here. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or later and the TFT 1. [

The flattening film 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, the first electrode 5 made of ITO is formed on the planarization film 4 by being connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.

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

Although not shown in Fig. 1, a hole transport layer, an organic luminescent layer, and an electron transport layer are sequentially evaporated through a desired pattern mask, then a second electrode made of Al is formed on the entire upper surface of the substrate, It is possible to obtain an active matrix type organic EL display device in which a glass plate and an ultraviolet curable epoxy resin are used to seal by adhering and a TFT 1 for driving each organic EL element is connected.

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

Example

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

&Lt; Synthesis Example 1 &

A cooling tube and a stirrer, 150 parts by weight of diethylene glycol ethyl methyl ether was placed, and the mixture was heated to 90 DEG C under a nitrogen atmosphere. 41.3 parts by weight of 1-ethoxyethyl methacrylate, 31.0 parts by weight of 3-ethyl-3-oxetanylmethyl methacrylate, 5.6 parts by weight of methacrylic acid, 17.0 parts by weight of 2-ethylhexyl methacrylate And 10.0 parts by weight of dimethyl-2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were dissolved and dissolved dropwise over 2 hours. After completion of dropwise addition, stirring was continued for 2 hours. 2.5 parts by weight of dimethyl-2,2'-azobis (2-methylpropionate) was further added to the solution, followed by further stirring for 2 hours to terminate the reaction. Thus, Copolymer A-1 was obtained. The weight average molecular weight was 11,000.

&Lt; Synthesis Examples 2 to 38 &

Copolymers A-2 to A-15, B-1 to B-16, and b-1 to b-5 shown in the following table were synthesized in the same manner as in Synthesis Example 1 except that the monomers used and amounts thereof were changed . The composition ratios (mol%) and weight average molecular weights (Mw) of the synthesized copolymers are shown in the following table.

The abbreviations in Tables 1 and 2 are as follows.

MAEVE: 1-ethoxyethyl methacrylate

MATHF: tetrahydro-2H-furan-2-yl methacrylate

MACHOE: 1- (cyclohexyloxy) ethyl methacrylate

MATHP: tetrahydro-2H-pyran-2-yl methacrylate

PHSEVE: 1-ethoxyethyl protective group of p-hydroxystyrene

OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

GMA: glycidyl methacrylate

NBMA: n-butoxymethyl acrylamide

VBGE: p-vinylbenzyl glycidyl ether

MAA: methacrylic acid

PHS: p-hydroxystyrene

HEMA: 2-ethylhexyl methacrylate

THFFMA: tetrahydrofurfuryl methacrylate

St: Styrene

α-MeSt: α-methylstyrene

MMA: methyl methacrylate

DCPM: methacrylic acid (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl)

(Examples 1 to 143 and Comparative Examples 1 to 34)

The amount (solid content) shown in the following table was dissolved in a mixed solvent of diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) so that the solid content concentration became 27% by weight, And filtered through a membrane filter to prepare respective photosensitive resin compositions.

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

C-1: Compound of the following structure (synthesized product)

C-2: Compound of the following structure (synthesized product)

C-3: Compound of the following structure (synthesized product)

C-4: CGI-1397 (BASF)

C-5: Compound of the following structure (synthesized according to the method described in paragraph 0108 of Japanese Patent Publication No. 2002-528451)

C-6: PAI-1001 (manufactured by Midori Kagaku Co., Ltd.)

C-7: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

<Synthesis of C-1>

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 ° C and reacted for 2 hours. 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution under ice-cooling, and ethyl acetate (50 mL) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 占 폚 for 1 hour. 2N HCl aqueous solution (60 mL) was added thereto to separate the liquid. The organic layer was concentrated and the crystals were reslurried with diisopropyl ether Filtered and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50 wt% hydroxylamine aqueous solution (8.0 g) were added to the suspension of the obtained ketone compound (3.0 g) and methanol (18 mL), and the mixture was heated under reflux for 10 hours. After cooling, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol and dried to obtain an oxime compound (2.4 g).

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

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

<Synthesis of C-2>

2-Naphthol (20 g) was dissolved in N, N-dimethylacetamide (150 mL), potassium carbonate (28.7 g) and ethyl 2-bromooxinate (52.2 g) were added and reacted at 100 ° C for 2 hours. Water (300 mL) and ethyl acetate (200 mL) were added to the reaction mixture to separate the layers. The organic layer was concentrated, and 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 mL) and water (50 mL) . The reaction solution was poured into 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a carboxylic acid mixture. Then, 30 g of polyphosphoric acid was added and reacted at 170 DEG C for 30 minutes. The reaction solution was poured into water (300 mL) and ethyl acetate (300 mL) was added to separate the layers. The organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).

Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g) and magnesium sulfate (4.5 g) were added to the resulting suspension of the ketone compound (10.0 g) and methanol (100 mL) and the mixture was refluxed for 24 hours. After cooling, water (150 mL) and ethyl acetate (150 mL) were added to separate the layers. The organic layer was partitioned four times with 80 mL of water, concentrated and purified by silica gel column chromatography to obtain an oxime compound (5.8 g).

The resulting oxime (3.1 g) was sulfonated in the same manner as C-1 to obtain C-2 (3.2 g).

In addition, ¹ H-NMR spectrum of _{B-2 (300㎒, CDCl 3} ) is δ = 8.3 (d, 1H) , 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (s, 3H), 2.2 (ddt, 1H), 1.9 (dd, 1H), 7.5 (dd, , 1H), 1.4-1.2 (m, 8H), 0.8 (t, 3H).

<Synthesis of C-3>

C-3 was synthesized in the same manner as C-1 except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in C-1.

In addition, C-3 ¹ H-NMR spectrum (300㎒, CDCl ³⁾ of the δ = 8.3 (d, 1H) , 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7 (M, 4H), 7.4 (dd, 1H), 7.1 (d, 1H), 5.6 (q,

D-1: DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.)

E-1: 1,5-Diazabicyclo [4,3,0] -5-nonene (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

E-2: Compound of the following structure

S-1: The following compound (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBE-3026)

S-6: The following compound (manufactured by Toray Industries, Ltd., product number: Z6920)

S-7: The following compound (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBE-846)

S-8: The following compound (manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-9659)

F-1: JER150S65 (manufactured by Mitsubishi Kagaku Co., Ltd.)

F-2: JER1031S (manufactured by Mitsubishi Kagaku Co., Ltd.)

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

H-1: Compound of the following structure

&Lt; Evaluation of chemical resistance (release liquid resistance) >

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

The resulting photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (energy intensity: 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 cured film was immersed in monoethanolamine at 60 DEG C for 5 minutes, and the film was taken up to wipe off the liquid on the surface, and the film thickness was immediately measured. The ratio of the film thickness before immersion and the film thickness after immersion was expressed in percent. The results are shown in the following table. The smaller the numerical value is, the better the peel solution resistance of the cured film is, and A or B is preferable.

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

A: 100% or more and less than 102%

B: 102% or more and less than 105%

C: 105% or more and less than 110%

D: 110% or more and less than 115%

E: 115% or more

&Lt; Evaluation of chemical resistance (NMP resistance) >

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

The resulting photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (energy intensity: 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 cured film was immersed in NMP at 80 DEG C for 10 minutes, and the film was pulled up to wipe out the liquid on the surface, and the film thickness was measured immediately. The ratio of the film thickness before immersion and the film thickness after immersion was expressed in percent. The results are shown in the following table. The smaller the numerical value is, the better the NMP resistance of the cured film is, and A or B is preferable.

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

A: 100% or more and less than 102%

B: 102% or more and less than 105%

C: 105% or more and less than 110%

D: 110% or more and less than 115%

E: 115% or more

&Lt; Dry etching resistance >

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

The resulting photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (energy intensity: 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 cured film was dry etched under the conditions of CF ₄ 50 ml / min, O ₂ 10 ml / min, output of 400 mW, and etching time of 90 seconds as an etching gas using a dry etching apparatus "CDE-80N (Shibaura Mechatronics, . The etching rate was calculated from the film reduction amount. The smaller the numerical value is, the higher the dry etching resistance is, and A or B is preferable.

A: 30 Å / sec to 35 Å / sec

B: 35 Å / sec or more and less than 40 Å / sec

C: 40 Å / sec to 45 Å / sec

&Lt; Example 144 >

In the active matrix liquid crystal display device shown in Fig. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film in the following manner, and a liquid crystal display device of Example 144 was obtained. That is, the photosensitive resin composition of Example 1 was used to form a cured film 17 as an interlayer insulating film.

That is, as a pretreatment for improving the wettability of the substrate of the paragraph 58 of Japanese Patent No. 3321003 and the interlayer insulating film 17, the substrate is exposed for 30 seconds under steam of hexamethyldisilazane (HMDS), and thereafter The photosensitive resin composition of Example 1 was coated with a spin coat, prebaked on a hot plate at 90 캜 for 2 minutes, and the solvent was volatilized to form a photosensitive resin composition layer having a thickness of 3 탆. Subsequently, the obtained photosensitive resin composition layer was exposed using a Canon MPA 5500CF (high-pressure mercury lamp) through a mask having a hole pattern of 10 mu m phi to 40 mJ / cm2 (energy intensity: 20 mW / did. Then, the exposed photosensitive resin composition layer was developed with an alkaline developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 占 폚 for 60 seconds and rinsed with ultrapure water for 20 seconds. Subsequently, the entire surface of the substrate was exposed using an ultra-high pressure mercury lamp so that the cumulative irradiation dose was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2, i-line), and then the substrate was heated in an oven at 230 캜 for 30 minutes to obtain a cured film.

The coating properties when the photosensitive resin composition was applied were good, and no wrinkles or cracks were observed in the cured films obtained after exposure, development and firing.

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

&Lt; Example 145 >

Only the process of Example 144 and the following processes were modified to obtain the same liquid crystal display device. That is, even when the hexamethyldisilazane (HMDS) treatment as the substrate pretreatment was omitted and the photosensitive resin composition of Example 52 was applied, the obtained cured film was in a satisfactory state without any defect or peeling of the pattern. The performance as a liquid crystal display device was also good as in Example 144. [ This is considered to be due to the excellent adhesion of the composition of the present invention with the substrate. It is also preferable to omit the substrate pretreatment step from the viewpoint of improving the productivity.

&Lt; Example 146 >

The same liquid crystal display device was obtained by modifying only the process of Example 144 and the following. That is, even when the alkaline developing solution was changed from an aqueous solution of tetramethylammonium hydroxide of 0.4% to a solution of tetramethylammonium hydroxide of 2.38%, the obtained cured film was in a satisfactory state without any pattern defect or peeling. The performance as a liquid crystal display device was also good as in Example 144. [ This is considered to be due to the excellent adhesion of the composition of the present invention with the substrate.

<Example 147>

The same liquid crystal display device was obtained by modifying only the process of Example 144 and the following. That is, even when the alkaline developer was changed from a 0.4% aqueous solution of tetramethylammonium hydroxide to a 0.04% KOH aqueous solution, the obtained cured film was in a satisfactory state without any defects or peeling of the pattern. The performance as a liquid crystal display device was also good as in Example 144. [ This is considered to be due to the excellent adhesion of the composition of the present invention with the substrate.

&Lt; Example 148 >

The same liquid crystal display device was obtained by modifying only the process of Example 144 and the following. That is, omitting the step of front exposure after developing and rinsing, the cured film was obtained by heating at 230 ° C for 30 minutes in an oven. The obtained liquid crystal display device was as good as the performance in Example 144. This is considered to be because the composition of the present invention is excellent in drug resistance. From the viewpoint of improving the productivity, it is also preferable to omit the step of front exposure.

&Lt; Example 149 >

The same liquid crystal display device was obtained by modifying only the process of Example 144 and the following. That is, a step of heating on a hot plate at 100 占 폚 for 3 minutes between the step of front exposure and the step of heating at 230 占 폚 for 30 minutes in an oven was added. The obtained liquid crystal display device was as good as the performance of Example 149. It is also preferable to add the process from the viewpoint of having the shape of the hole pattern.

&Lt; Example 150 >

The same liquid crystal display device was obtained by modifying only the process of Example 144 and the following. That is, a process of heating on a hot plate at 100 ° C for 3 minutes was added between the development / rinsing process and the front exposure process. The obtained liquid crystal display device was as good as the performance in Example 144. It is also preferable to add the process from the viewpoint of having the shape of the hole pattern.

&Lt; Example 151 >

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) was formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole was formed on the insulating film 3 . The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or later and the TFT 1. [

The planarization layer 4 was 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. The formation of the planarization film 4 on the insulating film 3 was performed by spin-coating the photosensitive resin composition of Example 1 on a substrate, prebaking on a hot plate (90 占 폚 for 2 minutes), applying a high- (365 nm) was irradiated with 45 mJ / cm 2 (energy intensity 20 mW / cm 2) and then developed with an aqueous alkali solution (0.4% TMAH aqueous solution) to form a pattern. Using a super high pressure mercury lamp, the cumulative irradiation dose was 300 mJ / (Energy intensity: 20 mW / cm &lt; 2 &gt;, i-line) and subjected to heat treatment at 230 DEG C for 60 minutes. The coating properties when the photosensitive resin composition was applied were good, and no wrinkles or cracks were observed in the cured films obtained after exposure, development and firing. The average step of the wiring 2 was 500 nm, and the thickness of the planarization film 4 was 2,000 nm.

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

Then, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film, the insulating film 8 was formed by the above-described method using the photosensitive resin composition of Example 3. By forming this insulating film, it is possible to prevent a short circuit 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 deposited by vapor deposition in a vacuum vapor deposition apparatus via a desired pattern mask. Subsequently, a second electrode made of Al on the entire upper surface of the substrate was formed. The obtained substrate was taken out of the evaporator, sealed with a sealing glass plate and using an ultraviolet curable epoxy resin.

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

<Example 152>

A liquid crystal display device was similarly manufactured except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 16 in Example 144. The liquid crystal display device exhibits good display characteristics and is a highly reliable liquid crystal display device.

&Lt; Example 153 >

A liquid crystal display was manufactured in the same manner as in Example 144 except that the photosensitive resin composition of Example 31 was replaced with the photosensitive resin composition of Example 31. The liquid crystal display device exhibits good display characteristics and is a highly reliable liquid crystal display device.

&Lt; Example 154 >

An organic EL device was produced in the same manner as in Example 144 except that the photosensitive resin composition of Example 132 was replaced with the photosensitive resin composition of Example 132. [ The organic EL display device exhibits good display characteristics and is highly reliable.

&Lt; Example 155 >

An organic EL device was prepared in the same manner as in Example 151 except that the photosensitive resin composition of Example 16 was replaced with the photosensitive resin composition of Example 1. [ The organic EL display device exhibits good display characteristics and is highly reliable.

&Lt; Example 156 >

An organic EL device was prepared in the same manner as in Example 151, except that the photosensitive resin composition of Example 31 was replaced with the photosensitive resin composition of Example 31. The organic EL display device exhibits good display characteristics and is highly reliable.

&Lt; Example 157 >

An organic EL device was prepared in the same manner as in Example 151 except that the photosensitive resin composition of Example 133 was replaced with the photosensitive resin composition of Example 1. The organic EL display device exhibits good display characteristics and 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 (19)

(Component A) A polymer component comprising a polymer satisfying at least one of the following (1) and (2)
(1) (a1) the acid group is a polymer having a structural unit having a group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group,
(2) (a1) the acid group is a polymer having a structural unit having a group protected with an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group,
(Component C) photoacid generator, and
(Component D) solvent, and further comprises
(Component X) A positive-type photosensitive resin composition comprising a silicon compound having at least two hydrolyzable silyl groups and / or silanol groups represented by formula (X1) in one molecule.

Wherein at least one of R ^X1 to R ^X3 is a hydrolysable group selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, an allyloxy group and an isopropenoxy group, or Lt; / RTI &gt; And the remaining R ^X1 to R ^X3 independently represent a hydrogen atom, a halogen atom or a monovalent organic substituent group, The method according to claim 1,
Wherein at least two of R ^X1 to R ^X3 in said structural unit (X1) are alkoxy groups. 3. The method according to claim 1 or 2,
Wherein the content of the component X is 0.1% by weight or more based on the total amount of the components excluding the solvent of the resin composition. 3. The method according to claim 1 or 2,
Wherein the constituent unit (a1) is a constituent unit in which the carboxyl group has an acetal- or ketal-protected residue. 3. The method according to claim 1 or 2,
Wherein the structural unit (a1) is a structural unit represented by the formula (a1-1).

Wherein R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, R ³ is an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group, 3. The method according to claim 1 or 2,
Wherein at least two of R ^X1 to R ^X3 in said structural unit (X1) are a methoxy group or an ethoxy group. 3. The method according to claim 1 or 2,
Wherein the structural unit (a2) is a structural unit having at least one kind selected from an epoxy group and an oxetanyl group. 3. The method according to claim 1 or 2,
The component content W _A and W _B weight ratio of the content of the B component of the A is _{W A / W B = 98 /} 2~20 / 80 of the positive photosensitive resin composition according to claim. 3. The method according to claim 1 or 2,
Wherein the component C is an oxime sulfonate compound having at least one of oximesulfonate moieties represented by formula (c0).

3. The method according to claim 1 or 2,
Wherein at least two of R ^X1 to R ^X3 in the structural unit (X1) are alkoxy groups, and the content of the component X is 0.1% by weight or more based on the total of the components excluding the solvent of the resin composition. Composition. 3. The method according to claim 1 or 2,
At least two of R among ^{X1 X3} ~R the structural unit (X1) is an alkoxy group, and at least two of R ^X1 ~R ^X3 of the structural unit (X1) is positive, characterized in that a methoxy group or an ethoxy group Sensitive resin composition. 3. The method according to claim 1 or 2,
At least two of R ^X1 to R ^X3 in the structural unit (X1) are alkoxy groups, and the content of the component X is 0.1% by weight or more based on the total amount of the components excluding the solvent of the resin composition, Wherein at least two of R ^X1 to R ^X3 are a methoxy group or an ethoxy group. (1) a step of applying the positive photosensitive resin composition described in (1) above onto a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition,
(3) a step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray,
(4) a step of developing the exposed photosensitive resin composition by an aqueous developer, and
(5) a post-baking step of thermally curing the developed photosensitive resin composition. 14. The method of claim 13,
And a step of exposing the developed photosensitive resin composition to the whole before the post-baking step after the developing step. The method according to claim 13 or 14,
(6) The method for forming a cured film, further comprising a step of performing dry etching on the substrate having the cured film obtained by thermosetting. A cured film formed by the method for forming a cured film according to claim 13. 17. The method of claim 16,
Wherein the cured film is an interlayer insulating film. An organic EL display device comprising the cured film according to claim 16. A liquid crystal display device comprising the cured film according to claim 16.

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