KR101738464B1 - Photosensitive resin composition, method for forming cured film, cured film, organic el display device, and liquid-crystal display device - Google Patents

Abstract

A photosensitive resin composition capable of obtaining a cured film having high sensitivity, high transparency, high chemical resistance, high adhesion of a cured film to a substrate, excellent dry etching resistance, and low dielectric constant.
(A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2)
(1) a polymer comprising (a1) a structural unit having a residue protected by an acid-decomposable group and (a2) a structural unit having a structural unit having a crosslinkable group,
(2) a polymer having (a1) a constituent unit having a residue protected by an acid-decomposable group, and (a2) a polymer having a constituent unit having a crosslinkable group,
(B) a photoacid generator, (C) an adduct type block polyisocyanate compound, and (D) a solvent.

Description

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

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.

Description of the Related Art [0002] In order to insulate a wiring layer, which is generally arranged in layers, 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, Is installed. As the material for forming the interlayer insulating film, it is preferable that the number of steps for obtaining a necessary pattern shape is small and sufficient flatness is achieved, and thus a photosensitive resin composition is widely used. As such a photosensitive resin composition, for example, Patent Document 1 can be mentioned.

Among the above electronic components, for example, in a TFT type liquid crystal display element, a transparent electrode film (ITO) is formed on the interlayer insulating film, a wiring made of metal such as molybdenum (Mo) or titanium (Ti) , The liquid crystal alignment layer is formed. Therefore, the interlayer insulating layer may be exposed to high temperature conditions in the process of forming the transparent electrode layer, or may be exposed to a stripping liquid of a resist used for pattern formation of an electrode, an NMP N-methylpyrrolidone), so that sufficient resistance to these substances is required.

In addition, when the interlayer insulating film has poor adhesion to the transparent electrode film or the wiring (metal) formed thereon, problems are likely to occur in the display of the panel, and adhesion with the transparent electrode film or wiring is also required. Since the interlayer insulating film may be subjected to a dry etching process, sufficient resistance to dry etching is also required.

BACKGROUND ART In recent years, in the field of electronic materials, circuit resistance and capacitor capacity between wirings increase with progress of high integration, multifunctionalization, and high performance, resulting in increase of power consumption and delay time. Among them, the increase of the delay time is a factor of the decrease of the signal speed of the device and the generation of the crosstalk. Therefore, it is required to reduce the parasitic capacitance in order to reduce the delay time and increase the speed of the device. In order to reduce the parasitic capacitance, a demand for lowering the dielectric constant of the interlayer insulating film has been increasing. The interlayer insulating film made of an acrylic resin is lower than the silicon nitride film (SiN, relative dielectric constant: about 8), silicon oxynitride film (SiON, relative dielectric constant: about 4.5), silicon oxide film (SiO 2, relative dielectric constant: about 4) A reduction in the dielectric constant is desired.

Patent Document 2 discloses a resin composition comprising a block isocyanate which is chemically stable and excellent in weatherability and particularly low temperature curability, which is useful for paints (for automobiles, powders, coatings, precoated metals), adhesives, However, there is no description concerning the interlayer insulating film. An example of applying a block isocyanate compound to an interlayer insulating film is disclosed in Patent Document 3.

Japanese Patent Laid-Open Publication No. 2011-209681 Japanese Patent Laid-Open No. 8-165326 Japanese Patent Application Laid-Open No. 2008-3532

Here, the photosensitive resin composition proposed in Patent Document 3 includes a block isocyanate and a block isocyanate compound having a uretdione structure. The inventors of the present invention have found that a photosensitive resin composition containing a block isocyanate compound having a uretdione structure has low resistance to a resist remover or N-methyl pyrrolidone (NMP) used after forming an interlayer insulating film, The adhesion to the metal after the formation of the cured film was poor, and the resistance to dry etching was low. As a result, a display problem in a liquid crystal display device tends to occur, and improvement has been demanded. The photosensitive resin composition described in Patent Document 3 has a problem that the dielectric constant of the interlayer insulating film is higher and the occurrence of crosstalk is significant.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has as its object to provide a photosensitive resin composition which has high sensitivity, It is an object of the present invention to provide a resin composition. It is still another object of the present invention to provide a cured film obtained by curing a photosensitive resin composition, a method of forming the same, and an organic EL display device and a liquid crystal display device provided with the cured film.

It is generally considered that reducing the OH group is effective for lowering the dielectric constant of the photosensitive resin composition. If the OH group is reduced, it is considered that the ratio of the acid-decomposable group and the crosslinkable group in the polymer component is reduced. However, if the ratio of the crosslinkable group is reduced, the chemical resistance is reduced. In the present invention, by using an amine type block isocyanate compound having a good reactivity, the OH group was successfully reduced without reducing the ratio of the acid-decomposable group and the crosslinkable group.

Specifically, the above problem has been solved by the following means.

≪ 1 > A polymer composition comprising (A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2)

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

(2) a polymer having (a1) a constituent unit having a residue protected by an acid-decomposable group, and (a2) a polymer having a constituent unit having a crosslinkable group,

(B) a photoacid generator,

(C) an adduct type block polyisocyanate compound, and

(D) a solvent,

.

<2> (C) The photosensitive resin composition according to <1>, wherein the adduct block polyisocyanate compound is a compound represented by the following formula (C).

In the general formula (C)

Ra- {O (C = O) -NH-Rb-NHCO-B} n

[In the general formula (C), Ra is an n-valent hydrocarbon group, Rb is a divalent hydrocarbon group, and B represents a group blocking isocyanate. n is an integer of 3 to 6; n Rb and B may be the same or different,

&Lt; 3 > The photosensitive resin composition according to < 2 >, wherein Ra in general formula (C) is a branched aliphatic hydrocarbon group.

<4> A positive resist composition according to <4>, wherein B in the general formula (C) is at least one compound selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds and imide compounds Or a group derived from a compound selected from the group consisting of a halogen atom and a halogen atom.

<5> A photosensitive resin composition according to any one of <1> to <4>, which is a chemically amplified positive type.

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the acid-decomposable group is a group having a protected structure in the form of an acetal.

<7> The chemical amplification type positive photosensitive resin composition according to any one of <1> to <6>, wherein the structural unit (a1) is a structural unit represented by the following general formula (A2 ').

(A2 ')

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,

<8> The photosensitive resin composition according to any one of <1> to <7>, wherein any one of the polymer components (A) is a polymer further containing an acid group.

(A2) The crosslinkable group contained in the structural unit having a crosslinkable group is selected from the group consisting of an epoxy group, an oxetanyl group and -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) The photosensitive resin composition according to any one of < 1 > to < 8 &gt;, which is at least one selected.

(C) The isocyanate of a polyisocyanate prepolymer synthesized from at least one isocyanate compound selected from tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, wherein the adduct type block polyisocyanate compound 1 &gt; to &lt; 9 &gt;. 2. The photosensitive resin composition according to any one of &lt; 1 &gt;

<11> (C) The photosensitive resin composition according to any one of <1> to <10>, wherein the adduct block-type polyisocyanate compound is obtained by a reaction of a diisocyanate compound and trimethylolpropane.

<12> The photosensitive resin composition according to any one of <1> to <11>, further comprising an antioxidant.

(13) A method for producing a photosensitive resin composition, comprising the steps of: applying the photosensitive resin composition described in any one of <1> to <12>

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

(3) a step of exposing by actinic radiation,

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

(5) a post-baking step of thermally curing the cured film.

<14> The method of forming a cured film according to <13>, comprising a step of exposing the developed photosensitive resin composition to the whole surface after the development step and before the post-baking step.

(6) A method for forming a cured film as described in (13) or (14), further comprising a dry etching step of performing dry etching on the substrate having the cured film obtained by thermosetting.

<16> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <12>.

<17> The cured film according to <16>, which is an interlayer insulating film.

&Lt; 18 > A liquid crystal display device or an organic EL display device having a cured film according to < 16 > or < 17 >.

(Effects of the Invention)

According to the present invention, it is possible to provide a photosensitive resin composition capable of obtaining a cured film having high sensitivity, high transparency, high chemical resistance, high adhesion of a cured film to a substrate, excellent dry etching resistance, and low dielectric constant .

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

Hereinafter, the contents of the present invention will be described in detail. The following description of the constituent elements described below may be made on the basis of exemplary embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, &quot; &quot; is used to mean that the numerical values described before and after that are included as the lower limit value and the upper limit value.

In the present specification, the notation in which the substituent and the non-substituent are not described in the notation of the group (atomic group) 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).

[Photosensitive resin composition]

(A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2); (B) A photo acid generator, (C) an adduct type block polyisocyanate compound, and (D) a solvent.

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

(2) a polymer having (a1) a constituent unit having a residue protected by an acid-decomposable group, and (a2) a polymer having a constituent unit having a crosslinkable group,

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

Hereinafter, preferred embodiments of the components of the photosensitive resin composition of the present invention will be described in order.

<(A) Polymer Component>

(1) a polymer having (a1) a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group, and (2) (A2) a polymer having a constituent unit having a crosslinkable group and a polymer having a constituent unit having a moiety protected with an acid-decomposable group. In addition, polymers other than these may be contained. The polymer component (A) (hereinafter may be referred to as the "component (A)") in the present invention is not particularly limited unless otherwise specified in addition to the above (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 component (A) preferably contains a constituent unit derived from (meth) acrylic acid and / or an ester thereof in an amount of 50 mol% or more, more preferably 90 mol% or more, relative to all the constituent units in the polymer And a polymer comprising only constituent units derived from (meth) acrylic acid and / or esters thereof.

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

The copolymer (A) is preferably alkali-insoluble as a whole, and is preferably a resin that becomes alkali-soluble when the acid-decomposable group of the structural unit (a1) is decomposed. Herein, the acid-decomposable group means a functional group capable of decomposing in the presence of an acid. That is, the constituent unit having a protected carboxyl group protected by an acid-decomposable group in the carboxyl group is a constituent unit in which a protective group is decomposed by an acid to form a carboxyl group and the phenolic hydroxyl group is protected by an acid- By which the phenolic hydroxyl group can be generated. Here, in the present invention, the term "alkali solubility" means that the coating film (thickness 3 μm) of the compound (resin) formed by applying a solution of the above-mentioned compound (resin) onto a substrate and heating at 90 ° C. for 2 minutes at 23 ° C. Means that the dissolution rate in 0.4% aqueous solution of tetramethylammonium hydroxide in the solution is 0.01 m / sec or more. The term &quot; alkali insoluble &quot; means that the solution of the compound (resin) is coated on a substrate and heated at 90 DEG C for 2 minutes Means that the dissolution rate of the coating film (thickness 3 占 퐉) of the compound (resin) to be formed in an aqueous 0.4% tetramethylammonium hydroxide solution at 23 占 폚 is less than 0.01 占 퐉 / second.

The polymer (A) may have a structure derived from a carboxyl group, a carboxylic acid anhydride, and / or other structural units having a phenolic hydroxyl group, which will be described later. However, in the case of introducing an acidic group, it is preferable to introduce the acidic group in the range of keeping the entire polymer (A) insoluble in alkali.

<< Constituent unit (a1) >>

Component A has at least (a1) a constituent unit having an acid group having a residue protected by an acid-decomposable group. The component (A) has the structural unit (a1), whereby a highly sensitive photosensitive resin composition can be obtained.

The "residue in which an acid group is protected by an acid-decomposable group" in the present invention may be any known acid group or 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 below, an acetal such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group (Tertiary alkyl group such as tert-butyl ester group, tertiary alkylcarbonate group such as tert-butyl carbonate group) can be used.

(a1) The constituent unit in which the acid group has a residue protected by 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 the structural unit having a carboxyl group and having a protected carboxyl group protected by an acid-decomposable group described in detail below.

The structural unit having a carboxyl group which can be used for the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is not particularly limited and a known structural unit can be used. (A1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid; , And a structural unit (a1-1-2) having both an ethylenic unsaturated group and an acid anhydride derived structure.

(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 And structural units having both structures derived from anhydride 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, the following exemplified unsaturated carboxylic acids are used. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid used for obtaining the constituent 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 polymers thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have. Examples of the unsaturated carboxylic acid include acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene.

Among them, from the viewpoint of developability, 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, acrylic acid, methacrylic acid or an unsaturated polycarboxylic acid It is preferable to use anhydride or the like, and acrylic acid or methacrylic acid is more preferably used.

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 two or more kinds.

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

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 present in a structural unit having an ethylenic unsaturated group.

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

The reaction rate of the acid anhydride 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, particularly from the viewpoints of sensitivity and pattern shape, contact hole formation, 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 an acetal represented by the following general formula (a1-1). When the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-1), the structure of - (C═O) -O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) .

In general formula (a1-1)

[In the formula (a1-1), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms. 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 (a1-1), 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. Here, both of R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and 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 (a1-1) represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

The straight-chain or branched-chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and 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 a substituent having a halogen atom, R ^101, R ^102, R ¹⁰³ is a haloalkyl group, if having an aryl group as a substituent, R ^101, R ^102, R ¹⁰³ is an aralkyl group.

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 -methylphenyl group, a naphthyl group, etc., As the whole, that is, the aralkyl group, benzyl group,? -Methylbenzyl group, phenethyl group, naphthylmethyl group and the like can be exemplified.

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

When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent. When the alkyl group is a straight chain or branched chain alkyl group, Or a cycloalkyl group having 1 to 12 carbon atoms.

These substituents may be further substituted by the above substituents.

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

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may bond together to form a ring together with the carbon atom 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, An adamantyl group, and a tetrahydropyranyl group.

In the general formula (a1-1), it is preferable that either R ¹⁰¹ or R ¹⁰² is a hydrogen atom or a methyl group.

The radically polymerizable monomer used for forming the constituent unit having a protective carboxyl group represented by the general formula (a1-1) 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 the paragraphs Nos. 0037 to 0040 of Japanese Patent Laid-Open Publication No. 2011-221494.

A first preferred form of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit represented by the formula (A2 ').

The formula (A2 ')

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,

When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. Each of R ¹ and R ² is 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 an alkyl group having 1 to 6 carbon atoms.

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

A second preferred form 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 by the acid-decomposable group is a structural unit having a protected phenolic hydroxyl group, the structural unit having a phenolic hydroxyl group being protected 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. Of these structural units, hydroxystyrene or? -Methylhydroxystyrene-derived structural units Is preferable from the viewpoint of transparency. Among the structural units having a phenolic hydroxyl group, structural units represented by the following general formula (a1-2) are preferable from the viewpoints of transparency and sensitivity.

In general formula (a1-2)

Wherein R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and 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 5 or less. When two or more R &^lt; ²²² &gt; are present, these R ^{&lt; 222 &}

In the general formula (a1-2), 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 single-crystal combination, it is preferable since the sensitivity can be improved and the transparency of the cured film can be improved. Examples of the divalent linking group of R 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 easiness 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 thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert- butyl group, a pentyl group, an isopentyl group and a neopentyl group . Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable in view of easiness of 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 well as the acid-decomposable group, known ones can be used, and they are not particularly limited. Among the acid decomposable groups, structural units having a protective phenolic hydroxyl group protected by an acetal are preferred from the viewpoints of basic physical properties of the photosensitive resin composition, particularly from the viewpoints of sensitivity and pattern shape, storage stability of the photosensitive resin composition, and formability of contact holes. 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 (a1-1). Further, when the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-1), -Ar-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) . 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 monomer used to form a 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 And the like.

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 commercially available or may be synthesized by a known method. 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 with the acid-decomposable group include the following structural units, but the present invention is not limited thereto.

<<< Preferable Form 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% in the polymer containing the structural unit (a1) And more preferably from 30 to 90 mol%.

When the polymer containing the constituent unit (a1) contains the following constituent unit (a2), the constituent unit (a1) is preferably 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 carboxyl group, the content is preferably 20 to 50 mol%, more preferably 30 to 45 mol% desirable.

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 by the acid decomposable group. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferable. On the other hand, when it is desired to delay 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 crosslinking group >>

(A) has a structural unit (a2) having a crosslinking group. The crosslinking group is not particularly limited as long as it is a group which causes a curing reaction by a heat treatment. Preferable examples of the structural unit having a crosslinking group include at least one 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 from 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, an 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 a constituent unit containing at least one of an epoxy group and an oxetanyl group, and more preferably contains a constituent unit containing an oxetanyl group desirable. More specifically, the following can be mentioned.

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

The copolymer (A) preferably contains a structural unit (structural unit (a2-1)) having an epoxy group and / or an 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 is preferably a structural unit having an alicyclic epoxy group and / or an oxetanyl group, and more preferably a structural unit having an oxetanyl group.

The structural unit (a2-1) having an epoxy group and / or 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 an oxetanyl group. The epoxy group and / or the oxetanyl group is preferably, but not limited to, a total of 1 to 3 epoxy groups and / or an oxetanyl group, and the epoxy group and / More preferably an epoxy group or an oxetanyl group, and still more preferably one 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 Dicyclohexylmethyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, -Epoxy cyclohexylmethyl,? -Ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Compounds having an alicyclic epoxy skeleton described in paragraphs [0031] to [00300] of EP-A-4168443, and the like.

Specific examples of the radically polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 001 of JP-A No. 2001-330953 And the like.

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

Among these monomers, compounds containing an alicyclic epoxy skeleton described in paragraphs [0034] to [00300] of Japanese Patent No. 4168443 and oxetanyl groups described in paragraphs [0011] to [0000] of JP-A No. 2001-330953 (Meth) acrylic acid ester having an oxetanyl group as described in paragraphs 0011 to 001 of Japanese Patent Application Laid-Open No. 2001-330953. Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl, and most preferred are acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl. These structural units may be used singly or in combination of two or more.

As the above-mentioned structural unit (a2-1) having an epoxy group and / or an oxetanyl group, the description of paragraphs 0053 to 0055 of Japanese Patent Laid-Open Publication No. 2011-215590 may be taken into consideration.

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.

In the present invention, an oxetanyl group is preferable from the viewpoint of sensitivity. From the viewpoint of transmittance (transparency), alicyclic epoxy groups and oxetanyl groups are preferred. From the above, as the epoxy group and / or oxetanyl group in the present invention, an alicyclic epoxy group and an oxetanyl group are preferable, and an oxetanyl group is particularly preferable.

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

(A2-2) having an ethylenic unsaturated group (hereinafter also referred to as &quot; structural unit (a2-2) &quot;) as one of the structural units (a2) having a crosslinking group. As the structural unit (a2-2) having an ethylenically unsaturated group, a structural unit having an ethylenic unsaturated group at the side chain is preferable, a structural unit having an ethylenic unsaturated group at the end and a side chain having 3 to 16 carbon atoms is more preferable, And a structural unit having a side chain represented by the 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 linkage to the main chain of the structural unit (a2) Lt; / RTI &gt;

R ³⁰¹ may be a divalent linking group having 1 to 13 carbon atoms, such as an alkenyl group, a cycloalkenyl 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.

For the other (a2-2) constituent unit having an ethylenic unsaturated group, the description of paragraphs 0077 to 0090 in Japanese Patent Laid-Open Publication No. 2011-215580 may be taken into consideration.

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

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

In general formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 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.

<<< Preferable Form 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 from 5 to 90 mol% of the polymer containing the structural unit (a2) And more preferably 20 to 80 mol%.

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) To 70 mol%, and more preferably 10 mol% to 60 mol%.

In the present invention, 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 of the cured film obtained from the photosensitive resin composition and the ITO sputter resistance are improved.

<< (a3) Other constituent units >>

In the present invention, the component (A) may contain other structural units (a3) in addition to the structural units (a1) and / or (a2). These constituent units may contain the polymer (1) and / or (2). Further, apart from the polymer (1) or (2), a polymer component having another structural unit (a3) may be contained. When a polymer having another constituent unit (a3) is contained separately from the polymer (1) or (2), the amount of the polymer component is preferably 60 mass% or less, more preferably 40 mass% or less By mass, and more preferably not more than 20% by mass.

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

Hereinafter, preferred embodiments of the polymer component of the present invention are mentioned, but it is needless to say that the present invention is not limited to these.

(First Embodiment)

Wherein the polymer (1) further comprises one or more other structural units (a3).

(Second Embodiment)

(A1) a form in which the polymer having a constituent unit having a residue protected with an acid-decomposable group in the polymer (2) further contains one or more other constituent units (a3).

(Third Embodiment)

(A2) a form in which the polymer having a constituent unit represented by the following general formula (I) further comprises one or more other constituent units.

(Fourth Embodiment)

In any one of the first to third embodiments, a form including at least an acid group-containing constituent unit as another constituent unit.

(Fifth Embodiment)

In any one of the first to third embodiments, the polymer (1) and / or the polymer (2) as the other constitutional unit include a constitutional unit containing at least an acid group.

(Sixth Embodiment)

Apart from the polymer (1) or (2), a form having a polymer having another structural unit (a3). Examples of the other structural unit (a3) in this case include a structural unit containing an acid group, a structural unit having a crosslinkable group, and the like.

(Seventh Embodiment)

And a combination of two or more of the first to sixth embodiments.

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, ethylene glycol monoacetate mono And the like. In addition, the compounds described in paragraphs 0021 to 0024 of Japanese Patent Application Laid-Open No. 2004-264623 can be mentioned.

In addition, as the other structural unit (a3), a styrene group or a group having an alicyclic cyclic skeleton is preferable in view 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) in the polymer (A) is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. The lower limit value may be 0 mol%, for example, 1 mol% or more, and may be 5 mol% or more. Within the range of the above-mentioned numerical values, various 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 becomes easy to dissolve in an alkaline developing solution, and the effect of the present invention is more effectively exerted. The acid group in the present invention means a proton dissociable group having a pKa smaller than 7. The acid group is introduced into the resin as a constituent unit containing an acid group by using a monomer capable of forming an acid group. The inclusion of such a structural unit containing an acid group in the resin tends to increase the alkali solubility.

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, sulfonamide groups, And the like, and those derived from a carboxylic acid group and / or derived from a phenolic hydroxyl group are preferable.

The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, and (meth) acrylic acid and / or an ester thereof.

In the present invention, it is particularly preferable to contain a constituent unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group from the viewpoint of sensitivity.

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 most preferably 5 to 20 mol%.

In the present invention, in addition to the polymer (1) or (2), a polymer having another structural unit (a3) may be contained. Examples of the other structural unit (a3) in this case include a structural unit containing an acid group, a structural unit having a crosslinkable group, and the like.

As such a polymer, a resin having a carboxyl group in the side chain is preferable. For example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Application Laid-open No. 59-53836, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as disclosed in the respective publications of Japanese Patent Application Laid-Open No. 59-71048 Acidic cellulose derivatives having a carboxyl group in a side chain, acid anhydride added to a polymer having a hydroxyl group, and the like, and a polymer having a (meth) acryloyl group in the 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 A publicly known polymer compound described in Japanese Patent Application Laid-Open Nos. 2000-56118, 2003-233179, and 2009-52020 can be used.

These polymers may contain only one kind or two or more kinds.

As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (manufactured by Satoruma Corporation), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC- JUNCRYL 690, JONCRYL 678, JONCRYL 67 and JONCYLRY 586 (manufactured by BASF) may be used as the antifouling coating agent, such as UF-3910, ARUFON UC-3920 and ARUFON UC-3080.

<< (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 range of the above numerical values, various characteristics are 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 >>

Various methods are also known for the method of synthesizing the component (A). For example, a radical polymerization method comprising a radical polymerizable monomer used for forming at least the constituent units represented by (a1) and (a3) Can be synthesized by polymerization of a monomeric monomer mixture in an organic solvent using a radical polymerization initiator. 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 mass%, more preferably 70 to 98 mass%, based on the total solid content.

&Lt; (B) Photo acid generator >

The photoacid generator used in the present invention is preferably a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but 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 photoacid generator used in the present invention, 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.

The component (B) is preferably an oxime sulfonate compound from the viewpoint of sensitivity.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds . Among them, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators may be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazine, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives are disclosed in Japanese Patent Application Laid-Open No. 2011-221494 The compounds described can be exemplified.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following general formula (B1) can be preferably exemplified.

In general formula (B1)

[In the formula (B1), R ²¹ represents an alkyl group, an aryl group, an alkyl fluoride group or an aryl fluoride group. The dashed line indicates the combination with other tiles.

The alkyl group in R &lt; ²¹ &gt; may be linear, branched or cyclic. The permissible substituents are described below.

As the alkyl group for R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a polycyclic alicyclic group such as a 7,7-dimethyl-2-oxononyl group, An alkyl group or the like).

As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

It is also preferable that the compound containing an oxime sulfonate structure represented by the general formula (B1) is an oxime sulfonate compound represented by the following general formula (B2).

Of the formula (B2), R ⁴² is an alkyl group, an aryl group, represents a fluorinated alkyl group, a fluorinated aryl group, X is an alkyl group, an alkoxy group, or halogen atom, m4 represents an integer of 0~3, m4 is 2 or 3, the plurality of X's may be the same or different]

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

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

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

m4 is preferably 0 or 1.

In the above general formula (B2), and m4 are 1, X is a methyl group, and the substitution position of X in o-position, R ⁴² is a straight chain alkyl group, 7,7-dimethyl-2-oxo Novo carbonyl having 1 to 10 carbon atoms Methyl group, or p-toluyl group is particularly preferable.

The compound containing an oxime sulfonate structure represented by the general formula (B1) is more preferably an oxime sulfonate compound represented by the following general formula (B3).

Equation (B3) of, R ⁴³ is R ⁴² and agreed in the formula (B2), X ¹ is an alkoxy group of the alkyl group, having 1 to 4 carbon atoms a halogen atom, a hydroxyl group, having 1 to 4 carbon atoms, a cyano group or a nitro group And n4 represents an integer of 0 to 5,

Examples of R ⁴³ in the general formula (B3) include methyl, ethyl, n-propyl, n-butyl, n-octyl, A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.

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

n4 is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by the above general formula (B3) include? - (methylsulfonyloxyimino) benzyl cyanide,? - (ethylsulfonyloxyimino) benzyl cyanide,? - (n-propylsulfonyloxyimino) Benzyl cyanide,? - (methylsulfonyloxyimino) -4-methoxyphenyl, benzyl cyanide,? - (n-butylsulfonyloxyimino) benzyl cyanide, - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, alpha - [(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, and? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

Specific examples of the preferable oxime sulfonate compound include the following compounds (i) to (viii), and they may be used singly or in combination of two or more kinds. The compounds (i) to (viii) are commercially available. It may also be used in combination with other types of (B) photoacid generators.

The compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Lt; / RTI &gt; R ¹⁰² represents an alkyl group or an aryl group.

¹⁰¹ X is ^{-O-, -S-, -NH-, -NR 105} -, -CH 2 -, -CR 106 H-, or -CR ¹⁰⁵ R ¹⁰⁷ - represents a, R ¹⁰⁵ ~R ¹⁰⁷ is an alkyl group, or Lt; / RTI &gt;

R ¹²¹ to R ¹²⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

As R ¹²¹ to R ¹²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and at least two of R ¹²¹ to R ^{1 24} are bonded to each other to form an aryl group. Among them, a form in which all of R ¹²¹ to R ¹²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

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

Preferable examples of the compound represented by the above general formula (OS-1) include the general formulas described in paragraphs 0194 to 0202 of JP-A No. 2011-221496 and exemplified compounds thereof.

In the present invention, the compound having an oxime sulfonate structure represented by the general formula (B1) is represented by the following general formula (OS-3), the following general formula (OS-4) It is preferable that the luminescent oxime sulfonate compound is a luminescent oxime sulfonate compound.

In the formulas (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ each represent An alkyl group, an aryl group or a halogen atom; R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group; X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ^{1 to} m ³ each independently represent an integer of 0 to 6,

In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyl group for R ²² , R ²⁵ and R ²⁸ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

Of the above general formulas (OS-3) to (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

Among the above general formulas (OS-3) to (OS-5), the heteroaryl group for R ¹ is preferably a heteroaryl group having 4 to 30 total carbon atoms which may have a substituent.

Of the above-mentioned general formulas (OS-3) to (OS-5), the heteroaryl group for R ²² , R ²⁵ and R ²⁸ may be at least one of the rings is a heteroaromatic ring. For example, a heteroaromatic ring and a benzene ring are ring- There may be.

In the general formulas (OS-3) to (OS-5), R ²³ , R ²⁶ and R ²⁹ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

Of the above-mentioned general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in two or more of the compounds are preferably an alkyl group, an aryl group or a halogen atom, More preferably an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

In the general formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ may have a substituent. Examples of the substituent which the alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ may have include the same groups as the substituent which the alkyl group or aryl group in R ²² , R ²⁵ and R ²⁸ may have have.

The alkyl group in R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having 1 to 12 carbon atoms in total which may have a substituent and more preferably an alkyl group having 1 to 6 carbon atoms in total.

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

Examples of the halogen atom in R ²³ , R ²⁶ and R ²⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

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

In the general formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represents O or S, and is preferably O.

In the general formulas (OS-3) to (OS-5), the ring containing X ^{1 to} X ³ as a reduction is a 5-membered ring or a 6-membered ring.

In the above general formula (OS-3) ~ (OS -5), n1~n3 each independently represents 1 or 2, when X ¹ is O n1~n3 ~X ³ should preferably be each independently 1 , And when X ^{1 to} X ³ are S, n ^{1 to} n ³ are each independently preferably 2.

In the general formulas (OS-3) to (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. Among them, R ²⁴ , R ²⁷ and R ³⁰ are each independently preferably an alkyl group or an alkyloxy group.

The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.

Of the above-mentioned general formulas (OS-3) to (OS-5), the alkyl group for R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

Of the above-mentioned general formulas (OS-3) to (OS-5), the alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyloxy group having 1 to 30 total carbon atoms which may have a substituent.

In addition, for the preferred ranges of the general formulas (OS-3) to (OS-5) and the exemplified compounds, reference may be made to the description of paragraphs 0171 to 0200 of JP-A No. 2011-227449.

In the photosensitive resin composition of the present invention, the photoacid generator (B) is used in an amount of 0.1 to 10 parts by mass relative to 100 parts by mass of the total resin component (preferably solid content, more preferably the above (A) copolymer) in the photosensitive resin composition And it is more preferable to use 0.5 to 10 parts by mass. Two or more species may be used in combination.

&Lt; (C) Adduct type block polyisocyanate compound >

The photosensitive resin composition of the present invention contains (C) an adduct type block polyisocyanate compound. The duct-type block polyisocyanate compound is deprotected at the time of post-baking to produce an isocyanate group and reacted with a carboxyl group or a phenolic hydroxyl group of the constituent unit (a1) or the constituent unit (a2) of the active hydrogen compound, Structure. &Lt; / RTI &gt; Further, it is presumed that the isocyanate group forms a crosslinking structure with the hydroxyl group when the polymer component has the structural unit (a4) having a hydroxyl group or an alkyleneoxy group other than the phenolic hydroxyl group.

An adduct-type polyisocyanate compound means an adduct of a polyhydric alcohol and a polyisocyanate compound. The duct-type block polyisocyanate compound is usually obtained by reacting an adduct-type polyisocyanate compound with a block agent to form a blocked isocyanate group (hereinafter sometimes referred to as "block isocyanate group"). The duct-type block polyisocyanate compound used in the present invention is preferably capable of producing an isocyanate group by heat (for example, 90 ° C to 250 ° C).

The duct-type block polyisocyanate compound used in the present invention is preferably a compound having two or more block isocyanate groups in one molecule, more preferably a compound having 3 to 6 block isocyanate groups in one molecule.

As the polyisocyanate used in the synthesis of the adduct type block polyisocyanate compound of the present invention, a diisocyanate compound is preferable. The skeleton of the diisocyanate compound is not particularly limited, and any diisocyanate compound having two diisocyanate groups in one molecule may be used, and diisocyanate compounds having a hydrocarbon group (aliphatic group, alicyclic group or aromatic group) are preferable. The number of carbon atoms of the hydrocarbon group is preferably from 2 to 30, more preferably from 2 to 20.

In the present invention, particularly preferred is a group in which the hydrocarbon group is composed only of an aliphatic or aromatic 6-membered ring compound, a group formed of a combination of an aliphatic or aromatic 6-membered ring compound and -CH ₂ -, and an alkyl group (preferably a methyl group) .

The molecular weight of the diisocyanate compound is preferably 100 to 1000.

Examples of the diisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4 1,6-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 4-cyclohexane diisocyanate, 4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, (Cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, Cyanate, 3,3'-methylene ditolylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylenediisocyanate, norbornadiisocyanate, hydrogenated 1,3-xylylene diisocyanate , Hydrogenated 1,4-xylylene diisocyanate and the like, and compounds having a skeleton of a prepolymer type derived from these compounds can be preferably used. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are particularly preferable.

The lower limit of the number of polyhydric alcohols used in the synthesis of the adduct-type block polyisocyanate compound of the present invention is preferably 3 or more, and the upper limit of the number of polyhydric alcohols is preferably 6 or less. The molecular weight is preferably from 50 to 700, more preferably from 50 to 500. Further, it is preferably an aliphatic polyhydric alcohol, and is preferably an aliphatic polyhydric alcohol having no cyclic structure. The polyhydric alcohol used in the present invention is preferably a group in which three or more OH groups are bonded to the aliphatic hydrocarbon group of the branch. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 3 to 30, more preferably 4 to 20. The number of OH groups is preferably 3 to 6.

Specific examples include glycerol, trimethylolethane, trimethylolpropane (TMP), trimethylolooctane, 1,2,6-hexanetriol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1 Trihydric alcohols such as tris (bishydroxymethyl) propane and 2,2-bis (hydroxymethyl) butanol; Quaternary alcohols such as pentaerythritol and diglycerol; Pentahydric alcohols (pentit) such as arabit, ribitol and xylitol; Hexahydrate such as sorbitol, mannitol, galactitol, and arzoidate, and the like. Among them, trimethylol propane and pentaerythritol are particularly preferable.

Examples of the block agent used in the synthesis of the adduct type block polyisocyanate compound of the present invention include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, And imide compounds. Among them, a block agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound and a pyrazole compound is more preferable, and a block agent selected from oxime compounds, lactam compounds, phenol compounds and alcohol compounds More preferable.

Examples of the oxime compounds include oxime and ketooxime. Specific examples thereof include acetoxime, formaldehyde, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, acetoxime and the like .

Examples of the lactam compound include ε-caprolactam, γ-butyrolactam, and the like.

Examples of the phenol compound include phenol, naphthol, cresol, xylenol, halogen-substituted phenol, and the like.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.

Examples of the amine compound include primary amines and secondary amines, and aromatic amines, aliphatic amines, and alicyclic amines are preferred, and aniline, diphenylamine, ethyleneimine, and polyethyleneimine.

Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate.

Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole, and the like.

Examples of the mercaptan compound include alkyl mercaptans, aryl mercaptans, and the like.

The duct-type block polyisocyanate compound used in the photosensitive resin composition of the present invention can be obtained as a commercially available product, and examples thereof include tokenate D-120N [bis (isocyanate methyl) cyclohexane (H6XDI) and trimethylol propane D-110N (adduct of XDI and TMP), D-140N (adduct of IPDI and TMP), D-212L (adduct of TDI and TMP) [manufactured by Mitsui Chemicals, Inc.] .

In the present invention, the (C) adduct type block polyisocyanate compound is preferably a compound represented by the following formula (C).

In the general formula (C)

Ra- {O (C = O) -NH-Rb-NHCO-B} n

[In the general formula (C), Ra is an n-valent hydrocarbon group, Rb is a divalent hydrocarbon group, and B represents a group blocking isocyanate. n is an integer of 3 to 6; n Rb and B may be the same or different,

Ra in the general formula (C) is preferably an aliphatic hydrocarbon group, and is preferably a branched aliphatic hydrocarbon group. By employing branched aliphatic hydrocarbon groups, the compatibility with the polymer component is improved, and the effect of the present invention is more effectively exhibited.

The carbon number of Ra is preferably from 3 to 30, more preferably from 4 to 20, and even more preferably from 4 to 15.

Rb is a hydrocarbon group, which may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, any hydrocarbon group of straight chain, branched chain or cyclic hydrocarbon may be used. The carbon number of Rb is preferably from 2 to 30, more preferably from 2 to 20, and still more preferably from 2 to 15.

B is preferably a group derived from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound and an imide compound, A block agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, and an active methylene compound and a pyrazole compound is more preferable and a block agent selected from an oxime compound, a lactam compound, a phenol compound and an alcohol compound is particularly preferable Do.

n is an integer of 3 to 6, and 3 or 4 is more preferable.

In the photosensitive resin composition of the present invention, the block isocyanate compound, which is an adduct type polyisocyanate, is preferably contained in an amount of from 0.1 to 8% by mass, more preferably from 0.2 to 7% by mass, Most preferably 5% by mass. Two or more species may be used in combination.

The composition of the present invention may contain, in addition to the polymer having the polymer (1) or (2) and the other structural unit (a3) used in the present invention, a compound having a functional group capable of reacting with isocyanate produced from the adduct type block polyisocyanate . In this case, the term substantially does not affect the effect of the present invention, and refers to, for example, 1 mass% or less of the total components. By not including such a compound, the crosslinking between the isocyanate and the polymer is not inhibited, and the crosslinking density of the cured film can be further improved.

&Lt; Other crosslinking agent &

The photosensitive resin composition of the present invention may contain, as a crosslinking agent, other crosslinking agents in addition to the above-mentioned adduct type block polyisocyanate. Examples of other crosslinking agents include compounds having two or more epoxy groups or oxetanyl groups in the molecule, alkoxymethyl group-containing crosslinking agents, and / or compounds having at least one ethylenically unsaturated double bond.

- crosslinking agent containing an alkoxymethyl group -

In the photosensitive resin composition of the present invention, a known crosslinking agent other than the block isocyanate may be used, and for example, an alkoxymethyl group-containing crosslinking agent may be preferably used.

Specific examples of the alkoxymethyl group-containing crosslinking agent include alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea. These are obtained by converting the methylol group of methylol melamine, methylol benzoguanamine, methylol glycoluryl, or methylol group into an alkoxymethyl group, respectively.

The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of generated outgas, desirable.

Among these alkoxymethyl group-containing crosslinking agents, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable examples of the crosslinking agent containing an alkoxymethyl group, and alkoxymethylated melamine is particularly preferable from the viewpoint of chemical resistance effect.

These alkoxymethyl group-containing crosslinking agents are commercially available, for example, from Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 , 1174, UFR65, 300 or more, manufactured by Mitsui Cyanamid Co., Ltd., Nikarac MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Lack MS-11, NIKARAK MW-30HM, -100 LM, -390 (manufactured by Sanwa Chemical Co., Ltd.), and the like.

When the photosensitive resin composition of the present invention contains an alkoxymethyl group-containing crosslinking agent, the amount of the alkoxymethyl group-containing crosslinking agent to be added to the photosensitive resin composition of the present invention is preferably from 0.1 to 10% by mass relative to the total solid content of the photosensitive resin composition, More preferably 0.2 to 7% by mass, and most preferably 0.5 to 5% by mass.

- a compound having two or more epoxy groups or oxetanyl groups in the molecule -

The photosensitive resin composition of the present invention preferably contains, as Component C, 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 and aliphatic epoxy compound. The aliphatic epoxy compound may be a resin having a straight chain and / or branched carbon chain and an epoxy group, and the carbon chain may be bonded with an oxygen atom, a nitrogen atom, a sulfur atom, a chlorine atom, etc. in addition to a hydrogen atom. The aliphatic epoxy compound is particularly preferably a resin comprising a linear and / or branched carbon chain, a hydrogen atom and an epoxy group, or a resin in which the hydroxyl group is substituted with the resin. The number of epoxy groups is preferably 1 to 4, more preferably 2 or 3.

These are available as commercial products. Examples of the bisphenol A epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Co., Ltd.), and the like as the bisphenol F type epoxy resin, and JER806, JER807, JER4004, JER4005, JER4007, JER157, JER157S70, and JER157S65 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON (trade name, manufactured by Nippon Kayaku Co., Ltd.), and the like as the phenol novolak type epoxy resin, 660, EPICLON N-665, EPICLON N-770 (manufactured by DIC Corporation), and the like. Examples of the cresol novolac epoxy resin include EPICLON N-640, 670, EPICLON N-690, EPICLON N-690, EPICLON N-690 and EPOCLON N-695 (manufactured by DIC Corporation) and EOCN-1020 As the resin, ADE Examples of the aliphatic epoxy compounds include Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE 3150, EPOLEAD PB 3600 (manufactured by Nippon Polyurethane Industry Co., Ltd.), KA RESIN EP-4080S, Copper EP- , PB 4700 (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD- 501, EPPN-502 [manufactured by ADEKA Co., Ltd.].

Examples of the aliphatic epoxy compound include compounds represented by the following formula (X-1).

(In the formula (X-1), A represents a linear or branched hydrocarbon group, may have a hydroxyl group as a substituent, and n represents an integer of 1 to 4)

The carbon number of A in the formula (X-1) is preferably from 1 to 20, more preferably from 1 to 15, still more preferably from 2 to 10, and particularly preferably from 2 to 6.

N in the formula (X-1) represents an integer of 1 to 4, preferably 2 or 3.

The aliphatic epoxy compound is more preferably a compound represented by the following formula (X-2).

(In the formula (X-2), A 'represents a linear or branched hydrocarbon group, may have a hydroxyl group as a substituent, and n represents an integer of 1 to 4)

The carbon number of A 'in the formula (X-2) is preferably from 1 to 18, more preferably from 1 to 13, and still more preferably from 2 to 8.

N in the formula (X-2) represents an integer of 1 to 4, and 2 or 3 is preferable.

Exemplary aliphatic epoxy compounds that can be used in the present invention include DENACOL EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX- EX-821, EX-821, EX-821, EX-821, EX-821, EX- EX-941, EX-941, EX-941, EX-920, EX- 300, YH-301, YH-302, and YH-315 (manufactured by NAGASE CAMEDO CO., LTD.), DLC-203, DLC-203, DLC-205, DLC-206, DLC- , YH-324, and YH-325 [manufactured by Shinnitetsu Kagaku Co., Ltd.].

Of these, trimethylolpropane triglycidyl ether or neopentyl glycol diglycidyl ether shown below is particularly preferable. Among these, EX-321, EX-321L, EX-211 and EX-211L (manufactured by Nagase ChemteX Corporation) correspond to these.

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

Among them, an epoxy resin and an aliphatic epoxy compound are preferable, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin and an aliphatic epoxy compound are more preferable, and a bisphenol A type Epoxy resins, and aliphatic epoxy compounds are particularly preferred.

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 Doago Kosai Co., Ltd.) can be used.

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

When a compound having two or more epoxy groups or oxetanyl groups in the molecule is used in the photosensitive resin composition of the present invention, the addition amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to the photosensitive resin composition is preferably from 100 to 100 parts by weight, Is preferably from 0.1 to 50 parts by mass, more preferably from 0.5 to 30 parts by mass, further preferably from 1 to 10 parts by mass.

- a compound having at least one ethylenically unsaturated double bond -

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

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

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

Examples of the trifunctional or more (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These compounds having at least one ethylenically unsaturated double bond are used alone or in combination of two or more.

When a compound having one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is used, the use ratio of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably from 0.1 to 10 parts by weight, It is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass. By containing a compound having at least one ethylenically unsaturated double bond in such a ratio, heat resistance and surface hardness of the cured film obtained from the photosensitive resin composition of the present invention can be improved. When a compound having at least one ethylenically unsaturated double bond is added, it is preferable to add a heat radical generator described later.

&Lt; (D) Solvent >

The photosensitive resin composition of the present invention contains a solvent.

It is preferable that the photosensitive resin composition of the present invention is prepared as a solution obtained by dissolving or dispersing components A to C as essential components and optional components of various additives in a solvent.

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 (1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate and ethylene glycol monobutyl ether acetate; (4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; (5) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

(6) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; (7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether; (8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate; (9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether; (10) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;

(11) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate; (12) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate and isoamyl lactate; (13) A process for producing a compound represented by the general formula (13), wherein n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, Aliphatic carboxylic acid esters such as isobutyl, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate; (14) A process for producing a compound represented by the above formula (1), which comprises dissolving at least one compound selected from the group consisting of ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methoxypropionyl acetate, 3-methoxypropionyl acetate, Methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate;

(15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; (16) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; (17) lactones such as? -Butyrolactone, and the like.

In these solvents, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like may be further added.

Of the above solvents, particularly preferred are diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate.

Solvents usable in the present invention may be used alone or in combination of two or more.

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by mass, more preferably 100 to 2,000 parts by mass, and further preferably 150 to 1,500 parts by mass per 100 parts by mass of the polymer component.

&Lt; Other components >

The photosensitive resin composition of the present invention may contain the above-mentioned components A to D as essential components and may contain other arbitrary components. Examples of optional components include (component E) a sensitizer, (component F) basic compound, (component G) surfactant, (component H) adhesion improver, (component I) antioxidant, development accelerator, plasticizer, thermal radical generator, An acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. The additives usable in the present invention are not limited to these, and various additives known in the field can be used.

As the other components, the photosensitive resin composition of the present invention preferably contains an adhesion improver from the viewpoint of substrate adhesion, and preferably contains a basic compound from the viewpoint of the liquid storage stability. From the viewpoint of coating properties, the surfactant , A silicon-based surfactant, and the like).

Further, it is preferable to contain a phenomenon promoter from the viewpoint of sensitivity. It is also preferable to add a sensitizer from the viewpoint of sensitivity.

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

<Increase / decrease>

The photosensitive resin composition of the present invention preferably contains a sensitizer. It is effective for improving the exposure sensitivity by containing a photosensitizer, and the exposure light source is particularly effective in the case of g and h line mixed lines.

As the sensitizer, 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, diethylthioxanthone, 1-chloro-4-propoxythioxanthone 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 of the photosensitizer is 10 parts by weight or less, transparency of the coating film is easily ensured.

&Lt; Basic compound >

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

The basic compound can be arbitrarily selected from those used in the chemical amplification resistor. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

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

The basic compound can be arbitrarily selected from those used in the chemical amplification resistor. 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- Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

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

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl- Benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy Pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N'-2- (4-morpholinyl) ethyl 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 usable in the present invention may be used singly or in combination of two or more kinds.

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 1 part by mass based on 100 parts by mass of the polymer component.

&Lt; Surfactant (fluorine-based surfactant, silicon-based surfactant, etc.) >

The photosensitive resin composition of the present invention preferably contains (Component G) a surfactant (a fluorine-based surfactant, a silicon-based surfactant, etc.).

As the surfactant, a copolymer (3) containing the constituent unit A and the constituent unit B shown below may be mentioned as a preferable example. The weight average molecular weight (Mw) of the copolymer is preferably 1,000 or more and 10,000 or less, and more preferably 1,500 or more and 5,000 or less. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography.

In the copolymer (3), R ²¹ and R ²³ each independently represent a hydrogen atom or a methyl group, R ²² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ²⁴ represents a hydrogen atom or a C1- P is an integer of not less than 10 mass% and not more than 80 mass%, q is not less than 20 mass% And n represents an integer of 1 or more and 10 or less.

L in the constituent unit B is preferably an alkylene group represented by the following formula (4).

In the formula (4), R ²⁵ represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, more preferably an alkyl group having 2 or 3 carbon atoms .

It is also preferable that the sum (p + q) of p and q is p + q = 100, that is, 100% by mass.

Specific examples of the fluorine-based surfactant and the silicon-based surfactant include Japanese Patent Application Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, Japanese Patent Application Laid-Open Nos. 63-34540, 7-230165, 8-62834, 9-54432, 9-5988, 2001- 330953, and the like, and commercially available surfactants may also be used. (Commercially available from Shin-Akita Kasei Co., Ltd.), Fluorad FC430, 431 (manufactured by Sumitomo 3M Ltd.), Megafac F171 (available from Sumitomo Chemical Co., Ltd.) , F173, F176, F189, R08 (manufactured by DIC Corporation), Surfron S-382, SC101, 102, 103, 104, 105 and 106 (manufactured by Asahi Glass Co., OMNOVA), and silicone surfactants. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

These surfactants may be used singly or in combination of two or more. Further, a fluorine-based surfactant and a silicone-based surfactant may be used in combination.

The amount of the surfactant (fluorine surfactant, silicone surfactant, etc.) (component G) in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the component A And more preferably 0.01 to 3 parts by mass.

&Lt; Adhesion improving agent &

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

The adhesion improver (component H) that can be used in the photosensitive resin composition of the present invention is an adhesion improving agent that can be used as a substrate, an inorganic substance such as a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, aluminum, molybdenum, Of the present invention. Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the (H) adhesion improver used in the present invention is intended to modify the interface and is not particularly limited, and a known silane coupling agent can be used.

Preferred examples of the silane coupling agent 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) ( Vinyl trichlorosilane, 1,3-bis (trichlorosilane) propane, 1,3-bis (tribromosilane) propane, vinyltrimethoxysilane, vinyltriethoxysilane, Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, Methacryloxypropyltrimethoxysilane,? -Methacryloxypropylmethyldiethoxysilane,? -Methacryloxypropyltriethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane, (? -aminoethyl) -? - aminopropyltrimethoxysilane, N- (? - aminoethyl) -? - aminopropylmethyldimethoxysilane, N- -Aminoethyl) -? - aminopropyltriethoxysilane,? -Aminopropyltrimethoxysilane,? -Aminopropyltri Silane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, dimethoxy-3-mercapto (2-aminoethylthioethyl) diethoxymethylsilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, Bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, 1,4-bis (triethoxysilyl) silane, Benzene, bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) (Trimethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) urea,? -Chloropropyltrimethoxysilane,? -Triethoxysilylpropyl (meth) acrylate Agent, and the like in the γ- ureidopropyl triethoxysilane, 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.

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

The silane coupling agent can be suitably synthesized. However, it is preferable to use a commercially available product from the viewpoint of cost. For example, it is possible to use silane coupling agents such as Shin-Etsu Chemical Co., Ltd., Dorey Dow Corning Co., Ltd., Momentive Performance Materials A silane coupling agent, and the like, which are commercially available from Asahi Chemical Industry Co., Ltd., Chisso Co., Ltd., and silane coupling agent, etc., and these commercial products may be appropriately selected and used in the resin composition of the present invention.

Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane, bis (triethoxysilylpropyl) disulfide, and bis (triethoxysilylpropyl) tetrasulfide are preferably used .

Also, in the present invention, the adhesion improver represented by the general formula (1) is exemplified as the adhesion improver.

In general formula (1)

[In the general formula (1), R ¹ is a substituent having no reactive group, R ² is an alkyl group, and n is an integer of 1 to 3)

Examples of the adhesion improver represented by the general formula (1) include the following compounds.

In the above, Ph is a phenyl group.

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

The content of the (H) adhesion improver in the photosensitive resin composition of the present invention is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass, per 100 parts by mass of the component (A).

&Lt; Development accelerator &

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

As the development accelerator, any compound having a phenomenon of promoting development can be used. However, it is preferably a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group, and a carboxyl group or a phenolic hydroxyl group Is more preferable, and a compound having a phenolic hydroxyl group is most preferable.

The molecular weight of the development promoter is preferably 100 to 2,000, more preferably 150 to 1,500, and most preferably 150 to 1,000.

As examples of the development accelerator, those having an alkyleneoxy group include polyethylene glycol, monomethyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester, Polybutylene glycol, polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, alkyl ether of polyoxyethylene, alkyl ester of polyoxyethylene, and compounds described in JP-A 9-222724 .

Examples of compounds having a carboxyl group include compounds described in JP-A-2000-66406, JP-A-9-6001, JP-A-10-20501, JP-A-11-338150 .

Examples of compounds having a phenolic hydroxyl group include compounds disclosed in JP-A-2005-346024, JP-A-10-133366, JP-A-9-194415, JP-A-9-222724, 11-171810, JP-A-2007-121766, JP-A-9-297396, JP-A-2003-43679, etc. Among them, a phenol compound having 2 to 10 benzene ring is preferable, and a phenol compound having 2 to 5 benzene ring number is more preferable. Particularly preferred examples include phenolic compounds disclosed as dissolution accelerators in JP-A-10-133366.

The development accelerator may be used alone or in combination of two or more.

The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably from 0.1 to 30 parts by mass, more preferably from 0.2 to 20 parts by mass, more preferably from 0.5 to 10 parts by mass based on 100 parts by mass of the polymer component from the viewpoints of sensitivity and residual film ratio Minority is most desirable.

<Antioxidant>

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant may be contained. Addition of an antioxidant can prevent coloration of the cured film or reduce the reduction in film thickness due to decomposition and has an advantage of excellent heat-resistant transparency.

Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite, sulfite, thiophosphate , Hydroxylamine derivatives, and the like. Among these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring of a cured film and reduction of film thickness. These may be used singly or in combination of two or more.

Examples of commercially available products of phenolic antioxidants include Adekastab AO-15, Adekastube AO-18, Adekastube AO-20, Adekastube AO-23, Adekastube AO-30, Adekastube AO- 60, Adeka Stove AO-70, Adeka Stove AO-80, Adeka Stove AO-50, Adeka Stove AO-60, Adeka Stove AO- 330, ADEKA STUB AO-412S, ADEKA STUB AO-503, ADEKA STUB A-611, ADEKA STUB A-612, ADEKA STUB A-613, ADEKA STUB PEP-4C, ADEKA STUB PEP-8 , Adeka Stove PEP-8W, Adeka Stove PEP-24G, Adeka Stove PEP-36, Adeka Stove PEP-36Z, Adeka Stub HP-10, Adeka Stub 2112, Adeka Stab 260, Adeka Stab 522A Adeka Stove CDA-1, Adeka Stave CDA-6, Adeka Stove CDA-1, Adeka Stave CDA-1, Adeka Stave CDA-1, Adeka Stave CDA- (Manufactured by ADEKA Co., Ltd.), Igarox 245FF, Igarox 1010FF, Igarox MD1024, Igarazox 1035FF, Igarazox 1098, and Igarashi ZS-91 Knox 1330, Igaraz Knight 1520L, Igaraz Knight 3114, Igaraz Knight 1726, Igarashi Force 168, Family Mode 295 (manufactured by BASF), and the like. Of these, Adekastab AO-60, Adekastab AO-80, Igarox 1726, Igarox 1035FF and Igarox 1098 can be preferably used.

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

Further, various ultraviolet absorbers, metal deactivators, and the like described in "New developments of polymer additive (Nikkan Kogyo Seisakusho Co., Ltd. ", as an additive other than the antioxidant may be added to the photosensitive resin composition of the present invention.

<Plasticizer>

The photosensitive resin composition of the present invention may contain a plasticizer.

As the details of the plasticizer, reference may be made to the description of paragraph No. 0108 of Japanese Patent Application Laid-Open No. 2007-073609, the contents of which are incorporated herein by reference.

The content of the plasticizer in the photosensitive resin composition of the present invention is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the component A. [

&Lt; Heat radical generator >

The photosensitive resin composition of the present invention may contain a heat radical generator. As the heat radical generator, reference may be made to paragraph No. 0109 of JP-A-2007-073609, the contents of which are incorporated herein by reference .

One kind of thermal radical generator may be used alone, or two or more kinds of thermal radical generators may be used in combination.

The content of the heat radical generator in the photosensitive resin composition of the present invention is preferably from 0.01 to 50 parts by mass, more preferably from 0.1 to 20 parts by mass, more preferably from 0.5 to 10 parts by mass, Most preferred is the part by mass.

<Thermal acid generator>

In the present invention, a thermal acid generator may be used in order to improve physical properties of the film in low-temperature curing.

The thermal acid generator of the present invention is a compound which generates an acid by heat and is usually a compound having a thermal decomposition point in the range of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C. For example, a sulfonic acid, , A disulfonyl imide, and the like.

As the generated acid, a substituted alkylcarboxylic acid or arylcarboxylic acid having a pKa of not more than 2, such as a sulfonic acid or an electron-withdrawing group, and a disulfonylimide substituted with an electron-withdrawing group are preferable. Examples of the electron-attracting group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In the present invention, it is also preferable to use a sulfonate which generates an acid by heat without substantially generating an acid by irradiation with exposure light. It can be judged that there is no change in the spectrum by measuring the IR spectrum and the NMR spectrum before and after exposure of the compound, in which substantially no acid is generated by the irradiation of the exposure light.

The molecular weight of the sulfonic acid ester is preferably 230 to 1,000, more preferably 230 to 800.

The sulfonic acid esters usable in the present invention may be commercially available or may be synthesized by known methods. The sulfonic acid ester can be synthesized, for example, by reacting sulfonyl chloride or sulfonic anhydride with the corresponding polyhydric alcohol under basic conditions.

The content of the thermal acid generator in the photosensitive resin composition is preferably 0.5 to 20 parts by mass, particularly preferably 1 to 15 parts by mass, based on 100 parts by mass of the polymer component.

<Acid-proliferating agent>

For the purpose of improving the sensitivity, the photosensitive resin composition of the present invention can use an acid growth agent.

The acid-proliferating agent used in the present invention is a compound capable of increasing the acid concentration in the reaction system by further generating an acid by an acid catalytic reaction, and is a compound stably present in the absence of acid. These compounds accelerate the reaction progressively as the reaction progresses due to the increase of at least one acid in one reaction. However, since the generated acid itself undergoes self-decomposition, the strength of the acid generated here is the acid dissociation constant (pKa ) Is preferably 3 or less, and particularly preferably 2 or less.

Specific examples of acid proliferating agents are described in paragraphs 0203 to 023 of Japanese Patent Application Laid-Open No. 10-1508, paragraphs 0016 to 555 of Japanese Patent Application Laid-Open No. 10-282642, and Japanese Patent Publication No. 9-512498, Line to page 47, and the second line.

Examples of the acid growth agent that can be used in the present invention include acids having a pKa of 3 or less such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid decomposed by an acid generated from a photo- . &Lt; / RTI &gt;

The content of the acid proliferating agent in the photosensitive resin composition is preferably from 10 to 1,000 parts by mass based on 100 parts by mass of the photoacid generator from the viewpoint of dissolution contrast between the exposed portion and the unexposed portion, more preferably from 20 to 500 parts by mass .

[Process for producing a cured film]

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

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

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

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

(3) a step of exposing 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

Each step will be described below in order.

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

Further, it is preferable to clean the substrate before applying the photosensitive resin composition to the substrate, and more preferably, the substrate surface is treated with hexamethyldisilazane after the substrate is cleaned. By this treatment, the adhesion of the photosensitive resin composition to the substrate is improved. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and for example, a method of exposing the substrate to hexamethyldisilazane vapor may be mentioned.

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

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

Post-exposure heat treatment: Post Exposure Bake (hereinafter, also referred to as &quot; PEB &quot;) is performed to accelerate the hydrolysis reaction in the region where the acid catalyst is generated. PEB can promote the generation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The 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 100 占 폚.

The acid decomposable group in the constituent unit represented by the formula (a1-1) in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group A positive image can be formed by development without necessarily performing PEB. However, in the method for producing a cured film of the present invention, the cured film obtained by carrying out the post-baking step (5) using the photosensitive resin composition of the present invention, The flow can be reduced. Therefore, when the cured film obtained by the method for producing a cured film of the present invention is used, for example, as a resist, the resolution of the pattern hardly deteriorates even if the cured film of the present invention is heated for each substrate. In the present specification, the term &quot; heat flow &quot; means that the cross-sectional shape of the patterned cured film formed by the exposure and development processes is deformed when the cured film is heated (preferably 180 ° C or higher, more preferably 200 ° C to 240 ° C) Dimension, taper angle, etc. are deteriorated.

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

(A1) by thermally decomposing an acid-decomposable group in the constituent unit (a1) to produce a carboxyl group or a phenolic hydroxyl group in the post-baking step of the step (5) and crosslinking the crosslinking group, the crosslinking agent and the like of the constituent unit A cured film can be formed. This 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 240 ° C. The heating time can be appropriately set depending on the heating temperature and the like, but is preferably within a range of 10 to 120 minutes.

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

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

When the cured film obtained by thermal curing by the post baking step of the step (5) is used as a dry etching resist, dry etching treatment such as ashing, plasma etching, ozone etching and the like can be performed as the etching treatment.

Further, the forming method of the present invention may include (6) a dry etching step of performing dry etching on the substrate having the cured film obtained by thermosetting.

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

&Lt; Preparation method of photosensitive resin composition >

The essential components of (A) to (D) are mixed in a predetermined ratio in an arbitrary manner, and the mixture is stirred and dissolved to prepare a photosensitive resin composition. For example, it is also possible to prepare a solution in which the components (A) to (C) are respectively dissolved in a solvent (D), and then these components are mixed at a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be used after being filtered using a filter having a pore size of 0.2 mu m or the like.

<Application Process and Solvent Removal Process>

A desired dry film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking). As the substrate, for example, a glass plate in which a polarizing plate, a black matrix layer and a color filter layer, if necessary, and a transparent electroconductive circuit layer are further provided in the production of a liquid crystal display element can be exemplified. The method of applying the photosensitive resin composition to the substrate is not particularly limited, but in the present invention, it is preferable to apply the photosensitive resin composition to the substrate. The method of applying the coating liquid to the substrate is not particularly limited and slit coating, spraying, roll coating, spin coating, spin coating, slit-and-spin coating, and the like can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, a large substrate refers to a substrate having a size of 1 m or more on each side. When manufacturing a high-precision panel, a substrate having a size of 1 m or less in each side called a medium-small size may be used. In that case, the spin coating method and the slit-and-spin method are preferable.

(2) The heating conditions in the solvent removal step are those in which the acid-decomposable groups in the constituent unit (a1) in the component (A) in the unexposed portion are decomposed to make the component (A) not soluble in the alkali developer, But it is preferably about 70 to 130 占 폚 for 30 to 300 seconds depending on the kind of the component and the blending ratio.

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

In the exposure step, an active ray is irradiated onto a substrate provided with a coating film through a mask having a predetermined pattern. After the exposure process, if necessary, a heat treatment (PEB) is performed. In the development process, an exposed pattern area is removed using an alkaline developer to form an image pattern.

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

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

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

The developing time is preferably 30 to 500 seconds, and the developing method may be any of a liquid filling method and a dipping method. After the development, washing with water for 10 to 300 seconds is carried out to form a desired pattern.

After the development, a rinsing process may be performed. In the rinsing step, the developed substrate is cleaned with pure water or the like to remove the attached developing solution and remove the developing residue. As the rinsing method, known methods can be used. Examples thereof include shower rinses and deep rinses.

&Lt; Post baking step (crosslinking step) >

For example, 180 to 250 DEG C for a predetermined time, for example, from 5 to 90 DEG on a hot plate, using a heating apparatus such as a hot plate or an oven to a pattern corresponding to the unexposed area obtained by the development, Minute or in an oven for 30 to 120 minutes, a protective film or an interlayer insulating film excellent in heat resistance and hardness can be formed. Further, when the heat treatment is performed, transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

Post baking may be performed after baking at a relatively low temperature (post-baking) (addition of the middle baking process). In the case of performing the middle baking, post-baking is preferably performed at a high temperature of 200 DEG C or higher after heating at 90 to 150 DEG C for 1 to 60 minutes. In addition, middle baking and post baking may be divided into three or more stages and heated. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. For these heating, a known heating method such as a hot plate, an oven, and an infrared heater can be used.

Further, the substrate on which the pattern has been formed is re-exposed to the substrate by the actinic ray before the heat treatment, and then post baking (re-exposure / post baking) is performed to generate an acid from the component (B) present in the unexposed portion to accelerate the cross- As a catalyst.

That is, the method for producing a cured film of the present invention preferably includes a re-exposure step for re-exposure by an actinic ray between the developing step and the post-baking step. The exposure in the re-exposure step may be performed by the same means as in the exposure step. In the re-exposure step, however, it is preferable to perform the entire exposure on the side of the substrate where the film is formed by the photosensitive resin composition of the present invention.

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

[Coating film]

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.

The cured film of the present invention 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 for producing a cured film of the present invention.

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

[Organic EL display device, liquid crystal display device]

The organic EL display device and the liquid crystal display device of the present invention are characterized by including the cured film of the present invention.

The organic EL display device or the liquid crystal display device of the present invention is not particularly limited, except that it has a planarizing film, an interlayer insulating film, and a partition wall formed using the photosensitive resin composition of the present invention, and various known ones employing various structures Organic EL display devices and liquid crystal display devices.

As a flattening film, an interlayer insulating film, and an organic EL display device having partition walls formed using the specific photosensitive resin composition of the present invention, for example, Japanese Patent Laid-Open Publication No. 2011-107476, which is formed using the photosensitive resin composition of the present invention An organic EL device having the bank layer 16 and the planarization film 57 shown in Fig. 2, the partition wall 12 described in Fig. 4 (a) of JP-A No. 2010-9793 and the organic An EL device, an organic EL device having the bank layer 221 and the third interlayer insulating film 216b shown in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591, and Japanese Patent Application Laid-Open No. 2009-128577, An organic EL device having a second interlayer insulating film 125 and a third interlayer insulating film 126 described in Japanese Unexamined Patent Publication (Kokai) No. 2010-182638, a planarization film 12 and a pixel- EL devices and the like.

For example, specific examples of a 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 electric characteristics, it can be preferably used in combination with these TFTs.

As a method of a liquid crystal display device that can be employed in the liquid crystal display device of the present invention, a Twisted Nematic (TN) method, a VA (Virtical Alignment) method, an IPS (In-Place-Switching) method, a FFS , An OCB (Optical Compensated Bend) method, and the like.

Specific examples of the alignment method of the liquid crystal alignment film that can be employed in 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 the PSA (Polymer Sustained Alignment) technique described in Japanese Patent Application Laid-Open Nos. 2003-149647 and 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 and an interlayer insulating film, a protective film for a color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, and a microlens provided on the color filter in the solid- Can be used.

Fig. 1 shows a configuration diagram of an example of an organic EL display device. Sectional schematic 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 contact hole (not shown) is formed in the insulating film 3 and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is 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 flattening layer 4 is formed on the insulating film 3 in a state in which the irregularities by the wiring 2 are buried in order to planarize the irregularities due to the formation of the wiring 2. [

On the planarizing film 4, a bottom-emission organic EL element is formed. That is, a first electrode 5 made of ITO is formed on the flattening 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 providing the insulating film 8, a short circuit is formed between the first electrode 5 and the second electrode formed in the subsequent steps .

Although not shown in FIG. 1, a hole transporting layer, an organic light emitting layer, and an electron transporting layer are sequentially deposited 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 an organic EL element is sealed by bonding using an ultraviolet curable epoxy resin 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. The 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 constituted by a TFT corresponding to all pixels arranged between two glass substrates 14, (16) are disposed on the substrate. An ITO transparent electrode 19 for passing through the contact hole 18 formed in the cured film 17 and forming the pixel electrode is wired to each element formed on the glass substrate. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of a liquid crystal 20 and a black matrix are arranged is provided.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts used, the ratios, the contents of processing, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless specifically stated, &quot; part &quot; and &quot;% &quot; are based on mass.

In the following Synthesis Examples, the following symbols respectively represent the following compounds.

MATHF: tetrahydrofuran-2-yl methacrylate (synthetic)

MAEVE: 1-ethoxyethyl methacrylate (synthetic)

MATHP: tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.)

StOEVE: 4- (1-ethoxyethyloxy) styrene (synthetic)

OXE-30: methacrylic acid (3-ethyloxetan-3-yl) methyl [manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.]

GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

NBMA: n-butoxymethyl acrylamide [manufactured by Mitsubishi Rayon Co., Ltd.]

MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

AA: Acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

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

St: styrene (manufactured by Wako Pure Chemical Industries, Ltd.)

DCPM: dicyclopentanyl methacrylate (manufactured by Hitachi Kasei Kogyo Co., Ltd.)

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

BzMA: Benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

V-601: Dimethyl-2,2'-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

V-65: 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

CHOEMA: 1- (cyclohexyloxy) ethyl methacrylate (synthetic)

THFFMA: tetrahydrofurfuryl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

HS-EDM: Diethylene glycol ethyl methyl ether (High-Solv EDM, manufactured by Toho Chemical Industries, Ltd.)

PGMEA: Methoxypropyl acetate [manufactured by Showa Denko K.K.]

<Synthesis of MATHF>

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

<Synthesis of MAEVE>

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

CHOEMA and MATHF were synthesized in the same manner as in the above 1-ethoxyethyl methacrylate except that ethyl vinyl ether was changed to the corresponding compound.

[Synthesis of polymer A1]

HS-EDM (82 parts) was heated and stirred in a nitrogen stream at 90 占 폚. MATHF [43 parts (corresponding to 40.5 mol% of total monomer components)], OXE-30 [48 parts (corresponding to 37.5 mol% in total monomer components)], MAA [6 parts (corresponding to 9.5 mol% ), A mixed solution of HEMA [11 parts (corresponding to 12.5 mol% in total monomer components)], radical polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 4.3 parts) and PGMEA Was added dropwise over 2 hours and further reacted at 90 DEG C for 2 hours to obtain a PGMEA solution of polymer A1 (solid concentration: 40%).

The polymer A1 thus obtained had a weight average molecular weight of 15,000 as measured by gel permeation chromatography (GPC).

&Lt; Synthesis of other polymers A2 to A12 >

Each of the copolymers was synthesized in the same manner as in the synthesis of the polymer A1, except that the monomers used and the amounts of the monomers used were changed to those shown in Table 2 below.

The numerical values not specifically given in the above table are in mol%. The numerical value of the polymerization initiator is mol% when the monomer component is taken as 100 mol%.

The solid content concentration can be calculated by the following equation.

Solid concentration: mers weight of monomers / (monomer weight + solvent weight) x 100 (unit: mass%)

Further, when V-601 was used as the initiator, the reaction temperature was set to 90 ° C, and when V-65 was used, the reaction temperature was set to 70 ° C.

&Lt; Examples and Comparative Examples &

(1) Preparation of Photosensitive Resin Composition

Each component shown in the following table was mixed to prepare a homogeneous solution and then filtered using a polytetrafluoroethylene filter having a pore size of 0.1 mu m to prepare solutions of the photosensitive resin compositions of Examples and Comparative Examples .

The abbreviations in the tables are as follows.

<Polymer>

A1 to A12: Polymers synthesized according to Synthesis Example

A13: UC-3910 (manufactured by Toagosei Co., Ltd.)

A14: Joncryl 67 (manufactured by BASF)

&Lt;

B1: Compound of the following structure (synthesized product)

B2: Compound of the following structure (synthesized product)

B3: Compound of the following structure (synthesized product)

B4: CGI-1397 (manufactured by BASF)

B5: Compound having the following structure (synthesized according to the method described in paragraph 0108 of Japanese Patent Publication No. 2002-528451)

<Synthesis of B1>

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 ml), and the mixture was heated to 40 캜 for reaction for 2 hours . 4N HCl aqueous solution (60 ml) was added dropwise to the reaction solution under cooling with ice, and ethyl acetate (50 ml) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour. 2N HCl aqueous solution (60 ml) was added thereto to separate the liquid. The organic layer was concentrated, and crystals were dissolved in diisopropyl ether Filtered, and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50% by weight hydroxylamine aqueous solution (8.0 g) were added to the resulting suspension of the ketone compound (3.0 g) and methanol (18 ml), and the mixture was heated under reflux for 10 hours. After allowing to stand still, water (50 ml) was added to the precipitated crystals, 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), 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 B1 (2.3 g).

(D, 1H), 7.8 (d, 1H), 7.6 (d, 1H), 7.6 (dd, 1H ), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

<Synthesis of B2>

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% by weight aqueous sodium hydroxide solution (23 g), ethanol (50 ml) Lt; / RTI &gt; The reaction solution was immersed in a 1N HCl aqueous solution (500 ml), and the precipitated crystals were filtered and washed with water to obtain a carboxylic acid salt. Then, 30 g of polyphosphoric acid was added and reacted at 170 ° C for 30 minutes. The reaction solution was immersed in 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), hydrochloric acid hydroxylamine (25.9 g) and magnesium sulfate (4.5 g) were added to the suspension of the obtained ketone compound (10.0 g) and methanol (100 ml), and the mixture was heated to reflux for 24 hours. Water (150 ml) and ethyl acetate (150 ml) were added to separate the layers, and the organic layer was separated into four portions of 80 ml of water and concentrated. The residue was purified by silica gel column chromatography to obtain 5.8 g of oxime compound .

The obtained oxime (3.1 g) was sulfonated in the same manner as in B1 to give B2 (3.2 g).

(D, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.6 ), 7.5 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (dd, , 1.4 to 1.2 (m, 8H) and 0.8 (t, 3H).

<Synthesis of B3>

B3 was synthesized in the same manner as B1 except that benzene sulfonyl chloride was used in place of p-toluenesulfonyl chloride in B1.

(D, 1H), 7.8 (d, 1H), 7.7 (d, 1H), 7.7-7.5 (m, , 7.4 (dd, 1H), 7.1 (d, 1H), 5.6 (q, 1H), 1.7 (d, 3H).

<Cross-linking agent>

<Synthesis of C1>

100 parts of an adduct isocyanate &quot; Takenate D-120N &quot; (manufactured by Mitsui Chemicals, Inc.) obtained by reacting bis (isocyanatomethyl) cyclohexane (H6XDI) with trimethylol propane (TMP) and 100 parts of methyl ethyl ketone oxime 50 Was charged in a reaction vessel and reacted at 100 DEG C for 6 hours to obtain a block isocyanate C1 composed of a transparent viscous liquid. As a result of the IR measurement, it was confirmed that there is no absorption peak at 2250 cm ^-1 due to the NCO group (this mainly includes a block isocyanate compound having a trifunctional block isocyanate group).

<Synthesis of C2 to C20>

Synthesis was carried out in the same manner as in the synthesis of C1, except that the adduct isocyanate and the block compound used in the synthesis were changed to the following.

C2: Block isocyanate obtained by blockade of tokenate D-110N [m-xylylene-diisocyanate (XDI) and adduct of TMP, manufactured by Mitsui Chemicals, Inc.) with methyl ethyl ketone oxime

C3: Block isocyanate Block isocyanate obtained by blockade of D-140N [isophorone diisocyanate (IPDI) and adduct of TMP, manufactured by Mitsui Chemicals, Inc.) with methyl ethyl ketone oxime

C4: block isocyanate blocked with ε-caprolactam with tokenate D-140N

C5: Block isocyanate blocked with phenol D-140N

C6: block isocyanate obtained by blocking tocinate D-140N with ethyl acetoacetate

C7: Block isocyanate obtained by blockade of the tokenate D-140N with dimethyl pyrazole

C8: Block isocyanate obtained by blockade of tokenate D-212L (tolylene diisocyanate (TDI) and adduct of TMP, manufactured by Mitsui Chemicals, Inc.) with methyl ethyl ketone oxime

C9: Block isocyanate blocked with &lt; RTI ID = 0.0 &gt; epsilon -caprolactam &lt; / RTI &

C10: block isocyanate blocked with phenol D-212L

C11: Block isocyanate blocked with butanol D-212L

C12: Block isocyanate blocked with diphenylamine for tocinate D-212L

C13: Block isocyanate in which tocinate D-212L was blocked with ethyl acetoacetate

C14: Block isocyanate obtained by block copolymerization of tokenate D-212L with dimethyl pyrazole

C15: Block isocyanate blocked with butyl mercaptan on tokenate D-212L

C16: Coronate AP Stable M [block isocyanate blocked with adduct of tolylene diisocyanate (TDI) and TMP with phenol and xylenol, Nippon Polyurethane Coating Co., Ltd.)

C17: Block isocyanate (MDI) obtained by blocking adduct of diphenylmethane diisocyanate (MDI) and TMP with methyl ethyl ketone oxime

C18: A block isocyanate obtained by blocking an adduct of hexamethylene diisocyanate (HDI) and TMP with methyl ethyl ketone oxime

C19: Block isocyanate obtained by phenol blocking adduct of tolylene diisocyanate (TDI) and pentaerythritol

Block isocyanate obtained by blocking C20: C-2612 (hexamethylene diisocyanate (HDI) and adduct of 1,3-butanediol, manufactured by Nippon Polyurethane Coatings Co., Ltd.) with? -Caprolactam

C21: Block isocyanate obtained by blocking adduct of tolylene diisocyanate (TDI) and 1,3,5-cyclohexanetriol with phenol

C22: Block isocyanate obtained by blocking phenol with adduct of tolylene diisocyanate (TDI) and xylitol

C23: VESTAGON B1065 (block polyisocyanate having uretdione structure, manufactured by Degussa AG)

C24: VESTAGON BF1540 (block polyisocyanate having uretdione structure, manufactured by Degussa AG)

C25: JER-157S65 [polyfunctional novolak type epoxy resin, cross-linking agent, manufactured by Mitsubishi Chemical Corporation]

C26: Denacol EX-211L [liquid-phase aliphatic epoxy compound, manufactured by Nagase Chemtex Co., Ltd.]

<Solvent>

D1: Propylene glycol monomethyl ether acetate

<Increase / decrease>

E1: DBA [9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.]

&Lt; Basic compound >

F1: 1,5-Diazabicyclo [4,3,0] -5-nonene (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

F2: Compound of the following structure

<Surfactant>

G1: Compound of the following structure

<Antioxidant>

I1: Ilganox 1035FF (antioxidant, manufactured by BASF)

I2: Igarox 1098 (antioxidant, manufactured by BASF)

I3: ADEKA STUB AO-60 [Antioxidant, manufactured by ADEKA Co., Ltd.]

&Lt; Adhesion improving agent &

H1: 3-glycidoxypropyltrimethoxysilane {KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)}

H2: bis (triethoxysilylpropyl) disulfide {Z-6920 (manufactured by Toray Dow Corning)}

H3: Bis (triethoxysilylpropyl) tetrasulfide {KBE-846 (manufactured by Shin-Etsu Chemical Co., Ltd.)}

H4: decyltrimethoxysilane {KBM-3103 (manufactured by Shin-Etsu Chemical Co., Ltd.)}

(2) Evaluation of Photosensitive Resin Composition

(2-1) Evaluation of sensitivity

Each of the solutions of the photosensitive resin compositions of the examples and comparative examples was spin-coated on a silicon wafer having a silicon oxide film, and then pre-baked on a hot plate at 90 캜 for 120 seconds to form a coating film having a film thickness of 3 탆.

Subsequently, exposure was performed through a predetermined mask using an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.). After the exposure, the substrate was allowed to stand at room temperature for 10 minutes, then developed by 0.4% tetramethylammonium hydroxide aqueous solution at 23 占 폚 for 60 seconds by liquid filling, and further rinsed with ultra pure water for 45 seconds. By these operations, the optimum exposure amount (Eopt) at the time of resolving the line-and-space of 10 mu m at a ratio of 1: 1 was set as the sensitivity. The sensitivity can be said to be high in the case of a low exposure amount than 70 mJ / cm 2. The evaluation results are shown in the following table. In addition, "*" in the sensitivity column of the following table indicates that the pattern could not be formed at 200 mJ / cm 2.

(2-2) Evaluation of heat resistance transparency

A solution of the photosensitive resin compositions of Examples 1 to 52 and Comparative Examples 1 to 7 was spin-coated on a glass substrate (manufactured by Eagle 2000 Corporation), pre-baked on a hot plate at 90 캜 for 120 seconds, To form a coating film. The resulting coating film was developed by a liquid filling method at 23 캜 for 60 seconds with 0.4% tetramethylammonium hydroxide aqueous solution, rinsed with ultra pure water for 45 seconds, and then developed with a PLA-501F exposure machine (super high pressure mercury lamp) And the total amount of irradiation was 300 mJ / cm 2 (light intensity: 20 mW / cm 2). Thereafter, this substrate was heated in an oven at 230 캜 for one hour to obtain a cured film. The obtained cured film was further heated in an oven at 230 DEG C for 2 hours, and then the light transmittance was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer &quot; 150-20 type double beam [manufactured by Hitachi Seisakusho] Respectively. Evaluation of the lowest light transmittance (evaluation of heat resistance transparency) at that time is shown in the following table.

The evaluation criteria are as follows. In addition, the value of the lowest light transmittance is converted into a value per film thickness of 2 占 퐉 after being heated at 230 占 폚 for 2 hours.

A: 92% or more

B: 87% or more and less than 92%

C: less than 87%

(2-3) 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 90 ° C / 120 sec hot plate to obtain a photosensitive resin composition layer .

The thus-obtained photosensitive resin composition layer was exposed to a cumulative irradiation dose of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) with a PLA-501F exposure apparatus (ultra high pressure mercury lamp) manufactured by Canon Inc., Lt; 0 &gt; C 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 pulled up to wipe off the liquid on the surface, and the film thickness was immediately measured. The film thickness before immersion and the film thickness after immersion were compared, and the increased ratio 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.

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

A: 100% or more and less than 105%

B: 105% or more and less than 110%

C: 110% or more

(2-4) Evaluation of Chemical Resistance (NMP Tolerance)

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 90 ° C / 120 sec hot plate to obtain a photosensitive resin composition layer .

The thus-obtained photosensitive resin composition layer was exposed to a cumulative irradiation dose of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) with a PLA-501F exposure apparatus (ultra high pressure mercury lamp) manufactured by Canon Inc., Lt; 0 &gt; C 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 immediately measured. The film thickness before immersion and the film thickness after immersion were compared, and the increased ratio 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 105%

B: 105% or more and less than 110%

C: 110% or more

(2-5) Evaluation of adhesion of a cured film

Each of the photosensitive resin compositions was coated with a slit on a Mo (molybdenum) substrate, 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 having a film thickness of 4.0 mu m. The thus-obtained photosensitive resin composition layer was exposed to a cumulative irradiation dose of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) with a PLA-501F exposure apparatus (ultra high pressure mercury lamp) manufactured by Canon Inc., Lt; 0 &gt; C for 1 hour to obtain a cured film. The cured film was cut at intervals of 1 mm vertically and horizontally using a cutter, and a tape peeling test was conducted using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred on the back side of the tape. The results are shown in the following table. The smaller the numerical value is, the higher the adhesion to the base substrate is, and A or B is preferable.

A: Less than 1% of transferred area

B: Transferred area is 1% or more and less than 5%

C: Transferred area of 5% or more

(2-6) Evaluation of 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 90 ° C / 120 sec hot plate to obtain a photosensitive resin composition layer .

The thus-obtained photosensitive resin composition layer was exposed to a cumulative irradiation dose of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) with a PLA-501F exposure apparatus (ultra high pressure mercury lamp) manufactured by Canon Inc., Lt; 0 &gt; C for 1 hour to obtain a cured film. The cured film was subjected to dry etching under the conditions of CF4 50 ml / min, O2 10 ml / min, output 400 mW, and etching time 90 seconds as a dry etching apparatus "CDE-80N" (Shibaura Mechatronics, Etching was performed. The etching rate was calculated from the film reduction amount. The results are shown in Tables 5 and 6. 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

(2-7) Measurement of relative dielectric constant

The solution was mixed on a glass substrate (10 cm x 10 cm x 0.5 mm) so that the ratio of the material: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) was applied to the dried film to a dry film thickness of 0.35 m using a spin coater Then, it was dried at 90 DEG C for 2 minutes. Further, the film was exposed at 300 mJ with an ultra-high-pressure mercury lamp, and further heated in an oven at 230 DEG C for 60 minutes to form a film thickness cured film. The cured film was conditioned at 23 ° C and 60% RH for 24 hours, and then the relative dielectric constant was measured at 1 MHz using CV-Map (Four Dimensions, inc.). The results are shown in the following table. The smaller the numerical value, the better, and A or B is preferable.

A: less than 3.6

B: 3.6 or more and less than 3.9

C: Less than 3.9

(2-8) Evaluation of display irregularity (display irregularity of panel) in the display device

A liquid crystal display device using a thin film transistor (TFT) was produced by the following method (see Figs. 1 and 2). In the active matrix type liquid crystal display device described in Figs. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 as an interlayer insulating film was formed as follows to obtain a liquid crystal display device.

That is, the bottom gate type TFT 1 was formed on the glass substrate 6, and the insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Subsequently, a contact hole 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.

In order to planarize the irregularities formed by the formation of the wirings 2, the flattening film 4 was formed on the insulating film 3 in a state in which irregularities by the wirings 2 were buried. Formation of the planarization film 4 on the insulating film 3 was carried out by spin-coating each of the photosensitive resin compositions of Examples 1 to 52 and Comparative Examples 1 to 9 on a substrate, prebaking (90 DEG C x 2 minutes) on a hot plate, Thereafter, an i-line (365 nm) was irradiated from the mask top with a high-pressure mercury lamp at 25 mJ / cm 2 (illuminance of 20 mW / cm 2) and then developed with an alkali aqueous solution to form a pattern and subjected to heat treatment at 230 ° C. for 60 minutes. The coating property when the photosensitive resin composition was applied was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and firing. In addition, the average step of the wiring 2 was 500 nm, and the film thickness of the prepared planarization film 4 was 2,000 nm.

The obtained gray scale display was visually observed when a driving voltage was applied to the obtained liquid crystal display device and a gray test signal was inputted, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.

A: I can not see completely unevenness (very good)

B: The edge portion of the glass substrate shows a slight irregularity, but no problem on the display portion (good)

C: The display shows faint unevenness, but at a practical level (normal)

D: There is irregularity on the display part (slightly bad)

E: There is strong unevenness on the display (very bad)

The following table shows that the photosensitive resin composition of the present invention has a high sensitivity, a good heat-resistant transparency, excellent chemical resistance, good adhesion to a transparent electrode film and metal, and excellent dry etching resistance . Further, it was found that it is possible to manufacture a panel of high quality without any liquid crystal display unevenness.

On the other hand, all of the photosensitive resin compositions of Comparative Examples other than the photosensitive resin composition of the present invention do not satisfy all the items of sensitivity, heat resistance transparency, chemical resistance and display unevenness.

&Lt; Example 58 >

In the evaluation of display unevenness in Example 41, only the following coating process was changed to obtain the same liquid crystal display device.

That is, the photosensitive resin composition of Example 41 was applied by a slit coating method (CL1700, manufactured by Tokyo Electron Co., Ltd.), and then the solvent was removed by heating on a hot plate at 90 DEG C for 120 seconds to obtain a photosensitive resin composition Layer. The obtained coating film was flat and had a good surface without any unevenness. The performance as a liquid crystal display device was also good as in Example 41. [

<Example 59>

In the evaluation of display unevenness in Example 41, only the following coating process was changed to obtain the same liquid crystal display device.

That is, the photosensitive resin composition of Example 41 was applied by a slit-and-spin method (SF-700, manufactured by Dainippon Screen Seal Co., Ltd.), and then the solvent was removed by heating on a hot plate at 90 deg. Thereby forming a photosensitive resin composition layer having a thickness of 4.0 m. The obtained coating film was flat and had a good surface without any unevenness. The performance as a liquid crystal display device was also good as in Example 41. [

&Lt; Example 60 >

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. A contact hole (not shown) is formed in the insulating film 3 and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 did. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or a later step to the TFT 1. [

The planarization layer 4 was formed on the insulating film 3 in a state in which the irregularities due to the wirings 2 were buried in order to planarize the irregularities due to the formation of the wirings 2. The formation of the planarization film 4 on the insulating film 3 was performed by spin-coating the photosensitive resin composition of Example 41 on a substrate, pre-baking (90 占 폚 for 2 minutes) on a hot plate, (365 nm) was irradiated with 45 mJ / cm 2 (roughness 20 mW / cm 2) and then developed with an aqueous alkali solution to form a pattern, and heat treatment was performed at 230 ° C. for 60 minutes. The coating properties when the photosensitive resin composition was applied were good, and wrinkles and cracks were not observed in the cured films obtained after exposure, development and firing. In addition, the average step of the wiring 2 was 500 nm, and the film thickness of the prepared planarization film 4 was 2,000 nm.

Subsequently, a bottom-emission organic EL device was formed on the obtained planarization film 4. Then, 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 applied, pre-baked, exposed through a mask of a desired pattern, and developed. Pattern processing was performed by wet etching using ITO etchant using this resist pattern as a mask. Thereafter, the resist pattern was peeled off using a resist stripping solution (mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The thus obtained first electrode 5 corresponds to the anode of the organic EL element.

Then, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. An insulating film 8 was formed in the same manner as above using the photosensitive resin composition of Example 41 as an insulating film. By providing this insulating film, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in a subsequent step.

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

As described above, an active matrix type organic EL display device in which TFTs 1 for driving the organic EL elements were connected to each organic EL element was obtained. As a result of applying a voltage through the driving circuit, it was found that the organic EL display device exhibited good display characteristics and was 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: curing film 18: contact hole
19: ITO transparent electrode 20: liquid crystal
22: Color filter

Claims (19)

A polymer component comprising a polymer which satisfies at least one of the following 1 or 2;
1: a polymer having a constituent unit a1 having a residue protected by an acid-decomposable group and a constituent unit a2 having a crosslinkable group, wherein the crosslinking group contained in the constituent unit a2 is an epoxy group, an oxetanyl group and -NH-CH ₂ -OR, R is at least one selected from the group consisting of a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
2: a polymer having a structural unit a1 having a residue protected by an acid-decomposable group and a structural unit a2 having a crosslinkable group, wherein the crosslinkable group contained in the structural unit a2 is an epoxy group, an oxetanyl group, NH-CH ₂ -OR, R is at least one selected from the group consisting of a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
Photoacid generators;
An adduct type block polyisocyanate compound represented by the following formula (C); And
solvent
Wherein the photosensitive resin composition is a photosensitive resin composition.
In the general formula (C)
Ra- {O (C = O) -NH-Rb-NHCO-B} n
In the general formula (C), Ra is an n-valent hydrocarbon group, Rb is a divalent hydrocarbon group, and B represents a group blocking isocyanate; n is an integer from 3 to 6; n Rb and B may be the same or different, delete The method according to claim 1,
The photosensitive resin composition according to (C), wherein Ra is a branched aliphatic hydrocarbon group. The method according to claim 1 or 3,
B in the general formula (C) is selected from the group consisting of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound and an imide compound A group derived from a compound. The method according to claim 1,
Wherein the photosensitive resin composition is a chemically amplified positive type. The method according to claim 1,
Wherein the acid-decomposable group is a group having a protected structure in the form of an acetal. The method according to claim 1,
Wherein the constituent unit a1 is a constituent unit represented by the following formula (A2 ').
(A2 ')

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, The method according to claim 1,
Wherein any one of the polymer components is a polymer further containing an acid group. delete The method according to claim 1,
The duct-type block polyisocyanate compound is a block-blocked isocyanate group of a polyisocyanate prepolymer synthesized from at least one isocyanate compound selected from tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate Wherein the photosensitive resin composition is a photosensitive resin composition. The method according to claim 1,
Wherein the adducted block polyisocyanate compound is obtained by a reaction between a diisocyanate compound and trimethylol propane. The method according to claim 1,
The photosensitive resin composition according to claim 1, further comprising an antioxidant. A step of applying the photosensitive resin composition according to claim 1 onto a substrate,
A step of removing the solvent from the applied photosensitive resin composition,
A step of exposing with active radiation,
A step of developing with an aqueous developer, and
And a post-baking step of thermally curing the cured film. 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. 14. The method of claim 13,
Further comprising a dry etching step of performing dry etching on the substrate having the cured film obtained by thermal curing. A cured film formed by curing the photosensitive resin composition according to claim 1. 17. The method of claim 16,
Wherein the cured film is an interlayer insulating film. A liquid crystal display device having the cured film according to claim 16. An organic EL display device having the cured film according to claim 16.

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