TW201324053A - Positive photosensitive resin composition for electronic component, hardened film and method for manufacturing the same, and display device - Google Patents

Abstract

The invention relates to a positive photosensitive resin composition for electronic components, a hardened film and a method for manufacturing the same, and a display device. The invention provides a photosensitive resin composition with excellent sensitivity, coating properties and liquid-crystal contamination property (electrical characteristic). The positive photosensitive resin composition for electronic components of the invention is characterized by including (A) a polymer formed by at least copolymerize (a1) a structural unit having a residue obtained from an acid group protected by an acid degradable group and (a2) a structural unit having a cross-linking group; (B) a photoacid generator; and (C) a chain aliphatic epoxy compound.

Description

Positive photosensitive resin composition for electronic component, cured film and formation thereof Method and display device

The present invention relates to a positive photosensitive resin composition for an electronic component, a cured film using the positive photosensitive resin composition for the electronic member, a liquid crystal display device having the cured film, or an organic electroluminescence (EL) ) device. Further, the present invention relates to a method for producing a cured film using a positive photosensitive resin composition for an electronic member.

In an organic EL display device, a liquid crystal display device or the like, an interlayer insulating film in which a pattern has been formed is provided. In the formation of the interlayer insulating film, a photosensitive resin composition is widely used because the number of steps for obtaining a necessary pattern shape is small, and sufficient flatness can be obtained.

An interlayer insulating film or a planarizing film in which a pattern is formed using a photosensitive resin composition as described above is required to be an etching liquid or a resist for a pattern for forming an electrode, in addition to being excellent in transparency. A cured film having high reliability (resistance to solvent resistance) or liquid crystal contamination (electrical characteristics) of the peeling liquid. In addition, in recent years, in order to provide high-definition display characteristics of an organic EL display device or a liquid crystal display device, it is required to apply a photosensitive resin composition to a substrate without unevenness, and it is required to have high resolution of the photosensitive resin composition. .

As a photosensitive resin composition which can ensure high reliability (transparency and solvent resistance) of the formed cured film, for example, the following radiation-sensitive resin composition is known, and the radiation-sensitive resin composition contains a resin having a aldehyde structure or a ketal structure (meth) acrylate compound, a copolymer of a radical polymerizable compound having an epoxy group, and a copolymer of another radical polymerizable compound, and a radiation having a pKa of 4.0 or less. An acid compound (for example, refer to JP-A-2004-264623).

In addition, Japanese Laid-Open Patent Publication No. 2009-258722 proposes a positive photosensitive resin composition characterized in that (A1) contains a structural unit having an acid dissociable group. (A2) a polymer or copolymer containing a structural unit derived from an epoxy group-containing radical polymerizable monomer, (B) a compound having two or more epoxy groups in the molecule, and (C) A compound that generates an acid by irradiating an activated light having a wavelength of 300 nm or more.

Further, a resist underlayer film material as disclosed in Japanese Laid-Open Patent Publication No. 2007-17949 has been disclosed, but it is not used for an electronic member such as an interlayer insulating film.

The photosensitive resin composition as described above is known, but the present state of the art is that it has not been found to have high sensitivity, to ensure high reliability (solvent resistance) of the formed cured film, and to have both coating property and liquid crystal contamination. Photosensitive resin composition of properties (electrical properties).

An object of the present invention is to provide a photosensitive resin composition excellent in sensitivity, applicability, and liquid crystal contamination (electrical characteristics). Further, another object of the present invention is to provide an organic EL display device and a liquid crystal display device, which are provided with the organic EL display device and the liquid crystal display device. The cured film formed of the photosensitive resin composition is used as an interlayer insulating film, and has high reliability and productivity.

In the inventors of the present invention, it has been found that the problem of the above-mentioned problem can be solved by adding a chain-like aliphatic epoxy compound to improve the streaky unevenness without deteriorating the electrical properties. Specifically, the above problem is solved by the following method <1>, preferably by <2> to <13>.

<1> A positive photosensitive resin composition for an electronic component, comprising: (A) a polymer satisfying the following (1) or (2), (1) at least (a1) having an acid group (acid) Group) a structural unit in which a residue obtained by an acid-degradable group is protected, and a polymer obtained by copolymerizing a structural unit having a cross-linking group, (2) a polymer comprising (a1) a structural unit having a residue obtained by protecting an acid group with an acid-decomposable group, and a polymer comprising (a2) a structural unit having a crosslinkable group; (B) a photoacid generator; (C) A chain aliphatic epoxy compound.

<2> The positive photosensitive resin composition for electronic components according to <1>, wherein the (C) chain aliphatic epoxy compound has a molecular weight of 2,000 or less.

<3> The positive photosensitive resin composition for electronic components according to <1> or <2>, wherein (C) a chain aliphatic epoxy compound at 25 ° C The viscosity below is 3000 mPa. s below.

The positive photosensitive resin composition for electronic components according to any one of <1>, wherein the (C) chain aliphatic epoxy compound is represented by the following formula (X-1). Represented resin,

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

The positive photosensitive resin composition for electronic components according to any one of the above aspects, wherein the structural unit (a1) is a residue having a carboxyl group protected by acetal, or The structural unit of the residue obtained by protecting the carboxyl group with a ketal.

The positive photosensitive resin composition for electronic components according to any one of the above aspects, wherein the structural unit (a1) is a structural unit represented by the formula (A2'),

(In the formula (A2'), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms or a carbon number of 4 to 7; A cycloalkyl group, R ² and R ³ may also be bonded to form a ring).

The positive photosensitive resin composition for electronic components according to any one of the above-mentioned, wherein the (C) chain aliphatic epoxy compound is represented by the following formula (X-2). Represented resin,

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

The positive photosensitive resin composition for electronic components according to any one of the above-mentioned, wherein the structural unit (a2) is selected from a ring having a 3-membered ring or a 4-membered ring. At least one of a structural unit composed of an ether group and a structural unit having a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms).

(9) A method of forming a cured film comprising the positive photosensitive resin composition for an electronic component according to any one of <1> to <8>; 2) a step of removing a solvent from the photosensitive resin composition to be applied; (3) a step of exposing the photosensitive resin composition from which the solvent is removed by using active light; and (4) exposing the exposed photosensitive material with an aqueous developing solution Resin composition a step of performing development; and (5) a post-baking step of thermally curing the developed photosensitive resin composition.

<10> The method for forming a cured film according to <9>, which comprises the step of performing total exposure of the developed photosensitive resin composition after the developing step and before the post-baking step.

<11> A cured film formed by the method for forming a cured film according to <9> or <10>.

<12> The cured film according to <11>, which is an interlayer insulating film.

<13> An organic EL display device or a liquid crystal display device comprising the cured film according to <11> or <12>.

According to the present invention, a photosensitive resin composition excellent in sensitivity, applicability, and liquid crystal contamination (electrical property) is provided.

Hereinafter, the contents of the present invention will be described in detail. In addition, the "~" in the present specification is used to include the numerical values described before and after the lower limit value and the upper limit value. Further, the term "organic EL element" as used in the present invention means an organic electroluminescence element.

The positive photosensitive resin composition for electronic components of the present invention (hereinafter also referred to simply as "photosensitive resin composition") is characterized by containing (A) one or two of the following (1) and/or (2). More than one type of polymer (hereinafter also referred to simply as (component A)), (1) at least (a1) a structural unit having a residue obtained by protecting an acid group with an acid-decomposable group, and (a2) having cross-linking a polymer obtained by copolymerizing a structural unit of a group, (2) a polymer containing (a1) a structural unit having a residue obtained by protecting an acid group with an acid-decomposable group, and (a2) having a crosslinkable group a polymer of a structural unit; (B) a photoacid generator; and (C) a chain aliphatic epoxy compound.

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

Further, in the expression of the group (atomic group) of the present specification, the description of the substituted and unsubstituted includes a group having no substituent, and also includes a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

Further, the method of introducing the structural unit contained in the polymer used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, after a monomer having a predetermined functional group is synthesized in advance, the monomers are copolymerized. In the polymer reaction method, after the polymerization reaction, the necessary functional groups are introduced into the structural unit by using the reactive group contained in the structural unit of the obtained polymer. Here, the functional group may be a crosslinking group which protects an acid group such as a carboxyl group or a phenolic hydroxyl group and decomposes in the presence of a strong acid to release these acid groups, a crosslinking group such as an epoxy group or an oxetanyl group, Further, an alkali-soluble group (acid group) such as a phenolic hydroxyl group or a carboxyl group is used.

(ingredient A)

The positive photosensitive resin composition of the present invention contains (Component A). The polymer of (Component A) may be contained alone or in combination of two or more. By using (Component A), it is excellent in resistance to a resist stripping liquid or N-methyl-pyrrolidone (NMP), and also excellent in sensitivity and adhesion to a substrate when used as a cured film.

Further, the structural unit (a1) and the structural unit (a2) may be the same structural unit, and preferably different structural units.

The component A is preferably a resin which is alkali-insoluble and which is alkali-soluble when the acid-decomposable group is decomposed. Here, the "acid-decomposable group" means a functional group which can be decomposed in the presence of an acid. In addition, "alkali-soluble" means that a solution of a compound (resin) is applied (usually applied) to a substrate, and heated at 90 ° C for 2 minutes to form a coating film (thickness: 3 μm), which is 23 ° C. The dissolution rate of the lower 0.4% by weight aqueous solution of tetramethylammonium hydroxide is 0.01 μm/s or more. On the other hand, the term "alkali-insoluble" means that the dissolution rate is less than 0.01 μm/s. The alkali dissolution rate of component A is more preferably less than 0.005 μm/s.

The component A is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth)acrylic acid and/or an ester thereof. Further, the component A 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 vinyl compound.

The component A preferably contains 50 mol% or more of a monomer unit derived from (meth)acrylic acid and/or an ester thereof, more preferably 80 mol% or more, and further preferably It contains 90% by mole or more, and particularly preferably contains 100% by mole.

In addition, the method of introducing the structural unit contained in the component A may be polymerization. The method may also be a polymer reaction method, or both methods may be used in combination.

In the polymerization method, for example, an ethylenically unsaturated compound having a residue obtained by protecting an acid group with an acid-decomposable group, an ethylenically unsaturated compound having a crosslinkable group, and an ethylene having a carboxyl group and/or a phenolic hydroxyl group may be used. The unsaturated compound or the like is mixed and subjected to addition polymerization to obtain a target polymer.

In the polymer reaction method, a polymer obtained by copolymerizing epichlorohydrin with 2-hydroxyethyl methacrylate can be exemplified, and an epoxy group is introduced. In this manner, after the copolymerization of the ethylenically unsaturated compound having a reactive group, the reactive group based on the side chain can be used to protect the phenolic hydroxyl group or the carboxyl group by the acid-decomposable group through a polymer reaction. A functional group such as a group and/or a crosslinkable group is introduced into the side chain.

<Structural unit (a1)>

Component A contains at least (a1) a structural unit having a residue obtained by protecting an acid group with an acid-decomposable group. When the component A contains the structural unit (a1), a photosensitive resin composition having an extremely high sensitivity can be obtained.

The "residue obtained by protecting an acid group with an acid-decomposable group" in the present invention is a residue obtained by protecting a carboxyl group by an acetal, a residue obtained by protecting an acid group with a ketal, and a group obtained by protecting a acid group with a tertiary alkyl group. The residue obtained by protecting the residue or the acid group with a tertiary alkyl carbonate group.

The acid group may preferably be a carboxyl group or a phenolic hydroxyl group.

In addition, specific examples of the residue obtained by protecting the acid group with an acid-decomposable group include an ester structure of a group represented by the following formula (A1), and an acetal such as a tetrahydropyranyl ester group or a tetrahydrofuran ester group. Or a ketal-based functional group, or a tertiary alkyl-based functional group such as a tert-butyl ester group or a tert-butyl carbonate group.

(a1-1) a structural unit having a residue obtained by protecting a carboxyl group with an acid-decomposable group

The structural unit having a residue obtained by protecting the carboxyl group with an acid-decomposable group preferably has the acid-decomposable group described in (a1-1-1) and (a1-1-2). The carboxyl group contained in the structural unit protects the structural unit of the resulting residue.

The acid-decomposable group is not particularly limited as long as it is a group known as an acid-decomposable group in a positive resist for KrF or a positive resist for ArF. As the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an acetal functional group such as a tetrahydropyranyl group or an ethoxyethyl group) or a group which is relatively difficult to be decomposed by an acid is known. (e.g., a tert-butyl functional group such as a tert-butyl ester group or a tert-butyl carbonate group). The structural unit (a1-1) is preferably a structure having a residue obtained by protecting a carboxyl group by acetal or a residue obtained by protecting a carboxy group with a ketal, from the viewpoint of sensitivity or pattern shape and formation of a contact hole. unit.

Further, among the acid-decomposable groups, from the viewpoint of sensitivity, a residue obtained by protecting a carboxyl group with an acetal or a ketal represented by the formula (A1) is more preferable. Further, in the case where the carboxyl group is subjected to an acetal or ketal-protected residue represented by the formula (A1), the residue as a whole has a structure of -C(=O)-O-CR ¹ R ² (OR ³ ).

(In the formula (A1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group. R ¹ and R ³ or R ² and R ³ may be bonded to each other to form a cyclic ether. Further, the portion of the wave line in the formula (A1) indicates a bonding position with another structure)

In the formula (A1), the alkyl group in R ¹ , R ² and R ³ may be any of a linear chain, a branched chain or a cyclic group.

The linear or branched alkyl group preferably has a carbon number of from 1 to 12, more preferably a carbon number of from 1 to 6, more preferably a carbon number of from 1 to 4. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2,3- Dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like. Among them, a methyl group or an ethyl group is preferred.

The cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably a carbon number of 4 to 8, and further preferably has a carbon number of 4 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group. Among them, a monocyclic group is preferred, and a cyclohexyl group is more preferred.

The alkyl group may have a substituent, and the substituent may, for example, be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. . When a halogen atom is used as a substituent, R ¹ , R ² and R ^{3 are} a halogenated alkyl group, and when an aryl group is used as a substituent, R ¹ , R ² and R ^{3 are} aralkyl groups. The aralkyl group is preferably a benzyl group.

In the formula (A1), the aryl group in R ¹ , R ² and R ³ preferably has a carbon number of 6 to 12, more preferably a carbon number of 6 to 10. The aryl group may have a substituent, and the substituent may preferably be an alkyl group having 1 to 6 carbon atoms. The aryl group may, for example, be a phenyl group, a tolyl group, a xylyl group, a cumyl group or a 1-naphthyl group, and is preferably a phenyl group.

Further, in the formula (A1), R ¹ , R ² and R ³ may be bonded to each other and form a ring together with the carbon atom to which they are bonded. Examples of the ring structure in the case where R ¹ and R ² , R ¹ and R ³ or R ^{2 are} bonded to R ³ include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, and an adamantane. Base and tetrahydropyranyl group and the like.

Further, in the formula (A1), it is preferred that either of R ¹ and R ² is a hydrogen atom or a methyl group.

A commercially available product may be used as the radical polymerizable monomer to form a structural unit having a residue represented by the formula (A1), and it is also possible to use, for example, paragraphs 0025 to 0026 of JP-A-2009-098616. A monomer synthesized by a well-known method such as the method described.

The structural unit (a1-1) having a residue obtained by protecting the carboxyl group with an acid-decomposable group is more preferably a structural unit represented by the formula (A2).

(In the formula (A2), R ¹ each independently represents a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, and R ¹ is R ³ or R ² and R ³ may be bonded 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.

In the formula, R ^{1 is} preferably a methyl group.

In the formula (a1-1), R ^{2 is} preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

In the formula, R ^{3 is} preferably an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, more preferably an ethyl group or a cyclohexyl group.

In the formula, when R ² and R ^{3 are} bonded to each other to form a ring, the group in which R ² and R ^{3 are} bonded is preferably an alkylene group having a carbon number of 3 to 6, more preferably a 1,3-stretch. Propyl or 1,4-tert-butyl.

Among these, from the viewpoint of sensitivity, the structural unit (a1) is preferably a structural unit represented by the following formula (A2').

(In the formula (A2'), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms or a carbon number of 4 to 7; a cycloalkyl group, R ² and R ³ may also be bonded to form a ring)

A preferred embodiment of the structural unit (a1-1) can exemplify the following structural unit. Further, R represents a hydrogen atom or a methyl group.

The structural unit (a1-1) may also be a structural unit having a residue obtained by protecting a carboxyl group by a tertiary alkyl group represented by the formula (A3). The sensitivity is inferior to the residue obtained by the protection of the acetal or the ketal, but it is preferable in terms of excellent storage stability. Further, in the case where the carboxyl group is subjected to the residue obtained by the tertiary alkyl group represented by the formula (A3), the residue is generally a structure of -C(=O)-O-CR ¹ R ² R ³ .

In the formula (A3), R ¹ , R ² and R ³ each independently represent an alkyl group or an aryl group, and any two of R ¹ , R ² and R ³ may be bonded to each other to form a ring. The portion of the wave line in the formula (A3) indicates the bonding position with other structures. Specific examples of the alkyl group and the aryl group in R ¹ to R ³ of the formula (A3) are the same as those of the alkyl group and the aryl group in the formula (A1).

In the formula (A3), a combination of R ¹ = R ² = R ³ = methyl group, or a combination of R ¹ = R ² = methyl group and R ³ = benzyl group can be exemplified.

(a1-2) a structural unit having a residue obtained by protecting a phenolic hydroxyl group with an acid-decomposable group

(a1-2) The structural unit having a residue obtained by protecting the phenolic hydroxyl group with an acid-decomposable group is preferably a structural unit having a structural unit having a phenolic hydroxyl group (a1-2-1) by an acid-decomposable group. The phenolic hydroxyl group protects the structural unit of the resulting residue.

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

The structural unit having a phenolic hydroxyl group may be a structural unit in a hydroxystyrene structural unit or a novolak-based resin, and from the viewpoint of transparency, a structural unit derived from α-methylhydroxystyrene is preferred. In the structural unit having a phenolic hydroxyl group, the structural unit represented by the formula (A4) is preferred from the viewpoint of transparency and sensitivity.

(In the formula (A4), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents a single bond or a divalent linking group, R ²² each independently represents a halogen atom or an alkyl group, a represents an integer of 1 to 5, and b represents 0. An integer of ~4, a+b is 5 or less)

R ^{20 is} preferably a methyl group.

The divalent linking group of R ²¹ may, for example, be an ester bond (-COO-) or an alkylene group in which a carbon atom is bonded to a main chain. The alkylene group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. In the case of -COO-, the sensitivity can be improved, and the transparency of the cured film can be improved, which is preferable. Among them, R ^{21 is} preferably a single bond or an ester bond. Further, the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group and the like.

Further, a represents an integer of 1 to 5, and it is preferable that a is 1 or 2 from the viewpoint of ease of manufacture, and it is more preferable that a is 1.

Further, as for the bonding position of the hydroxyl group on the benzene ring, when it is based on the carbon atom bonded to R ²¹ (1 position), it is preferred to bond to the 4-position.

R ²² is a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferred from the viewpoint of ease of production.

(a1-2) a structural unit having a residue obtained by protecting a phenolic hydroxyl group with an acid-decomposable group

The structural unit having a residue obtained by protecting a phenolic hydroxyl group with an acid-decomposable group is a residue having a phenolic hydroxyl group protected by a structural unit having a phenolic hydroxyl group (a1-2-1) by an acid-decomposable group. Structural unit.

As described above, a well-known group can be used for the acid-decomposable group, and it is not specifically limited.

Among the residues obtained by protecting the phenolic hydroxyl group by the acid-decomposable group, the basic physical properties of the resist, particularly the sensitivity or pattern shape, the preservation stability of the photosensitive resin composition, and the formation of contact pores In view of the above, a structural unit having a residue obtained by protecting a phenolic hydroxyl group with an acetal or a ketal is preferred. Further, among the residues obtained by protecting the phenolic hydroxyl group by the acid-decomposable group, from the viewpoint of sensitivity, the residue obtained by protecting the phenolic hydroxyl group with the acetal or ketal represented by the formula (A1) is more preferable. In this case, the entire residue has a structure of -Ar-O-CR ¹ R ² (OR ³ ). Further, Ar represents an aryl group.

A preferred example of the acetal ester structure of the phenolic hydroxyl group can be exemplified by a combination of R ¹ = R ² = R ³ = methyl or R ¹ = R ² = methyl and R ³ = benzyl.

Further, examples of the radical polymerizable monomer used to form a monomer unit having a residue obtained by protecting a phenolic hydroxyl group with an acetal or a ketal may be exemplified by a 1-alkoxyalkyl protecting group of hydroxystyrene. , tetrahydropyranyl protecting agent for hydroxystyrene, 1-alkoxyalkyl protecting agent for α-methylhydroxystyrene, tetrahydropyranyl protecting agent for α-methyl-hydroxystyrene, α- Tetrahydrofuranyl protecting agent for methyl hydroxystyrene, 1-alkoxyalkyl protecting agent for 4-hydroxyphenyl methacrylate, tetrahydropyranyl protecting agent for 4-hydroxyphenyl methacrylate and A tetrahydrofuranyl protective body of 4-hydroxyphenyl acrylate or the like. Among these radically polymerizable monomers, a 1-alkoxyalkyl protecting agent of α-methylhydroxystyrene or a tetrahydrofuranyl protecting agent of α-methylhydroxystyrene is preferred.

Specific examples of the acetal protecting group and the ketal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include 1-ethoxyethyl group, 1-methoxyethyl group, and 1- n-Butoxyethyl, 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-n-propoxy B , 1-cyclohexyloxyethyl, 1-(2-cyclohexylethoxy)ethyl, 1-benzyloxyethyl, tetrahydropyranyl, tetrahydrofuranyl, etc., preferably 1-B Oxyethyl or tetrahydrofuranyl. These groups may be used alone or in combination of two. the above.

A commercially available product may be used as the radical polymerizable monomer to form the structural unit (a1-2), or a monomer synthesized by a known method may be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. The synthesis may also pre-polymerize a monomer having a phenolic hydroxyl group with another monomer and then react with the vinyl ether in the presence of an acid catalyst.

Preferred specific examples of the structural unit (a1-2) may be exemplified by the following structural units, but the present invention is not limited to these structural units. Further, R represents a hydrogen atom or a methyl group.

In the monomer unit constituting the component (A), the content of the monomer unit (a1) is preferably from 3 mol% to 70 mol%, based on the sensitivity of the copolymer of the component (A). More preferably, it is 5 mol% to 60 mol%, and further preferably 10 mol% to 50 mol%.

The structural unit having a residue obtained by protecting a carboxyl group with an acid-decomposable group is developed faster than a structural unit having a residue obtained by protecting a phenolic hydroxyl group with an acid-decomposable group. Therefore, in the case of rapid development, a structural unit having a residue obtained by protecting a carboxyl group with an acid-decomposable group is preferred. On the other hand, in the case of desirably developing slowly, it is preferred to use a structural unit having a residue obtained by protecting a phenolic hydroxyl group with an acid-decomposable group.

<Structural unit (a2)>

The component (A) contains a monomer unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group which causes a curing reaction during heat treatment. The preferred monomer unit having a crosslinkable group preferably comprises a structural unit selected from a cyclic ether residue having a 3-membered ring or a 4-membered ring, and has -NH-CH ₂ -OR (R a monomer unit of at least one of a structural unit of a group represented by an alkyl group having 1 to 20 carbon atoms and a structural unit having an ethylenically unsaturated group, more preferably 3 a structural unit of a cyclic ether residue of a member ring or a 4-membered ring; and a structural unit having a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms), and further preferably It is a structural unit having a cyclic ether residue of a 3-membered ring or a 4-membered ring.

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

The (A) copolymer is preferably a structural unit (monomer unit (a2-1)) containing a cyclic ether residue having a 3-membered ring and/or a 4-membered ring. The cyclic ether residue of the 3-membered ring is also referred to as an epoxy group, and the cyclic ether residue of the 4-membered ring is also referred to as an oxetanyl group. The structural unit (a2-1) having an epoxy group and/or an oxetanyl group is preferably a monomer unit having an alicyclic epoxy group and/or an oxetanyl group, more preferably A structural unit having an oxetanyl group. It is preferably contained in the component A in the form of a structural unit having an epoxy group or an oxetanyl group. In addition, the structural unit (a2-1) may also contain a ring Both an oxy group and an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring forms a condensed ring with an epoxy ring, and specifically, for example, a 3,4-epoxycyclohexyl group or a 2,3-epoxy ring can be preferably used. Hexyl, 2,3-epoxycyclopentyl and the like.

The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, and (3-ethyloxetan-3-yl)methyl group can be preferably exemplified.

The structural unit having an epoxy group or an oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may have one or more epoxy groups and one or more oxetane groups. The base may have two or more epoxy groups or two or more oxetanyl groups, and is not particularly limited, and preferably has one to three epoxy groups and oxetanyl groups in total. It is preferred to have one or two epoxy groups and oxetanyl groups in total, and it is more preferred to have one epoxy group and oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α. - glycidyl propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylate-6,7-ring Oxyheptyl ester, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, P-vinylbenzyl glycidyl ether, a compound containing an alicyclic epoxy skeleton described in paragraphs 0031 to 0035 of Japanese Patent No. 4,164,843, and the like.

Examples of the radical polymerizable monomer used to form the structural unit having an oxetanyl group include an oxygen heterocyclic ring described in paragraphs 0011 to 0016 of JP-A-2001-330953. Butyl (meth) acrylate and the like.

As an example of the radical polymerizable monomer used to form a structural unit having an epoxy group or an oxetanyl group, a monomer having a methacrylate structure or a monomer having an acrylate structure is preferable.

Among these radically polymerizable monomers, a compound containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4,184,443, and a paragraph 0011 of JP-A-2001-330953 are more preferable. The (meth) acrylate having an oxetanyl group described in paragraph 0016 is particularly preferably an oxetanyl group described in paragraphs 0011 to 0016 of JP-A-2001-330953 ( Methyl) acrylate. Among these radically polymerizable monomers, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and acrylic acid (3-ethyloxetane). -3-yl)methyl ester and (3-ethyloxetan-3-yl)methyl methacrylate, the most preferred is (3-ethyloxetan-3-yl)-acrylic acid Ester and (3-ethyloxetan-3-yl)methyl methacrylate. These structural units may be used alone or in combination of two or more.

A preferred specific example of the structural unit (a2-1) can exemplify the following structural unit.

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

In the copolymer used in the present invention, a structural unit (a2-2) having a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) is also preferable. By containing the structural unit (a2-2), a hardening reaction can be caused in a slow heat treatment, and a cured film excellent in various characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group. More preferably, the structural unit (a2) is a structural unit having a group represented by the following formula (a2-20).

General formula (a2-20)

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

R ^{2 is} preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group.

Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a cyclohexyl group, and a n-hexyl group. Among them, isobutyl, n-butyl and methyl groups are preferred.

(a2-3) a structural unit having an ethylenically unsaturated group

One of the structural units (a2) having a crosslinkable group is a structural unit (a2-3) having an ethylenically unsaturated group (hereinafter also referred to as "monomer unit (a2-3)"). The structural unit (a2-3) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in a side chain, more preferably an ethylenically unsaturated group at the terminal, and having a carbon number of The structural unit of the side chain of 3 to 16 is more preferably a structural unit having a side chain represented by the formula (a2-3-1).

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

R ¹ is a divalent linking group having a carbon number of 1 to 13, and contains an alkenyl group, an aryl group or a group obtained by combining these groups, and may also contain an ester bond, an ether bond, a guanamine bond, or an amine group. A bond such as a formate button. The alkenyl group may also be a cyclic alkenyl group. Further, the divalent linking group may have a substituent such as a hydroxyl group or a carboxyl group at any position. Specific examples of R ¹ include a divalent linking group represented by the formula (A-1) to the formula (A-10).

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

Further, the ethylenically unsaturated group contained in the side chain represented by the formula (a2-3-1) is preferably contained in an amount of 1 mol with respect to 150 g to 2,000 g of the (A) polymer. More preferably, it contains 1 mole per 200 g to 1,300 g of the (A) polymer.

The method of obtaining the monomer unit (a2-3) having the side chain represented by the formula (a2-3-1) is not particularly limited, and for example, a polymer having a specific functional group can be produced by a polymerization method such as radical polymerization in advance. A compound having a group reactive with the specific functional group and a compound having an ethylenically unsaturated group at the terminal (hereinafter referred to as a specific compound) is reacted to prepare a copolymer containing the monomer unit (a2-3).

Here, the specific functional group may, for example, be a carboxyl group, an epoxy group, a hydroxyl group, an active hydrogen-containing amine group, a phenolic hydroxyl group, an isocyanate group or the like. The monomer having a specific functional group for synthesizing a polymer having a specific functional group will be described below.

The combination of the specific functional group and the group reactive with the specific functional group possessed by the specific compound may be exemplified by a combination of a carboxyl group and an epoxy group, a combination of a carboxyl group and an oxetanyl group, a hydroxyl group and an isocyanate group. Combination, a combination of a phenolic hydroxyl group and an epoxy group, a combination of a carboxyl group and an isocyanate group, a combination of an amine group and an isocyanate group, a combination of a hydroxyl group and a halogen group, and the like.

Further, examples of the specific compound include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl acrylate. Isocyanate ethyl methacrylate, isocyanate ethyl acrylate, methacrylic acid, propylene chloride, A Acrylic acid, acrylic acid, and the like.

Preferred combinations of specific functional groups and specific compounds include a combination of a carboxyl group as a specific functional group and a glycidyl methacrylate as a specific compound, a hydroxyl group as a specific functional group, and methacrylic acid as a specific compound. Combination of isocyanate ethyl esters.

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

(In the formula (a2-3-2), R ¹ in the formula (a2-3-1) R ¹ is the same meaning as the preferred ranges are also the same .R ^2, R ³ each independently represent a hydrogen atom or a methyl group )

Specific examples of the monomer having a specific functional group necessary for obtaining a polymer having a specific functional group are listed below, but are not limited to these specific examples.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono(2-(acryloxy)ethyl) phthalate, and mono(2-(methyl) phthalic acid. Acryloxy)ethyl)ester, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and the like.

Examples of the monomer having an epoxy group include: glycidyl methacrylate Oil ester, glycidyl acrylate, allyl glycidyl ether, 3-vinyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, 1,7-octane Diene monoepoxide, -3,4-epoxycyclohexylmethyl methacrylate, -3,4-epoxycyclohexylmethyl acrylate, and the like.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and acrylic acid-4- Hydroxybutyl ester, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol Monomethacrylate, caprolactone 2-(acryloxy)ethyl ester, caprolactone 2-(methacryloxy)ethyl ester, poly(ethylene glycol) diethyl ether acrylate, poly(ethylene) Alcohol) diethyl ether methacrylate, 5-propenyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 5-methylpropenyloxy-6-hydroxynorbornene-2-carboxyl -6-lactone and the like.

The monomer having an active hydrogen-containing amine group may, for example, be 2-aminoethyl acrylate or 2-aminomethyl methacrylate.

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

Further, examples of the monomer having an isocyanate group include acrylonitrile ethyl isocyanate, methacryl methyl ethyl isocyanate, m-tetramethyl xylene isocyanate, and the like.

Further, in the present invention, when a polymer having a specific functional group is obtained, a structural unit having a specific functional group as described above and (a1) a residue having a carboxyl group which is protected by an acid-decomposable group, or Phenolic hydroxyl A structural unit of a residue obtained by protecting an acid-decomposable group. Further, a monomer which is a monomer unit (a3) other than the following (a1) and (a2) can be used in combination.

The method for obtaining the polymer having a specific functional group used in the present invention is not particularly limited, and is, for example, obtained by polymerizing a monomer having a specific functional group, a monomer other than the above, and optionally using the polymerization. The polymerization reaction is carried out at a temperature of from 50 ° C to 110 ° C in a solvent in which a starter or the like is coexisted. In this case, the solvent to be used is not particularly limited as long as the monomer constituting the polymer having a specific functional group and the polymer having a specific functional group are dissolved. Specific examples thereof include the solvents described in the solvent (D) described later. The polymer having a specific functional group obtained as such is usually in a state of a solution dissolved in a solvent.

Then, the obtained polymer having a specific functional group can be reacted with a specific compound to obtain a monomer unit (a2-3) having an ethylenically unsaturated group at the terminal of the side chain. At this time, a solution of a polymer having a specific functional group is usually supplied to the reaction. For example, glycidyl methacrylate can be reacted in a solution of an acrylic polymer having a carboxyl group in the presence of a catalyst such as benzyltriethylammonium chloride at a temperature of from 80 ° C to 150 ° C. Monomer unit (a2-3).

Further, in order to form the monomer unit (a2-3), in addition to the above-described polymer reaction, allyl methacrylate, allyl acrylate or the like may be used as the radical polymerizable monomer. These monomer units may be used alone or in combination of two or more.

In the present invention, it is preferred to contain a monomer unit (a2-1) as a single Body unit (a2).

In the case where the polymer containing the structural unit (a2) contains substantially no structural unit (a1), the structural unit (a2) is preferably 5 mol% in the polymer containing the structural unit (a2). 90% by mole, more preferably 20% by mole to 80% by mole.

In the case where the polymer containing the structural unit (a2) contains the structural unit (a1), the structural unit (a2) contains the structural unit (a1) and the structural unit from the viewpoint of chemical resistance. The polymer of (a2) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%.

In the present invention, it is preferred to contain, in any of the structural units of the component (A), 3 to 70 mol% of the structural unit (a2), and more preferably 10 Mole %~60 mol% of structural unit (a2).

When it is within the range of the numerical value, the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.

<Other structural units (a3)>

The component A may further contain other structural units (a3) within a range that does not impair the effects of the present invention.

The radically polymerizable monomer to be used for forming the structural unit (a3) is, for example, a compound described in paragraphs 0021 to 0024 of JP-A-2004-264623 (wherein the structural unit (a1) is used) And structural unit (a2) except).

In addition, from the viewpoint of sensitivity, component A is preferably further included There is a structural unit having an acid group as a structural unit (a3).

The acid group is more preferably a structural unit having a carboxyl group and/or a phenolic hydroxyl group, and further preferably a structural unit having a carboxyl group.

The structural unit (a3) is preferably derived from a structural unit selected from at least one of the group consisting of acrylic acid, methacrylic acid, p-hydroxystyrene, and α-methyl-p-hydroxystyrene, and more preferably A structural unit derived from acrylic acid or methacrylic acid is particularly preferred as a structural unit derived from methacrylic acid.

Further, preferred examples of the structural unit (a3) include those derived from a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, and an N-substituted maleimide. A structural unit of at least one of the group consisting of.

These structural units, from the viewpoint of improving electrical characteristics, preferably a (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl ester, (meth) acrylate, tricyclo [5.2. 1.0 ^2,6 ]decane-8-yloxyethyl ester, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate A (meth) acrylate having a ring structure or a hydrophobic monomer such as styrene. From the viewpoint of sensitivity, 2-hydroxyethyl (meth)acrylate and N-substituted maleimide are preferred. Among these structural units, a (meth) acrylate having an alicyclic structure is more preferable. Further, from the viewpoint of etching resistance, styrene such as styrene or α-methylstyrene is preferred.

These structural units (a3) may be used alone or in combination of two or more.

All monomer units constituting component A contain structural unit (a3) In the case of forming the structural unit (a3), the lower limit of the content ratio of the monomer unit is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 20 mol% or more. Further, the upper limit is preferably 70% by mole or less, more preferably 60% by mole or less, still more preferably 50% by mole or less, further preferably 40% by mole or less, and particularly preferably 30% by mole%. the following.

The component A in the present invention may be used alone or in combination of two or more. That is, the component A may be in any one of the following (1) and/or (2).

(1) A state of a polymer obtained by copolymerizing at least one structural unit having at least (a1) a residue having an acid group protected by an acid-decomposable group, and (a2) a structural unit having a crosslinkable group

(2) A polymer containing (a1) a structural unit having a residue obtained by protecting an acid group with an acid-decomposable group and a polymer containing (a2) a structural unit having a crosslinkable group in combination with at least two

The molecular weight of the component A in the present invention is preferably from 2,000 to 100,000, more preferably from 3,000 to 50,000, still more preferably from 4,000 to 30,000, particularly preferably from 10,000 to 16,000. Further, the molecular weight of the component A in the present invention is preferably a polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography (GPC) in the case of using tetrahydrofuran (THF) as a solvent.

The content of the component A in the photosensitive resin composition of the present invention is preferably from 20% by weight to 99% by weight, more preferably from 30% by weight to 95% by weight, based on the total solid content of the photosensitive resin composition. Preferably, it is 30% by weight to 70% by weight. If the content is in this range, pattern formation during development Sex has changed. In addition, the solid content of the photosensitive resin composition means an amount excluding a volatile component such as a solvent.

(ingredient B) photoacid generator

The photosensitive resin composition of the present invention contains (Component B) a photoacid generator.

Component B is preferably a compound which induces an acid generated by an active light having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, and has a chemical structure which is not limited. In addition, the photoacid generator which does not directly induce active light having a wavelength of 300 nm or more can be sensitized as long as it is an active light which generates an acid having a wavelength of 300 nm or more and a compound which generates an acid when used in combination with a sensitizer. The agents are preferably used in combination.

Component B is preferably a photoacid generator which produces an acid having a pKa of 4 or less, and more preferably a photoacid generator which produces an acid having a pKa of 3 or less.

Examples of the photoacid generator include a phosphonium salt or a phosphonium salt, a quaternary ammonium salt, a diazomethane compound, a trichloromethyl-s-triazine, a sulfhydryl sulfonate compound, and an oxime sulfonate compound. Wait.

Specific examples of these photoacid generators include the following compounds.

Trichloromethyl-s-triazines can be used: 2-(3-chlorophenyl)bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)bis ( 4,6-trichloromethyl)-s-triazine, 2-(4-methylthiophenyl)bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxy- Β-styryl) bis(4,6-trichloromethyl)-s-triazine, 2-piperidinylbis(4,6-trichloromethyl)-s-triazine, 2-[2-(furan- 2-yl)vinyl]bis(4,6-trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]bis(4,6-trichloro Methyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl] (4,6-trichloromethyl)-s-triazine or 2-(4-methoxynaphthyl)bis(4,6-trichloromethyl)-s-triazine; diarylsulfonium salts Use: diphenylsulfonium trifluoroacetate, diphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenylphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenylphenylphosphonium Fluoroacetate, phenyl-4-(2'-hydroxy-1'-tetradecyloxy)phenylphosphonium triflate, 4-(2'-hydroxy-1'-tetradecyloxy Phenylhydrazine hexafluoroantimonate or phenyl-4-(2'-hydroxy-1'-tetradecyloxy)phenylhydrazine p-toluenesulfonate; triarylsulfonium salt: triphenyl Base trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methyl Oxyphenyl diphenyl sulfonium trifluoroacetate, 4-phenylthiophenyl diphenyl fluorene trifluoromethanesulfonate or 4-phenylthiophenyl diphenyl fluorene trifluoroacetate; The ammonium salt can be used: tetramethylammonium butyl tris(2,6-difluorophenyl)borate, tetramethylammonium hexyltris(p-chlorophenyl)borate, tetramethylammonium hexyltris(3- Trifluoromethylphenyl)borate, benzyldimethyl Phenyl ammonium butyl tris(2,6-difluorophenyl)borate, benzyldimethylphenylammonium hexyltris(p-chlorophenyl)borate, benzyldimethylphenylammonium hexyl tris(3) -Trifluoromethylphenyl)borate; etc.; diazomethane derivatives can be used: bis(cyclohexylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(p-toluene) Hydrazine-based diazomethane, etc.; ruthenium sulfinate derivative can be used: trifluoromethylsulfonyloxybicyclo[2.2.1]hept-5-ene-dicarboxy quinone imine, butyl quinone imine Trifluoromethanesulfonic acid Ester, phthalimide, triflate, N-hydroxynaphthylimine methane sulfonate, N-hydroxy-5-norbornene-2,3-dicarboxy quinone A sulfonate or the like; in addition to the compound, a compound described in Paragraph No. 0031 to Paragraph No. 0052 of JP-A-2010-282228 may be used.

In the present invention, it is preferred to use an oxime sulfonate compound from the viewpoint of high sensitivity. These photoacid generators may be used alone or in combination of two or more. Specific examples of the photoacid generator include the photoacid generator described in paragraphs 0029 to 0032 of JP-A-2004-264623, and 4,7-di-n-butoxy group can be preferably used. 1-naphthyltetrahydrothiophene trifluoromethanesulfonate and the like.

The photosensitive resin composition of the present invention preferably further contains at least one oxime sulfonate compound having an oxime sulfonate residue represented by the following formula (b0) as a (component B) photoacid generator. In addition, the waveline portion indicates the bonding position with other chemical structures.

The oxime sulfonate compound having at least one of the oxime sulfonate residues represented by the formula (b0) is preferably a compound represented by the following formula (b1).

(In the formula (b1), R ⁵ and R ⁶ each independently represent a monovalent organic group, and R ⁵ and R ⁶ may be bonded to form a ring, and R ⁷ represents an alkyl group, a cycloalkyl group or an aryl group)

In the formula (b1), R ⁵ represents an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, and a 2-thiophene group. An alkoxy group or a cyano group having 1 to 4 carbon atoms. In the case where R ⁵ is a phenyl group, a biphenyl group, a naphthyl group or a fluorenyl group, these groups may also be selected from a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and a carbon number of 1 to 4. Substituted in the group consisting of an alkoxy group and a nitro group.

In the formula (b1), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and 1 to 1 carbon atom. a halogenated alkoxy group of 5, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W, a dialkylamino group, a morpholinyl group or a cyano group. R ⁶ and R ⁵ may also be bonded to each other to form a 5-membered ring or a 6-membered ring, which may also be bonded to a benzene ring which may have 1 or 2 arbitrary substituents.

In the formula (b1), R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and 1 to 1 carbon atom. a halogenated alkoxy group of 5, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a carbon atom number of 1 to 5 halogenated alkoxy groups.

The alkyl group having 1 to 6 carbon atoms represented by R ⁵ can be referred to the description of Paragraph No. 0139 of JP-A-2011-227449.

The halogenated alkyl group having 1 to 4 carbon atoms represented by R ⁵ can be referred to the description of Paragraph No. 0140 of JP-A-2011-227449.

The alkoxy group having 1 to 4 carbon atoms represented by R ⁵ may, for example, be a methoxy group or an ethoxy group.

In the case where R ⁵ represents a phenyl group, a biphenyl group, a naphthyl group or a fluorenyl group, these groups can be referred to the description of Paragraph No. 0142 of JP-A-2011-227449.

A specific example of the alkyl group having 1 to 10 carbon atoms represented by R ⁶ can be referred to the description of Paragraph No. 0142 of JP-A-2011-227449.

A specific example of the alkoxy group having 1 to 10 carbon atoms represented by R ⁶ can be referred to the description of Paragraph No. 0143 of JP-A-2011-227449.

A specific example of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁶ can be referred to the description of Paragraph No. 0144 of JP-A-2011-227449.

A specific example of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ⁶ can be referred to the description of Paragraph No. 0144 of JP-A-2011-227449.

Specific examples of the phenyl group which can be substituted by W represented by R ⁶ can be referred to the description of Paragraph No. 0145 of JP-A-2011-227449.

A specific example of the W-substituted naphthyl group represented by R ⁶ can be referred to the description of Paragraph No. 0146 of JP-A-2011-227449.

A specific example of the W-substituted fluorenyl group represented by R ⁶ can be referred to the description of Paragraph No. 0147 of JP-A-2011-227449.

The dialkylamine group represented by R ⁶ may, for example, be a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group or a diphenylamino group.

A specific example of the alkyl group having 1 to 10 carbon atoms represented by R ⁷ can be referred to the description of Paragraph No. 0148 of JP-A-2011-227449.

A specific example of the alkoxy group having 1 to 10 carbon atoms represented by R ⁷ can be referred to the description of Paragraph No. 0148 of JP-A-2011-227449.

A specific example of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁷ can be referred to the description of Paragraph No. 0149 of JP-A-2011-227449.

A specific example of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ⁷ can be referred to the description of Paragraph No. 0149 of JP-A-2011-227449.

A specific example of the phenyl group which can be substituted by W represented by R ⁷ can be referred to the description of Paragraph No. 0150 of JP-A-2011-227449.

A specific example of the W-substituted naphthyl group represented by R ⁷ can be referred to the description of Paragraph No. 0151 of JP-A-2011-227449.

A specific example of the W-substituted fluorenyl group represented by R ⁷ can be referred to the description of Paragraph No. 0152 of JP-A-2011-227449.

An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy group having 1 to 5 carbon atoms represented by W Specific examples of the group include an alkyl group having 1 to 10 carbon atoms represented by R ⁶ or R ⁷ , an alkoxy group having 1 to 10 carbon atoms, and a halogen atom having 1 to 5 carbon atoms. Specific examples of the alkyl group and the halogenated alkoxy group having 1 to 5 carbon atoms are the same groups as those exemplified.

R ⁶ and R ⁵ may also be bonded to each other to form a 5-membered ring or a 6-membered ring.

In the case where R ⁶ and R ⁵ are bonded to each other to form a 5-membered ring or a 6-membered ring, the 5-membered ring or the 6-membered ring may be a carbocyclic group or a heterocyclic ring group, and for example, may be a cyclopentane. , cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, acridine or pyridazine ring. The 5-membered ring or the 6-membered ring may also be bonded to a benzene ring which may have an arbitrary substituent, and examples thereof include tetrahydronaphthalene, indoline, anthracene, benzodihydrofuran, anthracene, xanthene ( Xanthene) or thioxanthene ring system. The 5-membered ring or the 6-membered ring may also contain a carbonyl group, and examples thereof include a cyclohexadienone, a naphthone, and an anthrone ring system.

One of the suitable aspects of the compound represented by the formula (b1) is a compound represented by the following formula (b1-1). The compound represented by the formula (b1-1) is a compound in which R ⁶ and R ⁵ in the formula (b1) are bonded to each other to form a 5-membered ring.

(In the formula (b1-1), R ⁷ in the formula (B1) is the same meaning as R ^7, X represents an alkyl group, an alkoxy group or a halogen atom, t represents an integer of 0 to 3, when t is 2 or 3 When multiple Xs can be the same or different)

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

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

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

t is preferably 0 or 1.

In the formula (b1-1), particularly preferred are the following compounds: t is 1, X is a methyl group, the substitution position of X is an ortho position, and R ⁷ is a linear alkyl group having 1 to 10 carbon atoms, and 7, 7-Dimethyl-2-oxanorbornylmethyl or p-tolylmethylhydrazine.

Specific examples of the oxime sulfonate compound represented by the formula (b1-1) include the following compounds (i), (ii), (iii), and (iv), and these compounds may be used alone. It is also possible to use two or more types together. The compound (i) to the compound (iv) can be obtained as a commercial product.

Further, it may be used in combination with other types of photoacid generators.

One of the preferable aspects of the compound represented by the formula (b1) is the following compound: R ⁵ represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group or an anthracenyl group; R ⁶ represents a cyano group; and R ⁷ represents an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W, And a halogen atom, or a carbon atom number of 1 or 5; ~5 of a halogenated alkoxy group.

The compound represented by the formula (b1) is also preferably a compound represented by the following formula (b1-2).

In the formula (b1-2), R ⁸ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group, and L represents an integer of 0 to 5. R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. a phenyl group which may be substituted by W, a naphthyl group which may be substituted by W or a fluorenyl group which may be substituted by W, and W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, and a carbon number. It is an alkoxy group of 1 to 10, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms.

R ⁷ in the formula (b1-2) is preferably methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro-positive. Butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably methyl, ethyl, n-propyl, n-butyl or p-tolyl.

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

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

The alkoxy group having 1 to 4 carbon atoms represented by R ⁸ is preferably a methoxy group or an ethoxy group.

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

In the compound represented by the formula (b1), a preferred aspect of the compound contained in the compound represented by the formula (b1-2) is the following: in the formula (b1), R ⁵ represents a phenyl group or a 4-methyl group. Oxyphenyl, R ⁶ represents a cyano group, and R ⁷ represents a methyl group, an ethyl group, a n-propyl group, an n-butyl group or a 4-tolyl group.

In the following, a particularly preferable example of the compound represented by the formula (b1) in the compound represented by the formula (b1-2) is shown, but the present invention is not limited to these examples.

Α-(methylsulfonyloxyimino)benzyl cyanide (R ⁵ =phenyl, R ⁶ =cyano, R ⁷ =methyl)

Α-(ethylsulfonyloxyimino)benzyl cyanide (R ⁵ =phenyl, R ⁶ =cyano, R ⁷ =ethyl)

Α-(n-propylsulfonyloxyimino)benzyl cyanide (R ⁵ =phenyl, R ⁶ =cyano, R ⁷ =n-propyl)

Α-(n-butylsulfonyloxyimino)benzyl cyanide (R ⁵ =phenyl, R ⁶ =cyano, R ⁷ =n-butyl)

Α-(4-Toluenesulfonyloxyimino)benzyl cyanide (R ⁵ =phenyl, R ⁶ =cyano, R ⁷ =4-tolyl)

--[(Methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R ⁵ =4-methoxyphenyl, R ⁶ =cyano, R ⁷ =methyl)

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

--[(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R ⁵ =4-methoxyphenyl, R ⁶ =cyano, R ⁷ =n-propyl)

--[(n-butylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R ⁵ =4-methoxyphenyl, R ⁶ =cyano, R ⁷ =n-butyl)

--[(4-Toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile (R ⁵ =4-methoxyphenyl, R ⁶ =cyano, R ⁷ =4-tolyl)

Further, having at least one of the oxime sulfonate represented by the formula (b0) The compound of the residue is preferably an oxime sulfonate compound represented by the following formula (OS-3), formula (OS-4) or formula (OS-5).

(In the formula (OS-3) to the formula (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and a plurality of R ² present independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom. a plurality of R ⁶ present independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, and n represents 1 or 2. m represents an integer from 0 to 6)

In the above formula (OS-3) to formula (OS-5), the alkyl group, the aryl group or the heteroaryl group represented by R ¹ may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkyl group represented by R ¹ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), the aryl group represented by R ¹ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), the heteroaryl group represented by R ¹ is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent, as long as it is at least A heteroaromatic ring can be used, for example, a heteroaromatic ring and a benzene ring can also be condensed.

The substituent which the alkyl group, the aryl group or the heteroaryl group represented by R ¹ may have is a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group or an aryloxy group. Carbonyl, aminocarbonyl.

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

In the formula (OS-3) to (OS-5), two or more of R ² are present in the compound, and preferably one or two are an alkyl group, an aryl group or a halogen atom, more preferably One is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the remainder is a hydrogen atom.

In the above formula (OS-3) to formula (OS-5), the alkyl group or the aryl group represented by R ² may have a substituent.

The substituent which the alkyl group or the aryl group represented by R ² may have is the same as the substituent which the alkyl group or the aryl group of the R ¹ may have.

In the above formula (OS-3) to formula (OS-5), the alkyl group represented by R ² is preferably an alkyl group having a total carbon number of 1 to 12 which may have a substituent, and more preferably may have The substituent has a total carbon number of 1 to 6 alkyl groups.

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

In the above formula (OS-3) to formula (OS-5), the aryl group represented by R ² is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

The aryl group represented by R ² is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group or a p-phenoxyphenyl group.

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

In the above formula (OS-3) to (OS-5), X is included as a ring. The ring of the member is a 5-member ring or a 6-member ring.

In the formula (OS-3) to (OS-5), n represents 1 or 2. When X is 0, n is preferably 1, and when X is S, n is preferably 2.

In the above formula (OS-3) to formula (OS-5), the alkyl group and the alkoxy group represented by R ⁶ may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkyl group represented by R ⁶ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

The alkoxy group represented by R ⁶ is preferably a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, a phenoxyethoxy group, a trichloromethoxy group or an ethoxyethoxy group.

The aminosulfonyl group of R ⁶ may, for example, be a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group or an aminesulfonyl group.醯基.

The alkoxysulfonyl group represented by R ⁶ may, for example, be a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group or a butoxysulfonyl group.

Examples of the substituent which the alkyl group or the alkoxy group represented by R ⁶ may have include a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an amine. Alkylcarbonyl.

Further, in the above formula (OS-3) to formula (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Further, the compound represented by the formula (OS-3) is particularly preferably a compound represented by the following formula (OS-6), formula (OS-10) or formula (OS-11), which is (OS- 4) The compound represented by the formula (OS-7) is particularly preferably a compound represented by the formula (OS-5), and the compound represented by the formula (OS-5) is particularly preferably the following formula (OS-8) or formula (OS-). 9) The compound represented.

In the formula (OS-6)~(OS-11), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, and R ⁸ represents a hydrogen atom and has a carbon number of 1-8. An alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ¹⁰ represents A hydrogen atom or a methyl group.

The formula (OS-6) - in the formula (OS-11) R ¹ in the formula - (OS-5) R of the formula (OS-3) ¹ are the same meaning as the preferred aspects are also the same.

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

R ^{8 in} the formula (OS-6) to formula (OS-11) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, and a methoxy group. a methyl group, a phenyl group or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and further preferably having a carbon number of An alkyl group of 1 to 6 is particularly preferably a methyl group.

R ^{9 in} the formula (OS-8) and formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.

R ^{10 in} the formula (OS-8) to formula (OS-11) represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

Further, in the oxime sulfonate compound, the steric structure (E, Z) of ruthenium may be either a mixture or a mixture.

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

A suitable other aspect of the oxime sulfonate compound having at least one of the oxime sulfonate residues represented by the formula (b0) is described in paragraphs 0117 to 0129 of JP-A-2011-209719. compound of.

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

(Component C) chain aliphatic epoxy compound

In the present invention, a (component C) chain aliphatic epoxy compound is contained. By adding a chain aliphatic epoxy compound, it is possible to improve uneven streaks (especially radial streaks) when coating a composition (especially during spin coating) without deteriorating liquid crystal contamination (electrical properties). All). Although the reason for the improvement is not clear, it is presumed that the reason is that the fluidity of the composition applied to the substrate can be improved.

The chain aliphatic epoxy compound which can be used in the present invention preferably has a molecular weight (weight average molecular weight in the case of a polymer) of 2,000 or less, more preferably 1,500 or less, still more preferably 1,000 or less. The lower limit value can be set to, for example, 100 or more. In addition, when the weight average molecular weight of the chain aliphatic epoxy compound is not described in a catalogue or the like, it can be estimated by calculation of (epoxy equivalent) × (number of functional groups). Further, the viscosity of the chain aliphatic epoxy compound at 25 ° C is preferably 3000 mPa. Below s, more preferably 2000 mPa. s is below, and further preferably 1000 mPa. s below. The lower limit is not particularly limited and can be set, for example, to 5 mPa. s above.

The aliphatic epoxy compound used in the present invention is a resin having a linear chain and/or a branched carbon chain and an epoxy group, and an oxygen atom, a nitrogen atom, a sulfur atom, or a chlorine atom may be bonded to the carbon chain in addition to a hydrogen atom. Atoms, etc. Particularly preferred in the present invention are resins comprising a linear and/or branched carbon chain and a hydrogen atom, an epoxy group, or a group in which a hydroxyl group is substituted on the resin. The number of epoxy groups is preferably from 1 to 4, more preferably 2 or 3.

In the present invention, it is preferred that the cyclic aliphatic epoxy compound is substantially not contained. By setting such a configuration, there is a tendency that the effects of the present invention are more effectively exhibited. Here, the term "substantially free" means not affecting The level of the effect of the present invention is added, for example, to 1% by weight or less of the total solid content.

The chain aliphatic epoxy compound used in the present invention is preferably a resin represented by the following formula (X-1).

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

The carbon number of A is preferably from 1 to 20, and more preferably from 1 to 15, more preferably from 2 to 10, still more preferably from 2 to 6. n is an integer of 1 to 4, preferably 2 or 3.

The chain aliphatic epoxy compound used in the present invention is more preferably a resin represented by the following formula (X-2).

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

The carbon number of B is preferably from 1 to 18, and preferably from 1 to 13, more preferably from 2 to 2. 8. n is an integer of 1 to 4, preferably 2 or 3.

The chain aliphatic epoxy which can be preferably used in the present invention may be exemplified by Denacol EX-611 (11,800 mPa.s) and Denacol EX-612 (11,900 mPa.s). Denacol EX-614 (21,200 mPa.s), Denacol EX-614B (5,000 mPa.s), Denacol EX-622 (11,800 mPa.s), Denacol (Danaco) EX-512 (1,300 mPa.s), Denacol (Dencol) EX-521 (4,400 mPa.s), Denacol (Dencol) EX-411 (800 mPa.s), Denacol (generation) Naco) EX-421 (650 mPa.s), Denacol (Dencol) EX-313 (150 mPa.s), Denacol (Dencol) EX-314 (170 mPa.s), Denacol (Dencol) EX-321 (130 mPa.s), Denacol (Exnaco) EX-211 (20 mPa.s), Denacol (Dencol) EX-212 (20 mPa.s), Denacol (Danacol) EX -810 (20 mPa.s), Denacol EX-811 (20 mPa.s), Denacol (EXnaco) EX-850 (20 mPa.s), Denacol (Dencol) EX-851 (30 mPa.s), Denacol (Denaco) EX-821 (40 mPa.s), Denacol (Danacol) EX-830 (70 mPa.s), Denacol (Dencol) EX-832 (90 mPa.s), Denacol EX-841 (110 mPa.s), Denacol EX-911 (20 mPa.s) Denacol EX-941 (25 mPa.s), Denacol (Denaco) EX-920 (20 mPa.s), Denacol (Dencol) EX-931 (120 mPa.s), Denacol ( Denaco) EX-212L (15 mPa.s), Denacol (Denaco) EX-214L (15 mPa.s), Denacol (Danacol) EX-321L (800 mPa.s), Denacol (Denacol) Branch) EX-850L (90 mPa.s), Denacol EX-211L (20 mPa.s), Denacol (Exnaco) EX-946L (50 mPa.s), Denacol (Danacol) EX-946L (50 mPa.s), Denacol ( Danaco) DLC-201 (10 mPa.s), Denacol (Danacol) DLC-203 (8 mPa.s), Denacol (Danacol) DLC-204 (1,700 mPa.s), Denacol (Denacol) Branch) DLC-205 (15 mPa.s), Denacol (Danacol) DLC-206 (20 mPa.s), Denacol (Danacol) DLC-301 (60 mPa.s), Denacol (Danacol) DLC-402 (150 mPa.s) (The above is manufactured by Changchun Huacheng, viscosity at 25 °C in brackets), YH-300 (140 mPa.s~160 mPa.s), YH-301 (160 mPa.s) ~220 mPa.s), YH-302 (700 mPa.s~1100 mPa.s), YH-315 (700 mPa.s~1100 mPa.s), YH-324 (3500 mPa.s~5500 mPa.s) ), YH-325 (4000 mPa.s~6000 mPa.s) (above is Nippon Steel Chemical Manufacturing).

Among these compounds, particularly preferred is trimethylolpropane triglycidyl ether or neopentyl glycol diglycidyl ether shown in the following figure. Among the compounds, Denacol EX-321, Denacol EX-321L, Denacol EX-211, Denacol EX-211L (above is Changchun Huacheng) Manufactured) is equivalent to this compound.

The content of the (component C) chain aliphatic epoxy compound in the photosensitive resin composition of the present invention is preferably from 0.1 part by weight to 10 parts by weight, more preferably from 0.5 part by weight to 10 parts by weight per 100 parts by weight of the solid component. Parts by weight.

(ingredient D) solvent

The photosensitive resin composition of the present invention preferably contains (Component D) a solvent. The photosensitive resin composition of the present invention is preferably prepared in the form of a solution in which an essential component and an optional component are dissolved.

As the solvent to be used in the photosensitive resin composition of the present invention, a well-known solvent can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol monoalkyl ether acetate. , propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol single Alkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like. The solvent used in the photosensitive resin composition of the present invention is, for example, a Japanese patent. The solvent described in paragraph 0074 of JP-A-2009-258722.

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

These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably a single one or a combination of two, more preferably two kinds, and further preferably a propylene glycol monoalkyl ether acetate and a diethylene glycol dialkyl ether. .

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

The content of the (Component D) solvent in the photosensitive resin composition of the present invention is preferably from 50 parts by weight to 3,000 parts by weight, more preferably from 100 parts by weight to 2,000 parts by weight, based on 100 parts by weight of the total solid content. It is preferably from 150 parts by weight to 1,500 parts by weight.

<Other ingredients>

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

The photosensitive resin composition of the present invention preferably contains (L) a sensitizer from the viewpoint of sensitivity, and preferably contains (H) a base from the viewpoint of liquid storage stability. The compound is preferably a crosslinking agent from the viewpoint of film properties, and preferably contains a (G) adhesion improving agent from the viewpoint of adhesion of the substrate, and from the viewpoint of coating properties, It is preferred to contain (I) a surfactant.

Hereinafter, it may be contained in the photosensitive resin composition of the present invention. His ingredients are explained.

[sensitizer]

The photosensitive resin composition of the present invention preferably contains a sensitizer (usually a photosensitizer).

It is effective in improving the exposure sensitivity by containing a photosensitizer, and is particularly effective when the exposure light source is a g-ray or an h-ray mixing line.

The photosensitizer is preferably an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base styryl derivative, or a distyrylbenzene derivative.

The anthracene derivative is preferably ruthenium, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9- Bromide, 9-chloropurine, 9,10-dibromofluorene, 2-ethylhydrazine, 9,10-dimethoxyfluorene.

The acridone derivative is preferably acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone, N-ethyl-2-methoxy Acridinone.

The thioxanthone derivative is preferably thioxanthone, diethyl thioxanthone, 1-chloro-4-propylthioxanthone or 2-chlorothioxanthone.

The coumarin derivative is preferably coumarin-1, coumarin-6H, coumarin-110, coumarin-102.

Examples of the basic styryl derivative include 2-(4-dimethylaminostyryl)benzoxazole, 2-(4-dimethylaminostyryl)benzothiazole, and 2- (4-Dimethylaminostyryl)naphthylthiazole.

The distyrylbenzene derivative may, for example, be distyrylbenzene, bis(4-methoxystyryl)benzene or bis(3,4,5-trimethoxystyryl)benzene.

Among these compounds, an anthracene derivative is preferred, and a 9,10-dialkyloxy group is more preferred. Base (the alkoxy group has a carbon number of 1 to 6).

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

The content of the sensitizer in the photosensitive resin composition of the present invention is preferably from 0.1 part by weight to 10 parts by weight, more preferably from 0.5 part by weight to 10 parts by weight, per 100 parts by weight of the total solid content. When the content of the sensitizer is 0.1 part by weight or more, the desired sensitivity is easily obtained, and when the content of the sensitizer is 10 parts by weight or less, the transparency of the coating film is easily ensured.

[alkaline compound]

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 the compounds used in the chemical amplification resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium salt of a carboxylic acid, etc. are mentioned.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, and diethanolamine. 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, and N-methyl. 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine , nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, anthracene, pyrrolidine, acridine, pyridazine, morpholine, 4-methylmorpholine, N -cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo [5.3.0]-7-undecene and the like.

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

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

The basic compound which can be used in the present invention may be used alone or in combination of two or more. It is preferred to use two or more kinds in combination, more preferably two kinds in combination, and it is preferred to use two kinds of heterocyclic amines in combination. .

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 part by weight to 1 part by weight, more preferably 0.002 part by part to 0.2 part by weight, per 100 parts by weight of the total solid content.

[Close Connection Improver]

The photosensitive resin composition of the present invention preferably contains a adhesion improving agent from the viewpoint of substrate adhesion.

The adhesion improving agent which can be used in the photosensitive resin composition of the present invention is an inorganic substance (for example, an antimony compound such as antimony, cerium oxide or tantalum nitride), or a metal such as molybdenum, titanium, indium tin oxide, gold, copper or aluminum. A compound having improved adhesion to an insulator. Specific examples thereof include a decane coupling agent and a thiol compound. The decane coupling agent which is the adhesion improving agent used in the present invention is not particularly limited as long as it is modified by the interface, and a well-known decane coupling agent can be used.

Among these adhesion improvers, a decane coupling agent can be preferably exemplified. Here, the decane coupling agent of the present invention means a compound having one hydrolyzable alkylene group or stanol group in one molecule.

Preferred examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ- Glycidoxypropyl alkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ- Chloropropyltrialkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane.

More preferably, these compounds are γ-glycidoxypropyltrialkoxydecane and γ-methacryloxypropyltrialkoxydecane, and further preferably γ-glycidoxypropyl III. Alkoxydecane.

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

Photosensitive resin of the present invention with respect to 100 parts by weight of the total solid content The content of the adhesion improving agent in the composition is preferably from 0.1 part by weight to 20 parts by weight, more preferably from 0.5 part by weight to 10 parts by weight.

[Surfactant]

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

As the surfactant, any of an anionic, cationic, nonionic or amphoteric surfactant may be used, and a preferred surfactant is a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based and anthrone-based Surfactant.

More preferably, the photosensitive resin composition of the present invention contains a fluorine-based surfactant and/or an anthrone-based surfactant as a surfactant.

Examples of the fluorine-based surfactant and the anthrone-based surfactant include, for example, Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. Sho 61-226746, Japanese Patent Laid-Open No. 61-226745, and Japanese Patent. JP-A-62-170950, Japanese Patent Laid-Open No. Sho 63-34540, Japanese Patent Laid-Open No. Hei 7-230165, Japanese Patent Laid-Open No. Hei 8-62834, Japanese Patent Laid-Open No. Hei 9-54432, Japanese Patent Laid-Open No. 9 A commercially available surfactant can also be used as the surfactant described in each of the publications of JP-A No. JP-A No. 2001-330953.

Commercially available surfactants which can be used include, for example, F-top EF301, F-top EF303 (above, manufactured by New Akita Chemicals Co., Ltd.), and Fluorad (Fluorad). ) FC430, Vlaud (Fluorad) 431 (above is Sumitomo 3M (share) manufacturing), Megaface F171, Megaface F173, Megaface F176, Megaface F189, Megaface R08 (above Di Produced by Aisheng (DIC) Co., Ltd., Surflon S-382, Surflon SC101, Surflon 102, Surflon 103, Surflon 104, fluorine-based interfacial activity such as Surflon 105, Surflon 106 (above manufactured by Asahi Glass Co., Ltd.), and PolyFox series (made by OMNOVA) Agent or anthrone-based surfactant. Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as an anthrone-based surfactant.

In addition, as a surfactant, a copolymer containing a structural unit A and a structural unit B represented by the following formula (1) and having tetrahydrofuran (THF) as a solvent is preferable. The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography is 1,000 or more and 10,000 or less.

(In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴ represents a hydrogen atom or a carbon number of 1 In the above alkyl group, 4 or less, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are weight percentages indicating a polymerization ratio, and p is a numerical value of 10% by weight or more and 80% by weight or less, and q is a value. a numerical value of 20% by weight or more and 90% by weight or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less)

The L is preferably a branched alkyl group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and is preferably an alkane having 1 or more and 3 or less carbon atoms from the viewpoint of compatibility and wettability to a surface to be coated. More preferably, it is an alkyl group having 2 or 3 carbon atoms.

The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

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

The amount of the surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 parts by weight to 10 parts by weight, even more preferably 0.01% by weight based on 100 parts by weight of the total solid content. Parts ~ 1 part by weight.

<Other>

In the photosensitive resin composition of the present invention, other components such as a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, a development accelerator, and an antioxidant may be added as needed. For these ingredients, for example, you can use A compound described in JP-A-2009-98616, and JP-A-2009-244801, and other well-known compounds. In addition, various ultraviolet absorbers, metal deactivators, and the like described in "New Development of Polymer Additives (Nikko Kogyo Co., Ltd.)" may be added to the photosensitive resin composition of the present invention.

* (Method of forming a cured film)

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

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

* (1) a step of applying (preferably, coating) the positive photosensitive resin composition of the present invention to a substrate

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

(3) a step of exposing the photosensitive resin composition from which the solvent has been removed by using active light

(4) a step of developing the exposed photosensitive resin composition using an aqueous developing solution

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

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

Further, before the post-baking step, a step of performing full exposure of the developed photosensitive resin composition may be further included.

Each step will be described in order below.

In the (1) application step, it is preferred to apply the positive photosensitive resin composition of the present invention onto a substrate to form a wet film containing a solvent.

In the (2) solvent removal step, it is preferred to form a dry coating film on the substrate by removing the solvent from the applied film by pressure reduction (vacuum) and/or heating.

In the (3) exposure step, it is preferred that the obtained coating film is irradiated with active light having a wavelength of 300 nm or more and 450 nm or less. In this step, the specific acid generator is decomposed to generate an acid. The acid-decomposable group in the structural unit (a1) contained in the component A is decomposed by the catalytic action of the generated acid to form an acid group.

In the region where the acid catalyst is formed, in order to accelerate the decomposition reaction, post-exposure heat treatment (Post Exposure Bake (hereinafter also referred to as "PEB")) may be performed as needed. Through the PEB, an acid group derived from an acid-decomposable group can be promoted.

The acid-decomposable group in the structural unit (a1) in the specific resin is low in activation energy due to acid decomposition, and is easily decomposed by an acid derived from a photoacid generator due to exposure to generate an acid group, so that it is not necessary to carry out PEB. Therefore, it is preferred that the development step be carried out without performing a heat treatment after the exposure step. More specifically, it is preferable to carry out development by the (4) development step without performing PEB after the (3) exposure step, thereby forming a positive image.

Further, it is also possible to promote the decomposition of the acid-decomposable group without causing a crosslinking reaction by performing PEB at a relatively low temperature. The temperature at the time of PEB is preferably 30° C. or higher and 130° C. or lower, more preferably 40° C. The above is 110 ° C or less, and particularly preferably 50 ° C or more and 90 ° C or less.

In the (4) developing step, it is preferred to develop the component A having a free acid group and the component B having an acid group using an alkaline developing solution. A positive image can be formed by removing the exposed portion region, and the exposed portion region contains a photosensitive resin composition having an acid group which is easily dissolved in the alkaline developing solution.

In the (5) post-baking step, by heating the obtained positive image, for example, the acid group in the structural unit (b1) and the acid-decomposable group in the structural unit (a1) can be thermally decomposed to generate The acid group is crosslinked with the crosslinkable group in the structural unit (a2) and the structural unit (b2) to form a cured film. The heating is preferably carried out to a high temperature of 150 ° C or higher, more preferably to 180 ° C to 250 ° C, and particularly preferably to 200 ° C to 250 ° C. The heating time can be appropriately set depending on the heating temperature and the like, and is preferably set in the range of 10 minutes to 90 minutes.

Further, preferably, before the post-baking step, the step of performing total exposure of the developed photosensitive resin composition is carried out, and if the pattern of the developed photosensitive resin composition is further irradiated with active light, it is preferably In the ultraviolet light step, the acid generated by the irradiation of the active light can be used to promote the crosslinking reaction.

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

[Method for Preparing Photosensitive Resin Composition]

In the essential component of the specific resin and the acid generator, if necessary, the solvent is mixed at a predetermined ratio and by any method, and stirred and dissolved to prepare. A photosensitive resin composition. For example, a solution obtained by dissolving a specific resin or an acid generator in a solvent in advance may be prepared, and these solutions may be mixed at a predetermined ratio to prepare a photosensitive resin composition. The solution of the photosensitive resin composition prepared as described above may be used after being filtered using a filter having a pore size of 0.1 μm or the like.

<Application step and solvent removal step>

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

In addition, (2) the heating condition of the solvent removal step is such that the acid-decomposable group in the structural unit (a1) in the component A in the unexposed portion is decomposed and the component A is not soluble in the alkali developing solution. Depending on the type of each component or the mixing ratio, it is preferably from 70 ° C to 120 ° C for about 30 seconds to 300 seconds.

<Exposure step>

In the (3) exposure step, the substrate on which the dried coating film of the photosensitive resin composition is provided is irradiated with the active light of a predetermined pattern. Exposure can be covered The cover can be used to draw a predetermined pattern directly. Active light having a wavelength of 300 nm or more and 450 nm or less can be preferably used. After the exposure step, PEB can also be performed as needed.

In the exposure using active light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a laser generating device, a light emitting diode (LED) light source, or the like can be used.

In the case of using a mercury lamp, active light having a wavelength of g-ray (436 nm), i-ray (365 nm), h-ray (405 nm), or the like can be preferably used. Mercury lamps are preferred for exposure to large areas compared to lasers.

In the case of lasers, 343 nm and 355 nm can be suitably used in solid (Yttrium Aluminum Garnet (YAG)) lasers, and 351 nm (XeF) can be suitably used in excimer lasers. Further, 375 nm and 405 nm can be suitably used in the semiconductor laser. Among them, from the aspects of stability and cost, it is more preferably 355 nm or 405 nm. The laser can illuminate the coating film one or more times. Further, the specific examples or preferred ranges of the energy density, the pulse width, the laser frequency, the exposure apparatus, and the filter are described in paragraphs 0098 to 0100 of JP-A-2011-186398.

<Development step>

In the (4) development step, the exposed portion region is removed using an alkaline developer to form an image pattern. Examples of the basic compound used in the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate and heavy An alkali metal bicarbonate such as potassium carbonate; an ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline hydroxide; or an aqueous solution of sodium citrate or sodium metasilicate. Further, an aqueous solution of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the base as a developing solution.

The pH of the developer is not particularly limited as long as it can be developed, and is preferably from 10.0 to 14.0.

The development time is preferably from 30 seconds to 180 seconds, and the development method may be any one of a liquid-filling method, a dipping method, and a shower method. After development, it can be washed with running water for 10 seconds to 90 seconds to form a desired pattern.

<Post-baking step (cross-linking step)>

Use a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 ° C to 250 ° C for a predetermined period of time, for example, 5 minutes to 60 minutes on a hot plate, or 30 minutes to 90 minutes if it is an oven. Heat-treating the pattern corresponding to the unexposed area obtained by the development, thereby decomposing the acid-decomposable group in the specific resin to produce a carboxyl group and/or a phenolic hydroxyl group, and an epoxy group in the specific resin and/or The oxetanyl group, that is, the crosslinkable group, is crosslinked, whereby a protective film or an interlayer insulating film excellent in heat resistance, hardness, and the like can be formed. Further, when the heat treatment is performed, the transparency can be improved by performing the reaction under a nitrogen atmosphere.

Further, it is also preferred to perform post-baking (re-exposure/post-baking) on the patterned substrate by active light before the heat treatment, whereby the acid generator present in the unexposed portion is used. (B) An acid is generated to function as a catalyst for promoting crosslinking.

That is, the method of forming the cured film of the present invention is preferably a step of performing re-exposure with active rays between the developing step and the post-baking step.

The exposure in the re-exposure step may be carried out by the same method as the exposure step, and in the re-exposure step, it is preferred that the substrate is formed on the side of the substrate from which the photosensitive resin composition of the present invention is formed. Conduct a full exposure. A preferred exposure amount for the re-exposure step is from 100 mJ/cm ² to 1,000 mJ/cm ² .

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention, and can be suitably used as an electronic member, particularly an interlayer insulating film. Further, the cured film of the present invention is preferably a cured film obtained by the method for forming a cured film of the present invention.

According to the photosensitive resin composition of the present invention, it is possible to obtain a cured film having a high sensitivity, a generation of residue at the time of development, and a surface having excellent smoothness, and the cured film is useful as an interlayer insulating film. In addition, the interlayer insulating film which is obtained by using the photosensitive resin composition of the present invention has high transparency, can form a pattern shape of a good shape, and is excellent in smoothness of the surface, and therefore is in an organic EL display device or liquid crystal. Useful for the use of display devices.

In the organic EL display device or the liquid crystal display device to which the photosensitive resin composition of the present invention is applied, a cured film formed using the photosensitive resin composition of the present invention is used as a planarizing film, a protective film, or an interlayer insulating film. There is no particular limitation, and various well-known organic EL display devices or liquid crystal display devices having various structures can be cited.

[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 comprising 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 as long as it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various structures can be used. Various organic EL display devices or liquid crystal display devices are well known.

Specific examples of the thin film transistor (TFT) included in the organic EL display device and the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. . Since the cured film of the present invention is excellent in electrical characteristics, it can be used in combination with these TFTs.

Further, examples of the liquid crystal display device which can be used in the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and a coplanar switching (In-Plane-Switching). , IPS) mode, Fringe Field Switching (FFS) mode, Optical Compensated Bend (OCB) mode, etc.

Moreover, the specific alignment of the liquid crystal alignment film which can be used for the liquid crystal display device of the present invention may be, for example, a rubbing alignment method or a photoalignment method. In addition, the polymer alignment support can also be carried out by the Polymer Sustained Alignment (PSA) technique described in Japanese Patent Laid-Open No. 2003-149647 or Japanese Patent Laid-Open No. 2011-257734.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention It is not limited to the use and can be used for various purposes. For example, in addition to the planarization film or the interlayer insulating film, a protective film suitable for a color filter or a spacer or a solid-state imaging element for maintaining a liquid crystal layer in a liquid crystal display device with a certain thickness may be used. A microlens or the like provided on a color filter.

FIG. 1 is a conceptual view showing an example of an organic EL display device using the photosensitive resin composition of the present invention. A schematic cross-sectional view of a substrate in an organic EL display device of a bottom emission type, having a planarization film 4.

A bottom gate type TFT (thin film transistor) 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. After the contact hole (not shown) is formed in the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. The wiring 2 is a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent steps to the TFT 1.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is filled.

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

The insulating film 8 having a shape covering the edge of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, although not shown in FIG. 1, a hole transport layer, an organic light-emitting layer, and an electron transport layer are provided by sequentially vapor-depositing through a desired pattern mask, and then Al is formed on the entire upper surface of the substrate. The two electrodes are bonded and sealed by using a sealing glass plate and an ultraviolet curable epoxy resin, and an active matrix type organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to the respective organic EL elements is obtained. .

FIG. 2 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and an element of the TFT 16 is disposed in the liquid crystal panel. The elements of the TFT 16 are disposed on two glass substrates 14 and glass substrates 15 to which a polarizing film is attached. All pixels in between correspond. Wiring of the ITO transparent electrode 19 forming the pixel electrode is performed on each element formed on the glass substrate through the contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, a layer of the liquid crystal 20 and an RGB color filter 22 in which a black matrix is disposed are provided.

Instance

The invention will be more specifically described below by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Synthesis Example 1>

150 parts by weight of diethylene glycol ethyl methyl ether was placed in a flask equipped with a condenser and a stirrer, and the temperature was raised to 90 ° C in a nitrogen atmosphere. In this solution, 1-1.3% by weight of 1-ethoxyethyl methacrylate was used as a monomer component. Parts, 23.9 parts by weight of glycidyl methacrylate, 5.6 parts by weight of methacrylic acid, 13.5 parts by weight of styrene, and dimethyl-2,2'-azobis(2-methylpropionic acid) as a polymerization initiator 10.0 parts by weight of the ester (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved and added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was stirred for 2 hours. 2.5 parts by weight of dimethyl-2,2'-azobis(2-methylpropionate) was further added to the solution, and the mixture was further stirred for 2 hours to complete the reaction. Thus, the polymer A-1 was obtained. The weight average molecular weight was 13,000.

<Synthesis Example 2 to Synthesis Example 26>

Polymer A-2 to polymer A-26 shown in the following table were synthesized in the same manner as in Synthesis Example 1, except that the monomers used and the amounts thereof were changed. The composition ratio (% by mole) and the weight average molecular weight (Mw) of each of the synthesized polymers are shown in the following table.

The abbreviations in Table 1 are as follows.

MAEVE: 1-ethoxyethyl methacrylate (synthesis example will be described below)

MATHF: tetrahydro-2H-furan-2-yl methacrylate (synthesis example will be described below)

MACHOE: 1-(cyclohexyloxy)ethyl methacrylate (synthesis examples will be described below)

PHSEVE: 1-ethoxyethyl protector of p-hydroxystyrene (synthesis example will be described below)

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

OXE-30: (3-ethyloxetan-3-yl)methyl methacrylate (-3-ethyl-3-oxetanylmethyl methacrylate) (Osaka Organic Chemical Industry Co., Ltd.) Manufacturing)

VBGE: p-vinylbenzyl glycidyl ether

M-100: Cyclomer M-100 (-3,4-epoxycyclohexylmethyl methacrylate, manufactured by Daicel Chemical Co., Ltd.)

NBMA: n-Butoxymethyl propylene decylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

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

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

DCPM: methacrylic acid (tricyclo[5.2.1.0 ^2,6 ]decane-8-yl) ester (manufactured by Hitachi Chemical Co., Ltd., FA-513M)

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

<MAEVE (synthesis of 1-ethoxyethyl methacrylate)>

0.5 parts of phenothiazine was added to 144.2 parts (2 moles equivalent) of ethyl vinyl ether, and 86.1 parts of methacrylic acid (1 molar equivalent) was added dropwise while cooling the reaction system to 10 ° C or lower. Stir at temperature (25 ° C) for 4 hours. After 5.0 parts of pyridinium p-toluenesulfonate was added, 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 liquid, and the mixture was stirred at room temperature for 1 hour, and the insoluble matter was filtered, and concentrated under reduced pressure at 40 ° C or less. The yellow oil of the residue was distilled under reduced pressure. 134.0 parts of 1-ethoxyethyl methacrylate having a boiling point (bp.) of 43 ° C to 45 ° C / 7 mm Hg as a colorless oil was obtained.

<Synthesis of MATHF (tetrahydrofuran-2-yl methacrylate)>

Methacrylic acid (86 g, 1 mol) was previously cooled to 15 ° C, and camphorsulfonic acid (4.6 g, 0.02 mol) was added. 2,3-Dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise to the solution. After stirring for 1 hour, a saturated aqueous solution of sodium hydrogencarbonate (500 mL) was added, and the mixture was extracted with ethyl acetate (500 mL), dried over magnesium sulfate, and then filtered, and then concentrated under reduced pressure at 40 ° C. The yellow oil of the residue was distilled under reduced pressure to give THF (tetrahydrofuran-2-yl methacrylate) as a colorless oil (bp.) of 54 ° C to 56 ° C / 3.5 mm Hg. The yield was 80%).

<MACHOE (Synthesis of 1-(cyclohexyloxy)ethyl methacrylate)>

The synthesis of MACHOE was carried out in the same manner as the synthesis of the MAEVE.

*<PHSEVE (synthesis of 1-ethoxyethyl protecting group of α-methylhydroxystyrene)>

With regard to PHSEVE, α-methylhydroxystyrene was reacted with ethyl vinyl ether in the presence of an acid catalyst, whereby PHSEVE was obtained in the form of an ethyl acetal protecting agent of a phenolic hydroxyl group.

*(examples and comparative examples)

The components were blended as shown in the following table, and dissolved in diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether so that the solid content concentration was 27% by weight. After the acetic acid ester = 1:1 (by weight) mixed solvent, the photosensitive resin composition of the examples and the comparative examples was prepared by filtration using a membrane filter having a pore size of 0.2 μm.

The details of the abbreviations used for the respective compounds used in the examples and comparative examples are as follows.

(B) Acid generator

B-1: CGI-1397 (a compound of the structure shown below, manufactured by Ciba Specialty Chemicals Co., Ltd.)

B-2: triphenylsulfonium nonafluorobutanesulfonate

B-3: Compound of the structure shown below (NAI-101, manufactured by Green Chemicals)

(L) sensitizer

L-1: DBA (9,10-dibutoxyfluorene, the structure shown below, Chuan Saki Kasei Industrial Co., Ltd.)

Bu in the formula represents a butyl group.

(C) chain aliphatic epoxy compound

C-1: Denacol EX-612 (chain aliphatic epoxy compound, manufactured by Changchun Chemical Co., Ltd.), molecular weight: 664, viscosity at 25 ° C: 11,900 mPa. s

C-2: Denacol EX-212L (chain aliphatic epoxy compound, manufactured by Changchun Chemical Co., Ltd.), molecular weight: 270, viscosity at 25 ° C: 15 mPa. s

C-3: Denacol EX-321 (chain aliphatic epoxy compound, manufactured by Changchun Chemical Co., Ltd.), molecular weight: 280-420, viscosity at 25 ° C: 130 mPa. s

C-4: Denacol EX-321L (chain aliphatic epoxy compound, manufactured by Changchun Chemical Co., Ltd.), molecular weight: 320 to 480, viscosity at 25 ° C: 800 mPa. s

C-5: Denacol EX-252 (cyclic aliphatic epoxy compound, manufactured by Changchun Chemical Co., Ltd., molecular weight: 426, viscosity at 25 ° C: 2200 mPa.s

C-6: JER-1004 (bisphenol A type epoxy compound, manufactured by Mitsubishi Chemical Corporation), molecular weight: 1650 (catalog value)

C-7: Denacol EX-211L (chain aliphatic epoxy compound, manufactured by Changchun Chemical Co., Ltd.), weight average molecular weight: 216, viscosity at 25 ° C: 20 mPa. s

(G) Adhesive improver

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

G-2: KBE-403 (3-glycidoxypropyl triethoxy decane, manufactured by Shin-Etsu Chemical Co., Ltd.)

(H) basic compound

H-1:1,5-diazabicyclo[4.3.0]-5-pinene (manufactured by Tokyo Chemical Industry Co., Ltd.)

H-2: Tributylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

(I) surfactant

I-1: Fluorad FC-430 (acrylic resin containing saturated perfluoroalkyl group, manufactured by 3M Company)

I-2: Polyether modified anthrone-based surfactant (KF-6012, manufactured by Shin-Etsu Chemical Co., Ltd.)

I-3: Emalgen 105 (made by Kao), polyoxyethylene ethyl lauryl ether

Each of the photosensitive resin compositions of the examples and the comparative examples obtained in the above manner was subjected to the following evaluations. The results are shown below.

<Evaluation of sensitivity>

Each of the photosensitive resin compositions was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then prebaked on a hot plate at 90 ° C for 120 seconds. The solvent was volatilized to form a photosensitive resin composition layer having a film thickness of 3.0 μm.

Then, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon. Next, the exposed photosensitive resin composition layer was developed by an alkali developer (0.4% by weight aqueous solution of tetramethylammonium hydroxide) at 23 ° C for 60 seconds, and then rinsed with ultrapure water for 20 seconds. .

The optimum i-ray exposure amount (Eopt) when the line and the gap of 10 μm are analyzed by 1:1 by these operations is used as the sensitivity. In addition, the evaluation criteria are as follows. "1" and "2" are practically problem-free levels. The results are shown in the following table.

1: Eopt is less than 40 mJ/cm ²

2: Eopt is 40 mJ/cm ² or more and less than 60 mJ/cm ²

3: Eopt is 60 mJ/cm ² or more and less than 80 mJ/cm ²

4: Eopt is 80 mJ/cm ² or more

5: Unable to pattern

<Evaluation of chemical resistance (peeling resistance)>

On a glass substrate (Corning 1737, 0.7 mm thick (Kang (manufactured by Corning Co., Ltd.)) After coating each photosensitive resin composition in a slit, the solvent was removed by heating on a hot plate at 90 ° C for 120 seconds to form a photosensitive resin composition having a film thickness of 3.0 μm. Floor.

The obtained photosensitive property was obtained by using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd. in a cumulative irradiation amount of 300 mJ/cm ² (illuminance: 20 mW/cm ² , i-ray). The resin composition layer was exposed, and thereafter, the substrate was heated at 230 ° C for 1 hour in an oven to obtain a cured film.

The cured film was immersed in monoethanolamine at 60 ° C for 5 minutes, and the film was lifted to wipe off the liquid on the surface, and the film thickness was measured immediately. The film thickness before immersion and the film thickness after immersion were compared, and the increased ratio was expressed as a percentage. The results are shown in the following table. The smaller the value, the better the peeling resistance of the cured film is, and it is preferably 1 or 2.

Swelling rate (%) = film thickness after immersion (μm) / film thickness before immersion (μm) × 100

1:100% or more and less than 102%

2: 102% or more, less than 105%

3: 105% or more and less than 110%

4:110% or more and less than 115%

5:115% or more

<Evaluation of coating property>

In the preparation of each photosensitive resin composition, the amount of solvent is adjusted to be sticky The degree is set to 18.0 mPa. In addition to the above, a photosensitive resin composition was prepared in the same manner, and applicability was evaluated. SF-700G manufactured by Dainippon Screen Co., Ltd. was spin-coated on a glass substrate of 550 mm × 650 mm so that the coating film thickness after drying became 4.1 μm. The drying was carried out by using a hot plate at 90 ° C for 120 seconds. The coated surface was visually observed, and the number of stripe unevenness was counted, and evaluated according to the following criteria. The results are shown in the table. If it is 1, 2, 3, it is within the scope of the license.

No streaky unevenness on the coated surface: 1

1 to 3: 2

4 to 5: 3

6 or more: 4

<Evaluation of Liquid Crystal Contamination (Electrical Characteristics Evaluation)>

The photosensitive resin compositions prepared in the respective examples and the comparative examples were spin-coated on a glass substrate of 100 mm × 100 mm so that the dried film thickness was 5 μm, and dried at 90 ° C for 120 seconds. After full exposure at 300 mJ/cm ² , post-baking was carried out at 230 ° C for 60 minutes in a convection oven. After the prepared coating film was peeled off from the substrate and pulverized, 9 mg was mixed in 2 g of liquid crystal (MLC-6608, manufactured by Merck), and heated at 120 ° C for 5 hours, and then used in ultrafine A small galvanometer (digital ultra-high resistance/micro galvanometer manufactured by ADC): 8340A was used to measure the liquid crystal resistivity. The evaluation result is determined as follows.

1: The resistivity is 1.0 × 10 ¹³ (Ω·cm) or more.

2: The specific resistance is 1.0 × 10 ¹² (Ω·cm) or more and less than 1.0 × 10 ¹³ (Ω·cm).

3: The specific resistance is 1.0 × 10 ¹¹ or more and less than 1.0 × 10 ¹² (Ω.cm).

4: The resistivity is less than 1.0 × 10 ¹¹ (Ω.cm).

When the liquid crystal resistivity shows a high numerical value, the degree of contamination of the liquid crystal is low, and it is excellent in the reliability of the panel.

According to the above-mentioned table, it is clear that when the composition of the present invention is used, it is a composition excellent in sensitivity, solvent resistance, coatability, and electrical properties (only Example 67 is known to be absent from (A) MAA becomes low sensitivity).

(Example 124)

The same evaluation as in the above Example 1 was carried out by using the photosensitive resin composition of Example 1 using a UV-LED source exposure machine in place of a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon. As a result, the same results as in Example 1 were obtained.

(Example 125)

The sensitivity was evaluated in the same manner as in the evaluation of the sensitivity of the photosensitive resin composition of Example 25 except that the photosensitive resin composition of Example 25 was used and the substrate was changed from a glass substrate to a ruthenium wafer. As a result, the same results as in Example 25 were obtained.

(Example 126)

Except that the photosensitive resin composition of Example 52 was used, and the exposure machine was changed from a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon (Canon) to FX-803M manufactured by Nikon (manufactured by Nikon) ( The sensitivity was evaluated in the same manner as the evaluation of the sensitivity of the photosensitive resin composition of Example 52 except for the gh-line stepper. As a result, the same results as in Example 52 were obtained.

(Example 127)

Except that the photosensitive resin composition of Example 103 was used, and the exposure machine was changed from a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon (Canon) to a 355 nm laser exposure machine to perform 355 nm laser exposure. In the same manner as in the evaluation of the sensitivity of the photosensitive resin composition of Example 103, the sensitivity was evaluated. As a result, the same result as in Example 103 can be obtained.

In addition, the 355 nm laser exposure machine is manufactured by V-Technology (EGIS) (wavelength 355 nm, pulse width 6 nsec), and the exposure is using Orphe The "PE10B-V2" manufactured by the company (OPHIR) was measured.

As described above, the photosensitive resin composition of the example exhibited excellent sensitivity regardless of the substrate or the exposure machine.

(Example 128)

A liquid crystal display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2). In the active matrix liquid crystal display device described in FIG. 1 and FIG. 2 of the Japanese Patent No. 3321003, the cured film 17 is formed as an interlayer insulating film in the following manner to obtain a liquid crystal display device. That is, a bottom gate type TFT 1 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. Then, after a contact hole is formed in the insulating film 3, a wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is filled. The planarization film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 115 on a substrate, prebaking on a hot plate (90 ° C, 2 minutes), and then using it from the mask. The high-pressure mercury lamp was irradiated with i-rays (365 nm) at 25 mJ/cm ² (illuminance of 20 mW/cm ² ), developed by an alkaline aqueous solution to form a pattern, and heat-treated at 230 ° C for 60 minutes. When the photosensitive resin composition was applied, the coating property was good, and after exposure, development, and firing, wrinkles or cracks were not observed in the obtained cured film. Further, the average step of the wiring 2 was 500 nm, and the thickness of the flattening film 4 produced was 2,000 nm.

The driving voltage was applied to the obtained liquid crystal display device, and the gray scale display when the test signal of the gray scale was input was visually observed to evaluate whether or not display unevenness occurred, and as a result, display unevenness was not observed at all.

(Example 129)

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 is formed on the glass substrate 6, and an insulating film 3 containing Si ₃ N ₄ is formed in a state of covering the TFT 1. Then, after the contact hole (not shown) is formed in the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. This wiring 2 is a wire for connecting the organic EL element formed between the TFTs 1 or in the subsequent steps to the TFT 1.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness due to the wiring 2 is filled. The planarization film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 107 on a substrate, prebaking on a hot plate (90 ° C, 2 minutes), and then using it from the mask. The high-pressure mercury lamp was irradiated with i-rays (365 nm) at 45 mJ/cm ² (illuminance of 20 mW/cm ² ), developed by an alkaline aqueous solution to form a pattern, and subjected to heat treatment at 230 ° C for 60 minutes. When the photosensitive resin composition was applied, the coating property was good, and after exposure, development, and firing, wrinkles or cracks were not observed in the obtained cured film. Further, the average step of the wiring 2 was 500 nm, and the thickness of the flattening film 4 produced was 2,000 nm.

Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 including ITO is formed on the planarization film 4 via the contact hole 7 and connected to the wiring 2. Thereafter, the resist is applied and prebaked, exposed through a mask of a desired pattern, and developed. The resist pattern was used as a mask, and pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was peeled off using a resist stripping solution (a mixture of monoethanolamine and dimethylsulfoxide (DMSO)). The first electrode 5 obtained in this manner corresponds to the anode of the organic EL element.

Next, an insulating film 8 covering the shape of the edge of the first electrode 5 is formed. For the insulating film, using the photosensitive resin composition of Example 108, the insulating film 8 was formed by the same method as described above. By providing the insulating film, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, in the vacuum vapor deposition apparatus, a hole transport layer, an organic light-emitting layer, and an electron transport layer are provided by sequentially vapor-depositing through a desired pattern mask. Then, a second electrode containing Al is formed on the entire upper surface of the substrate. The obtained substrate was taken out from the vapor deposition machine, and sealed with an ultraviolet curable epoxy resin and a glass plate for sealing.

As described above, an active matrix type organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to the respective organic EL elements can be obtained. The organic EL display device exhibits good display characteristics when a voltage is applied through a driving circuit, and is known to be a highly reliable organic EL display. Display device.

1‧‧‧TFT

2‧‧‧Wiring

3,8‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

16‧‧‧TFT

17‧‧‧ hardened film

18‧‧‧Contact hole

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

FIG. 1 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device having a planarization film 4.

FIG. 2 is a conceptual diagram showing an example of a liquid crystal display device. A schematic cross-sectional view showing an active matrix substrate in a liquid crystal display device having a cured film 17 as an interlayer insulating film.

1‧‧‧TFT

2‧‧‧Wiring

3,8‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7‧‧‧Contact hole

Claims (15)

A positive photosensitive resin composition for an electronic component, comprising: (A) a polymer satisfying the following (1) or (2), (1) at least having an acid group which is protected by an acid-decomposable group; a polymer obtained by copolymerizing a structural unit (a1) of a residue and a structural unit (a2) having a crosslinkable group, and (2) a structural unit containing a residue obtained by protecting an acid group with an acid-decomposable group ( a polymer of a1) and a polymer containing a structural unit (a2) having a crosslinkable group; (B) a photoacid generator; and (C) a chain aliphatic epoxy compound. The positive photosensitive resin composition for electronic components according to the first aspect of the invention, wherein the (C) chain aliphatic epoxy compound has a molecular weight of 2,000 or less. The positive photosensitive resin composition for electronic components according to claim 1 or 2, wherein the (C) chain aliphatic epoxy compound has a viscosity of 3000 mPa at 25 ° C. s below. The positive photosensitive resin composition for electronic components according to the first aspect of the invention, wherein the (C) chain aliphatic epoxy compound is represented by the following formula (X-1) Represented resin, In the above formula (X-1), A is a linear or branched hydrocarbon group, and may have a hydroxyl group as a substituent, and n is an integer of 1 to 4. The positive photosensitive resin composition for an electronic component according to the above aspect, wherein the structural unit (a1) is a residue having a carboxyl group protected by acetal, or a carboxyl group is reduced. The ketone protects the structural unit of the resulting residue. The positive photosensitive resin composition for an electronic component according to the first aspect of the invention, wherein the structural unit (a1) is a structural unit represented by the following formula (A2'), In the formula (A2'), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms or a carbon number of 4 to 7 The cycloalkyl group, R ² and R ³ may also be bonded to form a ring. The positive photosensitive resin composition for an electronic component according to the first aspect of the invention, wherein the (C) chain aliphatic epoxy compound is represented by the following formula (X-2) Resin expressed, general formula (X-2) In the above formula (X-2), B is a linear or branched hydrocarbon group, and may have a hydroxyl group as a substituent, and n is an integer of 1 to 4. The positive photosensitive resin composition for electronic components according to the above aspect, wherein the structural unit (a2) comprises a cyclic ether group selected from a ring having a 3-membered ring or a 4-membered ring. At least one of a group consisting of a structural unit and a structural unit having a group represented by -NH-CH ₂ -OR, wherein R is an alkyl group having 1 to 20 carbon atoms. The positive photosensitive resin composition for electronic components according to claim 1 or 2, wherein the (C) chain aliphatic epoxy compound has a viscosity of 3000 mPa at 25 ° C. s or less, and is a resin represented by the following formula (X-1), In the above formula (X-1), A is a linear or branched hydrocarbon group, and may have a hydroxyl group as a substituent, and n is an integer of 1 to 4. The positive photosensitive resin composition for electronic components according to claim 1 or 2, wherein the (C) chain aliphatic epoxy compound has a viscosity of 3000 mPa at 25 ° C. s or less, and is a resin represented by the following formula (X-2), In the above formula (X-2), B is a linear or branched hydrocarbon group, and may have a hydroxyl group as a substituent, and n is an integer of 1 to 4. A method for forming a cured film, comprising: (1) applying a positive photosensitive resin composition for an electronic component according to the first or second aspect of the invention to a substrate; 2) a step of removing a solvent from the photosensitive resin composition to be applied; (3) a step of exposing the photosensitive resin composition from which a solvent is removed by using an active light; (4) using an aqueous developing solution a step of developing the exposed photosensitive resin composition; and (5) a post-baking step of thermally curing the developed photosensitive resin composition. The method for forming a cured film according to claim 11, comprising the step of performing full exposure of the developed photosensitive resin composition after the developing step and before the post-baking step . A cured film characterized in that it is utilized as a patent application The method for forming a cured film according to item 12 is formed. The cured film according to claim 13, which is an interlayer insulating film. A display device which is an organic EL display device or a liquid crystal display device, and the display device is characterized by comprising the cured film according to claim 13 of the patent application.