JP6080543B2 - Negative photosensitive resin composition - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition for thick film, a thick photosensitive dry film comprising a thick photosensitive resin layer made of the negative photosensitive resin composition for thick film, and the thickness The present invention relates to a method for forming a thick film resist pattern using a negative photosensitive resin composition for a film.

  In recent years, MEMS (Micro Electro Mechanical System), which is attracting attention as a mass-productivity system that integrates fine parts in the same chip using semiconductor manufacturing technology and realizes high performance and high integration, Expansion to various fields such as automobiles, consumer devices, medical care, and biotechnology is expected. On the other hand, demands for downsizing in these fields are increasing, and development of a photosensitive resin composition capable of forming a fine resist pattern having a high film thickness and a high aspect ratio is required.

  As a photosensitive resin composition capable of forming a thick photosensitive resin layer excellent in developability and resolution that meets such requirements, for example, an alkali-soluble resin and an acid or radical by irradiation with actinic radiation There is known a negative photosensitive resin composition containing a compound capable of generating an acid, a compound that can be cross-linked by an acid or a radical, an epoxy resin having a specific structure, and a solvent (see Patent Document 1).

JP 2011-227246 A

  The negative photosensitive resin composition described in Patent Document 1 is excellent in resolution. However, miniaturization and high integration in the MEMS technology are progressing day by day, and in order to form a resist film with a high film thickness and extremely fineness, the resolution is further improved than the negative photosensitive resin composition described in Patent Document 1. There is a need for a photosensitive resin composition capable of forming a thick photosensitive resin layer having excellent properties.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a negative photosensitive resin composition for thick film capable of forming a thick photosensitive resin layer having excellent resolution. And Another object of the present invention is to provide a thick film photosensitive dry film comprising a thick photosensitive resin layer made of the negative photosensitive resin composition for the thick film. Furthermore, an object of the present invention is to provide a method for forming a thick film resist pattern using the negative photosensitive resin composition for the thick film.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, the above problem can be solved by blending a compound having a specific structure with a negative-type photosensitive resin composition for thick film containing (A) an alkali-soluble resin and (B) a photopolymerizable monomer. As a result, the present invention has been completed. Specifically, the present invention provides the following.

（式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又は有機基を示す。ただし、Ｒ^１及びＲ^２の少なくとも一方は有機基を示す。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^３は、単結合又は有機基を示す。Ｒ^４及びＲ^５は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基を示す。Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基を示す。ただし、Ｒ^６及びＲ^７が水酸基となることはない。Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^１０は、水素原子又は有機基を示す。） A first aspect of the present invention is a negative type for a thick film containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a compound represented by the following formula (1). It is a photosensitive resin composition.

(Wherein, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2} are they are attached It may form a cyclic structure and may contain a heteroatom bond, R ³ represents a single bond or an organic group, and R ⁴ and R ⁵ each independently represents a hydrogen atom, a halogen atom, or a hydroxyl group , mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group .R ^6, R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group Shows a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group. However, never R ⁶ and R ⁷ is a hydroxyl group .R ^6, R ⁷ , R ⁸ , and R ⁹ may be bonded to each other to form a cyclic structure, and may include a heteroatom bond, and R ¹⁰ may be a hydrogen atom or an organic group. Show.)

  The second aspect of the present invention includes a base film and a thick photosensitive resin layer formed on the surface of the base film, and the thick photosensitive resin layer has a thickness according to the first aspect. A thick photosensitive dry film made of a negative photosensitive resin composition for a film.

According to a third aspect of the present invention, a step of forming a thick photosensitive resin layer made of the negative photosensitive resin composition for a thick film according to the first aspect on a substrate;
Selectively exposing the thick photosensitive resin layer;
And developing the exposed thick photosensitive resin layer. A method for forming a thick film resist pattern.

  ADVANTAGE OF THE INVENTION According to this invention, the negative photosensitive resin composition for thick films which can form the thick photosensitive resin layer excellent in resolution can be provided. Moreover, according to this invention, a thick film photosensitive dry film provided with the thick photosensitive resin layer which consists of the said negative photosensitive resin composition for thick films can be provided. Furthermore, according to this invention, the formation method of the thick film resist pattern using the negative photosensitive resin composition for the said thick film can be provided.

≪Negative photosensitive resin composition for thick film≫
The negative photosensitive resin composition for thick films (hereinafter also referred to as “negative photosensitive resin composition”) includes (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) the above formula. A compound represented by (1). The film thickness of the thick photosensitive resin layer formed using the negative photosensitive resin composition for thick film is particularly limited as long as it is generally recognized by those skilled in the art to be a thick film. Not. Typically, the thickness of the photosensitive resin layer formed using the thick photosensitive resin layer is preferably 5 to 300 μm, more preferably 25 to 150 μm, and particularly preferably 40 to 130 μm. Hereinafter, the components contained in the negative photosensitive resin composition for thick film will be described in order.

[(A) Alkali-soluble resin]
(A) As alkali-soluble resin, what is conventionally used for the radical polymerization type negative photosensitive resin composition can be used without being restrict | limited in particular. Examples of (A) alkali-soluble resins include, for example, (meth) acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, phenol novolac resins, Examples include cresol novolac resins. Among these resins, from the viewpoint of alkali developability of the negative photosensitive resin composition, it is preferable to use the resin (A1) which is a (meth) acrylic resin as the (A) alkali-soluble resin.

  (A) Although the molecular weight of alkali-soluble resin is not specifically limited, 5000-200000 are preferable as a mass mean molecular weight, 10000-100000 are more preferable, 20000-80000 are further more preferable. By using the (A) alkali-soluble resin having such a molecular weight, it is easy to obtain a negative photosensitive resin composition having a viscosity suitable for forming a thick photosensitive resin layer.

  (A) It is preferable that alkali-soluble resin contains a carboxyl group from the point of the alkali developability of a negative photosensitive resin composition. Such (A) alkali-soluble resin can be produced, for example, by radical polymerization of a monomer having a carboxyl group and another monomer. As the monomer having a carboxyl group, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid, sorbic acid, Examples thereof include ethylenically unsaturated acids such as propolic acid and half-esters or anhydrides thereof, and (meth) acrylic acid is more preferable.

  (A) Although the acid value of alkali-soluble resin is not specifically limited, 15 mgKOH / g or more and 500 mgKOH / g or less are preferable, 15 mgKOH / g or more and 400 mgKOH / g or less are more preferable, 15 mgKOH / g or more and 300 mgKOH / g or less are especially preferable. When such an acid value (A) alkali-soluble resin is used, the releasability of the negative photosensitive resin composition is improved when a metal wiring pattern is formed by plating.

  Hereinafter, (A1) (meth) acrylic resin will be described. As the (A1) (meth) acrylic resin, for example, a polymer obtained by polymerizing or copolymerizing the following monomers can be used. In addition, these monomers can also be mix | blended as (B) photopolymerizable monomer mentioned later. As such a monomer, for example, (meth) acrylic acid ester, ethylenically unsaturated carboxylic acid, and other copolymerizable monomers can be preferably used. Specifically, styrene, benzyl (meth) acrylate, Cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, nonylphenoxypolypropylene mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, methyl ( Acrylate), ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meta ) Acrylate, 4-hydroxybutyl (meth) acrylate, 3-ethylhexyl (meth) acrylate, ethylene glycol mono (meth) acrylate, glycerol (meth) acrylate, dipentaerythritol mono (meth) acrylate Rate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3 , 3-trifluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, β-furyl (meth) acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid Maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and the like. Among these, (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferably used.

  Examples of other copolymerizable monomers include, for example, fumaric acid esters in which the above exemplary compounds of (meth) acrylic acid esters are replaced with fumarate, maleic acid esters in place of maleate, crotonic acid esters in place of crotonate, Itaconic acid esters instead of itaconate, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m -Methoxystyrene, p-methoxystyrene, vinyl acetate, vinyl butyrate, vinyl propionate, (meth) acrylamide, (meth) acrylonitrile, isoprene, chloroprene, 3-butadiene, vinyl-n-butyl ether and the like.

  The reaction between (a1) an acid group-containing acrylic resin and (a2) an alicyclic epoxy group-containing unsaturated compound that does not contain an ester bond formed by a ring-opening addition reaction between an epoxy group and a carboxyl group It is also preferable to use the resin (A2) which is a product as the alkali-soluble resin (A).

  (A1) Acid group-containing acrylic resins include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid , Sorbic acid, propolic acid, and ethylenically unsaturated acids such as half esters or anhydrides thereof, and (meth) acrylic acid esters, vinyl aromatic compounds, amide unsaturated compounds , Hydroxyl group-containing acrylate or phthalate, polyolefin compound, (meth) acrylonitrile, methyl isopropenyl ketone, vinyl acetate, vinyl butyrate, vinyl propionate, methacrylonitrile, isoprene, chloroprene, 3-butadiene, vinyl pivalate, etc. 1 or 2 types Known copolymers of polymerizable monomer above is copolymerized is used.

  Examples of the esters of (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 3-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (Meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, etc. can be mentioned.

  As the vinyl aromatic compound, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxy Examples thereof include styrene and p-methoxystyrene.

  Examples of the amide unsaturated compound include acrylamide and methacrylamide.

  Examples of the acrylate or phthalate containing a hydroxyl group include 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloylethyl-2-hydroxyethyl phthalate, 2-methacryloyloxyethyl-2-hydroxyprop Phthalate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, glycerol (meth) Examples include acrylate, dipentaerythritol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene. Kill.

  The alicyclic epoxy group-containing unsaturated compound (a2) is a compound having one radical polymerizable unsaturated group and an alicyclic epoxy group in one molecule, and for example, preferably 3.4-epoxy. Cyclohexylmethyl acrylate.

  Resin (A2) reacts part of the acid group derived from the above (a1) acid group-containing acrylic resin and (a2) an epoxy group derived from the alicyclic epoxy group-containing unsaturated compound, and (a1) ) It is produced by introducing an unsaturated group into an acid group-containing acrylic resin. Since this unsaturated group is a group necessary for curing with exposure light, the acid value of the (a1) acid group-containing acrylic resin is preferably 15 mgKOH / g or more, and 40 mgKOH / g or more and 500 mgKOH / g or less. More preferred.

  (A) As an alkali-soluble resin, in addition to the polymer / copolymer of the above monomers, cellulose derivatives such as cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, carboxyethyl methyl cellulose, and Copolymers of these cellulose derivatives with ethylenically unsaturated carboxylic acids or (meth) acrylate compounds can be used. Furthermore, polyvinyl alcohols such as polybutyral resin which is a reaction product of polyvinyl alcohol and butyraldehyde, δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β-propiolactone, β- Methyl-β-propiolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, α, α-dimethyl-β-propiolactone, β, β-dimethyl-β-propio Polyesters obtained by ring-opening polymerization of lactones such as lactone, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol and other alkylene glycols alone or two or more diols, maleic acid, fumarate Dicarbo such as acid, glutaric acid, adipic acid Polyesters obtained by condensation reaction with acids, polyethers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and polypentamethylene glycol, diols such as bisphenol A, hydroquinone and dihydroxycyclohexane, diphenyl carbonate, Examples thereof include polycarbonates which are reaction products with carbonyl compounds such as phosgene and succinic anhydride. The above component (A) may be used alone or in combination.

  The photosensitive resin composition may contain (A) binder resin other than alkali-soluble resin in the range which does not inhibit the objective of this invention. When (A) other binder resin is added to the negative photosensitive resin composition in addition to the alkali-soluble resin, the amount of the binder resin is 20% by mass with respect to the total amount of (A) the alkali-soluble resin and the binder resin. The following is preferable, and 10 mass% or less is more preferable. If the amount of the binder resin is excessive, the resolution of the thick photosensitive resin layer formed using the negative photosensitive resin composition may be lowered.

  As binder resins other than the alkali-soluble resin (A), (meth) acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, phenol novolac resins, Examples include cresol novolac resins. A (meth) acrylic resin is preferable from the viewpoint of alkali developability.

[(B) Photopolymerizable monomer]
(B) The photopolymerizable monomer is an active species generated when the compound represented by the formula (1) described later in the negative photosensitive resin composition or (D) the polymerization initiator is exposed. By the action, they are cross-linked to become a polymer.

Such polymerizable monomers include monofunctional monomers and polyfunctional monomers.
Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers may be used alone or in combination of two or more.

  Polyfunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di ( (Meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, penta Erythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol Acrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxy Propyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate Di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie tolylene diisocyanate), trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate Reaction product, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyfunctional monomers such as a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers may be used alone or in combination of two or more.

  The content of the (B) photopolymerizable monomer in the negative photosensitive resin composition is preferably 10 to 200 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the (A) alkali-soluble resin. -80 mass parts is more preferable. When the content of the (B) photopolymerizable monomer in the negative photosensitive resin composition is within this range, the curability and patterning characteristics of the negative photosensitive resin composition are improved.

[(C) Compound represented by Formula (1)]
The negative photosensitive resin composition contains a compound represented by the following formula (1). By adding a compound represented by the following formula (1) to the negative photosensitive resin composition, the resolution of the thick photosensitive resin layer formed using the negative photosensitive resin composition is improved. Can be made. In addition, when the negative photosensitive resin composition contains a compound represented by the following formula (1), when the resist pattern is formed on the substrate using the negative photosensitive resin composition, the substrate and the resist pattern Adhesiveness can be improved.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of R ¹ and R ² represents an organic group.

Examples of the organic group in R ¹ and R ² include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic. This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.

R ¹ and R ² may be bonded to each other to form a cyclic structure, and may further include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired, and includes a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. It is done. Specific examples include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (—N═C (—R) —, —C (═NR) —: R is A hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.

From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group of R ¹ and R ² includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond ( -N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group. , Cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy Group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, alkyl ether group, alkenyl ether group, alkyl thioether group, alkenyl thioether group, aryl ether group, aryl thioether Group, an amino group _{(-NH 2, -NHR, -NRR '} : R and R' each independently represent a hydrocarbon group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

Substituents other than hydrocarbon groups in the organic groups of R ¹ and R ² include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups. Group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, A phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an alkyl thioether group, an alkenyl thioether group, an aryl ether group, and an aryl thioether group are preferred.

Among the above, as R ¹ and R ² , at least one of them is an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or a heterocycloalkyl group having 2 to 20 carbon atoms bonded to each other. Alternatively, it preferably forms a heteroaryl group. Examples of the heterocycloalkyl group include a piperidino group and a morpholino group, and examples of the heteroaryl group include an imidazolyl group and a pyrazolyl group.

In the above formula (1), R ³ represents a single bond or an organic group.

Examples of the organic group for R ³ include groups in which one hydrogen atom has been removed from an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group, aralkyl group, and the like. This organic group may contain a substituent in the organic group. Examples of the substituent include those exemplified for R ¹ and R ² . Further, this organic group may be either linear or branched.

Among these, R ³ is preferably a single bond, or a group in which one hydrogen atom is removed from an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms.

In the above formula (1), R ⁴ and R ⁵ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group. A group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group;

Examples of the organic group for R ⁴ and R ⁵ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

Among these, R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, or 7 carbon atoms. -16 aryloxyalkyl group, C7-20 aralkyl group, C2-C11 alkyl group having a cyano group, C1-C10 alkyl group having a hydroxyl group, C1-C10 alkoxy group , An amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group. ), An aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted with an aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted benzyl group , Amino group is preferably a methylthio group. More preferably, both R ⁴ and R ⁵ are hydrogen atoms, or R ⁴ is a methyl group and R ⁵ is a hydrogen atom.

In the above formula (1), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, A sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group is shown.
Examples of the organic group for R ⁶ , R ⁷ , R ⁸ , and R ⁹ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

In the above formula (1), R ⁶ and R ⁷ do not become a hydroxyl group.

Two or more of R ⁶ , R ⁷ , R ⁸ , and R ⁹ may be bonded to form a cyclic structure, and may include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring. For ^{example, R 6, R 7, R} 8, and ^{R 9} may combine two or more of ^{them, R 6, R 7, R} 8, and share an atom of the benzene ring ^{to which R 9} is attached A condensed ring such as naphthalene, anthracene, phenanthrene, and indene may be formed.

Among these, R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, or a group having 4 to 13 carbon atoms. A cycloalkenyl group, an aryloxyalkyl group having 7 to 16 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, carbon C1-C10 alkoxy group, C2-C11 amide group, C1-C10 alkylthio group, C1-C10 acyl group, C2-C11 ester group, C6-C20 Aryl group, electron donating group and / or electron withdrawing group substituted aryl group having 6 to 20 carbon atoms, electron donating group and / or electron withdrawing group substituted benzyl group, cyano group, methylthio group, nitro On the basis Preferably there is.

In addition, as R ⁶ , R ⁷ , R ⁸ , and R ⁹ , two or more of them are bonded to share a benzene ring atom to which R ⁶ , R ⁷ , R ⁸ , and R ⁹ are bonded. In the case where condensed rings such as naphthalene, anthracene, phenanthrene, and indene are formed, it is preferable from the viewpoint that the absorption wavelength becomes longer.

More preferably, all of R ⁶ , R ⁷ , R ⁸ , and R ⁹ are hydrogen atoms, or any one of R ⁶ , R ⁷ , R ⁸ , and R ⁹ is a nitro group, and the remaining 3 One is a hydrogen atom.

In the formula ^{(1), R 10} represents a hydrogen atom or an organic group.

Examples of the organic group for R ¹⁰ include those exemplified for R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

Since the compound represented by the above formula (1) has an —OR ¹⁰ group at the para-position of the benzene ring, the solubility in a solvent is good.

Among these, R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.

  (C) Among the compounds represented by the above formula (1), particularly preferred specific examples include compounds represented by the following formulas.

  The compound represented by the above formula (1) is more preferably a compound that generates a base upon irradiation or heating.

  The method for synthesizing the compound represented by the above formula (1) is not particularly limited, but it can be synthesized according to the method described in Examples described later.

  Content of the compound represented by the said Formula (1) in a negative photosensitive resin composition is not specifically limited in the range which does not inhibit the objective of this invention. The content of the compound represented by the formula (1) is typically preferably 0.1 to 10 parts by mass, and 0.5 to 3 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. Is more preferable. By making the content of the compound represented by the above formula (1) in the negative photosensitive resin composition within such a range, the photosensitive property of the thick film formed using the negative photosensitive resin composition The resolution of the resin layer can be made particularly excellent.

[(D) Polymerization initiator]
The negative photosensitive resin composition may contain (D) a polymerization initiator. As the polymerization initiator (D), a conventionally known polymerization initiator capable of radical polymerization of the photopolymerizable monomer (B) can be used without any particular limitation.
Specifically, thioxanthone derivatives such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2-chlorothioxanthone, and 2,4-dimethylthioxanthone; benzophenone, N, N, N ′, N′-tetramethyl-4,4 ′ -Diaminobenzophenone, N, N, N ', N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholino Aromatic ketones such as phenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl 1,4- Quinones such as naphthoquinone and 2,3-dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl)- , 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4 2,4,5-triarylimidazole dimers such as 1,5-triarylimidazole dimer; acridine derivatives such as 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane; Oxime esters such as 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); N-phenylglycine; Can be mentioned.
These (D) polymerization initiators may be used alone or in combination of two or more. (D) When two or more polymerization initiators are used in combination, it is preferable to use a combination of an aromatic ketone-based polymerization initiator and a 2,4,5-triarylimidazole dimer.

  When the negative photosensitive resin composition contains (D) a polymerization initiator, the content of (D) the polymerization initiator is preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of (A) the alkali-soluble resin. 0.5 to 10 parts by mass is more preferable. When the content of the (D) polymerization initiator in the negative photosensitive resin composition is within this range, the curability of the negative photosensitive resin composition is improved.

[(E) solvent]
The negative photosensitive resin composition may contain a solvent (E) as necessary. By containing the (E) solvent in the negative photosensitive resin composition, the coating property of the negative photosensitive resin composition and the thick photosensitive resin layer formed using the negative photosensitive resin composition The film thickness can be adjusted.

As the solvent (E), conventionally known solvents for negative photosensitive resin compositions can be used without particular limitation.
Specifically, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like Propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Propylene glycol monoalkyl ether acetates such as propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; methyl lactate, ethyl lactate and n-propyl lactate Lactic acid esters such as isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate, etc. Aliphatic carboxylic acid esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Other esters such as ru, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; ketones such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N -Amides such as dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; and lactones such as γ-butyrolacun. These solvents may be used alone or in combination of two or more.

  In particular, when the negative photosensitive resin composition is used for thick film photosensitive dry film applications, the boiling point of the solvent (E) is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and particularly preferably 80 ° C. or lower. . Among the solvents having such a boiling point, 2-butanone (methyl ethyl ketone), tetrahydrofuran and the like are preferable.

  The content of the solvent (E) in the negative photosensitive resin composition is not particularly limited, but in general, the amount in which the solid content concentration of the negative photosensitive resin composition is 10 to 60% by mass is preferable, and 20 to 20%. An amount of 50% by mass is more preferable.

[(F) Other ingredients]
The negative photosensitive resin composition may contain an additional resin, a stabilizer, a colorant, a color former, a surfactant, and the like as desired.

  The negative photosensitive resin composition is prepared by uniformly mixing the components described above at a desired blending ratio.

≪Thick film photosensitive dry film≫
The thick film photosensitive dry film has a base film and a thick photosensitive resin layer formed on the surface of the base film, and this thick photosensitive resin layer is the above-mentioned negative photosensitive film. It consists of a resin composition.

  As a base film, what has a light transmittance is preferable. Specific examples include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, and the like, and a polyethylene terephthalate (PET) film is preferable in terms of excellent balance between light transmittance and breaking strength.

  When forming a thick photosensitive resin layer on a base film, an applicator, bar coater, wire bar coater, roll coater, curtain flow coater, etc. are preferably used for the film thickness after drying on the base film. Is applied to the negative photosensitive resin composition according to the present invention so as to have a thickness of 5 to 300 μm, more preferably 25 to 150 μm, and particularly preferably 40 to 130 μm, and is dried.

  The thick photosensitive dry film may further have a protective film on the photosensitive resin layer. Examples of the protective film include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, and a polyethylene (PE) film.

≪Method for forming thick film resist pattern≫
Using the above-mentioned negative photosensitive resin composition, a thick film resist pattern is formed by the following method. Specifically, a step of forming a thick photosensitive resin layer comprising a negative photosensitive resin composition on a substrate, a step of selectively exposing the thick photosensitive resin layer, and exposure were performed. A thick film resist pattern is formed by a method including a step of developing the thick photosensitive resin layer.

  The method for forming a thick photosensitive resin layer on the substrate is not particularly limited as long as the method can form a photosensitive resin layer having a desired thickness. For example, the above-mentioned negative photosensitive resin composition may be applied on a substrate, or the above-mentioned thick photosensitive dry film may be attached on the substrate. The method of applying the negative photosensitive resin composition on the substrate is not particularly limited, and contact transfer type coating devices such as roll coaters, reverse coaters, bar coaters, spinners (rotary coating devices), curtain flow coaters, etc. A method using a contact-type coating apparatus is exemplified. When the negative photosensitive resin composition contains the solvent (E), the coating film formed on the substrate is heated as necessary, and the photosensitive resin layer is removed by removing the solvent (E) from the coating film. It is formed. The film thickness of the thick photosensitive resin layer is preferably 5 to 300 μm, particularly preferably 25 to 150 μm and 40 to 130 μm.

The thick photosensitive resin layer formed by the method as described above is selectively exposed according to the pattern shape of the thick film resist pattern. The selective exposure of the thick photosensitive resin layer is usually performed through a mask having a shape corresponding to the pattern shape of the thick film resist pattern. Examples of the radiation used for the exposure include ultraviolet rays, electron beams, and laser beams emitted from a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a g-line stepper, an i-line stepper, and the like. The amount of exposure varies depending on the light source used, the thickness of the coating film, and the like, but is usually 1 to 1000 mJ / cm ² , preferably 10 to 500 mJ / cm ² .

  The thick film resist pattern is developed by dissolving and removing the uncured portion of the selectively exposed thick film photosensitive resin layer using a developer. As the developer, an alkali developer, that is, alkali metal hydroxides such as lithium, sodium, potassium, carbonates, bicarbonates, phosphates, pyrophosphates; primary amines such as benzylamine and butylamine; dimethyl Secondary amines such as amine, dibenzylamine and diethanolamine; tertiary amines such as trimethylamine, triethylamine and triethanolamine; cyclic amines such as morpholine, piperazine and pyridine; polyamines such as ethylenediamine and hexamethylenediamine; tetraethylammonium hydroxy Ammonium hydroxide such as trimethylbenzylammonium hydroxide, trimethylphenylbenzylammonium hydroxide; trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide And aqueous solutions comprising sulfonium hydroxides such as dimethylbenzylsulfonium hydroxide; other general-purpose alkaline developers such as choline and silicate-containing buffers; organic solvents such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, Ketones such as 2-heptanone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or their monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Polyhydric alcohols and derivatives thereof such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, Ethyl bottles acid, methyl methoxypropionate, can be used esters such as ethyl ethoxypropionate.

  In addition, as an application example of a method of forming a thick film resist pattern using a thick film photosensitive dry film, a method of forming a plating pattern using a thick film photosensitive dry film will be described below.

  When the thick film photosensitive dry film includes a protective film, first, the protective film is peeled off from the thick film photosensitive dry film. Next, the exposed photosensitive resin layer side is applied to a workpiece (substrate), and a photosensitive dry film is deposited on the substrate. For deposition, a so-called thermocompression bonding method is generally employed in which a substrate is heated in advance and a photosensitive dry film is placed on the substrate and pressed. Examples of the workpiece include an electrolytic copper foil substrate, an electroless copper plated substrate, a sputtered copper foil substrate, and a glass substrate. When the workpiece is an electrolytic copper foil substrate, the thermocompression bonding heats the surface temperature of the electrolytic copper foil substrate to 80 to 140 ° C., roll pressure 0.1 to 0.5 MPa (G), and movement speed 0.1 to It is good to carry out in the range of 10.0 m / min. The said electrolytic copper foil board | substrate may be pre-heated, and the range of 40-100 degreeC is selected as preheating temperature, for example.

  Next, the photosensitive resin layer on which the base film is laminated is selectively exposed by exposing through a mask or direct drawing exposure. The exposure method is as described above.

After the exposure, the base film is peeled off and developed to selectively remove the unexposed portions of the photosensitive resin layer, thereby forming a thick film resist pattern in which the exposed photosensitive resin layer remains. As the treatment after development, the thick film resist pattern may be further cured by heating at about 60 to 250 ° C. or exposure at about 100 to 2000 mJ / cm ² as necessary.

  Next, using the thick film resist pattern as a mask, the metal wiring pattern is formed by etching the substrate or plating the thick film resist pattern non-formed portion.

  Thereafter, the thick film resist pattern is peeled and removed from the substrate with an aqueous solution having a pH of about 12 to 14 containing sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide (TMAH), organic amines and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

In the examples, the following compounds C-1 and C-2 were used as the compound represented by the formula (1). As C-1 and C-2, those prepared according to Synthesis Examples 1 and 2 below were used. In Comparative Examples 4 and 5, a compound C-3 represented by the following formula was used instead of the compound represented by the formula (1).

[Synthesis Example 1]
3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, and triethylamine 4.59 ml (equivalent ratio 1.1) and imidazole 2.25 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The reaction mixture was washed with 50 ml of water, 50 ml of saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain C-1 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis Example 2]
3- (4-Methoxyphenyl) acrylic acid chloride 5.90 g (30 mmol) was dissolved in 50 ml of dry ether, triethylamine 4.59 ml (equivalent ratio 1.1), diethylamine 2.41 ml (equivalent ratio 1.1). And stirred at room temperature for 1 hour. The extract was washed with 50 ml of water, 50 ml of a saturated aqueous NaHCO ₃ solution, and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain C-2 (4.65 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Example 1]
100 parts by mass of a copolymer of 20 mol% methacrylic acid and 80 mol% benzyl methacrylate (mass average molecular weight 70000, acid value 190 mgKOH / g), trimethylolpropane triacrylate (Aronix (registered trademark) M309, manufactured by Toagosei Co., Ltd.) ) 40 parts by mass, 30 parts by mass of tetraethylene glycol dimethacrylate, 0.2 parts by mass of N, N, N ′, N′-tetraethyl-4,4′-diaminobenzophenone, 2- (o-chlorophenyl) -4,5 -Diphenyl imidazole dimer 4.0 mass part, dye (diamond green) 0.2 mass part, and C-1, 1.0 mass part is mixed uniformly, and the negative type for thick films of Example 1 A photosensitive resin composition was obtained.

[Comparative Example 1]
A negative photosensitive resin composition for thick film of Comparative Example 1 was obtained in the same manner as Example 1 except that C-1 was not used.

[Example 2]
After the photosensitive resin composition of Example 1 was applied onto a PET film with an applicator, the coating film was dried to obtain a thick film photosensitive dry film of Example 2 having a photosensitive resin layer having a thickness of 120 μm. It was.

[Comparative Example 2]
A thick photosensitive dry film of Comparative Example 2 was obtained in the same manner as the thick photosensitive dry film of Example 2 except that the photosensitive resin composition of Comparative Example 1 was used.

[Example 3]
Using the thick photosensitive dry film of Example 2, using a dry film laminator (EXL-1200HSF1-CE, manufactured by Teikoku Taping System Co., Ltd.), speed 1 m / min, pressure 0.5 MPa (G), stage temperature A thick photosensitive resin layer was attached to the surface of the copper sputter wafer substrate at 80 ° C. and a roll temperature of 30 ° C. to form a 120 μm-thick photosensitive resin layer on the substrate. The formed photosensitive resin layer is selected by “PLA-501F” (manufactured by Canon Inc.) at the exposure amount shown in Table 1 so that holes having the opening diameters shown in Table 1 are formed after development. Exposed to light. The photosensitive resin layer after exposure was spray-developed using a sodium carbonate aqueous solution having a concentration of 1% by mass as a developer under the conditions of a spray pressure of 0.12 MPa and a development time of 360 seconds. A thick film resist pattern having holes was formed. The cross section of the formed thick film resist pattern was observed by SEM, and the quality of the pattern shape was determined. A case where a cylindrical hole reaching the bottom of the thick film resist pattern was formed was judged as ◯, and a case where the hole did not reach the bottom of the thick film resist pattern was judged as x. Table 1 shows the determination results of the pattern shape for each exposure condition.

[Comparative Example 3]
A thick resist pattern was formed in the same manner as in Example 3 except that the thick photosensitive dry film of Comparative Example 2 was used. The quality of the pattern shape of the hole pattern formed in Comparative Example 3 was determined in the same manner as in Example 3. Table 1 shows the determination results of the pattern shape for each exposure condition.

  From the result of Comparative Example 3, when forming a thick photosensitive resin layer using a negative photosensitive resin composition for a thick film that does not contain the compound represented by formula (1), a hole having a good shape It can be seen that can be formed up to a hole having an opening diameter of 60 μm. On the other hand, from the result of Example 3, when forming the thick photosensitive resin layer using the negative photosensitive resin composition for thick film containing the compound represented by the formula (1), the opening diameter is 20 μm. It can be seen that the holes can be formed satisfactorily. That is, the negative photosensitive resin composition for thick film containing the compound represented by Formula (1) is excellent in resolution.

[Examples 4 to 6 and Comparative Examples 4 and 5]
As the component (C) or a component corresponding to the component (C) (referred to as a photobase generator in Table 2 below), the compound described in Table 2 below was used in an amount other than the amount shown in Table 2 below. A negative photosensitive resin composition for Example 1 and a thick film was prepared. A thick photosensitive dry film was prepared in the same manner as in Example 2 using the obtained negative photosensitive resin composition for thick film. A hole pattern was formed in the same manner as in Example 3 except that exposure was performed at an exposure amount of 150 mJ / cm ² using the obtained thick photosensitive dry films of Examples and Comparative Examples. When forming the hole pattern, after forming the hole pattern a plurality of times while changing the opening diameter of the hole by 5 μm from 20 μm to 100 μm, the shape of the formed hole pattern is determined according to the criteria described in Example 3. The minimum hole opening diameter (minimum resolution dimension) capable of forming a hole pattern as a judgment was measured. The measurement results of the minimum resolution dimension are shown in Table 2.

  According to Examples 3 to 6, when the photosensitive resin composition contains the compound represented by the general formula (1) as the component (C), the thick photosensitive resin layer is exposed and developed to reduce the diameter. It can be seen that a pattern having holes can be formed. On the other hand, according to Comparative Examples 3 to 5, the photosensitive resin composition does not include the compound represented by the general formula (1) or does not include the compound represented by the general formula (1). It is understood that a pattern having a small-diameter hole cannot be formed by exposing and developing a thick photosensitive resin layer when a compound having a structure similar to) is included.

Claims (6)

A negative photosensitive resin for a thick film having a film thickness of 5 to 300 μm, comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a compound represented by the following formula (1). Composition.

(Wherein, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic group. However, .R ¹ and ^{R 2} represents an organic group at least one of the ^{R 1} and ^{R 2} are they are attached may form a cyclic structure, optionally .R ³ also contain binding heteroatoms, .R ⁴ and R ⁵ represents a single binding are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto Group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group, R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group , Sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, or organic group, provided that R ⁶ and R ⁷ do not become a hydroxyl group, R ⁶ , R ⁷ , R ⁸ and R ⁹ may be bonded to each other to form a cyclic structure, and may include a heteroatom bond, and R ¹⁰ represents a hydrogen atom or an organic group.) The negative photosensitive resin composition for thick films according to claim 1, wherein the (A) alkali-soluble resin has a mass average molecular weight of 5,000 to 200,000. The negative photosensitive resin composition for thick films according to claim 1 or 2 , wherein the acid value of the (A) alkali-soluble resin is 15 mgKOH / g or more. Furthermore, (D) The negative photosensitive resin composition for thick films of any one of Claims 1-3 containing a polymerization initiator. A base film and a thick photosensitive resin layer formed on the surface of the base film, the thickness of the thick photosensitive resin layer is 5 to 300 μm, and the thick film thick photosensitive dry film photosensitive resin layer is formed of negative photosensitive resin composition according to any one of claims 1-4. Forming a thick photosensitive resin layer comprising the negative photosensitive resin composition according to any one of claims 1 to 4 on a substrate;
Selectively exposing the thick photosensitive resin layer;
A step of developing the exposed photosensitive resin layer having a thick film , wherein the thick photosensitive resin layer has a thickness of 5 to 300 μm. Method for forming a film resist pattern .