JP2011186214A - Photosensitive resin composition - Google Patents

Abstract

Photosensitive resin composition and photosensitive resin laminate capable of forming a resist pattern with excellent adhesion to a substrate, good image-forming properties, and little composition exudation and sublimation products even when used for a long time Body offer.
(A) An alkali-soluble polymer having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, 30 to 70% by mass; (B) Compound 20 having an ethylenically unsaturated double bond -60 mass%, (C) a photopolymerization initiator 0.1-20 mass%, and (F) a nonionic compound having an absorption maximum in the range of 455-600 nm and a melting point of 120 ° C or higher. A photosensitive resin composition comprising:
[Selection figure] None

Description

  The present invention relates to a photosensitive resin composition and a laminate, and relates to a method for producing a resist pattern having excellent adhesion, good colorability, excellent color stability during heating, and less generation of sublimates.

  As the electronic material or the display material, a fine structure material using a photosensitive resist pattern is widely used. Some applications require that the resist pattern be colored. For example, a light shielding layer called a color filter or a black matrix of a liquid crystal display. In general, a colored photosensitive resist pattern is added with a pigment or a dye for the purpose of coloring in the visible light region. However, these colorants absorb the light having the exposure wavelength, and are exposed and cured to the bottom. It becomes difficult. There was a problem of ensuring such adhesion. Such a problem becomes conspicuous when the film thickness is increased, but as a technique relating to this, a black photosensitive fat composition containing red, yellow and blue pigments is disclosed (Patent Document 1).

  In general, when a photosensitive resist pattern is used as a permanent pattern for an electronic material or a display material, the adhesion between the resist pattern and the substrate is excellent, the image forming property is good, and even if used for a long time, from the resist pattern A resist pattern in which there is little exudation and sublimation of the composition is preferred.

JP 2008-304710 A

  It is an object of the present invention to provide a photosensitive resin composition and a photosensitive resin laminate capable of forming a resist pattern having excellent adhesion, excellent colorability, excellent color stability during heating, and less generation of sublimates. To do.

  The present inventor has found that by using a specific photosensitive resin composition, it is possible to form a resist pattern having excellent adhesion, good colorability, excellent color stability during heating, and less generation of sublimates. . That is, the present invention is as follows.

  [1] (A) 30 to 70% by mass of an alkali-soluble polymer having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, (B) Compound 20 having an ethylenically unsaturated double bond 60% by mass, (C) 0.1-20% by mass of photopolymerization initiator, and (F) a nonionic compound having an absorption maximum in the range of 455-600 nm and a melting point of 120 ° C. or higher. The photosensitive resin composition characterized by the above-mentioned.

｛式中、Ｒ^１は、水素または炭素数１〜４のアルキル基であり、そしてＲ^２は、水素、水酸基、カルボキシル基、ハロゲン基、炭素数１〜４のアルキル基、置換基を有してもよいアミノ基、置換基を有してもよいアミド基、ニトロ基、またはスルホニル基を表す。｝
で表される基を有する、前記［１］に記載の感光性樹脂組成物。 [2] The nonionic compound (F) has the following formula (I) in its molecule:

{Wherein R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ² has hydrogen, a hydroxyl group, a carboxyl group, a halogen group, an alkyl group having 1 to 4 carbon atoms, or a substituent. An amino group that may be substituted, an amide group that may have a substituent, a nitro group, or a sulfonyl group. }
The photosensitive resin composition as described in said [1] which has group represented by these.

  [3] The photosensitive resin composition according to [2], wherein the nonionic compound (F) has two or more groups represented by the formula (I) in its molecule.

  [4] A photosensitive resin laminate in which a photosensitive resin layer made of the photosensitive resin composition according to any one of [1] to [3] is laminated on at least a support layer.

  [5] A method for forming a resist pattern, comprising a step of laminating the photosensitive resin laminate according to the above [4] on a substrate, an exposure step, and a development step.

  [6] A resist pattern forming method including a step of laminating the photosensitive resin laminate according to the above [4] on a substrate, an exposure step, a development step, and a baking step.

  By using the photosensitive resin composition of the present invention, it is possible to form a resist pattern having excellent adhesion, good colorability, excellent color stability during heating, and less generation of sublimates.

  In the photosensitive resin composition of the present invention, (A) an alkali-soluble polymer having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000 is 30 to 70% by mass, and (B) an ethylenically unsaturated dimer. 20 to 60% by mass of a compound having a heavy bond, (C) 0.1 to 20% by mass of a photopolymerization initiator, and (F) an absorption maximum in the range of 455 to 600 nm and a melting point of 120 ° C. or higher. It contains certain nonionic compounds.

<(F) Nonionic compound>
(F) A nonionic compound is demonstrated.
In the present invention, the (F) nonionic compound has an absorption maximum in the range of 455 to 600 nm, more preferably in the range of 455 to 550 nm.

  The wavelength of the absorption maximum is larger than 455 nm from the viewpoint of adhesion. Moreover, in order to have sufficient coloring property when combined with a green or blue dye, the wavelength of the absorption maximum is smaller than 600 nm. More preferably, the wavelength of the absorption maximum is 550 nm or less.

In the present invention, the absorption maximum is confirmed as follows.
In the present invention, (A) 60 parts by mass of an alkali-soluble polymer, (B) 40 parts by mass of a compound having an ethylenically unsaturated double bond, and (F) 0.1 part by mass of a nonionic compound, using methyl ethyl ketone as a solvent. Mix uniformly at a solid content of 50% by weight. The obtained resin composition solution is uniformly applied to a PET film with a bar coater. The film thickness is adjusted to 50 um after drying. The transmittance of the obtained film is measured for each wavelength, and the wavelength having the largest absorption is taken as the absorption maximum.

  (F) Melting | fusing point of a nonionic compound is 120 degreeC or more from a viewpoint of a sublimate generation amount. The melting point is more preferably 130 ° C. or higher, and further preferably 140 ° C. or higher.

｛式中、Ｒ^１は水素または炭素数１〜４のアルキル基、Ｒ^２は水素、水酸基、カルボキシル基、ハロゲン基、炭素数１〜４のアルキル基、置換基を有してもよいアミノ基、置換基を有してもよいアミド基、ニトロ基、またはスルホニル基を表す。｝ In the present invention, the nonionic compound (F) is represented by the following formula (I):

{In the formula, R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ² is hydrogen, a hydroxyl group, a carboxyl group, a halogen group, an alkyl group having 1 to 4 carbon atoms, or an amino group which may have a substituent. Represents an amide group, a nitro group, or a sulfonyl group which may have a substituent. }

It is preferable that the compound which has group represented by these is included.

R ¹ is preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of colorability and solubility in an organic solvent, and a methyl group is preferred from the viewpoint of synthetic yield. R ² is preferably a hydroxyl group from the viewpoint of the maximum absorption wavelength, solubility in an organic solvent, and colorability.

  In the present invention, the amount of the nonionic compound (F) having a group represented by the formula (I) is preferably 0.01% by mass to 1% by mass with respect to 100 parts by mass of the photosensitive resin composition. 0.01 mass% or more is preferable from a viewpoint of coloring property, and 1 mass% or less is preferable from a viewpoint of the sensitivity of the photosensitive resin composition. (F) The compounding quantity of a nonionic compound becomes like this. More preferably, it is 0.05-0.7 mass%, More preferably, it is 0.1-0.5 mass%.

下記式（ＩＩＩ）：

及び下記式（ＩＶ）：

などで表される化合物が挙げられる。 In the present invention, when the (F) nonionic compound has two or more groups represented by the formula (I) in the molecule, the colorability, heat resistance, and photosensitive resin laminate are obtained. It is preferable from the viewpoint of colorability to the protective layer. Examples of such a compound include the following formula (II):

Formula (III) below:

And the following formula (IV):

And the like.

<(A) Alkali-soluble polymer>

Next, (A) the alkali-soluble polymer will be described.
In the present invention, the (A) alkali-soluble polymer refers to a resin that is soluble in an alkaline aqueous solution. As long as it is soluble in an alkaline aqueous solution, it may be soluble in other liquids. (A) Examples of the alkali-soluble polymer include vinyl resins containing carboxyl groups, polyvinyl alcohol and derivatives thereof, polyvinyl ether, polyethylene glycol, polyhydroxystyrene and derivatives thereof, polyamic acid resins and derivatives thereof, novolak resins and derivatives thereof. , Cellulose and its derivatives. Among these, a vinyl resin containing a carboxyl group is preferable from the viewpoints of solubility in an organic solvent, film-forming properties when a photosensitive resin laminate is used, and laminating properties. For example, it is a copolymer such as (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide.

  (A) The alkali-soluble polymer contains a carboxyl group and has an acid equivalent of 100 to 600. The acid equivalent means the mass of the alkali-soluble polymer having 1 equivalent of a carboxyl group therein. The acid equivalent is more preferably 250 or more and 450 or less. The acid equivalent is 100 or more from the viewpoint of improving development resistance and improving resolution and adhesion, and is 600 or less from the viewpoint of improving developability and peelability. The acid equivalent is measured by a potentiometric titration method using Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. and 0.1 mol / L sodium hydroxide.

  (A) The weight average molecular weight of the alkali-soluble polymer is 5,000 or more and 500,000 or less. (A) The weight average molecular weight of the alkali-soluble polymer is 500,000 or less from the viewpoint of improving the developability, the properties of the development aggregate, the edge fuse property when the photosensitive resin laminate is used, and the cut chip property From the viewpoint of the properties of the unexposed film such as 5,000 or more. The edge fuse property refers to a phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll. The cut chip property is the phenomenon that the chip flies when the unexposed film is cut with a cutter. If the chip adheres to the top surface of the photosensitive resin laminate, it is transferred to the mask during the subsequent exposure process, etc. It becomes. The weight average molecular weight of the alkali-soluble polymer is more preferably 20,000 or more and 200,000 or less, and more preferably 40,000 or more and 70,000 or less. The weight average molecular weight was measured by Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M). , KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) as polystyrene conversion.

  (A) The alkali-soluble polymer is preferably a copolymer comprising at least one or more of the first monomers described below and at least one or more of the second monomers described below.

  The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Particularly preferred is (meth) acrylic acid. Here, (meth) acryl refers to acryl and / or methacryl. The same applies hereinafter.

  The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl alcohol esters such as vinyl acetate, (meth) Examples include acrylonitrile, styrene, and styrene derivatives. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferable. From the viewpoint of adhesion of the resist pattern, benzyl (meth) acrylate is preferred.

  The copolymerization ratio of the first monomer and the second monomer is preferably 10 to 60% by mass of the first monomer and 40 to 90% by mass of the second monomer. More preferably, the first monomer is 15 to 35% by mass, and the second monomer is 65 to 85% by mass.

  Preferred combinations of the first monomer and the second monomer include the following combinations. That is, butyl acrylate, methyl methacrylate, methacrylic acid copolymer, styrene, methyl methacrylate, methacrylic acid copolymer, styrene, benzyl methacrylate, methacrylic acid copolymer, benzyl methacrylate, methacrylic acid A copolymer, a benzyl methacrylate, 2-ethylhexyl acrylate, a copolymer of methacrylic acid, etc. can be mentioned. A combination of benzyl methacrylate, 2-ethylhexyl acrylate, and a copolymer of methacrylic acid is preferable from the viewpoint of imparting appropriate flexibility to the resist pattern and obtaining adhesion.

  (A) The compounding quantity of alkali-soluble polymer is the range of 30-70 mass% with respect to 100% of total solid of the photosensitive resin composition, Preferably it is 40-60 mass%. From the viewpoint of development time, it is 70% by mass or less, and from the viewpoint of edge fuse property, it is 30% by mass or more.

<(B) Compound having an ethylenically unsaturated double bond>
Next, (B) the compound having an ethylenically unsaturated double bond will be described.
(B) The compound having an ethylenically unsaturated double bond is preferably a compound having an acryloyl group in the molecule from the viewpoint of curability and compatibility with an alkali-soluble resin.

  For example, a compound in which (meth) acrylic acid is added to one end of polyalkylene oxide, or (meth) acrylic acid is added to one end and the other end is converted to alkyl ether or allyl ether. Can do.

  As such a compound, phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to a phenyl group, or polypropylene glycol added with an average of 2 mol of propylene oxide and an average of 7 mol of 4-Normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth) acrylate, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol with addition of ethylene oxide to nonylphenol, average of 5 with polypropylene glycol with addition of 1 mol of propylene oxide on average 4-normal nonyl which is a (meth) acrylate of a compound obtained by adding polyethylene glycol added with moles of ethylene oxide to nonylphenol E Bruno carboxymethyl pentaethylene glycol monopropylene glycol (meth) acrylate. Examples also include 4-normal nonylphenoxyoctaethylene glycol (meth) acrylate (manufactured by Toagosei Co., Ltd., M-114), which is an acrylate of a compound obtained by adding polyethylene glycol with an average of 8 moles of ethylene oxide added to nonylphenol.

  For example, a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain or a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in blocks. be able to.

  Examples of such compounds include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, and octaethylene glycol di (meth). Examples thereof include acrylates, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of 12 moles of ethylene oxide chain. Furthermore, a polyalkylene oxide di (meth) acrylate compound containing at least an ethylene oxide group and a propylene oxide group in the compound is preferable from the viewpoints of resolution, flexibility, and plating resistance. From the same viewpoint, the molecular weight is preferably 600-1500. More preferably, it is 900-1300, More preferably, it is 1000-1200. Examples of the polyalkylene oxide di (meth) acrylate compound containing at least an ethylene oxide group and a propylene oxide group in the compound include, for example, glycol in which ethylene oxide is further added to both ends at an average of 3 mol on polypropylene glycol added with an average of 12 mol of propylene oxide. And diglycol of glycol obtained by adding an average of 15 moles of ethylene oxide to both ends of polypropylene glycol having an average of 18 moles of propylene oxide added thereto.

  A compound having bisphenol A modified with alkylene oxide and having (meth) acryloyl groups at both ends is preferred from the viewpoints of adhesion and plating resistance. Examples of the alkylene oxide modification include ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and hexylene oxide modification. A compound having bisphenol A modified with ethylene oxide and having (meth) acryloyl groups at both ends is preferred. As such a compound, for example, 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Roxypentaethoxy) phenyl) propane (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2 2-bis (4-((meth) acryloxynonaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxyundecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2 2,2-bis (4-((meth) acryloxypolyether) such as 2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) propane ) Phenyl) propane and the like. Furthermore, di (meth) acrylate of polyalkylene glycol obtained by adding an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide to both ends of bisphenol A, or an average of 2 mol of propylene oxide and an average of 15 respectively at both ends of bisphenol A Preference is also given to compounds modified with ethylene oxide and propylene oxide, such as di (meth) acrylates of polyalkylene glycols to which a molar amount of ethylene oxide has been added. The number of moles of ethylene oxide in the compound having a (meth) acryloyl group at both ends modified with alkylene oxide of bisphenol A is preferably 10 to 30 moles from the viewpoint of adhesion, plating resistance and flexibility. 20 mol or less is more preferable.

  For example, a compound having more than 2 (meth) acryloyl groups in one molecule has at least 3 moles of a group to which an alkylene oxide group can be added in the molecule as a central skeleton, and an ethylene oxide group and propylene oxide or It can be obtained by using an alcohol obtained by adding an alkylene oxide group such as butylene oxide as a (meth) acrylate. Examples of compounds that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.

  Examples of such compounds include trimethylolpropane EO3 mol-modified triacrylate, trimethylolpropane EO6 mol-modified triacrylate, trimethylolpropane EO9 mol-modified triacrylate, trimethylolpropane EO12 mol-modified triacrylate, and the like. Can do. Examples of such compounds include glycerol EO3 mol-modified triacrylate (A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.), glycerol EO9 mol-modified triacrylate (Shin-Nakamura Chemical Industry Co., Ltd. A-GLY-). 9E), EO 6 mol PO6 mol modified triacrylate of glycerin (A-GLY-0606PE), EO 9 mol PO9 mol modified triacrylate of glycerin (A-GLY-0909PE). As such compounds, pentaerythritol 4EO-modified tetraacrylate (SR-494 manufactured by Sartomer Japan Co., Ltd.), pentaerythritol 35EO-modified tetraacrylate (NK Nakamura Chemical Co., Ltd. NK ester ATM-35E) ).

  In addition to the above compounds, the following compounds can be included as appropriate. For example, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi (meth) acrylate, 2,2-bis [(4- (Meth) acryloxypolypropyleneoxy) phenyl] propane, 2,2-bis [(4- (meth) acryloxypolybutyleneoxy) phenyl] propane, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Polyoxypropyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, β-hydroxypropyl-β '-(acryloyloxy) propyl Examples thereof include tartrate, nonylphenoxypolypropylene glycol (meth) acrylate, nonylphenoxypolybutylene glycol (meth) acrylate, and polypropylene glycol mono (meth) acrylate. Furthermore, the following urethane compounds are also mentioned. For example, hexamethylene diisocyanate, tolylene diisocyanate or diisocyanate compound (for example, 2,2,4-trimethylhexamethylene diisocyanate) and a compound having a hydroxyl group and a (meth) acryl group in one molecule, for example, 2-hydroxypropyl Examples thereof include urethane compounds with acrylates and oligopropylene glycol monomethacrylates. Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Blenmer PP1000). In addition, diisocyanate or di (tri) acrylate of isocyanurate modified with polypropylene glycol or polycaprolactone is also included. Moreover, the urethane oligomer obtained by making the terminal of the urethane compound obtained as a polyaddition product of a diisocyanate and a polyol react with the compound which has an ethylenically unsaturated double bond and a hydroxyl group etc. can be mentioned, for example.

  (B) The compounding quantity of the compound which has an ethylenically unsaturated double bond is 20-60 mass% with respect to 100 mass% of total solid content of the photosensitive resin composition. (B) The compounding quantity of the compound which has an ethylenically unsaturated double bond is 20 mass% or more from a viewpoint of a sensitivity, resolution, and adhesiveness, and is 60 mass% or less from a viewpoint of resolution and adhesiveness. is there. Also from the viewpoint of film physical properties of an unexposed film when coated on a support film to form a dry film, it is 60% by mass or less, and more preferably 30 to 45% by mass.

<(C) Photopolymerization initiator>
Next, (C) the photopolymerization initiator will be described.
In the present invention, (C) the photopolymerization initiator alone absorbs light at the exposure wavelength, cures the photosensitive resin composition, and makes it insoluble in the developer, and alone the photosensitive resin composition. However, the effect of the photopolymerization initiator is promoted by using it in combination with the photopolymerization initiator. However, in the present invention, (D) leuco dye is not included in (C) the photopolymerization initiator.

  (C) Photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters , Acridines, hexaarylbiimidazole, pyrazoline derivatives, N-arylamino acids or ester compounds thereof, and halogen compounds.

  As quinones, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2 And quinones such as 3-dimethylanthraquinone and 3-chloro-2-methylanthraquinone.

  Examples of aromatic ketones include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone. Can do.

  Examples of acetophenones include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and 1- (4 -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-benzyl- Mention may be made of 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Examples of acylphosphine oxides include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phosphine oxide, and bis (2,6-dimethoxybenzoyl) -2. , 4,4-trimethyl-pentyl phosphine oxide and the like. Commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

  Examples of benzoin or benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.

  Examples of dialkyl ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of thioxanthones include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

  Examples of the dialkylaminobenzoates include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4- (dimethylamino) benzoate and the like.

  Examples of the oxime esters include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. Examples of commercially available products include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals.

  Examples of acridines include 1,7-bis (9,9′-acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9- Ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- ( 4-tert-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9- (4-bromophenyl) acrylic Gin, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3- Diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine Can be mentioned.

  Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ′ , 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole,

2,2′-bis- (2,3-difluoromethylphenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4 -Difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,5-difluorophenyl) -4,4', 5 5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,6-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl)- Biimidazole, 2,2′-bis- (2,3,4-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis -(2,3,5-trifluoroph Nyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,6-trifluorophenyl) -4,4 ′, 5 , 5′-Tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3- Methoxyphenyl) -biimidazole, 2,2′-bis- (2,4,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2, 2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2 , 3,4,6-tetrafluorophenyl) -4, ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, and 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5 Examples include 5'-tetrakis- (3-methoxyphenyl) -biimidazole.

  Examples of the pyrazoline derivative include 1- (4-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4- tert-butyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-butyl-phenyl) -3- (4-tert-butyl-styryl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-ethoxy-phenyl) -pyrazoline, 1-phenyl-3- (4-tert- Octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline,

1,5-bis- (4-tert-octyl-phenyl) -3- (4-tert-octyl-styryl) -pyrazoline, 1- (4-dodecyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-dodecyl-stynyl) -5- (4 -Dodecyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4 -Tert-butyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-dodecyl- Enyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1 -(4-tert-octyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (2,4-dibutyl-phenyl) -3- (4- Dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1-phenyl-3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert Butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,6-di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3 -(2,5-di-tert-butyl-styryl) -5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,6-di-n-butyl- Styryl) -5- (2,6-di-n-butyl-phenyl) -pyrazoline, 1- (3,4-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- ( 3,5-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3,5-di-tert-butyl-phenyl) -5-phenyl-pi Lazoline, 1- (3,5-di-tert-butyl-phenyl) -3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl)- Pyrazoline, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl)- 3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (4-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazolin, 1- (4- (5-tert-octyl-benzoxazol-2-yl) fe Le) -3-styryl-5-phenyl - pyrazoline,

1- (4- (Benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5- tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl- Benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4 -Dodecyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-stynyl) -5 4-dodecyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert- Butyl-phenyl) -pyrazolin, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl- Phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline , 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodeci - phenyl) - pyrazoline,

  1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4 -(5-tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (4,6- Dibutyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl)- 3- (3,5-di-tert-butylstyryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (2,6-di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (2,5-di-tert-butyl-styryl) -5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (2,6-di-n-butyl-styryl) -5- (2,6-di-n-butyl-phenyl) -pyrazoline, 1- (4- (4,6-di-tert) -Butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazolin, 1- (4- (5,7-di-tert-butyl-benzoxazol-2-yl) phenyl) -3 -Styryl-5-pheny -Pyrazoline, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3,5-di-tert-butyl-styryl) -5-phenyl-pyrazoline, 1- ( 4- (4,6-di-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert- Butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-amino-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-N-ethyl-phenyl) -pyrazoline and 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-N, N-diethyl-phenyl) -pyrazoline It is done.

  Further, for example, 1-phenyl-3- (4-biphenyl) -5- (4-n-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl) -Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-isobutyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-n-pentyl) -Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-isopentyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-neopentyl-phenyl) ) -Pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-hexyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-hept Ru-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-n-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4- tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-nonyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4- Decyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-undecyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-dodecyl- Phenyl) -pyrazoline.

  Among them, from the viewpoint of adhesion and rectangularity of the resist pattern, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-Biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferred.

  It is preferable that a pyrazoline derivative is 0.01-0.3 mass% with respect to 100 mass% of solid content of the photosensitive resin composition. 0.01 mass% or more is preferable from a viewpoint of sensitivity, and 0.3 mass% or less is preferable from an adhesive viewpoint.

  Examples of N-aryl amino acids or ester compounds thereof include N-phenylglycine, methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, and isopropyl of N-phenylglycine. Ester, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, N-phenyl Examples include pentyl ester of glycine and octyl ester of N-phenylglycine. In particular, N-phenylglycine is preferable because of its high sensitizing effect.

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds, diallyl iodonium compounds, and the like. It is done.

  (C) 0.1-20 mass% of photoinitiators are contained with respect to 100 mass% of solid content of the photosensitive resin composition. It is 0.1% by mass or more from the viewpoint of practical photosensitivity and resist pattern adhesion, and is 20% by mass or less from the viewpoint of solubility in scum and organic solvent generated in the developer. (C) As for the compounding quantity of a photoinitiator, 0.1-5 mass% is more preferable, and 0.5-1 mass% is further more preferable.

<(D) leuco dye>
The photosensitive resin composition of this invention can contain the (D) leuco dye as needed. A leuco dye is a colorless intermediate of a triphenylmethane dye and is also called a leuco base (see Iwanami Shoten, “Iwanami Physical Dictionary, 5th Edition”, page 1505).

  Examples of the leuco dye include tris (4-dimethylaminophenyl) methane, tris (4-diethylaminophenyl) methane, bis (4-diethylaminophenyl)-(4-diethylamino-2-methylphenyl) methane, and bis (4- Diethylamino-2-methylphenyl)-(4-diethylaminophenyl) methane, bis (1-ethyl-2-methylindol-3-yl) -phenylmethane, (4-dimethylamino-2-methoxyphenyl) -bis (4 -Dimethylaminophenyl) methane, (4-dimethylamino-2-ethoxyphenyl) -bis (4-dimethylaminophenyl) methane, (4-dimethylamino-2-butoxyphenyl) -bis (4-dimethylaminophenyl) methane , (4-Dimethylamino-2-chlorophenyl) -bi (4-dimethylaminophenyl) methane, (4-dimethylamino-2-fluorophenyl) -bis (4-dimethylaminophenyl) methane, (4-diethylamino-2-methoxyphenyl) -bis (4-diethylaminophenyl) methane (4-diethylamino-2-ethoxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-isopropoxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-butoxy Phenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-hexyloxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-octyloxyphenyl) -bis (4-diethylamino) Phenyl) Tan, (4-diethylamino-2-dodecyloxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-benzyloxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2) -Chlorophenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-fluorophenyl) -bis (4-diethylaminophenyl) methane, (4-dimethylamino-2-methoxyphenyl) -bis (4-diethylamino) Phenyl) methane, (4-dimethylamino-2-ethoxyphenyl) -bis (4-diethylaminophenyl) methane,

(4-Diethylamino-2-methoxyphenyl) -bis (4-dimethylaminophenyl) methane, (4-diethylamino-2-ethoxyphenyl) -bis (4-dimethylaminophenyl) methane, (4-piperidylino-2-ethoxy Phenyl) -bis (4-dimethylaminophenyl) methane, [4- (1-pyrrolidinyl) -2-ethoxyphenyl] -bis (4-diethylaminophenyl) methane, (4-morpholino-2-ethoxyphenyl) -bis ( 4-dimethylaminophenyl) methane, (4-piperidylino-2-ethoxyphenyl) -bis (4-dimethylaminophenyl) methane, [4- (1-pyrrolidinyl) -2-ethoxyphenyl] -bis (4-diethylaminophenyl) ) Methane, (4-morpholino-2-ethoxyphenyl) -bis 4-diethylaminophenyl) methane, (4-N-ethyl-Np-tolylamino-2-ethoxyphenyl) -bis (4-diethylaminophenyl) methane, (4-N-ethyl-N-phenylamino-2-ethoxy) Phenyl) -bis (4-diethylaminophenyl) methane, (4-diphenylamino-2-ethoxyphenyl) -bis (4-diethylaminophenyl) methane, (4-diethylamino-2-benzyloxyphenyl) -bis (4-dimethyl) Aminophenyl) methane and the like. Of these, tris (4-dimethylaminophenyl) methane is preferable from the viewpoints of sensitivity and mask line width reproducibility of the resist pattern. Tris (4-dimethylaminophenyl) methane is also called leuco crystal violet.

  (D) It is preferable that the compounding quantity of a leuco dye is 0.1-1 mass% with respect to 100 mass% of solid content of the photosensitive resin composition. From the viewpoint of sensitivity, 0.1% by mass or more is preferable, and from the viewpoint of mask line width reproducibility of the resist pattern, 1% by mass or less is preferable. 0.2-0.8 mass% is more preferable, and 0.4-0.6 mass% is further more preferable.

<(E) Colorant>
The photosensitive resin composition of this invention can contain the coloring agent which has an absorption maximum in (E) 550-700nm as needed.

In the present invention, the absorption maximum is confirmed as follows.
In the present invention, (A) 60 parts by weight of an alkali-soluble polymer, (B) 40 parts of a compound having an ethylenically unsaturated double bond, and (E) 0.1 part of a colorant as a solvent using methyl ethyl ketone as a solvent and a solid content of 50% by mass. Mix evenly. The obtained resin composition solution is uniformly applied to a PET film with a bar coater. The film thickness is adjusted to 50 um after drying. The transmittance of the obtained film is measured for each wavelength, and the wavelength having the largest absorption is taken as the absorption maximum.

  Examples of the (E) colorant having an absorption maximum at 550 to 700 nm include a blue or green colorant. For example, α type copper phthalocyanine blue, α type monochloro copper phthalocyanine blue, β type copper phthalocyanine blue, ε type copper phthalocyanine blue, cobalt phthalocyanine blue, metal free phthalocyanine blue dye, Examples thereof include pigments, anthraquinone dyes or pigments such as aminoanthraquinone, and triphenylmethane dyes or pigments such as diamond green, Victoria pure blue, and malachite green.

  Using the color index (C.I .; issued by The Society of Dyers and Colorists) number, the following can be mentioned.

  Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60, as dye system Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. Can be used.

  In addition, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used as a green pigment or dye. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

  The colorant having an absorption maximum at (E) 550 to 700 nm in the present invention is preferably nonionic from the viewpoint of sublimation and transmittance stability after baking.

｛式中、Ｒ^３およびＲ^４は、各々独立に、直鎖もしくは分岐アルキル基、アルキル置換もしくは無置換フェニル基、シクロヘキシル基、カルボニル基、カルボニル基を介した直鎖もしくは分岐アルキル基、置換もしくは無置換フェニル基である。Ｒ^５およびＲ^６は、各々独立に、水素、水酸基、シクロヘキシル基、直鎖もしくは分岐アルキル基、置換もしくは無置換フェニル基、ＮＨ基を介して直鎖もしくは分岐アルキル基、アルキル置換もしくは無置換フェニル基、シクロヘキシル基、アミド基を介した直鎖もしくは分岐アルキル基、置換もしくは無置換フェニル基を表す。｝で表されるアントラキノン系染料が好ましい。 The colorant having an absorption maximum at (E) 550 to 700 nm in the present invention is represented by the following formula (V) from the viewpoints of sublimation, colorability, and storage stability:

{Wherein R ³ and R ⁴ are each independently a linear or branched alkyl group, an alkyl-substituted or unsubstituted phenyl group, a cyclohexyl group, a carbonyl group, a linear or branched alkyl group via a carbonyl group, a substituted or An unsubstituted phenyl group. R ⁵ and R ⁶ are each independently hydrogen, hydroxyl group, cyclohexyl group, linear or branched alkyl group, substituted or unsubstituted phenyl group, linear or branched alkyl group via NH group, alkyl substituted or unsubstituted phenyl Represents a linear or branched alkyl group or a substituted or unsubstituted phenyl group via a group, a cyclohexyl group or an amide group. } Anthraquinone dyes represented by

R ³ and R ⁴ are preferably an alkyl-substituted or unsubstituted phenyl group, and more preferably an alkyl-substituted phenyl group, from the viewpoints of sublimation, colorability, and storage stability. R ⁵ and R ⁶ are preferably hydrogen or a hydroxyl group.

  (E) It is preferable that the compounding quantity of the coloring agent which has an absorption maximum in 550-700 nm is 0.1-1 mass% with respect to 100 mass% of solid content of the photosensitive resin composition. The content is preferably 0.1% by mass or more from the viewpoint of colorability, and preferably 1% by mass or less from the viewpoints of sensitivity, sublimation property and storage stability. 0.1-0.5 mass% is more preferable.

  Further, in order to improve the thermal stability and storage stability of the photosensitive resin composition, the photosensitive resin composition is composed of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and bisphenol A epoxy compounds. You may further contain the 1 or more types of compound chosen from the group which consists of.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. A nitrosophenylhydroxyamine aluminum salt is preferred from the viewpoint of not impairing sensitivity.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like.

  Examples of the bisphenol A epoxy compounds include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminals.

  The total content of the radical polymerization inhibitor, benzotriazoles, carboxybenzotriazoles and epoxy compounds of bisphenol A is preferably 0.001 to 0.2% by mass with respect to the entire photosensitive resin composition, More preferably, it is 0.01-0.1 mass%. The content is preferably 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and 0.1% by mass from the viewpoint of maintaining sensitivity and suppressing decolorization and color development of the dye. The following is more preferable.

  Another aspect of the present invention relates to a photosensitive resin laminate in which a photosensitive resin layer composed of the photosensitive resin composition is laminated on at least a support layer.

  The photosensitive resin laminated body of this invention contains the photosensitive resin layer and support layer which consist of a photosensitive resin composition. If necessary, you may have a protective layer on the surface on the opposite side to the support layer side of the photosensitive resin layer. The support layer used here is preferably a transparent layer that transmits light emitted from the exposure light source. As such a support layer, for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can be stretched if necessary. The haze is preferably 5 or less. More preferably, it is 1 or less, More preferably, it is 0.5 or less, Most preferably, it is 0.2 or less. The thinner the film, the more advantageous in terms of image formation and economy, but a film having a thickness of 10 to 30 μm is preferably used in order to maintain the strength.

  An important characteristic of the protective layer used for the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support layer in terms of adhesion to the photosensitive resin layer and can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Also, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm. The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but is preferably 5 to 100 μm, more preferably 7 to 60 μm. The thinner the resolution is, the higher the film strength is. .

  When polyethylene is used for the protective layer, there is a gel called fish eye on the surface of the polyethylene film, which may be transferred to the photosensitive resin layer. When the fish eye is transferred to the photosensitive resin layer, air may be entrained during the lamination, resulting in voids, leading to a defect in the resist pattern. From the viewpoint of fisheye, the protective layer is preferably made of stretched polypropylene. A specific example is Alfane E-200A manufactured by Oji Paper Co., Ltd.

  A publicly known method can be adopted as a method for producing a photosensitive resin laminate by sequentially laminating a support layer, a photosensitive resin layer, and, if necessary, a protective layer. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition to form a uniform solution, first applied onto the support layer using a bar coater or roll coater, and then dried to form a support film. A photosensitive resin layer made of a photosensitive resin composition can be laminated thereon.

  The thickness of the photosensitive resin layer after drying can be appropriately selected depending on the application. The thickness of the photosensitive resin layer after drying can be adjusted in the range of 10 to 200 μm when a die coater is used, and in the range of about 1 to 150 μm when a reverse roll coater is used.

  The photosensitive resin laminate of the present invention can be produced by coating a photosensitive resin composition on a support layer and drying it, and then laminating a protective layer on the photosensitive resin layer.

  Examples of the solvent that dissolves the photosensitive resin composition include ketones typified by methyl ethyl ketone (MEK), alcohols typified by methanol, ethanol, and isopropanol. The solvent is appropriately selected and blended depending on the coating method and the desired film thickness. For example, when coating using a die coater, it is added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support layer is 500 to 4000 mPa · s at 25 ° C. It is preferable.

<Resist pattern formation method>
The resist pattern using the photosensitive resin laminate can be formed by a process including a laminating process for laminating, an exposing process for exposing active light, and a developing process for removing unexposed portions. Furthermore, a baking process for heating the pattern at a constant temperature can be added in consideration of the strength of the resist pattern and the generation of sublimates.

Hereinafter, a specific example of the resist pattern forming method will be described.
As a substrate, a copper-clad laminate, a glass substrate on which transparent electrodes such as ITO and IZO are sputtered or deposited, a similar film substrate, a glass substrate coated with a dielectric paste, a silicon wafer, a glass on which amorphous silicon is deposited A wafer, a silicon wafer on which a metal thin film such as copper, tantalum, or molybdenum is sputtered can be used.

  In order to laminate the photosensitive resin on the substrate, first, a laminating process is performed using a laminator. In the case where the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is laminated on the substrate surface by thermocompression bonding with the laminator. In this case, the photosensitive resin layer may be laminated only on one side of the substrate surface, or may be laminated on both sides. The heating temperature at this time is generally about 40 to 160 ° C. In addition, adhesion and chemical resistance are improved by performing the thermocompression bonding twice or more. For thermocompression bonding, a two-stage laminator provided with two rolls may be used, or it may be repeatedly crimped through a roll several times.

  Next, an exposure process is performed using an exposure machine. If necessary, the support layer is peeled off and exposed to active light through a photomask. The exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter. Examples of the exposure machine include a scattered light exposure machine using an ultra-high pressure mercury lamp as a light source, a parallel light exposure machine with the same degree of parallelism, and a proximity exposure machine with a gap between the mask and the workpiece. Furthermore, a projection type exposure machine having a mask to image size ratio of 1: 1, a reduction projection exposure machine called a high illuminance stepper (registered trademark), or an exposure machine using a concave mirror called a mirror projection aligner (registered trademark). be able to.

  In the exposure process, a direct drawing exposure method may be used. Direct drawing exposure is a method in which a pattern is directly drawn and exposed on a substrate without using a photomask. As the light source, for example, a semiconductor laser having a wavelength of 350 to 410 nm or an ultrahigh pressure mercury lamp is used.

Next, a developing process is performed using a developing device. After the exposure, if there is a support film on the photosensitive resin layer, this is removed if necessary, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, and a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2 to 2% by mass and a temperature of about 20 to 40 ° C. is generally used. A surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. An amine-based alkaline aqueous solution such as a tetraammonium hydroxide (TMAH) aqueous solution can also be used in consideration of the influence on the substrate. The density can be appropriately selected according to the developing speed.

  Although a resist pattern can be obtained through each of the above steps, a heating step at about 100 to 300 ° C. can be further performed in some cases. By carrying out this heating step, a compound having an unreacted ethylenically unsaturated double bond in the resist pattern can be reacted or a sublimable component can be sublimated before the resist pattern is incorporated as a member. . Moreover, chemical resistance is also improved by this heating step. For heating, a hot-air, infrared, or far-infrared heating furnace can be used.

<Conductor Pattern Manufacturing Method and Printed Wiring Board Manufacturing Method>
The printed wiring board can be obtained through the following steps following the resist pattern forming method using a copper-clad laminate or a flexible substrate as a substrate.

  First, the copper surface of the substrate exposed by development is etched or plated to produce a conductor pattern.

  Thereafter, the resist pattern is peeled from the substrate with an aqueous solution having alkalinity stronger than that of the developer to obtain a desired printed wiring board. The alkaline aqueous solution for peeling (hereinafter also referred to as “peeling solution”) is not particularly limited, but an aqueous solution of NaOH and / or KOH having a concentration of about 2 to 5% by mass and a temperature of about 40 to 70 ° C. is generally used. . A small amount of a water-soluble solvent can also be added to the stripping solution.

<Lead frame manufacturing method>
The lead frame can be obtained through the following steps following the above-described resist pattern forming method using a metal plate, for example, copper, a copper alloy, or an iron-based alloy as a substrate.

  First, a conductive pattern is formed by etching the substrate exposed by development. Thereafter, the resist pattern is peeled off by a method similar to the method for manufacturing a printed wiring board described above to obtain a desired lead frame.

<Production method of ITO electrode>
The ITO electrode can be obtained through the following steps following the above-described resist pattern forming method using a glass substrate or a film substrate on which an ITO film is formed as a base material.

  First, the ITO film exposed by development is etched. Etching solutions include iron chloride-based, oxalic acid-based, and mixed acid-based ones, which can be appropriately selected according to the film quality of the ITO film. After the etching, the desired electrode pattern can be obtained by peeling off by the same method as the above-described printed wiring board manufacturing method.

<Black matrix production method>
The black matrix can be obtained through the following steps following the above-described resist pattern forming method using a glass substrate on which glass or ITO film is formed.

  First, the resist pattern is baked together with the substrate. It can be baked by heating with a hot air drying oven or an infrared heater. Depending on the purpose, baking can be performed in an atmosphere other than air, such as a nitrogen atmosphere. After baking at a baking temperature and time according to the purpose, a black matrix can be obtained.

<Semiconductor bump manufacturing method>
The semiconductor bump can be produced by the following method.
An insulating layer is provided on the silicon wafer substrate, and electrodes for connecting to the silicon wafer are formed on necessary portions. Next, a conductive film such as copper is formed by a method such as sputtering.

  When a liquid resist is used, the liquid resist is spin-coated on the substrate thus obtained. The solvent is removed by pre-baking and drying is performed to obtain a resist coating film. Next, a pattern is formed by exposure and development. In the case of using a dry film, the pattern is formed by the same method as the above <Method for forming resist pattern>.

  Thereafter, plating is performed in the pattern, and examples of the pretreatment include a method of immersing in water or a plating solution itself. When forming a solder bump, a nickel film called an under bump metal is formed by plating in order to ensure adhesion with the bump, and solder is plated thereon to form a bump. When forming a copper post, copper plating is performed in the pattern, and then a solder bump is formed. Examples of the plating bath used for plating include the following. Examples of the nickel plating bath include a watt bath and a sulfamic acid bath. As the solder plating bath, a bath of high lead, eutectic, lead-free or the like is selected according to the properties of the solder. As the copper plating bath, an electrolytic copper plating bath such as copper sulfate is generally used.

  After plating, the resist is stripped with a stripping solution. The stripping solution is composed of an alkali component such as ethanolamine, tetramethylammonium hydroxide (TMAH) or the like, an alkali component combining one or more organic alkalis, a highly polar water-soluble organic solvent such as glycol and dimethyl sulfoxide, water An organic stripping solution in combination of the above can be used. Copper plating is generally a plating bath such as copper sulfate.

  After removing the resist, the conductive film is removed by etching. For the etching, a known method using copper chloride or the like can be used. After the etching, the solder portion is heated by a heating process called reflow to produce solder balls to form semiconductor bumps.

Hereinafter, examples of embodiments of the present invention will be specifically described.
(Examples 1-5, Comparative Examples 1-4)
First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.

1. Production of Evaluation Samples Evaluation samples in Examples and Comparative Examples were produced as follows.
<Preparation of photosensitive resin laminate>
A photosensitive resin composition mixed solution obtained by sufficiently stirring and mixing a photosensitive resin composition and a solvent having a composition shown in the following Table 1 (however, each component number indicates a blending amount (part by mass) as a solid content). And coated uniformly on the surface of a 16 μm thick polyethylene terephthalate film (GR-16, manufactured by Teijin Films Ltd.) as a support using a bar coater, and dried for 5 minutes in a dryer at 95 ° C. for photosensitivity. A resin layer was formed. The thickness of the photosensitive resin layer was 45 μm.

  Next, a 20 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-18) was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.

  Table 1 shows the names of the material components in the photosensitive resin composition preparation liquid, and Table 2 shows the amounts and evaluation results in the photosensitive resin composition preparation liquid.

<About absorption maximum of material component>
When the absorption maximum of the material component described in Table 1 was measured by the method described above, the wavelengths of the absorption maximums of F-1 to F-6 were as follows. F-1: 525 nm, F-2: 480 nm, F-3: 500 nm, F-4: 425 nm, F-5: 420 nm, F-6: 400 nm.
<Melting point of material components>
Moreover, when melting | fusing point of the material component described in Table 1 was measured, melting | fusing point was as follows. F-1: 180 ° C, F-2: 130 ° C, F-3: 160 ° C, F-4: 95 ° C, F-5: 180 ° C, F-6: 180 ° C.

2. Adhesion evaluation <substrate>
A transparent conductive film (Toyobo Co., Ltd., 300R (125Ω, 20 nm)) obtained by sputtering ITO on the PET surface was used.

<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, lamination was performed at a roll temperature of 105 ° C. with a hot roll laminator (AL-700, manufactured by Asahi Kasei Electronics Co., Ltd.). The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min. It was.

<Exposure>
Using a chrome glass photomask, exposure was performed at 1 J / cm ² with a high-precision exposure machine (HMW-801, ghi line, 7 mW) manufactured by Oak Co., Ltd.

  As the chrome glass photomask, an independent fine line pattern mask having a ratio of the exposed area to the unexposed area of 1: 100 was used. The gap between the chromium glass photomask and the photosensitive resin laminate was 100 μm.

<Development>
After peeling the polyethylene terephthalate film, a 0.4 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed and developed to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required for completely dissolving the photosensitive resin layer of the unexposed portion was measured as the minimum development time, and development was performed under the same conditions twice as long as the minimum development time to prepare a resist pattern. The minimum mask line width in which the resist pattern was normally formed was used as an adhesion value, and evaluated and rated according to the following evaluation criteria.
A: Adhesion value is 20 μm or less.
○: Adhesiveness value exceeds 20 μm and 30 μm or less.
(Triangle | delta): The value of adhesiveness exceeds 30 micrometers and is 50 micrometers or less.
X: Adhesion value exceeds 50 μm.

3. Sublimation evaluation <Preparation of evaluation substrate>
The above 2. except that a chrome glass photomask is used. Similar to the adhesion evaluation, development was performed to prepare a solid pattern for evaluation. This was heat-treated in a hot air oven at 120 ° C./1 hour to produce an evaluation substrate.

<Sublimation evaluation>
The evaluation substrate was cut into 2 mm × 5 mm, heated with a pyrolyzer (made by FRONTIER LAB, DOUBLE SHOT PYROLYZER), and the generated sublimate was connected to gas chromatography (Agilent Technologies, 6890N Network GC System 30). And continuously monitored by a FID detector. The pyrolyzer condition was 100 ° C. to 10 ° C./min. The interface temperature was 300 ° C. The conditions for gas chromatography were detection of sublimates for 15 minutes at an injection temperature of 350 ° C. and a column oven temperature of 350 ° C. The temperature of the FID detector was 370 ° C., and the flow rate of the carrier gas (He) was 2.0 m / min.

The detection time is output on the horizontal axis and the FID detection intensity is output on the vertical axis, and the integrated value of the detection intensity over the entire detection time is defined as the amount of generated sublimation. The sublimate generation amount of the composition used in Example 1 was set to 1, and the sublimate generation amount of each Example and Comparative Example was calculated as a relative amount, and was evaluated and rated according to the following evaluation criteria based on the value. .
○: The value of the sublimate generation amount relative value is 1.5 or less.
(Triangle | delta): The value of a sublimate generation amount relative value exceeds 1.5.

4). Transmittance <Production of evaluation substrate>
The above 2. except that a chrome glass photomask is used. Similar to the adhesion evaluation, development was performed to prepare a solid pattern for evaluation. This was heat-treated at 200 ° C. for 1 hour using a hot air oven to produce an evaluation substrate.

<Transmittance evaluation>
The absorbance of the evaluation substrate was measured with a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, U3010), the difference from the base material was determined, and the value obtained by converting this to the transmittance was defined as the transmittance of the resist pattern. The transmittance at a wavelength of 400 nm to 700 nm was obtained every 1 nm, and a value obtained by averaging the transmittances was evaluated and rated according to the following evaluation criteria.
○: The average value of transmittance is 40% or less.
(Triangle | delta): The value of the transmittance | permeability average value exceeds 40%, and is 60% or less.
X: The value of the average transmittance exceeds 60%.

5. Colorability <Colorability of protective layer>
After producing the photosensitive resin laminate, it was stored for 1 week in an environment of 23 ° C. and 50% relative humidity (RH), and the protective layer was peeled off. The coloring of the protective layer was visually observed, evaluated according to the following evaluation criteria, and rated.
○: Almost no coloring of the protective layer is observed.
Δ: Coloring of the protective layer is observed.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition and photosensitive resin laminated body which can form the resist pattern which is excellent in adhesiveness, is excellent in coloring property, is excellent in the color stability at the time of a heating, and can generate | occur | produce little sublimation can be provided. The present invention is also useful for producing a black matrix and other fine patterns that require coloring.

Claims (6)

  (A) 30-70% by mass of an alkali-soluble polymer having an acid equivalent of 100-600 and a weight average molecular weight of 5000-500000, (B) 20-60% by mass of a compound having an ethylenically unsaturated double bond (C) 0.1 to 20% by mass of a photopolymerization initiator, and (F) a nonionic compound having an absorption maximum in the range of 455 to 600 nm and a melting point of 120 ° C. or higher. A photosensitive resin composition. The nonionic compound (F) has the following formula (I) in its molecule:

{Wherein R ¹ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ² has hydrogen, a hydroxyl group, a carboxyl group, a halogen group, an alkyl group having 1 to 4 carbon atoms, or a substituent. An amino group that may be substituted, an amide group that may have a substituent, a nitro group, or a sulfonyl group. }
The photosensitive resin composition of Claim 1 which has group represented by these.   The photosensitive resin composition according to claim 2, wherein the nonionic compound (F) has two or more groups represented by the formula (I) in the molecule.   The photosensitive resin laminated body by which the photosensitive resin layer which consists of the photosensitive resin composition as described in any one of Claims 1-3 was laminated | stacked on the support layer at least.   A method for forming a resist pattern, comprising a step of laminating the photosensitive resin laminate according to claim 4 on a substrate, an exposure step, and a development step.   A method for forming a resist pattern, comprising a step of laminating the photosensitive resin laminate according to claim 4 on a base material, a step of exposing, a step of developing, and a step of baking.