Photosensitive resin composition

Abstract

Provided are: a photosensitive resin composition having better sensitivity (productivity), resolution, and adhesion than sensitizers used in the past in laser direct imaging exposure methods; etc. A photosensitive resin composition comprising the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and (D) a photosensitizer, wherein the photosensitizer (D) comprises a distyrylbenzene derivative represented by the general formula (2). In the formula (2), R 3 , R 4 , R 5 Each of them represents a cyano group, c and e each independently represent an integer of 1 to 5, and d represents an integer of 0 to 4.

Description

[0001] The present application is a divisional application of an application with a filing date of March 28, 2018, an application number of 201880013871.3, and an invention name of photosensitive resin composition. Technical Field

[0002] The present invention relates to a photosensitive resin composition and the like. Background Art

[0003] Printed circuit boards are used in electronic devices such as personal computers and mobile phones for mounting components or semiconductors. As resists for manufacturing printed circuit boards, photosensitive resin laminates, so-called dry film resists (hereinafter sometimes referred to as DF), have been used in the past. The resists are formed by laminating a photosensitive resin layer on a support film and further laminating a protective film on the photosensitive resin layer as needed.

[0004] As the photosensitive resin layer used here, at present, an alkali-developable photosensitive resin layer using a weak alkali aqueous solution as a developer is generally used. When using DF to make a printed circuit board, etc., in the case of having a protective film, first, after peeling off the protective film, use a laminator to laminate DF on a permanent circuit manufacturing substrate such as a copper-clad laminate or a flexible substrate, and expose it through a wiring pattern mask film. Then, the supporting film is peeled off as needed, and the photosensitive resin layer of the unexposed part (in the case of a negative type) is dissolved or dispersed and removed by a developer to form a cured anti-etching pattern (hereinafter, sometimes referred to as an anti-etching pattern) on the substrate.

[0005] The process of forming a circuit after the formation of the resist pattern is roughly divided into two methods. The first method is: after etching away the substrate surface not covered by the resist pattern (for example, the copper surface of the copper-clad laminate), the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer (etching method). The second method is: after plating the above-mentioned substrate surface with copper, solder, nickel or tin, etc., the resist pattern portion is removed in the same manner, and the exposed substrate surface (for example, the copper surface of the copper-clad laminate) is further etched (plating method). Solutions of cupric chloride, ferric chloride, copper ammonia complex, etc. can be used for etching.

[0006] Therefore, in such a manufacturing process, high sensitivity is required from the perspective of improving productivity. On the other hand, the exposure method is also diversified according to the purpose. In recent years, it can be seen that maskless exposure based on direct laser drawing without a photomask has developed rapidly. As a light source for maskless exposure, light with a wavelength of 350 to 410 nm, especially i-rays or h-rays (405 nm) are mostly used. Therefore, light sources that can form highly sensitive and high-resolution resist patterns in these wavelength regions, especially h-rays, are valued. Furthermore, with the miniaturization and lightweight of electronic equipment, the miniaturization and high-density of printed circuit boards have been promoted, and high-performance DFs with excellent resolution and the like are sought.

[0007] As a photosensitive resin composition that achieves high sensitivity and high resolution, a blue-violet laser photosensitive composition is described in Patent Document 1. This photosensitive composition has high sensitivity to laser light in the blue-violet region and excellent safe light properties under yellow light, and is particularly suitable as a dry film resist material for direct drawing using a blue-violet laser.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2005-091593 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] However, the photosensitive resin composition described in Patent Document 1 cannot simultaneously satisfy sensitivity (productivity), resolution, adhesion, and the like, and there is room for further improvement.

[0013] Therefore, an object of the present invention is to provide a photosensitive resin composition or the like which is superior to conventional ones in sensitivity (productivity), resolution, and adhesion in a laser direct imaging exposure method.

[0014] Solutions for solving problems

[0015] The present inventors have conducted intensive studies and repeated experiments to solve the above problems, and as a result, have found that the above problems can be solved by containing a specific component as (D) a photosensitizer.

[0016] That is, the present invention is as follows. [1]

[0018] A photosensitive resin composition comprising the following ingredients:

[0019] (A) Alkali soluble polymer;

[0020] (B) a compound having an ethylenically unsaturated double bond;

[0021] (C) a photopolymerization initiator; and,

[0022] (D) photosensitizer,

[0023] The aforementioned (D) photosensitizer contains a distyrylbenzene derivative represented by the following general formula (2).

[0024]

[0025] In formula (2), R 3 , R 4 , R 5 Each of them represents a cyano group, c and e each independently represent an integer of 1 to 5, and d represents an integer of 0 to 4. [2]

[0027] The photosensitive resin composition according to [1], wherein the photosensitizer (D) comprises at least one compound selected from the group consisting of 4'-(2-cyanostyryl)-2-cyanostyryl, 4'-(2-cyanostyryl)-3-cyanostyryl, 4'-(2-cyanostyryl)-4-cyanostyryl, and 1,4-bis(4-cyanostyryl)benzene. [3]

[0029] The photosensitive resin composition according to [2], wherein the photosensitizer (D) comprises 4'-(2-cyanostyryl)-2-cyanostyryl and 4'-(2-cyanostyryl)-3-cyanostyryl. [4]

[0031] The photosensitive resin composition according to [2], wherein the (D) photosensitizer contains 4'-(2-cyanostyryl)-4-cyanostilbene. [5]

[0033] The photosensitive resin composition according to [2], wherein the (D) photosensitizer contains 1,4-bis(4-cyanostyryl)benzene. [6]

[0035] The photosensitive resin composition according to any one of [1] to [5], wherein the (D) photosensitizer is a fluorescent dye having a maximum absorption peak at 330 nm to 450 nm. [7]

[0037] The photosensitive resin composition according to any one of [1] to [6], wherein the (C) photopolymerization initiator contains a hexaarylbiimidazole compound. [8]

[0039] The photosensitive resin composition according to any one of [1] to [7], wherein the transmittance of the photosensitive resin composition for light of a wavelength of 405 nm when the film thickness is 25 μm is greater than 10%. [9]

[0041] The photosensitive resin composition according to any one of [1] to [8], wherein the photosensitive resin composition is a photosensitive resin composition for forming metal wiring.

[10]

[0043] A photosensitive resin laminate comprising: a support; and a photosensitive resin layer provided on the support and containing the photosensitive resin composition according to any one of 1 to 9.

[11]

[0045] A method for forming an anti-etching pattern comprises the following steps:

[0046] A step of laminating the photosensitive resin laminate described in

[10] on a substrate;

[0047] The process of exposing the photosensitive resin layer to light; and

[0048] A step of developing the exposed photosensitive resin layer.

[12]

[0050] According to the resist pattern forming method described in

[11] , the exposure is performed by direct drawing of a drawing pattern.

[13]

[0052] A method for forming a metal wiring comprises the following steps:

[0053] A step of forming a resist pattern by the method described in

[11] or

[12] ;

[0054] A step of forming metal wiring using the aforementioned resist pattern; and

[0055] A step of peeling off the resist pattern.

[14]

[0057] A method for manufacturing a semiconductor package, comprising the following steps: forming a resist pattern on a semiconductor package substrate as a base material by the resist pattern forming method described in

[11] or

[12] ; and etching or plating the semiconductor package substrate on which the resist pattern is formed.

[15]

[0059] A photosensitive resin composition comprising the following ingredients:

[0060] (A) Alkali soluble polymer;

[0061] (B) a compound having an ethylenically unsaturated double bond;

[0062] (C) a photopolymerization initiator; and,

[0063] (D) photosensitizer,

[0064] The acid dissociation constant pKa of the aforementioned (D) photosensitizer is greater than 9 and less than 12, and the molar absorption coefficient at a wavelength of 405 nm is 100M -1 cm -1 The above (wherein M is the unit of molar concentration, and the above molar absorption coefficient is the value when acetone is used as the solvent.).

[16]

[0066] The photosensitive resin composition according to

[15] , wherein the (D) photosensitizer is 4-[3-(4-chlorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]benzenesulfonamide.

[17]

[0068] The photosensitive resin composition according to

[16] , wherein the compound (B) having an ethylenically unsaturated double bond contains a hydroxyl group in the molecule.

[18]

[0070] The photosensitive resin composition according to any one of

[15] to

[17] , wherein the photosensitizer (D) is a fluorescent dye having a maximum absorption peak at 330 nm to 450 nm.

[19]

[0072] The photosensitive resin composition according to any one of

[15] to

[18] , wherein the (C) photopolymerization initiator contains a hexaarylbiimidazole compound.

[20]

[0074] The photosensitive resin composition according to any one of

[15] to

[19] , wherein the transmittance of the photosensitive resin composition for light of a wavelength of 405 nm when the film thickness is 25 μm is greater than 10%. [twenty one]

[0076] The photosensitive resin composition according to any one of

[15] to

[20] , wherein the acid dissociation constant pKa of the (D) photosensitizer is greater than 9.5 and less than 11. [twenty two]

[0078] The photosensitive resin composition according to any one of

[15] to

[21] , wherein the (B) compound having an ethylenically unsaturated double bond contains a hydroxyl group in the molecule. [twenty three]

[0080] The photosensitive resin composition according to any one of

[15] to

[22] , wherein the photosensitive resin composition is a photosensitive resin composition for forming metal wiring. [twenty four]

[0082] A photosensitive resin laminate comprising: a support; and a photosensitive resin layer provided on the support and containing the photosensitive resin composition according to any one of

[15] to

[23] .

[25]

[0084] A method for forming an anti-etching pattern comprises the following steps:

[0085] A step of laminating the photosensitive resin laminate described in

[24] on a substrate;

[0086] The process of exposing the photosensitive resin layer to light; and

[0087] A step of developing the exposed photosensitive resin layer.

[26]

[0089] The resist pattern forming method according to

[25] , wherein the exposure is performed by direct drawing of a drawing pattern.

[27]

[0091] A method for forming a metal wiring comprises the following steps:

[0092] A step of forming a resist pattern by the method described in

[25] or

[26] ;

[0093] A step of forming metal wiring using the aforementioned resist pattern; and

[0094] A step of peeling off the resist pattern.

[28]

[0096] A method for manufacturing a semiconductor package, comprising the following steps: forming a resist pattern on a semiconductor package substrate as a base material by the resist pattern forming method described in

[25] or

[26] ; and etching or plating the semiconductor package substrate on which the resist pattern is formed.

[0097] Effects of the Invention

[0098] According to the present invention, a photosensitive resin composition or the like having excellent sensitivity (productivity), resolution, and adhesion can be provided. DETAILED DESCRIPTION

[0099] Hereinafter, exemplary modes for implementing the present invention (hereinafter, simply referred to as "embodiments") are described in detail. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

[0100] <Photosensitive resin composition>

[0101] In the embodiment, the photosensitive resin composition includes the following components (A) to (E): (A) alkali-soluble polymer (also referred to as component (A) in the present disclosure), (B) compound having ethylenically unsaturated double bonds (also referred to as component (B) in the present disclosure), (C) photopolymerization initiator (also referred to as component (C) in the present disclosure), (D) photosensitizer (also referred to as component (D) in the present disclosure). (E) additives (also referred to as component (E) in the present disclosure) may also be included. Hereinafter, each component will be described in order.

[0102] (A) Alkali-soluble polymer

[0103] (A) The alkali-soluble polymer is a polymer that is easily soluble in an alkaline substance, specifically, a polymer having a functional group (e.g., a carboxyl group) that is conducive to alkali solubility in an amount sufficient to dissolve in the desired alkaline substance. In addition, typically, the amount of carboxyl groups contained in the (A) alkali-soluble polymer is 100 to 600, preferably 250 to 450, in terms of acid equivalent. Acid equivalent refers to the mass (unit: gram) of a linear polymer having 1 equivalent of carboxyl groups in the molecule. The carboxyl groups in the (A) alkali-soluble polymer are necessary to provide the photosensitive resin layer with developability and stripping properties in an alkaline aqueous solution. From the viewpoint of improving development resistance, resolution and adhesion, it is preferred that the acid equivalent is 100 or more, and it is also preferred that the acid equivalent is 250 or more. On the other hand, from the viewpoint of improving developability and stripping properties, it is preferred that the acid equivalent is 600 or less, and it is also preferred that the acid equivalent is 450 or less.

[0104] (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less, more preferably 300,000 or less, and further preferably 200,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as the edge fusion and chipping properties of the photosensitive resin laminate, the weight average molecular weight is preferably 5,000 or more, more preferably 10,000 or more, and further preferably 20,000 or more. Edge fusion refers to the phenomenon that when the photosensitive resin laminate is wound into a roll, the photosensitive resin layer overflows from the end surface of the roll. Chipping refers to the phenomenon that when the unexposed film is cut with a cutter, debris flies out. If the debris adheres to the upper surface of the photosensitive resin laminate, etc., the debris will be transferred to the mask in the subsequent exposure process, etc., causing defective products.

[0105] The dispersity (sometimes referred to as molecular weight distribution) of the (A) alkali-soluble polymer may be about 1 to 6, preferably 1 to 4. The dispersity is expressed as the ratio of the weight average molecular weight to the number average molecular weight, which is (dispersity) = (weight average molecular weight) / (number average molecular weight). The weight average molecular weight and the number average molecular weight are values ​​measured by gel permeation chromatography and converted to polystyrene.

[0106] (A) The alkali-soluble polymer is preferably a copolymer obtained from at least one of the first monomers described below and at least one of the second monomers described below.

[0107] The first monomer is a carboxylic acid or anhydride having one polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, etc. (meth)acrylic acid is particularly preferred. In this specification, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid. The same applies below.

[0108] The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. As the second monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, esters of vinyl alcohol, such as vinyl acetate, (meth) acrylonitrile, styrene, and styrene derivatives. Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferred. From the viewpoint of improving the resolution and adhesion of the resist pattern, styrene and benzyl (meth) acrylate are preferred.

[0109] From the viewpoint of adjusting the alkali solubility of the alkali-soluble polymer (A), the copolymerization ratio of the first monomer to the second monomer is preferably 10 to 60% by mass of the first monomer and 40 to 90% by mass of the second monomer, and more preferably 15 to 35% by mass of the first monomer and 65 to 85% by mass of the second monomer.

[0110] (A) The synthesis of the alkali-soluble polymer is preferably carried out as follows: in a solution formed by diluting a mixture of the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropanol, an appropriate amount of a free radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile is added and heated and stirred. Sometimes the synthesis is carried out while a part of the mixture is added dropwise to the reaction solution. After the reaction is completed, sometimes a solvent is further added to adjust the concentration to the desired concentration. As a synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used.

[0111] The ratio of the alkali-soluble polymer (A) (or a mixture thereof when a plurality of alkali-soluble polymers are used in combination) to the total amount of the components (A), (B), (C), (D) and (E) (hereinafter, sometimes referred to as the total amount of the components (A) to (E)) is preferably in the range of 10 to 90% by mass, more preferably 30 to 70% by mass, and still more preferably 40 to 60% by mass. From the viewpoint of controlling the development time, the ratio of the component (A) to the total amount of the components (A) to (E) is preferably 90% by mass or less, while from the viewpoint of improving the edge blending property, the ratio of the component (A) to the total amount of the components (A) to (E) is preferably 10% by mass or more.

[0112] The ratio of the (A) alkali-soluble polymer to the total solid content mass of the photosensitive resin composition may be 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. In addition, it may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less. The range of 10% to 90% by mass is preferred, 30% to 70% by mass is more preferred, and 40% to 60% by mass is further preferred. From the viewpoint of controlling the development time, it is preferred that the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is 90% by mass or less. On the other hand, from the viewpoint of improving the edge fusion resistance, it is preferred that the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is 10% by mass or more.

[0113] In terms of achieving high resolution, the photosensitive resin composition preferably contains, as component (A), one or more components selected from the group consisting of the following (a-1) and (a-2).

[0114] (a-1) an acrylic copolymer derived from a polymerization component containing 15 to 60% by mass of styrene and at least one acrylic monomer selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters;

[0115] (a-2) An acrylic copolymer derived from a polymerization component containing 20 to 85% by mass of benzyl methacrylate and at least one acrylic monomer selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters other than benzyl methacrylate.

[0116] The ratio of the total amount of the components (a-1) and (a-2) to the total amount of the components (A) to (E) is preferably 10 to 60% by mass in terms of high resolution. The above ratio is preferably 20% by mass or more, more preferably 30% by mass or more from the viewpoint of resolution, and is preferably 55% by mass or less, more preferably 50% by mass or less from the viewpoint of machinability.

[0117] The polymerizable components in (a-1) may consist of only styrene and the above-mentioned acrylic monomers, or may further contain other monomers. Moreover, the polymerizable components in (a-2) may consist of only benzyl methacrylate and the above-mentioned acrylic monomers, or may further contain other monomers. Particularly preferred examples of the combination of polymerizable components include: a combination of 15 to 60% by mass of styrene and 20 to 35% by mass of methacrylic acid, with the balance being methyl methacrylate; a combination of 30 to 50% by mass of styrene and 20 to 40% by mass of methacrylic acid, 10 to 20% by mass of 2-ethylhexyl acrylate, with the balance being 2-hydroxyethyl methacrylate; a combination of 20 to 60% by mass of benzyl methacrylate and 10 to 30% by mass of styrene, with the balance being methacrylic acid; a combination of 60 to 85% by mass of benzyl methacrylate and 0 to 15% by mass of 2-ethylhexyl acrylate, with the balance being methacrylic acid, etc. From the viewpoint of chemical resistance, adhesion, high resolution, or hem shape of the resist pattern, it is preferred that a monomer having an aralkyl group and / or styrene be contained as a monomer.

[0118] (B) Compounds having ethylenically unsaturated double bonds

[0119] The compound (B) having an ethylenically unsaturated double bond preferably includes a compound having an acryloyl group in the molecule from the viewpoint of curability and compatibility with the alkali-soluble polymer (A). Examples of the compound having an acryloyl group in the molecule include a compound having (meth)acrylic acid added to one terminal of a polyalkylene oxide, or a compound having (meth)acrylic acid added to one terminal and the other terminal alkyl-etherified or allyl-etherified.

[0120] Examples of such compounds include: phenoxyhexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to a phenyl group; or 4-n-nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol to which an average of 2 mol of propylene oxide (hereinafter, sometimes abbreviated as PO) is added and polyethylene glycol to which an average of 7 mol of ethylene oxide (hereinafter, sometimes abbreviated as EO) is added to nonylphenol; and 4-n-nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol to which an average of 1 mol of propylene oxide is added and polyethylene glycol to which an average of 5 mol of ethylene oxide is added to nonylphenol. Another example is 4-n-nonylphenoxy octaethylene glycol (meth)acrylate (eg, M-114 manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol to which an average of 8 mol of ethylene oxide is added to nonylphenol.

[0121] For example, there may be mentioned a compound having (meth)acryloyl groups at both ends of an alkylene oxide chain, or a compound having (meth)acryloyl groups at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are randomly or block-bonded.

[0122] Examples of such compounds include polyethylene glycol (meth)acrylates such as tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, and compounds having (meth)acryloyl groups at both ends of 12 mols of ethylene oxide chains, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(meth)acrylate. Examples of polyalkylene oxide di(meth)acrylate compounds containing ethylene oxide and propylene oxide include: dimethacrylates of diols obtained by adding an average of 3 mol of ethylene oxide to each of the two ends of a polypropylene glycol obtained by adding an average of 12 mol of propylene oxide; dimethacrylates of diols obtained by adding an average of 15 mol of ethylene oxide to each of the two ends of a polypropylene glycol obtained by adding an average of 18 mol of propylene oxide. In terms of flexibility, resolution, adhesion, etc., polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and di(meth)acrylates containing both ethylene oxide and polypropylene oxide (e.g., "FA-023M, FA-024M, FA-027M, product names, manufactured by Hitachi Chemical Co., Ltd.") are more preferred.

[0123] In addition, from the viewpoint of resolution and adhesion, it is preferred that bisphenol A is modified with alkylene oxide and has (meth)acryloyl groups at both ends. Alkylene oxide modification includes ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentyl oxide modification, hexyl oxide modification, etc. Moreover, from the viewpoint of resolution and adhesion, it is particularly preferred that bisphenol A is modified with ethylene oxide and has (meth)acryloyl groups at both ends.

[0124] Examples of such compounds include 2,2-bis(4-((meth)acryloyloxydiethoxy)phenyl)propane (e.g., NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-((meth)acryloyloxytriethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypentaethoxy)phenyl)propane (e.g., NK ester BPE-500), 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)acryloxyundeethoxy)phenyl)propane 2,2-bis(4-((meth)acryloxypentadecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxyhexadecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytridecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytetradecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypentadecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxyhexadecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, etc. Furthermore, from the viewpoint of resolution and adhesion, preferred are ethylene oxide-modified and propylene oxide-modified compounds such as 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 di(meth)acrylate of polyalkylene glycol obtained by adding an average of 2 mol of propylene oxide and an average of 15 mol of ethylene oxide to both ends of bisphenol A. In these compounds obtained by modifying bisphenol A with alkylene oxide and having (meth)acryloyl groups at both ends, the number of moles of ethylene oxide per 1 mol of bisphenol A is preferably 10 mol or more and 30 mol or less in total from the viewpoint of improving resolution, adhesion and flexibility.

[0125] In the present embodiment, as (B) a compound having an ethylenically unsaturated double bond, in terms of embodying high resolution, it is preferred to include a compound having more than 2 (meth) acryloyl groups in one molecule. The number of (meth) acryloyl groups in one molecule is more preferably 3 or more. From the viewpoint of strippability, the number of (meth) acryloyl groups in one molecule is preferably 6 or less, and more preferably 4 or less. A compound having more than 2 (meth) acryloyl groups in one molecule is obtained by forming (meth) acrylate with (meth) acrylic acid as follows, wherein the alcohol has more than 3 moles (i.e., more than 3 in each central skeleton) of a group capable of adding an alkylene oxide as the central skeleton in the molecule, and an alkylene oxide such as an ethylene oxide group, a propylene oxide group or a butylene oxide group is added thereto. If the central skeleton is an alcohol, it can also be obtained by directly forming a (meth) acrylate with (meth) acrylic acid. As a compound that can become a central skeleton, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanurate ring, etc. can be cited.

[0126] Examples of such compounds include triacrylates modified by EO3 mole of trimethylolpropane, triacrylates modified by EO6 mole of trimethylolpropane, triacrylates modified by EO9 mole of trimethylolpropane, triacrylates modified by EO12 mole of trimethylolpropane, triacrylates modified by EO3 mole of glycerol (e.g., A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.), triacrylates modified by EO9 mole of glycerol (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), triacrylates modified by EO6 mole of glycerol by PO6 mole (A-GLY-0606PE), triacrylates modified by EO9 mole of glycerol by PO9 mole (A-GLY-0909PE), tetraacrylates modified by 4EO of pentaerythritol (e.g., SR-494 manufactured by Sartomer Japan Inc.), tetraacrylates modified by 35EO of pentaerythritol (e.g., NK-494 manufactured by Shin-Nakamura Chemical Co., Ltd.), and tetraacrylates modified by EO4 mole of pentaerythritol (e.g., NK-494 manufactured by Shin-Nakamura Chemical Co., Ltd.). esterATM-35E), dipentaerythritol tetraacrylate, etc. In addition, as a compound having at least three methacryloyl groups, trimethacrylates such as ethoxylated glycerol trimethacrylate, ethoxylated isocyanuric acid trimethacrylate, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate (for example, from the viewpoint of flexibility, adhesion, and oozing-out suppression, trimethacrylate obtained by adding an average of 21 mol of ethylene oxide to trimethylolpropane and trimethacrylate obtained by adding an average of 30 mol of ethylene oxide to trimethylolpropane are preferred); tetramethacrylates such as di(trimethylolpropane) tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, etc.; pentamethacrylates such as dipentaerythritol pentamethacrylate, etc.; hexamethacrylates such as dipentaerythritol hexamethacrylate, etc. Among them, tetramethacrylate, pentamethacrylate or hexamethacrylate is preferred.

[0127] Among them, for the preferred examples of (B) compounds having ethylenically unsaturated double bonds, from the viewpoint of operability, compounds having a melting point below room temperature and not easily solidified during storage are preferred, and EO3 mole-modified triacrylate of trimethylolpropane and 4EO-modified tetraacrylate of pentaerythritol are particularly preferred.

[0128] The content of the compound having more than 2 (meth)acryloyl groups in one molecule is preferably 50 to 100% by mass of the compound having an ethylenically unsaturated double bond (B). From the viewpoint of resolution, the content is preferably 50% by mass or more, more preferably 60% by mass or more. The content may be 100% by mass, and from the viewpoint of peelability, may be preferably 95% by mass or less, more preferably 90% by mass or less.

[0129] (B) component may suitably contain compounds other than the above compounds, for example, the compounds listed below. For example, 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 2-di(p-hydroxyphenyl)propane di(meth)acrylate, 2,2-bis[(4-(meth)acryloyloxypolypropylene oxide)phenyl]propane, 2,2-bis[(4-(meth)acryloyloxypolybutylene oxide)phenyl]propane, glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyoxypropyl trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, trimethylolpropane triglycidyl ether tri(meth)acrylate, phthalic acid β-hydroxypropyl-β'-(acryloyloxy)propyl, nonylphenoxypolypropylene glycol (meth)acrylate, nonylphenoxypolybutylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. may be mentioned. Further, the following carbamate compounds can be cited. For example, hexamethylene diisocyanate, toluene diisocyanate or diisocyanate compounds (such as 2,2,4-trimethylhexamethylene diisocyanate) and a compound having a hydroxyl group and a (meth) acryloyl group in one molecule, such as 2-hydroxypropyl acrylate, and carbamate compounds of oligopropylene glycol monomethacrylate can be cited. Specifically, there are reaction products of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (such as NOF Corporation, BLEMMER PP1000). In addition, di(meth)acrylates or tri(meth)acrylates of isocyanurates modified by polypropylene glycol or polycaprolactone can also be cited. In addition, for example, carbamate oligomers obtained by reacting the end of a carbamate compound obtained in the form of an addition polymer of a diisocyanate and a polyol with a compound having an ethylenically unsaturated double bond and a hydroxyl group can also be cited.

[0130] In addition, as the compound (B) having an ethylenically unsaturated bond, a compound having one ethylenically unsaturated bond such as 4-n-nonylphenoxy octaethylene glycol acrylate, 4-n-nonylphenoxy tetraethylene glycol acrylate, or γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl phthalate may be included. When γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl phthalate is preferably included from the viewpoint of peelability and softness of the cured film, it is also preferred from the viewpoint of sensitivity, resolution, and adhesion.

[0131] The compound (B) having an ethylenically unsaturated double bond preferably contains a hydroxyl group in the molecule, whereby the sensitivity (productivity), resolution, and adhesion are particularly excellent.

[0132] (B) the compound with ethylenically unsaturated double bonds is preferably 5 to 70% by mass relative to the total amount of the aforementioned (A) component to (E) component. From the viewpoint of sensitivity, resolution and adhesion, it is preferred that the ratio is 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. On the other hand, from the viewpoint of suppressing edge fusion and stripping delay of the cured resist, it is preferred that the ratio is 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

[0133] (B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid content mass of the photosensitive resin composition may be 5% by mass or more, 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more. In addition, it may be 70% by mass or less, 60% by mass or less, or 50% by mass or less. Preferably, it is 5% to 70% by mass. From the viewpoint of sensitivity, resolution, and adhesion, it is preferred that the ratio be 5% by mass or more. It is more preferred that the ratio be 20% by mass or more, and it is further preferred that the ratio be 30% by mass or more. On the other hand, from the viewpoint of suppressing edge fusion and delayed peeling of the cured resist, it is preferred that the ratio be 70% by mass or less. It is more preferred that the ratio be 50% by mass or less.

[0134] In the present embodiment, when the substances other than (A) alkali-soluble polymer and (B) compound having ethylenically unsaturated bonds contained in the solid content of the photosensitive resin composition are recorded as components other than (A)(B), the value of [the mass of the aforementioned components other than (A)(B)] / [the mass of the aforementioned compound having ethylenically unsaturated bonds (B)] is preferably 0.190 or less. If this value is 0.190 or less, the content of the components not added to the cross-linked structure can be made smaller relative to the content of the compound having ethylenically unsaturated bonds (B) forming the cross-linked structure. Therefore, it is preferred from the viewpoint of excellent adhesion and resolution under extremely harsh development conditions such as overdevelopment and overwashing, and high temperature of the developer. From the same viewpoint, it is more preferably 0.185 or less, further preferably 0.180 or less, particularly preferably 0.175 or less, and most preferably 0.170 or less. It can be 0.165 or less, or it can be 0.160 or less.

[0135] In addition, the lower limit value is not limited, and the value may be 0.005 or more, 0.010 or more, 0.030 or more, or 0.050 or more.

[0136] In the present embodiment, the value of [(A) alkali-soluble polymer content] / [(B) compound content having an ethylenically unsaturated bond] contained in the solid content of the photosensitive resin composition is preferably 5.00 or less. If it is 5.00 or less, it is preferred from the viewpoint of the flexibility of the cured film, and from the same viewpoint, it is more preferably 3.00 or less, further preferably 2.00 or less, particularly preferably 1.800 or less, and most preferably 1.600 or less. The lower limit is not particularly limited, and the value may be 0.200 or more, 0.300 or more, or 0.500 or more.

[0137] (C) Photopolymerization initiator

[0138] (C) The photopolymerization initiator preferably contains a hexaarylbiimidazole compound from the viewpoint of obtaining sensitivity and resolution.

[0139] Examples of the hexaarylbiimidazole compound 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-trifluorophenyl)-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)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, etc. Among them, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred from the viewpoint of sensitivity and resolution.

[0140] As for the photopolymerization initiator which is optionally contained as the component (C) other than the hexaarylbiimidazole compound, there can be mentioned N-aryl-α-amino acid compounds, quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters, acridines, ester compounds of N-aryl amino acids, and halogen compounds.

[0141] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, etc. In particular, N-phenylglycine is preferred because of its high sensitizing effect.

[0142] Examples of the quinones include 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-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0143] Examples of the aromatic ketones include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone.

[0144] Examples of the acetophenones include 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl-1-propanone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Chiba Specialty Chemicals Inc.

[0145] Examples of the acylphosphine oxides include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucirin TPO manufactured by BASF Corporation and Irgacure 819 manufactured by Chiba Specialty Chemicals Inc.

[0146] Examples of benzoin or benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin.

[0147] Examples of the dialkyl ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

[0148] Examples of the thioxanthones include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0149] Examples of the dialkylaminobenzoic acid esters include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, and 2-ethylhexyl 4-(dimethylamino)benzoate.

[0150] Examples of oxime esters include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime 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 Chiba Specialty Chemicals Inc.

[0151] Examples of the 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,

[0013] The following are some of the following: 9-(4-dimethylaminophenyl)acridine, 9-(4-chlorophenyl)acridine, 9-(4-bromophenyl)acridine, 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, and 9-(4-pyridyl)acridine.

[0152] Examples of the ester compound of an N-aryl amino acid include methyl N-phenylglycine, ethyl N-phenylglycine, n-propyl N-phenylglycine, isopropyl N-phenylglycine, 1-butyl N-phenylglycine, 2-butyl N-phenylglycine, tert-butyl N-phenylglycine, pentyl N-phenylglycine, hexyl N-phenylglycine, pentyl N-phenylglycine, and octyl N-phenylglycine.

[0153] Examples of the halogen compound include amyl bromide, isopentyl bromide, isobutylene bromide, vinyl bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenylsulfone, 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, and diallyl iodonium compounds, among which tribromomethylphenylsulfone is particularly preferred. The content of the halogen compound in the photosensitive resin composition is preferably 0.01 to 3% by mass relative to the total amount of the components (A) to (E) from the viewpoint of sensitivity.

[0154] These photopolymerization initiators may be used alone or in combination of two or more.

[0155] The ratio of the photopolymerization initiator (C) to the total amount of the components (A) to (E) is preferably 0.1 to 20% by mass. From the viewpoint of obtaining sufficient sensitivity, the ratio is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.5% by mass or more. On the other hand, from the viewpoint of obtaining high resolution and suppressing aggregation in the developer, the ratio is preferably 20% by mass or less, and more preferably 10% by mass or less.

[0156] In addition, the amount of the hexaarylbiimidazole compound as the photopolymerization initiator (C) is 0.01 to 10% by mass relative to the total amount of the aforementioned components (A) to (E). From the viewpoint of obtaining sufficient sensitivity, the amount must be 0.01% by mass or more, preferably 1% by mass or more, and more preferably 3% by mass or more. On the other hand, from the viewpoint of obtaining high resolution and suppressing aggregation in the developer, the amount must be 10% by mass or less, preferably 8% by mass or less, and more preferably 6% by mass or less.

[0157] (D) Photosensitizer

[0158] In the photosensitive resin composition of the present embodiment, the photosensitizer (D) comprises a distyrylbenzene derivative represented by the following general formula (2). In addition, in the present embodiment, distyrylbenzene itself is not contained.

[0159]

[0160] In formula (2), R 3 , R 4 , R 5 Each of them represents a cyano group, c and e each independently represent an integer of 1 to 5, and d represents an integer of 0 to 4.

[0161] By including the distyrylbenzene derivative represented by the general formula (2) as the (D) photosensitizer, the photosensitive resin composition of the present embodiment has better sensitivity (productivity), resolution, and adhesion than ever before in a laser direct imaging exposure method.

[0162] Unlike hydrogen atoms, alkyl groups, alkoxy groups, and halogen atoms, cyano groups are electron-withdrawing groups that have the effect of lowering the energy level of photosensitizers. It is presumed that they facilitate energy transfer with photoinitiators such as porphyrin, and are effective for increasing sensitivity.

[0163] The distyrylbenzene derivative represented by the general formula (2) includes at least one compound selected from 4'-(2-cyanostyryl)-2-cyanostyryl, 4'-(2-cyanostyryl)-3-cyanostyryl, 4'-(2-cyanostyryl)-4-cyanostyryl, and 1,4-bis(4-cyanostyryl)benzene.

[0164] Among them, 4'-(2-cyanostyryl)-2-cyanostyrene, 4'-(2-cyanostyryl)-3-cyanostyrene, and 1,4-bis(4-cyanostyryl)benzene are particularly preferred. Thus, the photosensitive resin composition of the present embodiment is particularly excellent in sensitivity (productivity), resolution, and adhesion.

[0165] In particular, 1,4-bis(4-cyanostyryl)benzene is particularly preferred from the viewpoints of sensitivity (productivity), resolution, and adhesion. 1,4-bis(4-cyanostyryl)benzene is presumably preferred because both of the two CN groups are in the para position, the conjugated system is extended, and the excitation energy gap becomes larger.

[0166] In addition, in the photosensitive resin composition of the present embodiment, the acid dissociation constant pKa of the (D) photosensitizer is greater than 9 and less than 12. Preferably, pKa is greater than 9.5 and less than 11. By having the acid dissociation constant pKa of the (D) photosensitizer be in the above range, the photosensitive resin composition of the present embodiment has better sensitivity (productivity), resolution, and adhesion than before in the laser direct imaging exposure method. It should be noted that the value of pKa uses a calculated value based on Advanced Chemistry Development (AD / Labs) Software V11.02 (1994-2018 ACD / Labs).

[0167] In addition, the molar absorption coefficient of the photosensitizer (D) at a wavelength of 405 nm is 100M -1 cm -1 Wherein, M is the unit of molar concentration, and the above molar absorption coefficient is the value when acetone is used as the solvent.

[0168] Examples of such a photosensitizer (D) include 4-[3-(4-chlorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]benzenesulfonamide. This can provide excellent sensitivity (productivity), resolution, and adhesion.

[0169] (D) The acid dissociation constant pKa of the photosensitizer is greater than 9 and less than 12, and the molar absorption coefficient at a wavelength of 405 nm is 100M -1 cm -1 The reason why the above is excellent in sensitivity (productivity), resolution, and adhesion is not yet clear, but is estimated as follows.

[0170] In order to strip the cured resist, it is necessary to immerse it in a strong alkaline solution. This is because the carboxyl groups in the resist are acid-dissociated, thereby increasing the ion concentration and osmotic pressure in the resist and promoting the swelling of the resist caused by the stripping solution. Therefore, in order to improve the stripping property, an ionic compound can be added to the resist. However, when simply adding an ionic compound, the resist swells during development and a normal pattern cannot be formed. Therefore, in order to maintain the pattern after development and improve the stripping property, a compound that does not dissociate in the developer but dissociates in the stripping solution is required.

[0171] Therefore, the acid dissociation constant pKa of the ionic compound is focused on. pKa is the pH value at which the dissociation rate of the ionic compound becomes 50%. At a pH below pKa, the dissociation rate becomes smaller, and at a pH above pKa, the dissociation rate becomes larger. The pH of the developer used in the dry film, i.e., sodium carbonate, is generally a weak alkaline of about 10, and the pH of the stripping solution such as sodium hydroxide and amine stripping solution is a strong alkaline of 14 or above. When the pKa here is equal to or greater than the pH of the stripping solution, the dissociation rate of the ionic compound in the stripping solution is small, and a significant improvement in stripping properties cannot be expected. Moreover, when the pKa is lower than the equal value of the pH of the developer, the dissociation rate of the ionic compound in the developer is large, and pattern swelling occurs during development. Therefore, by using a photosensitizer with an acid dissociation constant pKa greater than 9 and less than 12, it is possible to take into account both suppression of swelling during development and improvement of stripping properties. Furthermore, the molar absorption coefficient at a wavelength of 405nm is 100M -1 cm -1 When the above value is achieved, the resist can absorb laser light efficiently, and the sensitivity (productivity) is improved.

[0172] In addition, when a sensitizer having an acid dissociation constant pKa greater than 9 and less than 12 but not satisfying the molar absorptivity is used in combination with a photosensitizer satisfying the molar absorptivity, it is difficult to obtain the desired effect. As the reason, it is believed that the sensitizer compound satisfying the pKa undergoes an addition reaction with the monomer, thereby destroying the conjugated structure of the compound and failing to stably dissociate in the stripping solution. On the other hand, as in the present application, a photosensitizer satisfying both the pKa and the molar absorptivity transfers the light energy absorbed after light excitation to the hexaaryl biimidazole compound as an initiator, and returns to the original ground state. Therefore, the molecular structure of the compound will not be destroyed, and it can also stably dissociate in the stripping solution, which can improve the stripping property.

[0173] (D) The acid dissociation constant pKa of the photosensitizer is more preferably 9.1 or more and 11.9 or less from the viewpoint of sensitivity (productivity), resolution, and adhesion.

[0174] (D) The acid dissociation constant pKa of the photosensitizer may be 9.2 or more, 9.5 or more, 9.8 or more, 10.0 or more, 10.2 or more, 10.5 or more, 10.8 or more, 11.0 or more, 11.2 or more, 11.5 or more, or 11.8 or more. In addition, the acid dissociation constant pKa may be 11.8 or less, 11.6 or less, 11.4 or less, 11.2 or less, 11.0 or less, 10.8 or less, 10.6 or less, 10.4 or less, 10.2 or less, 10.0 or less, 9.8 or less, 9.6 or less, 9.4 or less, or 9.2 or less.

[0175] (D) The molar absorption coefficient of the photosensitizer at a wavelength of 405 nm is more preferably 200 nm from the viewpoint of sensitivity (productivity), resolution, and adhesion. -1 cm -1 Above and 1.0×10 10 M -1 cm -1 the following.

[0176] (D) The molar absorption coefficient of the photosensitizer at a wavelength of 405 nm can be 500M -1 cm -1 Above, it can be 1.0×10 3 M -1 cm -1 Above, it can be 2.0×10 3 M -1 cm -1 Above, it can be 3.0×10 3 M-1 cm -1 Above, it can be 5.0×10 3 M -1 cm -1 Above, it can be 1.0×10 4 M -1 cm -1 Above, it can be 5.0×10 4 M -1 cm -1 The upper limit is not particularly limited and may be 1.0×10 5 M -1 cm -1 Below, can be 5.0×10 4 M -1 cm -1 Below, can be 1.0×10 4 M -1 cm -1 Below, can be 5.0×10 3 M -1 cm -1 the following.

[0177] Furthermore, in the photosensitive resin composition of the present embodiment, (D) the photosensitizer preferably satisfies any of the following (1) or (2).

[0178] (1) The relative fluorescence intensity to 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-pyrazoline is greater than 100%.

[0179] (2) The relative fluorescence intensity to 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-pyrazoline is 5% or more, and the intersection wavelength of the absorption spectrum and the fluorescence spectrum is less than 400 nm.

[0180] By containing a component having specific properties as the (D) photosensitizer, the photosensitive resin composition of the present embodiment becomes excellent in sensitivity, resolution, and adhesion.

[0181] The initiation mechanism in the system of a sensitizer and porphyrin (2,4,5-triphenylimidazole) can be explained by energy transfer from the photoexcited sensitizer to porphyrin and subsequent cleavage of porphyrin.

[0182] The photoexcited sensitizer passes through the excited singlet state and the excited triplet state, releases fluorescence, phosphorescence, and heat, and then returns to the ground state. This process takes nanoseconds to microseconds. After returning to the ground state, when the excitation light is still irradiated, the sensitizer repeats the cycle of photoexcitation-decay again. The more cycles there are during the irradiation time of the excitation light, the greater the probability of the existence of the photoexcited state becomes, and therefore, it becomes easier to cause the sensitization reaction to porphyrin. In order to increase the cycle, it is important to use a singlet sensitizer with a short life span, that is, it can be considered that the greater the fluorescence of the sensitizer (the greater the fluorescence quantum yield), the higher the sensitivity. On the contrary, the triplet sensitizer has a long life span in a triplet state with low excitation energy, so the time until it returns to the ground state and is excited by light again is also longer, and the number of excitation cycles per unit time is less than that of the singlet sensitizer, so the sensitization efficiency to porphyrin is lowered.

[0183] This phenomenon is particularly notable in laser direct imaging exposure, which is a high-intensity, short-time exposure.

[0184] In addition, the change in free energy during the migration of photoelectrons is expressed by the Rehm-Weller equation, and it is considered that the larger the excitation energy, the easier it is to initiate a reaction.

[0185] From the above, it is believed that the greater the fluorescence quantum yield and the minimum excitation energy E of the photosensitizer, the higher the sensitivity.

[0186] In addition, it has been described that the above mechanism is particularly effective for the adhesion of thin wires.

[0187] Generally, if the exposure amount is increased, the adhesion of the resist is improved. However, if the exposure amount is increased, there is a tendency for the line width of the resist top to be wider, so it is important to compare the adhesion under the same line width.

[0188] In order to improve the close contact under the same line width, it is effective to reduce the amount of photosensitizer to increase the transmittance of the resist. This is because the difference between the absorption exposure amount of the top and bottom of the resist becomes smaller. However, the increase in transmittance reduces the absolute value of the absorption exposure amount itself, so the sensitivity becomes lower and becomes a problem.

[0189] Therefore, it is considered that a highly sensitive photosensitizer is effective for adhesion, and a photosensitizer that satisfies the following characteristics is particularly effective.

[0190] That is, in the photosensitive resin composition of the present embodiment, the (D) photosensitizer preferably satisfies any of the following (1) or (2). The photosensitive resin composition of the present embodiment contains a component having specific properties as the (D) photosensitizer, and therefore, both resolution and adhesion can be achieved without reducing sensitivity.

[0191] (1) The relative fluorescence intensity to 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-pyrazoline is greater than 100%.

[0192] The relative fluorescence intensity indicates how the excitation energy is used. The excitation energy is converted into heat and light. A large relative fluorescence intensity means that most of the excitation energy is converted into light and released.

[0193] The relative fluorescence intensity is preferably 110% or more, more preferably 120% or more, further preferably 130% or more, further preferably 140% or more, further preferably 150% or more, further preferably 160% or more, further preferably 170% or more, and particularly preferably 180% or more.

[0194] (2) The relative fluorescence intensity to 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-pyrazoline is 5% or more, and the intersection wavelength of the absorption spectrum and the fluorescence spectrum is less than 400 nm.

[0195] The intersection wavelength indicates the magnitude of the excitation energy. That is, the smaller the wavelength, the greater the excitation energy. The minimum excitation energy of the photosensitizer is the difference between the minimum energy of the ground state and the excited singlet state. According to the Franck-Condon principle, the energy of the intersection wavelength of the absorption spectrum and the fluorescence spectrum is equivalent to the minimum excitation energy. Therefore, when the intersection wavelength is small, the excitation energy is large, and therefore, the relative fluorescence intensity can be reduced. The greater the relative fluorescence intensity, the more preferred. The relative fluorescence intensity is preferably 10% or more, more preferably 20% or more, further preferably 30% or more, further preferably 40% or more, further preferably 50% or more, further preferably 60% or more, further preferably 70% or more, and particularly preferably 80% or more.

[0196] Such (D) photosensitizer is, for example, a fluorescent pigment having a maximum absorption peak at 330 nm to 450 nm. Examples of such fluorescent pigments include pyrazoline compounds, anthracene compounds, coumarin compounds, distyrylbenzene compounds, pyrene compounds, perylene compounds, and benzoxazole compounds. The substances satisfying the above conditions (1) and (2) are not limited to specific structures.

[0197] (D) The photosensitizer may contain a diphenylpyrazoline derivative represented by the following general formula (1). In addition, in the present embodiment, diphenylpyrazoline itself is not contained.

[0198]

[0199] In formula (1), R 1 , R 2R each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, an amino group, an alkylamino group having 1 to 20 carbon atoms, a fluoro group, a chloro group, a bromo group, a carboxyl group, a cyano group, a nitro group, an acetyl group, a sulfonyl group, or a sulfonamide group, and a and b each independently represent an integer from 0 to 5. When a is 2 or more, a plurality of R 1 Each of them may be the same or different. When b is 2 or more, a plurality of R 2 They may be the same or different.

[0200] Examples of the diphenylpyrazoline derivative represented by the general formula (1) include 4-[3-(4-chlorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]benzenesulfonamide.

[0201] The ratio of the photosensitizer (D) to the total amount of the components (A) to (E) is preferably 0.01 to 1% by mass. From the viewpoint of obtaining sufficient sensitivity, the ratio is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. On the other hand, from the viewpoint of obtaining high resolution, the ratio is preferably 1% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.5% by mass or less.

[0202] The total amount of the diphenylpyrazoline derivative or the distyrylbenzene derivative is 0.01 to 1% by mass relative to the total amount of the above-mentioned components (A) to (E). From the viewpoint of obtaining sufficient sensitivity, the amount must be 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. On the other hand, from the viewpoint of obtaining high resolution, the amount must be 1% by mass or less, preferably 0.8% by mass or less, and more preferably 0.5% by mass or less.

[0203] (E) Additives

[0204] In the present disclosure, "(E) additives" refer to components blended to impart desired functions to the photosensitive resin composition, and include components other than the above-mentioned (A) component, (B) component, (C) component, and (D) component.

[0205] (E) additives include carboxybenzotriazoles from the viewpoint of preventing the reddening of the substrate. The (E) additive includes 0.01 to 5% by mass of carboxybenzotriazoles relative to the total amount of the aforementioned (A) component to (E) component. From the viewpoint of laminating the photosensitive resin laminate on a substrate such as a copper-clad laminate and preventing the reddening of the substrate when developing after a period of time, the compounding amount must be 0.01% by mass or more, preferably 0.03% by mass or more, and more preferably 0.05% by mass or more. On the other hand, from the viewpoint of obtaining a high resolution, the compounding amount must be 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less.

[0206] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-5-carboxybenzotriazole containing an aminomethyl group which may be substituted, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-4-carboxybenzotriazole, 1-[N,N-bis(isopropyl)aminomethyl]- 〕-5-carboxybenzotriazole, 1-〔N-hydrogen-N-3-(2-ethylhexyloxy)-1-propylaminomethyl〕-5-carboxybenzotriazole, 1-〔N,N-bis(1-octyl)aminomethyl〕-5-carboxybenzotriazole, 1-〔N,N-bis(2-hydroxypropyl)aminomethyl〕-5-carboxybenzotriazole, 1-〔N,N-bis(1-butyl)aminomethyl〕-5-carboxybenzotriazole, etc. Among them, 1-〔N,N-bis(1-butyl)aminomethyl〕-5-carboxybenzotriazole is preferred from the viewpoint of the performance of preventing blushing. Regarding the substitution position of the carboxyl group, the 5-position and the 6-position may be mixed in the synthesis process, but both are preferred. For example, a mixture of the 5-position substitution form and the 6-position substitution form in a ratio of 0.5:1.5 to 1.5:0.5 (mass ratio), particularly a mixture of 1:1 (mass ratio) can be used. Sometimes it is simply recorded as "1-N-dibutylaminomethylcarboxybenzotriazole", which means a mixture of a 5-substitution body and a 6-substitution body. As carboxybenzotriazole, for example, compounds described in Japanese Patent Publication No. 2008-175957 can also be used. In addition, 2-mercaptobenzimidazole, 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-mercaptotriazole, 4,5-diphenyl-1,3-oxadiazole-2-yl, 5-amino-1H-tetrazole, etc. can also be used.

[0207] In the above-mentioned photosensitive resin composition, other additives which may be optionally added as the component (E) include colorants, radical polymerization inhibitors, benzotriazoles other than carboxybenzotriazoles, epoxy compounds of bisphenol A, plasticizers, and the like.

[0208] Examples of the colorant include fuchsin, phthalocyanine green, auramine base, para-fuchsin, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, malachite green (e.g., Aizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20, diamond green (e.g., Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), 1,4-bis(4-methylphenylamino)-9,10-anthraquinone (e.g., OPLASGREEN 533 manufactured by Orient Chemical Industries Co., Ltd.), 1,4-bis(butylamino)anthraquinone (e.g., OILBLUE 2N manufactured by Orient Chemical Industries Co., Ltd.), and 1,4-bis(isopropylamino)-9,10-anthraquinone (e.g., OILBLUE 630 manufactured by Orient Chemical Industries Co., Ltd.).

[0209] The ratio of the colorant to the total amount of the components (A) to (E) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, further preferably 0.5 to 2% by mass, and particularly preferably 0.5 to 1% by mass.

[0210] As a colorant, for example, a leuco dye or a fluorane dye may be contained. By containing them, the exposed part of the photosensitive resin layer is colored, which is preferable in terms of visibility. In addition, when an inspection machine or the like reads an alignment mark for exposure, it is easy to identify when the contrast between the exposed part and the unexposed part is large, which is advantageous.

[0211] As leuco dyes, tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenyl methane [leuco malachite green], etc. can be cited. From the viewpoint of good contrast, leuco crystal violet is particularly preferably used as a leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1 to 10% by mass relative to the total amount of the aforementioned (A) component to (E) component. From the viewpoint of making the contrast between the exposed part and the unexposed part good, it is preferred that the content is 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, it is preferred that the content is 10% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[0212] In addition, in the photosensitive resin composition, it is preferred to use a leuco dye in combination with a halogen compound from the viewpoint of optimizing adhesion and contrast. The halogen compound may be derived from the above-mentioned organic halogen compound as the component (C), and tribromomethylphenylsulfone is particularly preferred.

[0213] 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), nitrosophenylhydroxylamine aluminum salt, diphenylnitrosoamine, etc. Nitrosophenylhydroxylamine aluminum salt is preferred in order not to impair the sensitivity of the photosensitive resin composition.

[0214] Examples of benzotriazoles other than carboxybenzotriazoles 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, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0215] Examples of bisphenol A epoxy compounds include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminal.

[0216] It should be noted that the total content of the radical polymerization inhibitor, benzotriazoles other than carboxybenzotriazoles, carboxybenzotriazoles, and epoxy compounds of bisphenol A is preferably 0.001 to 3% by mass, more preferably 0.01 to 1% by mass, relative to the total amount of the above-mentioned components (A) to (E). From the viewpoint of imparting storage stability to the photosensitive resin composition, the content is preferably 0.001% by mass or more, and from the viewpoint of maintaining the sensitivity of the photosensitive resin composition and suppressing fading and coloring of the dye, the content is preferably 3% by mass or less.

[0217] Examples of the plasticizer include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like. In addition, compounds having a bisphenol skeleton such as ADEKANOL SDX-1569, ADEKANOL SDX-1570, ADEKANOL SDX-1571, and ADEKANOL SDX-479 (all manufactured by Asahi Denka Kogyo Co., Ltd.), NEWPOL BP-23P, NEWPOL BP-3P, NEWPOL BP-5P, NEWPOL BPE-20T, NEWPOL BPE-60, NEWPOL BPE-100, and NEWPOL BPE-180 (all manufactured by Sanyo Chemical Co., Ltd.), Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA-400, and Uniol DA-700 (all manufactured by NOF Corporation), BA-P4U glycol, and BA-P8 glycol (all manufactured by Nippon Emulsifier Co., Ltd.) may also be mentioned.

[0218] The content of the plasticizer relative to the total amount of the components (A) to (E) is preferably 1 to 50% by mass, more preferably 1 to 30% by mass. From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, the content is preferably 1% by mass or more, and from the viewpoint of suppressing insufficient curing and cold flow, the content is preferably 50% by mass or less.

[0219] The photosensitive resin composition of this embodiment preferably has a transmittance of light of a wavelength of 405 nm of more than 10% when the film thickness is 25 μm. The high transmittance improves adhesion and also improves sensitivity, thereby achieving excellent productivity.

[0220] <Photosensitive resin laminate>

[0221] The photosensitive resin laminated body of the present embodiment includes: a support; and a photosensitive resin layer provided on the support and containing a photosensitive resin composition.

[0222] Another embodiment provides a photosensitive resin laminate in which a photosensitive resin layer comprising the above-mentioned photosensitive resin composition is laminated on a support. If necessary, the photosensitive resin laminate may have a protective layer on the surface of the photosensitive resin layer opposite to the support side.

[0223] The support is usually a support film. As the support film, a transparent film that transmits the light radiated from the exposure light source is preferred. As such a support film, for example, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. can be cited. These films can also be stretched as needed, preferably with a haze of 5 or less. The thinner the film, the more advantageous it is for improving image formation and economy. In order to maintain the strength of the photosensitive resin laminate, it is preferred to use 10 to 30 μm.

[0224] The important characteristics of the protective layer used in the photosensitive resin laminate are as follows: the adhesion between the protective layer and the photosensitive resin layer is sufficiently smaller than the adhesion between the support and 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. In addition, for example, a film with excellent peelability as shown in Japanese Patent Publication No. 59-202457 can also be used. The film thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.

[0225] When polyethylene is used in the protective layer, there is a gel called fish eye on the surface of the polyethylene film, which is sometimes transferred to the photosensitive resin layer. If the fish eye is transferred to the photosensitive resin layer, air is entrained during lamination and sometimes becomes a void, resulting in a defect in the resist pattern. From the viewpoint of preventing fish eyes, the material of the protective layer is preferably stretched polypropylene. As a specific example, Alfan E-200A manufactured by Oji Paper Co., Ltd. can be cited.

[0226] The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The thinner the thickness, the better the resolution, and the thicker the thickness, the better the film strength.

[0227] The method for producing a photosensitive resin laminate is described. As a method for sequentially laminating a support, a photosensitive resin layer, and a protective layer as required to produce a photosensitive resin laminate, a known method can be used. For example, a photosensitive resin composition used in a photosensitive resin layer is mixed with a solvent for dissolving them to form a uniform solution, first, it is applied to a support film with a rod coater or a roller coater, and then, it is dried, and a photosensitive resin layer containing a photosensitive resin composition is laminated on the support film. Then, as required, a protective layer is laminated on the photosensitive resin layer, so that a photosensitive resin laminate can be produced.

[0228] It should be noted that examples of the solvent include ketones represented by methyl ethyl ketone (MEK), and alcohols represented by methanol, ethanol, or isopropanol. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support film becomes 500 to 4000 mPa·s at 25°C.

[0229] <Resist pattern forming method>

[0230] Another embodiment provides a method for forming an anti-etching pattern, which includes the following steps: laminating the above-mentioned photosensitive resin laminate on a substrate, exposing and developing. Below, an example of a method for forming an anti-etching pattern using the photosensitive resin laminate of the present embodiment is described. As the anti-etching pattern, a circuit substrate (printed circuit board), a flexible substrate, a lead frame substrate, a COF (chip on film) substrate, a semiconductor package substrate, a transparent electrode for a liquid crystal panel, a TFT wiring for a liquid crystal panel, a wiring for an organic EL display, a PDP (plasma display panel) electrode, etc. can be cited.

[0231] The resist pattern can be formed through the following steps.

[0232] The resist pattern forming method of the present embodiment includes the steps of laminating a photosensitive resin laminate on a substrate, exposing the photosensitive resin layer to light, and developing the exposed photosensitive resin layer.

[0233] (1) Lamination process

[0234] While peeling off the protective layer of the photosensitive resin layer, the photosensitive resin laminate is bonded to a substrate such as a copper-clad laminate or a flexible substrate using a hot roll laminator. The lamination conditions can be appropriately set under conventionally known conditions.

[0235] (2) Exposure process

[0236] A mask film having a desired pattern (e.g., a wiring pattern) is made to adhere to the support of the photosensitive resin laminate and exposed with an active light source, or by directly drawing a drawing pattern corresponding to the desired pattern. It is preferably exposed by direct drawing of the drawing pattern. As the exposure wavelength, i-rays, h-rays, g-rays, mixtures thereof, etc. can be appropriately used. For the photosensitive resin composition of the present embodiment, in terms of achieving high sensitivity and high resolution, exposure under i-rays or h-rays, especially h-rays, is advantageous. And thus, the photosensitive resin composition of the present embodiment is particularly useful in direct drawing. The exposure conditions can be appropriately set under previously known conditions.

[0237] (3) Development process

[0238] After exposure, the support on the photosensitive resin layer is peeled off, and then, an alkaline aqueous solution developer is used to develop and remove the unexposed portion to form a resist pattern on the substrate. As the alkaline aqueous solution, an aqueous solution of Na2CO3 or K2CO3 is used. The alkaline aqueous solution can be appropriately selected according to the characteristics of the photosensitive resin layer, and is generally a Na2CO3 aqueous solution with a concentration of about 0.2 to 2% by mass and a temperature of about 20 to 40°C.

[0239] After the above steps, a resist pattern can be obtained. However, depending on the situation, a heating step of about 100 to 300° C. can be further performed. By performing this heating step, it is possible to further improve the chemical resistance. A heating furnace using hot air, infrared rays, or far infrared rays can be used for heating.

[0240] The method for forming a metal wiring according to the present embodiment includes the steps of: forming a resist pattern by the above-mentioned method; forming a metal wiring (conductor pattern) using the resist pattern; and peeling off the resist pattern.

[0241] Another method provides a method for manufacturing a circuit substrate, which includes the following steps: laminating the above-mentioned photosensitive resin laminate on a substrate, and exposing, developing, and plating; and, a method for manufacturing a circuit substrate, which includes the following steps: laminating the above-mentioned photosensitive resin laminate on a substrate, and exposing, developing, and etching. The circuit substrate can be manufactured as follows: the substrate formed with a resist pattern in the above-mentioned steps of the resist pattern forming method is further etched or plated to manufacture. In particular, when the exposure is performed by direct drawing of the drawing pattern in the manufacture of the circuit substrate, there is no need to make a mask, so it is advantageous from the perspective of productivity. Etching and plating can be implemented as follows.

[0242] (4) Etching process or plating process

[0243] The surface of the substrate exposed by the development (for example, the copper surface in the case of a copper-clad laminate) is etched or plated to form a conductor pattern. The etching and plating methods can be appropriately used by conventionally known methods.

[0244] (5) Peeling process

[0245] Afterwards, the resist pattern is stripped from the substrate using an aqueous solution having a stronger alkalinity than the developer. There is no particular limitation on the aqueous alkaline solution used for stripping, and an aqueous solution of NaOH 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 may also be added to the stripping solution.

[0246] In particular, in the present embodiment, by using a diphenylpyrazoline derivative as the (D) photosensitizer, particularly excellent post-plating releasability is achieved.

[0247] The circuit substrate can be manufactured through the above steps.

[0248] In addition, the manufacturing method of the semiconductor package of the present embodiment provides a manufacturing method of the semiconductor package, which includes the following steps: a step of forming a resist pattern on a semiconductor package substrate as a base material by the above-mentioned resist pattern forming method; and a step of etching or plating the semiconductor package substrate on which the resist pattern is formed. The semiconductor package substrate and the semiconductor package can be appropriately configured by any conventionally known configuration. Moreover, the formation of the resist pattern and the etching or plating can be implemented in the above-mentioned steps respectively.

[0249] The photosensitive resin laminate of the present embodiment is a photosensitive resin laminate suitable for manufacturing conductor patterns of circuit substrates (printed circuit boards), flexible substrates, lead frame substrates, COF (chip on film) substrates, semiconductor package substrates, transparent electrodes for liquid crystal panels, TFT wiring for liquid crystal panels, wiring for organic EL displays, electrodes for PDP (plasma display panel), etc.

[0250] As described above, according to the present embodiment, a photosensitive resin composition and a photosensitive resin laminate having excellent sensitivity (productivity), resolution, and adhesion can be provided; and a method for forming a resist pattern and a method for forming a conductor pattern using the photosensitive resin laminate can be provided.

[0251] It should be noted that the above-mentioned various parameters were measured according to the measurement methods in the examples described later unless otherwise specified.

[0252] Example

[0253] Next, the present embodiment is described in more detail with reference to examples and comparative examples, but the present embodiment is not limited to the following examples unless it deviates from the gist thereof. It should be noted that the physical properties in the above-mentioned mode for implementing the invention and the examples described below were measured by the following methods.

[0254] <405nm transmittance of photosensitive resin layer>

[0255] The polyethylene film of the photosensitive resin laminate was peeled off, and the absorption spectrum was measured using a spectrophotometer (Hitachi U-3010). The absorbance at 405 nm was converted into transmittance as the measured value. Here, the amount of photosensitizer added was such that the transmittance at 405 nm was about 40, or so that the performance of the resist could be compared when the photosensitizer absorbed the same amount of light.

[0256] <Sensitivity evaluation>

[0257] First, a 0.4 mm thick copper-clad laminate on which a 35 μm rolled copper foil was laminated was jet-polished using a grinding material (manufactured by Japan Carlit Co., Ltd., Sakurandom R (registered trademark #220)) at a press pressure of 0.2 MPa.

[0258] Next, while peeling off the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was laminated on a copper-clad laminate preheated to 60° C. using a hot roll laminator (AL-700 manufactured by Asahi Kasei Corporation) at a roll temperature of 105° C. The air pressure was set to 0.35 MPa using a cylinder pressure gauge, the lateral width of the laminate was set to 20 cm, and the lamination speed was set to 1.5 m / min.

[0259] Next, exposure was performed at an illumination of 80 mW using a direct-drawing exposure device (manufactured by Hitachi Via Mechanics, Ltd., DE-1DH, light source: GaN blue-violet diode, main wavelength 405±5 nm) and a Stouffer 21-step step meter as a mask.

[0260] After the polyethylene terephthalate film is peeled off, an alkali developer (manufactured by FUJI MACHINERY LTD., CO., developer for dry film) is used to spray a 1 mass % Na2CO3 aqueous solution at 30°C for a specified time, and the unexposed portion of the photosensitive resin layer is dissolved and removed for a time twice the minimum development time. At this time, the minimum time required for the photosensitive resin layer in the unexposed portion to be completely dissolved is taken as the minimum development time. The actual development time is twice the minimum development time to develop and obtain a cured resist pattern.

[0261] For the substrate after development, the exposure amount at which the top line width of the resist in the mask pattern with a line / space of 20 μm / 20 μm becomes 20 μm as the mask value is taken as the sensitivity.

[0262] <Resolution evaluation>

[0263] The substrate was leveled and laminated in the same manner as in the sensitivity evaluation step, and the drawing data was used to expose a line pattern with a ratio of 1:1 between the width of the exposed part and the width of the unexposed part at an exposure amount of the line width obtained in the sensitivity evaluation. Thereafter, development was performed at a development time twice the minimum development time, and the minimum mask width at which a cured resist line was normally formed was taken as the resolution value.

[0264] <Adhesion Evaluation>

[0265] The substrate was leveled and laminated in the same manner as in the sensitivity evaluation step, and the drawing data was used to expose a line pattern with a ratio of 1:200 between the width of the exposed part and the width of the unexposed part at an exposure amount of the line width obtained in the sensitivity evaluation. Thereafter, development was performed at a development time twice the minimum development time, and the minimum mask width at which a cured resist line was normally formed was taken as the value of adhesion.

[0266] <Evaluation of peelability after plating>

[0267] The substrate was leveled and laminated in the same manner as in the sensitivity evaluation step, and the line pattern was exposed with the exposure amount of the line width obtained in the sensitivity evaluation, and the width of the exposed part and the unexposed part was 1:1. After that, the development was performed for a development time twice the minimum development time. The developed substrate was immersed in an acid degreasing FRX (10% aqueous solution, manufactured by Atotech Japan KK) bath at 40°C for 4 minutes. After washing with water, it was immersed in a 10% sulfuric acid aqueous solution at room temperature for 2 minutes.

[0268] COPPER SULFATE CONC. (Meltex Corporation) was diluted 3.6 times with 19wt% sulfuric acid, and 200ppm of concentrated hydrochloric acid was added. Then, 0.4ml / l and 20ml / l of Kaparacid HL and Kaparacid GS as brighteners were added respectively. The prepared sulfuric acid copper plating solution was used to plate the plating resistance evaluation substrate (6cm×12.5cm) after the pre-plating treatment for 65 minutes using a Haring tank uniform plating device (Yamamoto Gold Plating Tester Co., Ltd.) with an applied current of 0.4A. The thickness of the copper plating film at this time was 20μm thick.

[0269] The plated evaluation substrate was immersed in a 1.5 wt% caustic soda aqueous solution at 50°C for 4 minutes without stirring, and the resist film was peeled off. The minimum mask width at which the cured resist line between the plating patterns was completely peeled off was taken as the value of post-plating peelability.

[0270] [Examples 1 to 3 and Comparative Examples 1 to 7]

[0271] The photosensitive resin composition and the solvent having the composition shown in Table 1 (wherein the numbers of each component represent the compounding amount (mass part) in terms of solid content) were fully stirred and mixed to obtain a photosensitive resin composition preparation liquid having a solid content of 60 mass %. As a support, a 16 μm thick polyethylene terephthalate film (FB40 manufactured by Toray Industries, Ltd., haze value 0.6) was prepared, and the photosensitive resin composition preparation liquid was evenly applied to the surface of the film with a bar coater, and dried in a dryer at 95°C for 2 minutes and 30 seconds to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 25 μm.

[0272] Next, a 19 μm thick polyethylene film (GF-818 manufactured by Tamapoly Corporation) was attached as a protective layer to the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated, thereby obtaining a photosensitive resin laminate.

[0273] The obtained photosensitive resin laminate was subjected to various evaluations. The results are shown in Table 1. Table 2 also shows the components (A) to (E) used in the Examples and Comparative Examples.

[0274] [Table 1]

[0275]

[0276] [Table 2]

[0277]

[0278]

[0279]

[0280] The following can be seen from the results in Table 1.

[0281] First, it can be seen that Example 1 or 2, in which the acid dissociation constant pKa of the (D) photosensitizer is greater than 9 and less than 12, can exhibit high sensitivity and high resolution characteristics in H-ray exposure compared to Comparative Examples 1 to 6, in which the pKa is less than 9 or greater than 12. In addition, it can be seen that Example 1, in which a diphenylpyrazoline derivative is used as the (D) photosensitizer, exhibits particularly excellent post-plating peelability.

[0282] Comparison between Examples 1 and 2 shows that the compound (B) having an ethylenically unsaturated double bond contains a hydroxyl group in the molecule (Example 1), and thus is particularly excellent in sensitivity (productivity), resolution, and adhesion.

[0283] In addition, Examples 3 to 5 containing a distyrylbenzene derivative as the (D) photosensitizer can exhibit high sensitivity and high resolution characteristics in h-ray exposure compared to Comparative Example 7 not containing a distyrylbenzene derivative. It is found that sensitivity (productivity), resolution, and adhesion are particularly excellent.

[0284] As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably within the range which does not deviate from the summary of this invention.

[0285] Industrial Applicability

[0286] The photosensitive resin composition of the present invention can be suitably used for the production of conductor patterns in circuit substrates (printed circuit boards), flexible substrates, lead frame substrates, COF (chip on film) substrates, semiconductor package substrates, transparent electrodes for liquid crystal panels, TFT wiring for liquid crystal panels, wiring for organic EL displays, electrodes for PDP (plasma display panel), etc. due to its high sensitivity and high resolution.

Claims

1. A photosensitive resin composition comprising the following ingredients: (A) Alkali soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and, (D) a photosensitizer, The acid dissociation constant pKa of the photosensitizer (D) is greater than 9 and less than 12, and the molar absorption coefficient at a wavelength of 405 nm is 100M -1 cm -1 Above, among them, M is the unit of molar concentration, and the molar absorption coefficient is the value when acetone is used as the solvent. The alkali-soluble polymer (A) comprises one or more components selected from the group consisting of the following (a-1) and (a-2), (a-1) an acrylic copolymer derived from a polymerization component containing 15 to 60% by mass of styrene and at least one acrylic monomer selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters; (a-2) an acrylic copolymer derived from a polymerization component containing 20 to 85% by mass of benzyl methacrylate and at least one acrylic monomer selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters other than benzyl methacrylate, The (C) photopolymerization initiator includes a hexaarylbiimidazole compound.

2. The photosensitive resin composition according to claim 1, wherein The (D) photosensitizer is 4-[3-(4-chlorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]benzenesulfonamide.

3. The photosensitive resin composition according to claim 2, wherein The (B) compound having an ethylenically unsaturated double bond contains a hydroxyl group in the molecule.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein The (D) photosensitizer is a fluorescent pigment having a maximum absorption peak at 330nm-450nm.

5. The photosensitive resin composition according to any one of claims 1 to 3, wherein The photosensitive resin composition has a transmittance of greater than 10% for light having a wavelength of 405 nm when the film thickness is 25 μm.

6. The photosensitive resin composition according to any one of claims 1 to 3, wherein The (D) photosensitizer has an acid dissociation constant pKa greater than 9.5 and less than 11.

7. The photosensitive resin composition according to any one of claims 1 to 3, wherein The (B) compound having an ethylenically unsaturated double bond contains a hydroxyl group in the molecule.

8. The photosensitive resin composition according to claim 1, wherein The photosensitive resin composition is a photosensitive resin composition for forming metal wiring. 9 . A photosensitive resin laminate comprising: a support; and a photosensitive resin layer provided on the support and comprising the photosensitive resin composition according to claim 1 .

10. A method for forming a resist pattern, comprising the following steps: A step of laminating the photosensitive resin laminate according to claim 9 on a substrate; The process of exposing the photosensitive resin layer to light; and The step of developing the exposed photosensitive resin layer.

11. The resist pattern forming method according to claim 10, wherein: The exposure is performed by direct drawing of a drawing pattern.

12. A method for forming a metal wiring, comprising the following steps: A process of forming a resist pattern by the method according to claim 10 or 11; A step of forming a metal wiring using the resist pattern; and A step of peeling off the resist pattern.

13. A method for manufacturing a semiconductor package, comprising the following steps: a step of forming an anti-etching pattern on a semiconductor package substrate as a base material by the anti-etching pattern forming method according to claim 10 or 11; and a step of etching or plating the semiconductor package substrate on which the anti-etching pattern is formed.

Images