CN105793778B

CN105793778B - Photosensitive resin composition and photosensitive resin laminate

Info

Publication number: CN105793778B
Application number: CN201480064426.1A
Authority: CN
Inventors: 松田隆之
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp
Priority date: 2013-12-26
Filing date: 2014-12-26
Publication date: 2021-02-09
Anticipated expiration: 2034-12-26
Also published as: TWI721371B; JP6666944B2; TWI674478B; JP6320425B2; TW201616234A; TW201533526A; KR20180021226A; KR102248976B1; KR102437195B1; KR20160070801A; WO2015099137A1; TW201727369A; KR20210049995A; JP2018120242A; TWI541596B; MY174577A; CN111596526B; TW201922805A; CN105793778A; TWI592748B

Abstract

A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator, wherein in a resist pattern obtained by forming a photosensitive resin layer comprising the photosensitive resin composition on a substrate surface and performing exposure and development, the difference between a pattern resolution a at the time of performing the exposure with the substrate surface in focus and a pattern resolution B at the time of performing the exposure with the substrate surface in focus at a position shifted by 300 [ mu ] m in the thickness direction of the substrate is less than 15 [ mu ] m.

Description

Photosensitive resin composition and photosensitive resin laminate

Technical Field

The present invention relates to a photosensitive resin composition and the like.

Background

Electronic devices such as personal computers and cellular phones use printed wiring boards for mounting components, semiconductors, and the like. As a resist (resist) for manufacturing a printed wiring board or the like, a photosensitive resin laminate in which a photosensitive resin layer is laminated on a support film and a protective film is further laminated on the photosensitive resin layer as needed, a so-called dry film photoresist (hereinafter, also referred to as DF) has been conventionally used. As the photosensitive resin layer, an alkali development type photosensitive resin layer using a weak alkali aqueous solution as a developing solution is generally used at present. In order to manufacture a printed wiring board or the like using DF, for example, the following steps are performed. When the DF has a protective film, the protective film is peeled off first. Then, DF is laminated on a substrate for permanent circuit fabrication such as a copper-clad laminate or a flexible substrate using a laminating apparatus or the like, and exposed through a wiring pattern mask film or the like. Next, the support film is peeled off as necessary, and the photosensitive resin layer in an uncured portion (for example, an unexposed portion in the case of a negative type) is dissolved or dispersed and removed by a developer to form a cured resist pattern (hereinafter, also referred to simply as a resist pattern) on the substrate.

The process of forming a circuit after the resist pattern is formed is roughly classified into two methods. The first method is a method (etching method) of etching away a substrate surface (for example, a copper surface of a copper-clad laminate) not covered with a resist pattern and then removing the resist pattern with an alkaline aqueous solution stronger than a developer. The second method is a method (plating method) of performing plating treatment of copper, solder, nickel, tin, or the like on the substrate surface, removing the resist pattern portion in the same manner as in the first method, and etching the substrate surface (for example, the copper surface of the copper-clad laminate) that appears. Copper chloride, ferric chloride, copper ammonia complex solution, etc. are used for etching. In recent years, with the progress of miniaturization and weight reduction of electronic devices and miniaturization and densification of printed wiring boards, there has been a demand for providing a high-performance DF having a high resolution and the like in the above-mentioned manufacturing process. As a technique for realizing such high resolution, patent document 1 describes a photosensitive resin composition in which resolution is improved by a specific thermoplastic resin, a monomer and a photopolymerization initiator.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2010-249884

Disclosure of Invention

Problems to be solved by the invention

However, in the case of an exposure method using direct writing of a writing pattern or the like, which is frequently used in recent years, the position of the focal point has a large influence on the resolution. For example, if the position of the focal point during exposure is shifted from the substrate surface due to warpage or strain of the substrate or a problem of poor setting of the exposure apparatus, the resolution is greatly deteriorated. As a result, a short circuit problem occurs when a circuit is formed by an etching method, and a defect, an open circuit, a plating failure, and the like may occur when a circuit is formed by a plating method. The technique described in patent document 1 has room for further improvement from such a viewpoint.

Accordingly, an object of the present invention is to provide a photosensitive resin laminate exhibiting high resolution even when focus shifts during exposure, a photosensitive resin composition for forming the same, and a resist pattern forming method and a conductor pattern forming method using the photosensitive resin laminate.

Means for solving the problems

The present inventors have conducted extensive studies and repeated experiments to solve the above problems. As a result, the following technical means have been found to solve the above problems.

Namely, the present invention is as follows.

[1] A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator,

in a resist pattern obtained by forming a photosensitive resin layer containing the photosensitive resin composition on a substrate surface and performing exposure and development, the difference between a pattern resolution a when performing the exposure with the substrate surface in focus and a pattern resolution b when performing the exposure with the substrate surface in focus at a position shifted by 300 [ mu ] m toward the substrate inner side in the thickness direction of the substrate is less than 15 [ mu ] m.

[2] The photosensitive resin composition according to [1], which contains the photosensitive resin composition in an amount based on the mass of all solid components

The alkali-soluble polymer (A): 10 to 90 mass%;

the above-mentioned (B) compound having an ethylenically unsaturated double bond: 5 to 70 mass%; and

the above-mentioned (C) photopolymerization initiator: 0.01 to 20% by mass.

[3] The photosensitive resin composition according to [2], further comprising (D) a phenol derivative based on the mass of all solid components of the photosensitive resin composition: 0.001 to 10% by mass.

[4] The photosensitive resin composition according to [3], wherein the phenol derivative (D) contains a compound represented by the following general formula (I),

{ in formula (I), R¹Represents an optionally substituted straight-chain alkyl group, a branched-chain alkyl group, an aryl group, a cyclohexyl group, a straight-chain alkyl group via a divalent linking group, a branched-chain alkyl group via a divalent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group, and a plurality of R' s¹And optionally, m is an integer of 0 to 4, n is an integer of 1 or more, A is a monovalent organic group when n is 1, and A is a divalent or more organic group, a single bond, or a linking group comprising a conjugated bond when n is 2 or more. }.

[5] The photosensitive resin composition according to [3] or [4], wherein the phenol derivative (D) contains a compound represented by the following general formula (II),

{ formula (II), wherein R²Represents an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group via a divalent linking group, branched-chain alkyl group via a divalent linking group, cyclohexyl group via a divalent linking group, or aryl group via a divalent linking group, and R is³、R⁴And R⁵Each independently represents hydrogen, or an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group via a divalent linking group, branched-chain alkyl group via a divalent linking group, cyclohexyl group via a divalent linking group, or aryl group via a divalent linking group. }.

[6] The photosensitive resin composition according to [3] or [4], wherein the phenol derivative (D) contains a compound represented by the following general formula (III),

{ in formula (III), R⁶And R⁷Each independently represents an optionally substituted, straight-chain alkyl group, a branched-chain alkyl group, an aryl group, a cyclohexyl group, a straight-chain alkyl group via a divalent linking group, a branched-chain alkyl group via a divalent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group, and R's are independently present⁶And R⁷And p and q are each independently an integer of 0 to 4, and B represents a single bond or a linking group comprising a conjugated bond. }.

[7] A photosensitive resin composition comprising, based on the mass of the entire solid content of the photosensitive resin composition

(A) Alkali-soluble polymers: 10 to 90 mass%;

(B) compound having an ethylenically unsaturated double bond: 5 to 70 mass%;

(C) photopolymerization initiator: 0.01 to 20 mass%; and

(D) phenol derivatives: 0.001 to 10% by mass,

the phenol derivative (D) contains at least one selected from the group consisting of a compound represented by the following general formula (II) and a compound represented by the following general formula (III),

{ formula (II), wherein R²Represents an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group via a divalent linking group, branched-chain alkyl group via a divalent linking group, cyclohexyl group via a divalent linking group, or aryl group via a divalent linking group, and R is³、R⁴And R⁵Each independently represents hydrogen, orOptionally substituted, straight chain alkyl, branched alkyl, aryl, cyclohexyl, straight chain alkyl via a divalent linking group, branched alkyl via a divalent linking group, cyclohexyl via a divalent linking group, or aryl via a divalent linking group. }

[8] The photosensitive resin composition according to [6] or [7], wherein B is a single bond in the formula (III).

[9] The photosensitive resin composition according to any one of [6] to [8], wherein p ═ q ═ 0 in the formula (III).

[10]According to [3]～[9]The photosensitive resin composition of any of the above, wherein the (D) phenol derivative has a reaction rate constant of 20L mol with peroxy radicals^-1·sec^-1The above compounds.

[11] The photosensitive resin composition according to any one of [1] to [10], wherein the monomer component of the alkali-soluble polymer (A) has an aromatic hydrocarbon group.

[12] The photosensitive resin composition according to any one of [1] to [11], wherein the photopolymerization initiator (C) contains an acridine.

[13] A photosensitive resin laminate comprising a support layer and a photosensitive resin layer laminated thereon, wherein the photosensitive resin layer comprises the photosensitive resin composition according to any one of [1] to [12 ].

[14] A resist pattern forming method comprising a laminating step of laminating the photosensitive resin laminate of [13] on a substrate, an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and a development step of developing and removing an unexposed portion of the photosensitive resin layer.

[15] The resist pattern forming method according to [14], wherein the exposure step is performed by an exposure method using direct drawing of a drawn pattern or an exposure method in which an image of a photomask is projected through a lens.

[16] The resist pattern forming method according to [15], wherein the exposure step is performed by an exposure method using direct drawing of a drawn pattern.

[17] The photosensitive resin composition according to any one of [1] to [12], which is used in a resist pattern formation method in an exposure step by an exposure method in which a drawing pattern is directly drawn.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a photosensitive resin laminate exhibiting high resolution even when the focus shifts during exposure, a photosensitive resin composition for forming the same, and a resist pattern forming method and a conductor pattern forming method using the photosensitive resin laminate. As a result, even when the position of the focal point during exposure deviates from the substrate surface due to warpage or strain of the substrate, a problem of poor setting of the exposure apparatus, or the like, a problem of short circuit can be reduced when forming a circuit by the etching method, and problems such as a defect, disconnection, plating failure, or the like can be reduced when forming a circuit by the plating method.

Detailed Description

Exemplary modes for carrying out the present invention (hereinafter, simply referred to as "embodiments") will be described in detail below. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[ photosensitive resin composition ]

In an embodiment, the photosensitive resin composition has the following characteristics: in a resist pattern obtained by forming a photosensitive resin layer containing the photosensitive resin composition on a substrate surface and performing exposure and development, the difference between a pattern resolution a when performing the exposure with the substrate surface in focus and a pattern resolution b when performing the exposure with the substrate surface in focus at a position shifted by 300 [ mu ] m toward the substrate inner side in the thickness direction of the substrate is less than 15 [ mu ] m. Thus, even when the position of the focal point during exposure deviates from the substrate surface due to warpage or strain of the substrate, a problem of poor setting of the exposure apparatus, or the like, a problem of short circuit can be reduced when forming a circuit by the etching method, and problems such as a defect, disconnection, plating failure, or the like can be reduced when forming a circuit by the plating method. The difference between the pattern resolution a and the pattern resolution b is preferably 12 μm or less, and more preferably 10 μm or less. On the other hand, the difference between the pattern resolution a and the pattern resolution b is preferably 0 μm or more, more preferably 5 μm or more, and still more preferably 7 μm or more, from the viewpoint of ease of production, little sensitivity reduction, and the like. It should be noted that, unless otherwise specified, various measurement values in the present specification can be measured by the method described in [ example ] of the present disclosure or by a method equivalent thereto by those skilled in the art.

With the recent miniaturization and thinning of electronic devices, demands for higher density of wiring, application of flexible printed wiring boards, and further multilayering have been increasing. As the number of layers increases, surface waviness increases, and there is a possibility that resolution deteriorates due to focus shift during exposure and line width reproducibility deteriorates, and as a result, problems such as short-circuit defects, disconnection, plating defects, and failure to form a desired copper wire are becoming important. In the case of a large substrate, the same problem may occur due to adsorption failure at the time of exposure, non-uniformity of film thickness in the plane, and the like. Therefore, it has been found that it is effective to solve the above-mentioned problems by designing a photosensitive resin composition by focusing on the difference between a pattern resolution a when exposing a substrate surface to a focus position and a pattern resolution b when exposing the substrate surface to a position shifted by 300 μm from the substrate surface to the inside of the substrate in the thickness direction of the substrate (a reference value set so that the shift amount of the focus position such as the amount of undulation of the surface is a very large shift amount) to the focus position. That is, it has been found that, by selecting and using a specific photosensitive resin composition having a pattern resolution a and a pattern resolution b within a certain range, it is effective for reducing problems such as short-circuit defects, disconnections, plating defects, and failure to form a desired copper wire, even in recent situations such as high wiring density and multilayering.

The means for making the difference between the pattern resolution a and the pattern resolution b within the above-mentioned specific range is not particularly limited, and for example, the composition of the photosensitive resin composition is variously adjusted so that the details of each component are as described later.

In an embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator. The photosensitive resin composition preferably contains (a) an alkali-soluble polymer based on the mass of all solid components of the photosensitive resin composition: 10 to 90 mass%; (B) compound having an ethylenically unsaturated double bond: 5 to 70 mass%; and (C) a photopolymerization initiator: 0.01 to 20% by mass. The respective components will be explained in turn below.

Alkali-soluble Polymer (A)

In the present disclosure, the alkali-soluble polymer (a) includes a polymer that is easily soluble in an alkali substance. More specifically, the amount of carboxyl groups contained in the alkali-soluble polymer (A) is 100 to 600, preferably 250 to 450 in terms of acid equivalent. The acid equivalent means the mass (unit: g) of the polymer having 1 equivalent of carboxyl group in the molecule. (A) The carboxyl group in the alkali-soluble polymer is necessary to provide the photosensitive resin layer with developability and releasability against an alkali aqueous solution. From the viewpoint of improving development resistance, resolution, and adhesion, the acid equivalent is preferably 100 or more. And the acid equivalent is more preferably 250 or more. On the other hand, from the viewpoint of improving developability and releasability, the acid equivalent is preferably 600 or less. And the acid equivalent is more preferably 450 or less. In the present disclosure, the acid equivalent is a value measured by a potentiometric titration method using a potentiometric titrator and titration with a 0.1 mol/L NaOH aqueous solution.

(A) The weight average molecular weight of the alkali-soluble polymer is preferably 5000 to 500000. From the viewpoint of improving the resolution and the developability, the weight average molecular weight is preferably 500000 or less. The weight average molecular weight is more preferably 300000 or less, and still more preferably 200000 or less. On the other hand, from the viewpoint of controlling the properties of development aggregates and the properties of an unexposed film such as the burring property and the chipping property in forming a photosensitive resin laminate, the weight average molecular weight is preferably 5000 or more. The weight average molecular weight is more preferably 10000 or more, and still more preferably 20000 or more. The beading property refers to a degree to which a photosensitive resin layer (i.e., a layer containing a photosensitive resin composition) easily overflows from an end face of a roll when the photosensitive resin laminate is wound in a roll. The chipping property is a degree to which chips are likely to be scattered when an unexposed film is cut by a cutter. If the chips adhere to the upper surface of the photosensitive resin laminate, the chips are transferred to a mask in a subsequent exposure step or the like, and become a cause of defective products.

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

The first monomer is a carboxylic acid or an anhydride having one polymerizable unsaturated group in the molecule. The first monomer is classified into a first monomer having an aromatic hydrocarbon group and a first monomer having no aromatic hydrocarbon group. Examples of the first monomer having an aromatic hydrocarbon group include cinnamic acid and the like. Examples of the first monomer having no aromatic hydrocarbon group include (meth) acrylic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride, and maleic half ester. In particular, (meth) acrylic acid is preferable from the viewpoint of ease of production and developability. In the present disclosure, (meth) acrylic acid refers to acrylic acid and/or methacrylic acid. The same applies hereinafter.

The second monomer is a monomer which is not acidic and has at least one polymerizable unsaturated group in the molecule. The second monomer is classified into a second monomer having an aromatic hydrocarbon group and a second monomer having no aromatic hydrocarbon group. Examples of the second monomer having an aromatic hydrocarbon group include benzyl (meth) acrylate, styrene, and styrene derivatives. Examples of the second monomer having no aromatic hydrocarbon group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and esters of vinyl alcohol, such as vinyl acetate and (meth) acrylonitrile. Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferable. Styrene and benzyl (meth) acrylate are preferable from the viewpoint of improving the resolution and adhesion of the resist pattern. In addition, styrene and benzyl (meth) acrylate are preferable from the viewpoint of reducing the difference in resolution between when the position of the focal point at the time of exposure is aligned with the substrate surface and when the position of the focal point at the time of exposure is shifted from the substrate surface.

(A) The alkali-soluble polymer preferably contains a monomer component having an aromatic hydrocarbon group. The content ratio of the monomer component having an aromatic hydrocarbon group in the alkali-soluble polymer (a) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more, based on the total mass of all the monomer components. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 80% by mass or less.

In a preferred embodiment, the alkali-soluble polymer (a) may contain a polymer having a structure derived from (meth) acrylic acid, an alkyl (meth) acrylate, and styrene, and/or a polymer having a structure derived from (meth) acrylic acid, benzyl (meth) acrylate, and an alkyl (meth) acrylate.

The copolymerization ratio of the first monomer and the second monomer is preferably 10 to 60 mass% of the first monomer and 40 to 90 mass% of the second monomer, more preferably 15 to 35 mass% of the first monomer and 65 to 85 mass% of the second monomer, based on the mass of the entire polymerization components.

(A) The alkali-soluble polymer may be used alone or in combination of two or more. When two or more types of alkali-soluble polymers are used in combination, it is preferable to use two types of alkali-soluble polymers containing monomer components having an aromatic hydrocarbon group in combination, or use an alkali-soluble polymer containing monomer components having an aromatic hydrocarbon group in combination with an alkali-soluble polymer containing no monomer components having an aromatic hydrocarbon group in combination. In the latter case, the ratio of the alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group to be used is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the alkali-soluble polymer (a).

(A) The synthesis of the alkali-soluble polymer is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting a mixture of the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropyl alcohol, and heating and stirring the mixture. Sometimes, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As a synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

(A) The ratio of the alkali-soluble polymer to the total solid content of the photosensitive resin composition is preferably within a 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 alkali-soluble polymer (a) to the photosensitive resin composition is preferably 90% by mass or less. On the other hand, from the viewpoint of improving the melt-edge resistance, the ratio of the alkali-soluble polymer (a) to the photosensitive resin composition is preferably 10% by mass or more.

< Compound having an ethylenically unsaturated double bond >

(B) The compound having an ethylenically unsaturated double bond preferably contains a compound having a (meth) acryloyl group in the molecule from the viewpoint of curability and compatibility with the alkali-soluble polymer (a). (B) The number of (meth) acryloyl groups in the compound may be 1 or more.

Examples of the compound (B) having one (meth) acryloyl group include a compound obtained by adding (meth) acrylic acid to one end of a polyoxyalkylene, a compound obtained by adding (meth) acrylic acid to one end of a polyoxyalkylene and etherifying the other end with an alkyl group or an allyl group, and the like.

Examples of such compounds include:

phenoxy hexaethylene glycol mono (meth) acrylate which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to a phenyl group,

(meth) acrylate of a compound obtained by adding nonylphenol to polypropylene glycol to which propylene oxide is added in an amount of 2 moles on average and polyethylene glycol to which ethylene oxide is added in an amount of 7 moles on average, that is, 4-n-nonylphenoxypheylene glycol dipropylene glycol (meth) acrylate,

(meth) acrylic acid esters of compounds obtained by adding nonylphenol to polypropylene glycol to which propylene oxide is added in an average amount of 1 mole and polyethylene glycol to which ethylene oxide is added in an average amount of 5 moles, that is, 4-n-nonylphenoxypentaethylene glycol monopropylene glycol (meth) acrylate,

4-n-nonylphenoxy octaethylene glycol (meth) acrylate (e.g., M-114, manufactured by Tokya corporation) which is an acrylate of a compound obtained by adding nonylphenol to polyethylene glycol to which an average of 8 moles of ethylene oxide has been added.

Examples of the compound having two (meth) acryloyl groups in the molecule include a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain, and a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are randomly or blockwise bonded.

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 a (meth) acryloyl group at both ends of a 12-mole ethyleneoxy chain, and polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate. Examples of the polyoxyalkylene di (meth) acrylate compound having an ethyleneoxy group and a propyleneoxy group in the compound include a dimethacrylate of a diol obtained by adding an average of 3 moles of ethylene oxide to each of both ends of a polypropylene glycol to which an average of 12 moles of propylene oxide is added, and a dimethacrylate of a diol obtained by adding an average of 15 moles of ethylene oxide to each of both ends of a polypropylene glycol to which an average of 18 moles of propylene oxide is added.

As another example of the compound having two (meth) acryloyl groups in the molecule, a compound having (meth) acryloyl groups at both ends by modifying bisphenol a with an alkylene oxide is preferable from the viewpoint of resolution and adhesion. The alkylene oxide modification includes ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, hexylene oxide modification, and the like. Preferred is a compound having a (meth) acryloyl group at both ends by ethylene oxide modification of bisphenol a. Examples of such compounds include 2, 2-bis (4- ((meth) acryloyloxydiethoxy) phenyl) propane (for example, NK Ester BPE-200 manufactured by Mitsuoku chemical Co., Ltd.), 2-bis (4- ((meth) acryloyloxytetraethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxypentaethoxy) phenyl) propane (for example, NK Ester BPE-500 manufactured by Mitsuoku chemical Co., Ltd.), 2-bis (4- ((meth) acryloyloxythexaethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxytheptaethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxytetraethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxyt, 2, 2-bis (4- ((meth) acryloyloxyoctaethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxynonoethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxydodecethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxydodecoxyethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxytridecyloxy tridecoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxytetradecyloxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxydentadecaethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxydiethoxy) phenyl) propane, And 2, 2-bis (4- ((meth) acryloyloxypolyethoxy) phenyl) propane such as 2, 2-bis (4- ((meth) acryloyloxycetaethoxy) phenyl) propane. Further, ethylene oxide-modified and propylene oxide-modified compounds such as a polyalkylene glycol di (meth) acrylate obtained by adding an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide to both ends of bisphenol a, or a polyalkylene glycol di (meth) acrylate obtained by adding an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide to both ends of bisphenol a are also preferable. From the viewpoint of further improving the resolution, the adhesion, and the flexibility, the number of moles of ethylene oxide in the compound having a (meth) acryloyl group at both ends by oxyalkylene-modifying bisphenol a is preferably 10 to 30 moles.

For example, a compound having more than 2 (meth) acryloyl groups per molecule has, as a central skeleton, 3 moles or more of groups capable of adding an alkyleneoxy group in the molecule, and is obtained by forming (meth) acrylate from an alcohol obtained by adding an alkyleneoxy group such as an ethyleneoxy group, propyleneoxy group, butyleneoxy group, or the like thereto. In this case, examples of the compound capable of forming the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.

Examples of such a compound include Ethylene Oxide (EO)3 mol-modified triacrylate of trimethylolpropane, EO6 mol-modified triacrylate of trimethylolpropane, EO9 mol-modified triacrylate of trimethylolpropane, EO12 mol-modified triacrylate of trimethylolpropane, and the like. Examples of such a compound include glycerol EO3 mol-modified triacrylate (e.g., A-GLY-3E available from Nippon Korea Co., Ltd.), glycerol EO9 mol-modified triacrylate (e.g., A-GLY-9E available from Nippon Korea Co., Ltd.), glycerol EO6 mol and Propylene Oxide (PO)6 mol-modified triacrylate (A-GLY-0606PE), glycerol EO9 mol-PO 9 mol-modified triacrylate (A-GLY-0909PE), pentaerythritol 4 EO-modified tetraacrylate (e.g., Sartomer Japan Ltd., SR-494 available from Nippon Korea Co., Ltd.), and pentaerythritol 35 EO-modified tetraacrylate (e.g., NK Ester ATM-35E available from Nippon Korea Co., Ltd.).

In addition to the above compounds, the following compounds and the like can be suitably used. Examples thereof include 1, 6-hexanediol di (meth) acrylate, 1, 4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, 2-bis [ (4- (meth) acryloyloxypolypropylenoxy) phenyl ] propane, 2-bis [ (4- (meth) acryloyloxypolybutyleneoxy) phenyl ] propane, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, β -hydroxypropyl- β' - (acryloyloxy) propylphthalate, nonylphenoxypolypropylene glycol (meth) acrylate, Nonylphenoxy polytetramethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like. Further, the following urethane compounds can be exemplified. Urethane compounds such as hexamethylene diisocyanate, toluene diisocyanate or diisocyanate compounds (e.g., 2, 4-trimethylhexamethylene diisocyanate), and compounds having a hydroxyl group and a (meth) acryloyl group in one molecule, such as 2-hydroxypropyl acrylate, oligomeric propylene glycol monomethacrylate, are exemplified. Specifically, there is a reaction product of hexamethylene diisocyanate and an oligo-propylene glycol monomethacrylate (for example, Blemmer PP1000 manufactured by Nippon fat and oil Co., Ltd.). Further, di-or tri (meth) acrylate of isocyanurate modified with polypropylene glycol or polycaprolactone, and the like can be also mentioned. Further, for example, urethane oligomers obtained by reacting the terminal of a urethane compound obtained as an addition polymer of a diisocyanate and a polyol with a compound having an ethylenically unsaturated double bond and a hydroxyl group, and the like can also be cited.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the entire solid content of the photosensitive resin composition is preferably 5 to 70% by mass. From the viewpoint of sensitivity, resolution, and adhesion, the ratio is preferably 5% by mass or more. More preferably, the ratio is 20% by mass or more, and still more preferably 30% by mass or more. On the other hand, from the viewpoint of suppressing the peeling delay of the bead and the solidification resist, it is preferable that the ratio is 70 mass% or less. More preferably, the ratio is 50% by mass or less.

[ C ] photopolymerization initiator

Examples of the photopolymerization initiator (C) include hexaarylbiimidazole compounds, N-aryl-. alpha. -amino acid compounds, quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkyl aminobenzoate esters, oxime esters, acridines, pyrazoline derivatives, ester compounds of N-aryl amino acids, halogen compounds, and the like.

Examples of the hexaarylbiimidazole compound include 2- (o-chlorophenyl) -4, 5-diphenylbiimidazole, 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' -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 ' -bis- (2, 4-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 5-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 6-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3, 4-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 '-bis- (2,3, 5-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -biimidazole, 2' -bis- (2,3, 6-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 '-bis- (2,4, 5-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -biimidazole, 2' -bis- (2,4, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3,4, 6-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole and the like.

Examples of the N-aryl- α -amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Particularly, N-phenylglycine is preferable because of its high sensitizing effect.

Examples of the quinones include 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

Examples of the aromatic ketone include benzophenone, michler's ketone [4, 4' -bis (dimethylamino) benzophenone ], 4 '-bis (diethylamino) benzophenone, 4-methoxy-4' -dimethylamino benzophenone, and the like.

Examples of the acetophenone include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1, and the like. Commercially available acetophenone compounds include Irgacure-907, Irgacure-369 and Irgacure-379, manufactured by Ciba Specialty Chemicals Inc.

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

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

Examples of the dialkyl ketal include benzil dimethyl ketal and benzil diethyl ketal.

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

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

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

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, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9-phenylacridine, and the like, 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, 9- (4-pyridyl) acridine and the like. Among them, 1, 7-bis (9, 9' -acridinyl) heptane or 9-phenylacridine is preferable from the viewpoints of sensitivity, resolution, availability, and the like.

Examples of pyrazoline derivatives include 1- (4-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1, 5-bis- (4-tert-butyl-phenyl) -3- (4-tert-butyl-styryl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-ethoxy-phenyl) -pyrazoline, and salts thereof, 1-phenyl-3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1, 5-bis- (4-tert-octyl-phenyl) -3- (4-tert-octyl-styryl) -pyrazoline, 1- (4-dodecyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, and salts thereof, 1- (4-tert-octyl-phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, and optionally, a salt thereof, 1- (4-dodecyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (2, 4-dibutyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, and the like.

Examples of the pyrazoline derivative include 1-phenyl-3- (3, 5-di-tert-butyl-styryl) -5- (3, 5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2, 6-di-tert-butyl-styryl) -5- (2, 6-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2, 5-di-tert-butyl-styryl) -5- (2, 5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2, 6-di-n-butyl-styryl) -5- (2, 6-di-n-butyl-phenyl-pyrazoline, 1- (3, 4-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (3, 5-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3, 5-di-tert-butyl-phenyl) -5-phenyl-pyrazoline, 1- (3, 5-di-tert-butyl-phenyl) -3- (3, 5-di-tert-butyl-styryl) -5- (3, 5-di-tert-butyl-phenyl) -pyrazoline, and salts thereof, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (4-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-styryl) -dodecyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, and the like.

Examples of the pyrazoline derivative include 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, pyrazoline derivatives having a high refractive index, and their use as a binder for a coating material for a printed circuit board, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (4, 6-dibutyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (3, 5-di-tert-butylstyryl) -5- (3, 5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (2, 6-di-tert-butyl-styryl) -5- (2, 6-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (2, 5-di-tert-butyl-styryl) -5- (2, 5-di-tert-butyl-phenyl) -pyrazoline, their use as a medicament for treating diabetes, 1- (4- (benzoxazol-2-yl) phenyl) -3- (2, 6-di-n-butyl-styryl) -5- (2, 6-di-n-butyl-phenyl) -pyrazoline, 1- (4- (4, 6-di-tert-butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (5, 7-di-tert-butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3, 5-di-tert-butyl-styryl) -5-phenyl-pyrazoline, 1- (4- (4, 6-di-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3, 5-di-tert-butyl-styryl) -5- (3, 5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-amino-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-N-ethyl-phenyl) -pyrazoline, and 1-phenyl-3- (4-tert-butyl-styryl) -pyrazoline 5- (4-N, N-diethyl-phenyl) -pyrazoline, and the like.

Examples of the pyrazoline derivative include 1-phenyl-3- (4-biphenyl) -5- (4-n-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-isobutyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-n-pentyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-isopentyl-phenyl) -pyrazoline, and the like, 1-phenyl-3- (4-biphenyl) -5- (4-neopentyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-hexyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-heptyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-n-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-nonyl-phenyl) -pyrazoline ) Pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-decyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-undecyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-dodecyl-phenyl) -pyrazoline, and the like.

Among the pyrazoline derivatives listed above, from the viewpoint of adhesiveness and rectangularity of the resist pattern, at least one selected from the group consisting of 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline is preferably used.

Examples of the ester compound of an N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, N-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, t-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene dibromide, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, chlorotriazine compounds, and diallylium salt compounds, with tribromomethylphenylsulfone being particularly preferred.

The photopolymerization initiators (C) listed above may be used alone or in combination of two or more. Among these (C) photopolymerization initiators, at least one selected from the group consisting of hexaarylbiimidazole compounds, N-aryl- α -amino acid compounds, quinones, acridines, and pyrazoline derivatives is preferably used from the viewpoint of sensitivity, resolution, and the like of the photosensitive resin composition, and more preferably at least one selected from the group consisting of hexaarylbiimidazole compounds, N-aryl- α -amino acid compounds, and acridines is used. From the viewpoint of sensitivity, resolution, and the like of the photosensitive resin composition, acridines are more preferably used from the viewpoint of suppressing deterioration of resolution at the time of focus shift at the time of exposure, or from the viewpoint of suppressing narrowing of a line distance portion between adjacent resist lines at the time of focus shift at the time of exposure.

(C) The ratio of the photopolymerization initiator to the total solid content of the photosensitive resin composition is preferably 0.01 to 20% by mass. From the viewpoint of obtaining good sensitivity, the ratio is preferably 0.01 mass% or more. This ratio is more preferably 0.1% by mass or more, and still more preferably 0.5% by mass or more. On the other hand, from the viewpoint of obtaining high resolution and suppressing aggregation in the developer, it is preferable that the ratio is 20% by mass or less. The ratio is more preferably 10% by mass or less.

When hexaarylbiimidazole compounds are used as the photopolymerization initiator (C), the content of the hexaarylbiimidazole compounds is preferably 0.1 to 15% by mass based on the total solid content of the photosensitive resin composition. From the viewpoint of obtaining good sensitivity, the amount of the compound is preferably 0.1% by mass or more. The amount of the compound is more preferably 1% by mass or more, and particularly 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 of the compound is preferably 15% by mass or less. The amount of the compound is more preferably 10% by mass or less, and particularly preferably 6% by mass or less.

When an N-aryl- α -amino acid compound is used as the photopolymerization initiator (C), the content of the N-aryl- α -amino acid compound is preferably 0.001 to 5% by mass based on the total solid content of the photosensitive resin composition. From the viewpoint of obtaining good sensitivity, the amount of the compound is preferably 0.001% by mass or more. The amount of the compound is more preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, from the viewpoint of obtaining high resolution and improving color tone stability, the blending amount is preferably 5% by mass or less. The amount of the compound is more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

Further, when acridines are used as the photopolymerization initiator (C), the content of acridines is preferably 0.01 to 5% by mass based on the total solid content of the photosensitive resin composition. From the viewpoint of obtaining good sensitivity, the amount of the compound is preferably 0.01% by mass or more. The amount of the compound is more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. On the other hand, from the viewpoint of obtaining a rectangular resist shape and improving color tone stability, the amount of the addition is preferably 5% by mass or less. The amount of the compound is more preferably 3% by mass or less, and particularly preferably 2% by mass or less. In addition, the blending amount in the above range is also preferable from the viewpoint of reducing the difference in resolution between when the position of the focal point at the time of exposure is aligned with the substrate surface and when the position of the focal point at the time of exposure is shifted from the substrate surface.

[ phenol derivative (D) ]

In the embodiment, the photosensitive resin composition preferably further contains (D) a phenol derivative. Among them, the photosensitive resin composition preferably contains a compound represented by the following general formula (I) as the phenol derivative (D).

{ in formula (I), R¹Represents a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, a branched alkyl group via a divalent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group, which may be substituted, and a plurality of R' s¹And m is an integer of 0 to 4, n is an integer of 1 or more, A is a monovalent organic group when n is 1, and A is a divalent or more organic group, a single bond, or a linking group containing a conjugated bond when n is 2 or more }. The compound represented by the general formula (I) is excellent in terms of suppressing a decrease in sensitivity of the photosensitive resin composition and maintaining a good resolution without being affected by the position of a focus. From the same viewpoint, n is preferably an integer of 2 or more.

The compound represented by the general formula (I) preferably contains at least one selected from the group consisting of a compound represented by the following general formula (II) and a compound represented by the following general formula (III), and more preferably contains a compound represented by the general formula (III). The compound represented by the general formula (II) does not include a compound corresponding to the compound represented by the general formula (III).

{ formula (II), wherein R²Represents a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, a branched alkyl group via a divalent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group, which may be substituted, and R³、R⁴And R⁵Each independently represents hydrogen, or a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, a branched alkyl group via a divalent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group, which may be substituted,

{ in formula (III), R⁶And R⁷Each independently represents a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, a branched alkyl group via a divalent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group, which may be substituted, and a plurality of R' s⁶And R⁷And p and q may be the same or different from each other, each independently represent an integer of 0 to 4, and B represents a single bond or a linking group containing a conjugated bond }.

The compound represented by the general formula (II) and the compound represented by the general formula (III) are particularly excellent from the viewpoint of improving the resolution of the photosensitive resin composition, from the viewpoint of suppressing deterioration of the resolution at the time of focus shift at the time of exposure, from the viewpoint of suppressing narrowing of a line distance portion between a resist line and a resist line at the time of focus shift at the time of exposure, and from the viewpoint of suppressing reduction of sensitivity, respectively.

The compound represented by the general formula (II) is preferably R in the formula (II) from the viewpoints of improving the resolution of the photosensitive resin composition, suppressing deterioration of the resolution at the time of focus shift at the time of exposure, suppressing narrowing of the line distance portion between the resist line and the resist line at the time of focus shift at the time of exposure, and suppressing reduction in sensitivity²、R³、R⁴And R⁵At least one of them has an aromatic ring. From the same viewpoint, the compound represented by the general formula (II) preferably has two or more phenol nuclei.

From the same viewpoint, the hydroxyl group concentration of the compound represented by the general formula (II) is preferably 0.10 mol/100 g to 0.75 mol/100 g. From the same viewpoint, R in the general formula (II) is²At least one of them is preferably a linear or branched alkyl group, a benzyl group, a 1-phenylethyl group or a 2-phenylethyl group, or a phenylthio group which may be substituted by a hydroxyl group or an alkyl group. Examples of the preferred alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.

From the same viewpoint, the molecular weight of the compound represented by the general formula (II) is preferably about 130 to about 1000, more preferably about 130 to about 600, still more preferably about 130 to about 400, and particularly preferably about 180 to about 400. From the same viewpoint, the compound represented by the general formula (II) preferably has a specific gravity of about 1.02 to about 1.12, or a melting point of about 155 ℃ or higher (e.g., about 208 ℃ or higher), or is poorly soluble in water and readily soluble in an organic solvent such as methanol, acetone, or toluene, or is solid (e.g., powder, crystal, or the like) or liquid when used.

Examples of the compound represented by the general formula (II) include 4,4 '-thiobis (6-tert-butyl-m-cresol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, styrenated phenols (e.g., Kazuki Kaishiki chemical Co., Ltd., ANTAGE SP), and tribenzylphenols (e.g., Kazuki Kaishi chemical Co., Ltd., TBP, phenol having 1 to 3 benzyl groups).

In the compound represented by the general formula (III), B represents a single bond or a linking group containing a conjugated bond. The linking group having a conjugated bond is preferably a conjugated linking group formed of C, N, O, S or the like, and more preferably a group such as an alkenylene group, an alkynylene group, an arylene group, a divalent aromatic heterocycle, an azo group, an imine group, or a combination of one or more of these with N.

The compound represented by the general formula (III) is preferably a single bond in B in the formula (III) from the viewpoint of improving the resolution of the photosensitive resin composition, from the viewpoint of suppressing deterioration of the resolution at the time of focus shift at the time of exposure, from the viewpoint of suppressing narrowing of the line distance between the resist line and the resist line at the time of focus shift at the time of exposure, and from the viewpoint of suppressing reduction of sensitivity.

From the same viewpoint, the compound represented by the general formula (III) is preferably represented by the formula (III) wherein p ═ q ═ 0, and particularly preferably biphenol.

In an embodiment, the phenol derivative (D) may further contain a compound other than the compounds represented by the general formulae (II) and (III). Examples of the compounds other than the compounds represented by each of the general formulae (II) and (III) include 2, 6-di-tert-butyl-4-methylphenol, 2, 5-di-tert-amylhydroquinone, 2, 5-di-tert-butylhydroquinone, 2' -methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-tert-butyl-5-ethylphenyl) methane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 1, 6-hexanediol-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2-thio-diethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N' -hexamethylenebis (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, and the like.

The reaction rate constant with peroxy radicals of the (D) phenol derivative in the embodiment is preferably 20 L.mol^-1·sec^-1The above(more preferably 30L. mol.)^-1·sec^-1More preferably 40 L.mol or more^-1·sec^-1Above) is preferably 500 L.mol^-1·sec^-1The following (more preferably 300L. mol.)^-1·sec^-1Hereinafter, more preferably 200 L.mol^-1·sec^-1The following).

Here, although the detailed mechanism of selecting the above-mentioned phenol derivative (D) is not clear, it is considered that it affects whether or not the difference between the pattern resolution a and the pattern resolution b, and further affects whether or not the selection of the photosensitive resin composition which reduces the problems of short-circuit, disconnection, plating failure, failure in formation of desired copper wires, and the like even in a situation in which the wiring is densified, multilayered, and the like in recent years, the detailed mechanism is as follows.

The antioxidant action of the phenol derivative is considered to be the most suitable in terms of reactivity with radical species and stability of phenoxy radicals generated after the reaction with radical species. For example, the larger the ortho-position substituent, the more stable the phenoxy radical is for the phenol OH group. On the other hand, when the steric hindrance of the ortho-substituent is too large, the reactivity with the radical species decreases. The optimum value of the degree of steric hindrance varies depending on the characteristics (degree of easy oxidation) of the oxidized chemical species.

Here, since the photosensitive resin composition in the embodiment is photo-radical polymerizable, in order to capture peroxy radicals which may cause deterioration in resolution, the (D) phenol derivative is required to have high reactivity with radical species.

When the above various elements are taken into consideration in general, the phenol derivative (D) is preferably a compound represented by the general formula (I), and more preferably at least one selected from the group consisting of a compound represented by the general formula (II) and a compound represented by the general formula (III). The compound represented by the general formula (II) is considered to be excellent in both reactivity with peroxy radicals and stability of phenoxy radicals because the steric hindrance of the ortho-substituent is optimally adjusted. In addition, in the compound represented by the general formula (III), when the steric hindrance of the ortho-substituent is small, the reactivity with the peroxy radical is high, and the biphenyl type phenoxy radical is considered to be stabilized by the number of resonance structures of the phenoxy radical.

As to the compounds satisfying the range of the reaction rate constant described above, which are shown as specific examples of the compounds represented by the general formula (II) or the general formula (III), for example, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 45.4 L.mol^-1·sec^-1The molar ratio of 4, 4' -butylidenebis (3-methyl-6-tert-butylphenol) was 48.6L^-1·sec^-1。

The gamma value (gamma value) derived from the residual film ratio of the photosensitive resin composition is preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, and particularly preferably 5.0 or more. The γ value (gamma value) derived from the reaction rate of C ═ C double bonds is preferably 0.18 or more, more preferably 0.19 or more, still more preferably 0.20 or more, and particularly preferably 0.25 or more.

(D) The ratio of the phenol derivative to the total solid content of the photosensitive resin composition is preferably 0.001 to 10% by mass. From the viewpoint of improving the resolution of the photosensitive resin composition, suppressing deterioration of the resolution at the time of focus shift at the time of exposure, and suppressing narrowing of the line distance portion between the resist line and the resist line at the time of focus shift at the time of exposure, the ratio is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, further preferably 0.1 mass% or more, particularly preferably 0.2 mass% or more, and most preferably 0.5 mass% or more. On the other hand, from the viewpoint of reducing sensitivity reduction and improving resolution, the ratio is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1.5% by mass or less.

< additives >

(dyes and coloring matters)

In the embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of a dye (e.g., a leuco dye, a fluoran dye, etc.) and a coloring substance, as necessary.

Examples of the coloring substance include magenta, phthalocyanine GREEN, basic sophorae yellow, parafuchsin, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite GREEN (for example, Hodogaya Chemical co., ltd. manufactured Aizen (registered trademark) MALACHITE GREEN), basic blue 20, and DIAMOND GREEN (for example, Hodogaya Chemical co., ltd. manufactured Aizen (registered trademark) DIAMOND GREEN). The content of the coloring material in the photosensitive resin composition is preferably 0.001 to 1% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. From the viewpoint of improving the workability of the photosensitive resin composition, the content is preferably 0.001% by mass or more. On the other hand, from the viewpoint of maintaining the storage stability of the photosensitive resin composition, the content is preferably 1% by mass or less.

The photosensitive resin composition is preferably used from the viewpoint of visibility because the exposed portion develops color when it contains a dye, and is advantageous in that when a registration mark used for exposure is read by a tester or the like, it is easily recognized when the contrast between the exposed portion and the unexposed portion is large. From this viewpoint, preferable dyes include leuco dyes and fluoran dyes.

Examples of leuco dyes include tris (4-dimethylaminophenyl) methane [ leuco crystal violet ], bis (4-dimethylaminophenyl) phenylmethane [ leuco malachite green ], and the like. In particular, leuco crystal violet is preferably used as the leuco dye from the viewpoint of good contrast. The content of the leuco dye in the photosensitive resin composition is preferably 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition. From the viewpoint of improving the contrast between the exposed portion and the unexposed portion, the content is preferably 0.1% by mass or more. The content is 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, the content is preferably 10% by mass or less. The content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

In addition, from the viewpoint of optimizing the adhesiveness and contrast, it is preferable to use a leuco dye in combination with the halogen compound described above as the photopolymerization initiator (C) in the photosensitive resin composition. When a leuco dye is used in combination with the halogen compound, the content of the halogen compound in the photosensitive resin composition is preferably 0.01 to 3% by mass from the viewpoint of maintaining the storage stability of the color tone in the photosensitive layer, assuming that the total solid content mass of the photosensitive resin composition is 100% by mass.

(other additives)

In order to improve thermal stability and storage stability, the photosensitive resin composition may further contain at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles and carboxybenzotriazoles.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine. The nitrosophenylhydroxylamine aluminum salt is preferable in order not to impair the sensitivity of the photosensitive resin composition.

Examples of the benzotriazole include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.

Examples of the carboxybenzotriazole include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole.

The total content of the radical polymerization inhibitor, the benzotriazole compound and the carboxybenzotriazole compound is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, based on 100 mass% of the total solid content of the photosensitive resin composition. From the viewpoint of imparting storage stability to the photosensitive resin composition, the content is preferably 0.01 mass% or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye, the content is preferably 3% by mass or less.

In the embodiment, the photosensitive resin composition may further contain an epoxy compound of bisphenol a. Examples of the epoxy compound of bisphenol a include compounds obtained by modifying bisphenol a with polypropylene glycol and epoxidizing the terminal.

In an embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalates (e.g., diethyl phthalate, etc.), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether. Further, compounds having a bisphenol skeleton such as ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, ADEKA NOL SDX-479 (manufactured by Asahi Denka Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180 (manufactured by Sanyo chemical Co., Ltd.), UNIOL DB-400, UNIOL DAB-800, UNIOL DA-350F, UNIOL DA-400, Newpol DA-700 (manufactured by Nippon fat and oil Co., Ltd.), BA-P4U Glycol, and BA-P8Glycol (manufactured by Nippon emulsifier Co., Ltd.) can be exemplified.

The content of the plasticizer in the photosensitive resin composition is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass, based on the total solid content of the photosensitive resin composition. 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. On the other hand, from the viewpoint of suppressing insufficient curing and cold deformation, the content is preferably 50% by mass or less.

[ solvent ]

The photosensitive resin composition can be dissolved in a solvent and used for producing a photosensitive resin laminate in the form of a photosensitive resin composition preparation solution. Examples of the solvent include ketones and alcohols. The aforementioned ketones are represented by Methyl Ethyl Ketone (MEK). The alcohols are represented by methanol, ethanol and isopropanol. The solvent is preferably added to the photosensitive resin composition in an amount such that the viscosity of the photosensitive resin composition preparation solution applied to the support layer at 25 ℃ is from 500 to 4000 mPas in the production of the photosensitive resin laminate.

[ photosensitive resin laminate ]

In an embodiment, there is provided a photosensitive resin laminate in which a photosensitive resin layer containing the photosensitive resin composition is laminated on a support layer (for example, a support film). The photosensitive resin laminate may have a protective layer on the surface of the photosensitive resin layer opposite to the support layer, if necessary.

The support layer is preferably a transparent support film that transmits light emitted from the exposure light source. Examples of such a support film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may be stretched, if necessary. The support film is preferably a support film having a haze of 5 or less. The thinner the film thickness is, the more advantageous it is for improving image formability and economy, but in order to maintain the strength of the photosensitive resin laminate, a film of 10 μm to 30 μm is preferably used.

The important characteristics of the protective layer used in the photosensitive resin laminate are that the adhesion force with the photosensitive resin layer is sufficiently smaller than that of the support layer, and the protective layer can be easily peeled off. For example, a polyethylene film or a polypropylene film may be preferably used as the protective layer. Further, a film having excellent releasability as shown in Japanese patent application laid-open No. 59-202457 may be used. The thickness of the protective layer is preferably 10 to 100. mu.m, more preferably 10 to 50 μm.

There may be gels known as fish eyes on the surface of the polyethylene film. In the case where a polyethylene film having fish-eyes is used as the protective layer, the fish-eyes may be transferred to the photosensitive resin layer. When the fish eye is transferred to the photosensitive resin layer, air may be involved in lamination to form a void, which may result in a defect of the resist pattern. From the viewpoint of preventing fish eyes, the material of the protective layer is preferably stretched polypropylene. Specific examples thereof include ALPHAN E-200A manufactured by WANGZI PAPER (KOKAI).

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

Next, a method for producing the photosensitive resin laminate will be described.

As a method for producing a photosensitive resin laminate by sequentially laminating a support layer, a photosensitive resin layer, and a protective layer as needed, a known method can be employed. For example, a photosensitive resin layer containing a photosensitive resin composition can be laminated on a support layer by mixing the photosensitive resin composition used in the photosensitive resin layer with a solvent dissolving the composition to form a uniform solution, coating the solution on the support layer using a bar coater or a roll coater, and then drying the solution to remove the solvent. Then, a protective layer is laminated on the photosensitive resin layer as necessary, whereby a photosensitive resin laminate can be produced.

< method for Forming resist Pattern >

Next, an example of a method for producing a resist pattern using the photosensitive resin laminate of the present embodiment will be described. The method can comprise the following steps: the method for manufacturing the photosensitive resin laminate includes a laminating step of laminating a photosensitive resin laminate on a substrate, an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate to light, and a development step of developing and removing an unexposed portion of the photosensitive resin layer. Examples of the resist pattern include patterns of a printed wiring board, a semiconductor element, a printing plate, a liquid crystal display panel, a flexible substrate, a lead frame substrate, a substrate for COF (chip on film), a substrate for semiconductor encapsulation, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, an electrode for PDP (plasma display panel), and the like. As an example, a method for manufacturing a printed wiring board is described below.

The printed wiring board is manufactured through the following steps.

(1) Lamination step

In this step, the photosensitive resin laminate is bonded to a substrate such as a copper-clad laminate or a flexible substrate using a heat roll laminating apparatus while the protective layer of the photosensitive resin laminate is peeled off (when the protective layer is present).

(2) Exposure Process

In this step, the photosensitive resin layer is exposed by an exposure method using an active light source, an exposure method of directly drawing a drawing pattern as a desired wiring pattern, or an exposure method of projecting an image of a photomask through a lens by bringing a mask film having a desired wiring pattern into close contact with the support layer. The advantages of the photosensitive resin composition of the embodiment are more significant in an exposure method using direct drawing of a drawing pattern or an exposure method using an image projected through a lens photomask, and particularly significant in an exposure method using direct drawing of a drawing pattern.

(3) Developing process

In this step, after exposure, the support layer on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed with a developer containing an aqueous alkali solution, thereby forming a resist pattern on the substrate.

As the aqueous alkali solution, Na was used₂CO₃Or K₂CO₃An aqueous solution of (a). The aqueous alkali solution is appropriately selected in accordance with the characteristics of the photosensitive resin layer, and preferably contains Na in a concentration of about 0.2 to about 2% by mass and at a temperature of about 20 to about 40 ℃₂CO₃An aqueous solution.

Through the above steps (1) to (3), a resist pattern can be obtained. After these steps, a heating step at about 100 to about 300 ℃ may be further performed, if necessary. By performing this heating step, the chemical resistance can be further improved. The heating may be performed by a hot air, infrared ray, or far infrared ray heating furnace.

(4) Etching or plating process

The surface of the substrate exposed by the development (for example, the copper surface of the copper-clad laminate) is etched or plated to produce a conductor pattern.

(5) Peeling step

Then, the resist pattern is peeled from the substrate with an aqueous solution having a stronger alkalinity than the developer. The aqueous alkali solution for stripping is not particularly limited, and is preferably an aqueous solution of NaOH or KOH at a concentration of about 2 to about 5 mass% and at a temperature of about 40 to about 70 ℃. A small amount of water-soluble solvent may be added to the stripping solution.

The photosensitive resin laminate of the present embodiment is suitable for manufacturing conductor patterns of printed wiring boards, flexible substrates, lead frame substrates, COF substrates, semiconductor package substrates, transparent electrodes for liquid crystal, wirings for liquid crystal TFTs, electrodes for PDPs, and the like.

Unless otherwise specified, the various parameters described above can be measured by the measurement method in the examples described below or by a method equivalent thereto that can be understood by those skilled in the art.

Examples

Next, this embodiment will be specifically described by referring to examples and comparative examples. However, the present embodiment is not limited to the following examples unless the gist thereof is deviated. Physical properties in examples were measured by the following methods.

< evaluation of sensitivity >

First, a copper-clad laminate having a thickness of 0.4mm and a 35 μm rolled copper foil laminated thereon was subjected to spray polishing using a grinding material (Japan Carlit co., ltd., sakurndum R (registered trademark #220)) at a spray pressure of 0.2 MPa.

Subsequently, the photosensitive resin laminate was laminated at a roll temperature of 105 ℃ on a copper-clad laminate preheated to 60 ℃ while peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, by a hot roll laminating apparatus (AL-700, manufactured by asahi chemical corporation). The air pressure was set to 0.35MPa, and the lamination speed was set to 1.5 m/min.

Next, exposure was performed at various exposure levels using a Stouffer 21 stage exposure scale (step tape) as a mask by a direct drawing type exposure apparatus (manufactured by Orbotech Ltd., Paragon-Ultra 100). At this time, the position of the focal point at the time of exposure is aligned with respect to the substrate surface.

Further, after the polyethylene terephthalate film (support layer) was peeled off, 1 mass% Na at 30 ℃ was sprayed for a predetermined period of time using an alkali developing machine (FUJIKIKO CO., LTD., dry film developing machine)₂CO₃And (3) dissolving and removing the unexposed part of the photosensitive resin layer by using an aqueous solution in a time 2 times of the minimum development time. At this time, the minimum time required for the photosensitive resin layer of the unexposed portion to be completely dissolved is set as the minimum developing time.

Through the above operation, a curing resist pattern is obtained. The exposure amount was determined so that the limit number of residual films after development was 7.

< evaluation of resolution (general) >

Then, the unexposed portions were subjected to pattern exposure using a direct writing type exposure apparatus (manufactured by Orbotech Ltd., Paragon-Ultra 100) to form lines (line pitches). In this exposure, exposure is performed with the Stouffer 21 stage exposure scale (step tape) as a mask, and exposure is performed with an exposure amount at which the maximum residual film number in development is 7 stages. At this time, the position of the focal point at the time of exposure is aligned with respect to the substrate surface. Further, after peeling off the polyethylene terephthalate film (support layer), development was performed with a development time 2 times the minimum development time. At this time, the value of the minimum line width of the line and line pitch of the unexposed portion is normally formed as the pattern resolution a.

In the present disclosure, the minimum time required for the photosensitive resin layer of the unexposed portion to be completely dissolved is taken as the minimum development time. In the cured resist pattern, the minimum line width for normal formation was evaluated, in which no resist remained on the substrate surface in the unexposed portion, the substrate surface was exposed, no resist component was protruded such as stringing by the cured resist, linearity of the line was good, and adhesion between the cured resists was not present. As the value of the resolution, 30 μm or less is exposed using a drawing pattern obtained every 2 μm, and 30 μm or more is exposed using a drawing pattern obtained every 5 μm.

< resolution evaluation (Focus offset) >

The position of the focal point at the time of exposure was shifted from the substrate surface toward the substrate inner side in the thickness direction of the substrate by 300 μm. Except for this, the evaluation was (generally) the same as the above-described resolution evaluation. At this time, the value of the minimum line width of the line (line pitch) where the unexposed portion is normally formed is taken as the pattern resolution b.

< difference in resolution >

The difference between the resolution when the position of the focal point at the time of exposure is aligned with the substrate surface and the resolution when the position of the focal point at the time of exposure is shifted by 300 μm from the substrate surface is obtained by subtracting the value of the pattern resolution a of < resolution evaluation (normal) > from the value of the pattern resolution b of < resolution evaluation (focal shift) > described above.

< line pitch width Difference >

Next, a pattern in which the width of each of the exposed portion and the unexposed portion was 2:1 was exposed by a direct writing type exposure apparatus (manufactured by Orbotech ltd., pargon-Ultra 100). In this exposure, exposure is performed with the Stouffer 21 stage exposure scale (step tape) as a mask, and exposure is performed with an exposure amount at which the maximum residual film number in development is 7 stages. Further, after peeling off the polyethylene terephthalate film (support layer), development was performed with a development time 2 times the minimum development time. The line width (pitch) of the unexposed portion in the obtained pattern was actually measured by a microscope for a portion having a line width of 40 μm. The samples of each laminate were patterned by aligning the substrate surface with the position of the focal point during exposure and by shifting the position of the focal point during exposure from the substrate surface to the inside of the substrate in the thickness direction of the substrate by 300 μm.

The difference between the line width when the position of the focal point at the time of exposure is aligned with the substrate surface and the line width when the position of the focal point at the time of exposure is shifted by 300 μm from the substrate surface is obtained by subtracting the line width when the position of the focal point at the time of exposure is shifted by 300 μm from the substrate surface to the inside of the substrate from the line width when the position of the focal point at the time of exposure is aligned with the substrate surface.

< weight average molecular weight >

Gel Permeation Chromatography (GPC) by japan spectrography (ltd.) [ pump: gulliver, type PU-1580, chromatography column: shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5)4 groups manufactured by Showa Denko K.K.K.K.in serial, elution layer solvent: tetrahydrofuran, the weight average molecular weight was determined as a polystyrene conversion value using a calibration curve obtained using a polystyrene standard sample (Shodex STANDARD SM-105, Showa Denko K.K.).

< reaction Rate constant with peroxy radicals >

Based on the method described in j.macromol.sci.chem., a11(10), p1975 (1977).

< Gamma value (Gamma value) derived from residual film Rate >

Then, exposure was performed at various exposure amounts using a Stouffer 41 stage exposure scale (step tape) as a mask by a direct drawing type exposure apparatus (manufactured by Orbotech ltd., pargon-Ultra 100). At this time, the position of the focal point at the time of exposure is aligned with respect to the substrate surface.

Further, after the polyethylene terephthalate film (support layer) was peeled off, 1 mass% Na at 30 ℃ was sprayed for a predetermined period of time using an alkali developing machine (FUJIKIKO CO., LTD., dry film developing machine)₂CO₃And (3) dissolving and removing the unexposed part of the photosensitive resin layer by using an aqueous solution in a time 2 times of the minimum development time.

The film thickness of the curing resist pattern obtained in the above-described manner was measured by a surface roughness profile measuring instrument (SURFCOM 575A, tokyo co ltd.), and the residual film rate was determined from the film thickness. The actual exposure amount is calculated from the exposure amount and the transmittance of the Stouffer 41 stage exposure scale (step tape). The gamma value is determined based on the residual film rate and the substantial exposure amount. The γ value can be calculated by a method described in "photosensitive resin (ぶ photosensitive resin, initials から science), p.60, yohimoto, and the industrial society of research and study".

< gamma value (gamma value) derived from the reaction rate of C ═ C double bond >

From the side of the polyethylene terephthalate film (support layer) of the photosensitive resin laminate, exposure was performed with various exposure amounts using a Stouffer 41 stage exposure scale (step tape) as a mask by a direct drawing exposure apparatus (manufactured by Orbotech ltd., pargon-Ultra 100). At this time, the resist bottom is aligned with the position of the focal point at the time of exposure.

The reaction rate of C ═ C double bonds in the cured resist pattern obtained in the above-described manner was determined by FT-IR (NICOLET 380, manufactured by Thermo SCIENTIFIC). Incidentally, the C ═ C double bond measurement was 810cm^-1Peak height of (d). The actual exposure amount is calculated from the exposure amount and the transmittance of the Stouffer 41 stage exposure scale (step tape). The γ value is determined based on the reaction rate of the C ═ C double bonds together with the substantial amount of exposure. The method of calculating the γ value is the same as described above.

< color tone stability of photosensitive resin composition preparation solution >

The 600nm and 630nm transmittances of the photosensitive resin laminate were measured using an ultraviolet-visible light (UV-Vis) measuring apparatus (a spectrophotometer U-3010, manufactured by Hitachi High-Technologies Corporation) as follows:

(i) the polyethylene film of the photosensitive resin laminate was peeled off, and the transmittances at 600nm and 630nm were measured.

(ii) A photosensitive resin laminate was prepared using the prepared solution of the photosensitive resin composition stored at 40 ℃ for 3 days, and the polyethylene film of the photosensitive resin laminate was peeled off to measure the transmittances at 600nm and 630 nm.

The change in color tone was determined by calculation of the transmittance of (ii) and the transmittance of (i).

Examples 1 to 11 and comparative examples 1 to 15

A photosensitive resin composition preparation liquid (a photosensitive resin composition 55 mass% solution) was obtained by sufficiently stirring and mixing a photosensitive resin composition having the composition shown in tables 1 and 2 (wherein the number of each component represents the amount (parts by mass) of solid content) and a solvent (methyl ethyl ketone and ethanol). As the support layer, a 16 μm-thick polyethylene terephthalate film (GR-16, manufactured by Teijin DuPont Films Japan Limited) was prepared, and a photosensitive resin composition preparation liquid was uniformly applied to the surface of the film by using a bar coater, and dried in a dryer at 95 ℃ for 4 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 35 μm.

Subsequently, a 19 μm-thick polyethylene film (Tamapo Co., Ltd., GF-18) was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate. The obtained photosensitive resin laminate was subjected to various evaluations. The results are summarized in Table 1. As a result of the difference in pitch width, it was-5.9 μm in example 1, -5.2 μm in example 3, -5.6 μm in example 4, -6.0 μm in example 5, -7.5 μm in comparative example 1, and-9.5 μm in comparative example 2. In addition, the result of the γ value (gamma value) derived from the residual film ratio was 1.3 in example 4 and 0.6 in example 5. The result of the γ value (gamma value) derived from the reaction rate of C ═ C double bonds was 0.192 in example 3 and 0.177 in comparative example 1.

The circuit pattern formation by etching was repeated 8 times at L/S of 60/60 μm, and stacking was attempted, resulting in an undulation of about 30 μm at the outermost surface. In the outermost circuit pattern in this case, although a short circuit of the copper wire was observed in the composition of comparative example 1, no short circuit was observed in the composition of example 3, and it is estimated that the problem of failure could be reduced.

[ example 12]

The reaction rate constant of 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane (reaction rate constant with peroxy radicals ═ 45.4L · mol) was substituted for H-1(1 part by mass) of example 1 shown in table 1^-1·sec^-1) The same procedure as in example 1 was repeated except for (1 part by mass). As a result, the sensitivity (necessary exposure amount) was 21mJ/cm²The resolution (normal resolution) was 18 μm, the resolution (focus offset) was 30 μm, and the difference in resolution was 12 μm.

Comparative example 16

The same procedure as in example 1 was repeated except that H-1(1 part by mass) in example 1 shown in Table 1 was replaced with H-4(1 part by mass). As a result, the sensitivity (necessary exposure amount) was 80mJ/cm²The resolution is (usually) 45 μm.

As a result of the color tone stability of the photosensitive resin composition preparation liquid, example 1 was 1% at 600nm, 5% at 630nm, example 3 was 0% at 600nm, 5% at 630nm, example 12 was 2% at 600nm, 7% at 630nm, comparative example 1 was 0% at 600nm, 5% at 630nm, comparative example 2 was-21% at 600nm, 3% at 630nm, comparative example 8 was 5% at 600nm, 11% at 630nm, comparative example 9 was 11% at 600nm, 27% at 630nm, comparative example 16 was-41% at 600nm, and-8% at 630 nm. In comparative examples 13, 14 and 15, since the discoloration was extremely large at the transmittance of (i) in general, when the transmittance of (ii) was calculated from the transmittance of (i) in comparative example 1, the transmittance was 12% at 600nm, 30% at 630nm, 16% at 600nm, 37% at 630nm, 16% at 600nm and 37% at 630nm in comparative example 15.

TABLE 1 composition of photosensitive composition and evaluation results (one of all four sheets)

(Table 1. with the following)

TABLE 1 composition of photosensitive composition and evaluation results (two of four sheets)

(Table 1. with the following)

TABLE 1 composition of photosensitive composition and evaluation results (three of four sheets in total)

(Table 1. with the following)

TABLE 1 composition of photosensitive composition and evaluation results (four of all four)

(TABLE 1 END)

TABLE 2 list of ingredients used (one of all three)

(TABLE 2. with the following)

TABLE 2 list of ingredients used (two of all three)

(TABLE 2. with the following)

TABLE 2 list of ingredients used (three of all three)

(TABLE 2 END)

The following is evident from the results in tables 1 and 2.

As is clear from a comparison between examples and comparative examples, the photosensitive resin composition of the present embodiment can exhibit high resolution, and in particular, can exhibit high resolution even when the focus is shifted during exposure. Further, high sensitivity can be maintained. By using the photosensitive resin composition, even when the photosensitive resin composition is applied to a multilayer wiring, a short circuit problem can be suppressed when a circuit is formed by an etching method.

Industrial applicability

The photosensitive resin laminate of the present embodiment can exhibit high sensitivity and high resolution, and can exhibit high resolution particularly even when the focus is shifted during exposure, so that even when the position of the focus during exposure is shifted from the substrate surface due to problems such as warpage and deformation of the substrate and poor setting of the exposure apparatus, the problem of short circuit can be prevented when forming a circuit by etching, and problems such as a defect, disconnection, and plating failure can be prevented when forming a circuit by plating. Therefore, the photosensitive resin laminate can be suitably used for the production of conductor patterns such as printed wiring boards, flexible substrates, lead frame substrates, substrates for COF (chip on film), substrates for semiconductor packages, transparent electrodes for liquid crystals, wirings for TFTs for liquid crystals, electrodes for PDPs (plasma display panels), and the like.

Claims

1. A photosensitive resin composition comprising (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator,

the monomer component of the alkali-soluble polymer (A) has an aromatic hydrocarbon group, the content ratio of the monomer component having an aromatic hydrocarbon group in the alkali-soluble polymer (A) is 10 to 95 mass% based on the total mass of all the monomer components,

the (B) compound having an ethylenically unsaturated double bond comprises a compound having (meth) acryloyl groups at both ends by subjecting bisphenol A to alkylene oxide modification,

in a resist pattern obtained by forming a photosensitive resin layer containing the photosensitive resin composition on a substrate surface and performing exposure and development, the difference between the pattern resolution a when performing the exposure with the substrate surface in focus and the pattern resolution b when performing the exposure with the substrate surface in focus at a position shifted by 300 [ mu ] m from the substrate surface in the thickness direction of the substrate to the substrate inner side is 0 [ mu ] m or more and less than 15 [ mu ] m.

2. The photosensitive resin composition according to claim 1, which comprises the following components based on the mass of all solid components of the photosensitive resin composition

The alkali-soluble polymer (A): 10 to 90 mass%;

the (B) compound having an ethylenically unsaturated double bond: 5 to 70 mass%; and

the (C) photopolymerization initiator: 0.01 to 20% by mass.

3. The photosensitive resin composition according to claim 2, further comprising (D) a phenol derivative based on the mass of the entire solid content of the photosensitive resin composition: 0.001 to 10% by mass.

4. The photosensitive resin composition according to claim 3, wherein the phenol derivative (D) comprises a compound represented by the following general formula (I),

in the formula (I), R¹Represents an optionally substituted straight-chain alkyl group, a branched-chain alkyl group, an aryl group, a cyclohexyl group, a straight-chain alkyl group via a divalent linking group, a branched-chain alkyl group via a divalent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group, and a plurality of R' s¹And optionally, m is an integer of 0 to 4, n is an integer of 1 or more, A is a monovalent organic group when n is 1, and A is a divalent or more organic group, a single bond, or a linking group comprising a conjugated bond when n is 2 or more.

5. The photosensitive resin composition according to claim 3 or 4, wherein the phenol derivative (D) comprises a compound represented by the following general formula (II),

in the formula (II), R²Represents an optionally substituted straight-chain alkyl group, a branched-chain alkyl group, an aryl group, a cyclohexyl group, a straight-chain alkyl group via a divalent linking group, a branched-chain alkyl group via a divalent linking group, or a di-chain alkyl group via a divalent linking groupCyclohexyl of a divalent linking group or aryl via a divalent linking group, and R³、R⁴And R⁵Each independently represents hydrogen, or an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group via a divalent linking group, branched-chain alkyl group via a divalent linking group, cyclohexyl group via a divalent linking group, or aryl group via a divalent linking group.

6. The photosensitive resin composition according to claim 3, wherein the phenol derivative (D) comprises a compound represented by the following general formula (III),

in the formula (III), R⁶And R⁷Each independently represents an optionally substituted, straight-chain alkyl group, a branched-chain alkyl group, an aryl group, a cyclohexyl group, a straight-chain alkyl group via a divalent linking group, a branched-chain alkyl group via a divalent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group, and R's are independently present⁶And R⁷And p and q are each independently an integer of 0 to 4, and B represents a single bond or a linking group comprising a conjugated bond.

7. A photosensitive resin composition comprising, based on the mass of the entire solid content of the photosensitive resin composition

(A) Alkali-soluble polymers: 10 to 90 mass%;

(B) compound having an ethylenically unsaturated double bond: 5 to 70 mass%;

(C) photopolymerization initiator: 0.01 to 20 mass%; and

(D) phenol derivatives: 0.001 to 10% by mass,

in the formula (II), R²Represents an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group via a divalent linking group, branched-chain alkyl group via a divalent linking group, cyclohexyl group via a divalent linking group, or aryl group via a divalent linking group, and R is³、R⁴And R⁵Each independently represents hydrogen, or an optionally substituted, straight-chain alkyl group, branched-chain alkyl group, aryl group, cyclohexyl group, straight-chain alkyl group via a divalent linking group, branched-chain alkyl group via a divalent linking group, cyclohexyl group via a divalent linking group, or aryl group via a divalent linking group,

in the formula (III), R⁶And R⁷Each independently represents an optionally substituted, straight-chain alkyl group, a branched-chain alkyl group, an aryl group, a cyclohexyl group, a straight-chain alkyl group via a divalent linking group, a branched-chain alkyl group via a divalent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group, and R's are independently present⁶And R⁷Optionally identical to or different from each other, p and q each independently represent an integer of 0 to 4, and B represents a single bond, or a linking group comprising a conjugated bond,

the (B) compound having an ethylenically unsaturated double bond includes a compound having (meth) acryloyl groups at both ends by subjecting bisphenol a to alkylene oxide modification.

8. The photosensitive resin composition according to claim 6 or 7, wherein in the formula (III), B is a single bond.

9. The photosensitive resin composition according to claim 6 or 7, wherein in the formula (III), p-q-0.

10. The photosensitive resin composition according to claim 3 or 7, wherein the phenolic derivative (D) has a reaction rate constant of 20L mol with peroxy radicals^-1Second of^-1Above and 500 L.mol^-1Second of^-1The following compounds.

11. The photosensitive resin composition according to claim 1 or 7, wherein the photopolymerization initiator (C) comprises acridines.

12. A photosensitive resin laminate comprising a support layer and a photosensitive resin layer laminated thereon, wherein the photosensitive resin layer comprises the photosensitive resin composition according to any one of claims 1 to 11.

13. A method for forming a resist pattern, comprising a laminating step of laminating the photosensitive resin laminate according to claim 12 on a substrate, an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate to light, and a development step of developing and removing an unexposed portion of the photosensitive resin layer.

14. The method for forming a resist pattern according to claim 13, wherein the exposure step is performed by an exposure method using direct drawing of a drawn pattern or an exposure method in which an image of a photomask is projected through a lens.

15. The method for forming a resist pattern according to claim 14, wherein the exposure step is performed by an exposure method using direct drawing of a drawn pattern.

16. The photosensitive resin composition according to claim 1 or 7, which is used in a resist pattern formation method by an exposure method in which a drawing pattern is directly drawn in an exposure step.