CN112534351A

CN112534351A - Photosensitive resin composition and method for forming resist pattern

Info

Publication number: CN112534351A
Application number: CN201980051908.6A
Authority: CN
Inventors: 小坂隼也
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp; Asahi Chemical Industry Co Ltd
Priority date: 2018-08-09
Filing date: 2019-08-07
Publication date: 2021-03-19
Also published as: KR20200139768A; TWI812546B; TWI811423B; KR102509152B1; WO2020032133A1; TW202016154A; JP7422664B2; TW202309103A; JPWO2020032133A1; JP2023061998A

Abstract

Provided is a photosensitive resin composition which has excellent sensitivity, adhesion, line width reproducibility and resolution when it is heated after exposure and then developed, and which particularly realizes excellent adhesion even when the time from exposure to development is long. An aspect of the present invention provides a photosensitive resin composition comprising: (A) alkali-soluble polymer: 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) a phenolic polymerization inhibitor: 1ppm to 300ppm, and the light transmittance of the photosensitive resin composition at least at one of 375nm and 405nm is 58% to 95%.

Description

Photosensitive resin composition and method for forming resist pattern

Technical Field

The present invention relates to a photosensitive resin composition, a method for forming a resist pattern, and the like.

Background

In electronic devices such as personal computers and cellular phones, printed wiring boards are used to mount components, semiconductors, and the like. As a resist for producing a printed wiring board or the like, a photosensitive resin laminate, a so-called dry film photoresist (hereinafter, referred to as DF) in some cases, has been conventionally used, 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. 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.

When a printed wiring board or the like is produced 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 laminator or the like, and exposure is performed 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, may be simply referred to as a resist pattern) on the substrate.

Processes for forming a circuit after forming a resist pattern are roughly classified into two methods. The first method is a method (etching method) in which a substrate surface not covered with a resist pattern (for example, a copper surface of a copper-clad laminate) is etched and removed, and then the resist pattern is partially removed with an alkaline aqueous solution stronger than a developer.

The second method is a method (plating method) in which after the plating treatment of copper, solder, nickel, tin, or the like is performed on the substrate surface, the resist pattern portion is removed in the same manner as in the first method, and the exposed substrate surface (for example, the copper surface of the copper-clad laminate) is etched. Copper chloride, ferric chloride, copper ammonia complex solution, etc. are used for etching.

In recent years, with the progress of miniaturization and densification of printed wiring boards with the miniaturization and weight reduction of electronic devices, there is a demand for a high-performance DF having high resolution and high adhesion 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

After the exposure step, the photosensitive resin layer may be subjected to a heating step and then developed, if necessary. By performing such a heating step, resolution and adhesion (i.e., adhesion between the resist pattern and the substrate) can be further improved. However, there are the following problems: even if a heating step is added after exposure, the adhesion and resolution are still insufficient when using conventional photosensitive resin compositions, or good adhesion cannot be obtained if the time from exposure to development is extended.

The present invention has been made in view of the above-described conventional circumstances, and an object of one embodiment of the present invention is to provide a photosensitive resin composition which is excellent in sensitivity, adhesion, line width reproducibility, and resolution when development is performed after exposure and heating, and which particularly realizes excellent adhesion even when the time from exposure to development is long.

Means for solving the problems

The present invention includes the following aspects.

[1] A photosensitive resin composition comprising:

(A) alkali-soluble polymer: 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-based polymerization inhibitor: 1ppm to 300ppm of the total amount of the catalyst,

the light transmittance of the photosensitive resin composition at least at one of 375nm and 405nm is 58-95%.

[2] The photosensitive resin composition according to the above aspect 1, which contains p-hydroxyanisole as the (D) phenolic polymerization inhibitor.

[3] The photosensitive resin composition according to the above aspect 1 or 2, which contains dibutylhydroxytoluene as the phenol-based polymerization inhibitor (D).

[4] The photosensitive resin composition according to the above aspect 3, wherein the content of the dibutylhydroxytoluene is 1 to 200 ppm.

[5] The photosensitive resin composition according to the above aspect 3, wherein the content of the dibutylhydroxytoluene is 10 to 150 ppm.

[6] The photosensitive resin composition according to any one of the above aspects 1 to 5, wherein the I/O value of the alkali-soluble polymer (A) is 0.600 or less.

[7] The photosensitive resin composition according to any one of the above aspects 1 to 6, wherein the photopolymerization initiator (C) contains at least one selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof.

[8] The photosensitive resin composition according to the above aspect 7, wherein the photopolymerization initiator (C) contains anthracene and/or an anthracene derivative.

[9] The photosensitive resin composition according to any one of the above aspects 1 to 8, wherein the structural unit of styrene and/or a styrene derivative in the alkali-soluble polymer (a) is 26% by mass or more.

[10] The photosensitive resin composition according to any one of the above aspects 1 to 9, wherein the alkali-soluble polymer (a) contains a structural unit of benzyl (meth) acrylate as a monomer component.

[11] The photosensitive resin composition according to any one of the above aspects 1 to 10, wherein the glass transition temperature of the alkali-soluble polymer (a) is 120 ℃ or lower.

[12] The photosensitive resin composition according to any one of the above aspects 1 to 11, wherein the compound (B) having an ethylenically unsaturated double bond contains a compound having 3 or more methacrylate groups in a molecule in an amount of 5% by mass or more relative to the total solid content of the photosensitive resin composition.

[13] The photosensitive resin composition according to any one of the above aspects 1 to 12, which is used for obtaining an exposed cured resin by using a 1 st laser beam having a center wavelength of less than 390nm and a 2 nd laser beam having a center wavelength of 390nm or more.

[14] The photosensitive resin composition according to any one of the above aspects 1 to 13, wherein the 1 st laser has a central wavelength of 350nm or more and 380nm or less, and the 2 nd laser has a central wavelength of 400nm or more and 410nm or less.

[15] The photosensitive resin composition according to any one of the above aspects 1 to 14, which is capable of forming a pattern by the following steps:

an exposure step of exposing the photosensitive resin composition;

a heating step of heating the exposed photosensitive resin composition; and

and a developing step of developing the heated photosensitive resin composition.

[16] The photosensitive resin composition according to any one of the above aspects 1 to 15, wherein the heating temperature in the heating step is in a range of 30 to 150 ℃.

[17] The photosensitive resin composition according to any one of the above aspects 1 to 16, wherein the heating step is performed within 15 minutes after the exposure.

[18] A method for forming a resist pattern, comprising the steps of:

an exposure step of exposing the photosensitive resin composition according to any one of the above aspects 1 to 17;

a heating step of heating the exposed photosensitive resin composition; and

[19] The method of forming a resist pattern according to mode 18 above, wherein the heating temperature in the heating step is in a range of 30 ℃ to 150 ℃.

[20] The method of forming a resist pattern according to any one of the above-described aspects 18 and 19, wherein the heating step is performed within 15 minutes after the exposure.

[21] The method of forming a resist pattern according to any one of the above-mentioned aspects 18 to 20, wherein the exposure step is performed by an exposure method using direct writing of a writing pattern or an exposure method of projecting an image of a photomask through a lens.

[22] The method of forming a resist pattern according to mode 21 above, wherein the exposure step is performed by an exposure method using direct writing of a writing pattern.

[23] The method of forming a resist pattern according to mode 22 above, wherein the exposure step is performed by a method of performing exposure using a 1 st laser beam having a center wavelength of less than 390nm and a 2 nd laser beam having a center wavelength of 390nm or more.

[24] The method of forming a resist pattern according to mode 23, wherein the 1 st laser light has a center wavelength of 350nm or more and 380nm or less, and the 2 nd laser light has a center wavelength of 400nm or more and 410nm or less.

[25] A method for manufacturing a circuit board, comprising the steps of:

a resist pattern forming step of forming a resist pattern on a substrate by the method according to any one of the above-mentioned aspects 18 to 24; and

and a circuit board forming step of forming a circuit board by etching or plating the substrate having the resist pattern.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a photosensitive resin composition can be provided which has excellent sensitivity, adhesion, line width reproducibility, and resolution when development is performed after exposure and heating, and which particularly realizes excellent adhesion even when the time from exposure to development is long.

Detailed Description

Exemplary modes for carrying out the 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. In addition, unless otherwise specified, various measurement values in the present specification are measured by the method described in [ example ] of the present disclosure or a method understood by those skilled in the art to be equivalent thereto.

< photosensitive resin composition >

In the present embodiment, the photosensitive resin composition contains (a) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a phenolic polymerization inhibitor. In addition, in the present embodiment, the photosensitive resin layer can be formed by applying the photosensitive resin composition to an arbitrary support. The above-described composition of the photosensitive resin composition of the present embodiment is useful for obtaining a cured resin product by heating and then developing after exposure.

The photosensitive resin composition of the present embodiment may be a photosensitive resin composition for obtaining a cured resin product by exposure to a 1 st active light having a central wavelength of less than 390nm and a 2 nd active light having a central wavelength of 390nm or more. The active light is, for example, laser light. In this embodiment, the photosensitive resin composition has photosensitivity to both 1 st active light having a central wavelength of less than 390nm and 2 nd active light having a central wavelength of 390nm or more. The center wavelength of the No. 1 active light is preferably 350 to 380nm, more preferably 355 to 375nm, and particularly preferably 375 nm. The center wavelength of the 2 nd active light is preferably 400 to 410nm, more preferably 402 to 408nm, and particularly preferably 405nm (h-ray).

The components contained in the photosensitive resin composition will be described below.

(A) Alkali soluble polymer

(A) The alkali-soluble polymer is a polymer that can be dissolved in an alkali substance. (A) The alkali-soluble polymer preferably has a carboxyl group from the viewpoint of alkali developability, and further preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component. (A) The alkali soluble polymer may be thermoplastic.

The photosensitive resin composition preferably contains a copolymer having an aromatic group as (a) the alkali-soluble polymer from the viewpoint of high resolution of the resist pattern and a curl shape (スソ shape). The photosensitive resin composition particularly preferably contains a copolymer having an aromatic group in a side chain as the alkali-soluble polymer (a). Examples of such an aromatic group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The ratio of the copolymer having an aromatic group in the component (a) is preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. The above ratio may be 100% by mass, but from the viewpoint of maintaining good alkali solubility, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass.

The copolymerization ratio of the aromatic group-containing comonomer in the alkali-soluble polymer (a) is preferably 40% by mass or more, preferably 50% by mass or more, preferably 60% by mass or more, preferably 70% by mass or more, preferably 80% by mass or more, from the viewpoint of high resolution of the resist pattern and the shape of the curl. The upper limit of the copolymerization ratio is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, from the viewpoint of maintaining good alkali solubility.

Examples of the aromatic group-containing comonomer include styrene, polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.), and aralkyl group-containing monomers. Among them, styrene and styrene derivatives are more preferable.

The total ratio of the structural units of styrene and/or a styrene derivative in the entire alkali-soluble polymer (a) is preferably 15% by mass or more, more preferably 25% by mass or more, more preferably 26% by mass or more, more preferably 30% by mass or more, more preferably 35% by mass or more, and more preferably 40% by mass or more, from the viewpoint of significantly improving the adhesion when development is carried out after exposure by heating, and particularly obtaining good adhesion even when the time from exposure to development is prolonged. The styrene skeleton is hydrophobic, so that swelling properties with respect to a developer can be suppressed, and good adhesion can be exhibited. However, when the content of the styrene skeleton is large, the fluidity of the polymer is low and the reactivity tends to be lowered, so that the adhesiveness tends to be lowered. Further, when the time from exposure to development is prolonged, radicals in the system are deactivated, and therefore, the effect of improving adhesion by heating after exposure is reduced. In the present invention, even in a system containing a large amount of a styrene skeleton, the fluidity of the polymer is improved by heating by performing development after exposure and heating, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly satisfied at the same time. Further, it is considered that, even when the time from exposure to development is prolonged, good adhesion can be obtained. The total ratio of the structural units of styrene and/or a styrene derivative in the entire alkali-soluble polymer (a) is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less, from the viewpoint of favorably obtaining the advantages achieved by the presence of other structural units.

Examples of the comonomer having an aralkyl group include a monomer having a substituted or unsubstituted benzyl group, a monomer having a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), and the like, and a monomer having a substituted or unsubstituted benzyl group is preferable.

Examples of the comonomer having a benzyl group include (meth) acrylates having a benzyl group, for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, and the like; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, vinylbenzyl alcohol, and the like.

(A) The alkali-soluble polymer preferably contains a structural unit of benzyl (meth) acrylate as a monomer component, from the viewpoint of significantly improving adhesion when development is performed after exposure by heating, and particularly achieving good adhesion even when the time from exposure to development is extended. (A) The ratio of the structural unit of benzyl (meth) acrylate in the alkali-soluble polymer is preferably 5 to 85 mass%, more preferably 10 to 80 mass%, more preferably 15 to 60 mass%, more preferably 20 to 40 mass%, and still more preferably 20 to 30 mass%. From the same viewpoint, the alkali-soluble polymer (a) preferably has both a structural unit of styrene and/or a styrene derivative and a structural unit of benzyl (meth) acrylate.

Examples of the comonomer having a phenylalkyl group (excluding a benzyl group) include phenylethyl (meth) acrylate and the like.

The copolymer having an aromatic group (preferably benzyl group) in a side chain is preferably obtained by polymerizing (i) a monomer having an aromatic group and (ii) at least one of the first monomer described later and/or at least one of the second monomer described later.

The alkali-soluble polymer (a) other than the copolymer having an aromatic group in the side chain is preferably obtained by polymerizing at least one of the first monomers described later, and more preferably obtained by copolymerizing at least one of the first monomers described later and at least one of the second monomers described later.

The first monomer is a monomer having a carboxyl group in a molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among them, (meth) acrylic acid is preferable.

In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acryloyl group" means acryloyl group or methacryloyl group, and "(meth) acrylate" means "acrylate" or "methacrylate".

The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components of the polymer obtained by polymerizing at least one of the first monomers. The copolymerization ratio is preferably 10% by mass or more from the viewpoint of exhibiting good developability, from the viewpoint of controlling edge fusion (edge fuse) properties, and the like. The copolymerization ratio is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, particularly preferably 22% by mass or less, and most preferably 20% by mass or less, from the viewpoint of high resolution of the resist pattern and the shape of the curl, and further from the viewpoint of chemical resistance of the resist pattern.

The second monomer is a monomer which is not acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth) acrylic acid esters such as 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, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; vinyl alcohol esters such as vinyl acetate; and (meth) acrylonitrile, and the like. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate are preferable.

(A) The alkali-soluble polymer can be produced by polymerizing one or more monomers described above by a known polymerization method, preferably addition polymerization, more preferably radical polymerization.

From the viewpoint of chemical resistance, adhesion, high resolution, or curl shape of the resist pattern, the monomer preferably contains a monomer having an aralkyl group and/or styrene. As the (a) alkali-soluble polymer, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene, and the like are particularly preferable.

(A) The I/O value of the alkali-soluble polymer is preferably 0.600 or less. The I/O value represents a ratio of (inorganic value)/(organic value), is a value for evaluating the polarity of various organic compounds based on an organic conceptual diagram, and is one of functional group contribution methods for setting parameters for functional groups in compounds. The I/O values are described in, for example, non-patent documents (organic conceptual diagrams (KUMAMOTO PHARMACEUTICAL BULLETIN, 1984), KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, items 1 to 16 (1954); fields of chemistry, Vol. 11, No. 10, items 719 to 725 (1957); items FRAGRANCE JOURNAL, No. 34, items 97 to 111 (1979); items FRAGRANCE JOURNAL, No. 50, items 79 to 82 (1981)); etc. are described in detail in the literature. The concept of the I/O value is to classify the properties of a compound into an organic group representing covalent bonding and an inorganic group representing ionic bonding, and to represent all organic compounds as points located on coordinates of orthogonal axes named organic axis and inorganic axis, respectively. The I/O value is closer to 0, which indicates that the organic compound is more nonpolar (i.e., hydrophobic or more organic), and the I/O value is larger, which indicates that the organic compound is more polar (i.e., hydrophilic or more inorganic).

(A) The I/O value of the alkali-soluble polymer is preferably 0.600 or less, more preferably 0.570 or less, further preferably 0.520 or less, and particularly preferably 0.490 or less from the viewpoint of adhesiveness and resolution of a resist pattern when development is performed after exposure by heating, and is preferably 0.300 or more, more preferably 0.400 or more, and further preferably 0.450 or more from the viewpoint of resolution and peelability when development is performed after exposure by heating.

The value obtained by Fox equation for the glass transition temperature of (A) an alkali-soluble polymer (in the case where (A) an alkali-soluble polymer contains a plurality of polymers, the glass transition temperature of all the polymers is calculatedThe glass transition temperature Tg of the mixture, i.e. the weight average Tg of the glass transition temperatures_total) From the viewpoint of chemical resistance, adhesion, high resolution, or curl shape of the resist pattern, it is preferably 130 ℃ or lower, more preferably 120 ℃ or lower, 110 ℃ or lower, 100 ℃ or lower, 95 ℃ or lower, 90 ℃ or lower, or 80 ℃ or lower. The lower limit of the glass transition temperature (Tg) of the alkali-soluble polymer (a) is not limited, but is preferably 30 ℃ or higher, more preferably 50 ℃ or higher, and still more preferably 60 ℃ or higher, from the viewpoint of controlling the edge fusibility. As the glass transition temperature of a homopolymer containing the same monomer as each of 1 or more monomers constituting the alkali-soluble Polymer (a), non-patent documents (Brandrup, j.immergut, e.h. eds. "Polymer handbook, Third edition, John wire) were used&sons,1989, p.209Chapter VI 'Glass transition temperatures of polymers' ").

(A) The acid equivalent of the alkali-soluble polymer (in the case where the component (a) contains a plurality of copolymers, the acid equivalent of the entire mixture) is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin layer, and the resolution and adhesion of the resist pattern, and is preferably 600 or less from the viewpoint of the development and peeling properties of the photosensitive resin layer. (A) The acid equivalent of the alkali-soluble polymer is more preferably 200 to 500, and still more preferably 250 to 450.

(A) The weight average molecular weight of the alkali-soluble polymer (in the case where the component (A) contains a plurality of copolymers, the weight average molecular weight of the mixture as a whole) is preferably 5000 to 500000. (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance against a developer, and is preferably 500000 or less from the viewpoint of maintaining the developability of the dry film resist, from the viewpoint of high resolution and curl shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 10000 to 200000, still more preferably 20000 to 100000, and particularly preferably 30000 to 70000. (A) The dispersion degree of the molecular weight of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 4.0, and still more preferably 1.0 to 3.0.

The content of the alkali-soluble polymer (a) in the photosensitive resin composition is in the range of 10 to 90% by mass, preferably in the range of 20 to 80% by mass, and more preferably in the range of 40 to 60% by mass based on the total solid content of the photosensitive resin composition (hereinafter, the same is true for each component unless otherwise specified). (A) The content of the alkali-soluble polymer is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and is preferably 90% by mass or less, more preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less from the viewpoint of sufficiently exhibiting the performance as a resist material of a resist pattern formed by exposure, from the viewpoint of high resolution of the resist pattern and the curl shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern.

(B) Compounds having ethylenic unsaturation

(B) The compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated bond (i.e., a double bond) in its structure. The ethylenic unsaturation is more preferably derived from a methacryloyl group. The compound (B) having an ethylenically unsaturated bond preferably has an oxyalkylene structure having 3 or more carbon atoms from the viewpoint of adhesion and from the viewpoint of suppression of foaming of the developer. The number of carbon atoms in the oxyalkylene structure is more preferably 3 to 6, and still more preferably 3 to 4.

Examples of the compound (B) having 1 (meth) acryloyl group as an ethylenically unsaturated bond include a compound obtained by adding (meth) acrylic acid to one end of a polyoxyalkylene group, a compound obtained by adding (meth) acrylic acid to one end of a polyoxyalkylene group and subjecting the other end to alkyl etherification or allyl etherification, a phthalic acid compound, and the like, and are preferable from the viewpoint of releasability and cured film flexibility.

Examples of such a compound include phenoxyhexaethyleneglycol mono (meth) acrylate which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to a phenyl group, 4-n-nonylphenoxypheylene glycol dipropylene glycol (meth) acrylate which is a (meth) acrylate of a compound obtained by adding a polypropylene glycol obtained by adding propylene oxide in an average amount of 2 moles and a polyethylene glycol obtained by adding ethylene oxide in an average amount of 7 moles to nonylphenol, 4-n-nonylphenoxypheylene glycol monopropylene glycol (meth) acrylate which is a (meth) acrylate of a compound obtained by adding a polypropylene glycol obtained by adding propylene oxide in an average amount of 1 mole and a polyethylene glycol obtained by adding ethylene oxide in an average amount of 5 moles to nonylphenol, and 4-n-nonylphenoxypheylene glycol monopropylene glycol (meth) acrylate which is an acrylate of a compound obtained by adding polyethylene glycol obtained by adding ethylene oxide in an average amount of 8 moles to nonylphenol N-nonylphenoxy octaethylene glycol (meth) acrylate (e.g., M-114 available from Toyo chemical Co., Ltd.).

In addition, when γ -chloro- β -hydroxypropyl- β' -methacryloyloxyethyl-phthalate is contained, it is preferable from the viewpoints of sensitivity, resolution, and adhesion, in addition to the above viewpoints.

Examples of the compound having 2 (meth) acryloyl groups in the molecule include a compound having a (meth) acryloyl group at each end of an oxyalkylene chain, and a compound having a (meth) acryloyl group at each end of an oxyalkylene chain in which an oxyethylene chain and an oxypropylene 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 oxyethylene chain, polypropylene glycol di (meth) acrylate, and polybutylene glycol di (meth) acrylate. Examples of the polyoxyalkylene di (meth) acrylate compound containing an oxyethylene group and an oxypropylene 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 terminals of a polypropylene glycol to which an average of 12 moles of propylene oxide is added, a dimethacrylate of a diol obtained by adding an average of 15 moles of ethylene oxide to each of both terminals of a polypropylene glycol to which an average of 18 moles of propylene oxide is added, FA-023M, FA-024M, FA-027M (product name, manufactured by hitachi chemical industries), and the like. They are preferable from the viewpoint of flexibility, resolution, adhesion, and the like.

As another example of the compound having 2 (meth) acryloyl groups in the molecule, a compound having (meth) acryloyl groups at both ends by alkylene oxide modification of bisphenol a is preferable from the viewpoint of resolution and adhesion.

Specifically, compounds represented by the following general formula (I) can be used.

{ formula (II) wherein R₁And R₂Each independently represents a hydrogen atom or a methyl group, A is C₂H₄B is C₃H₆，n₁And n₃Each independently an integer of 0 to 39, and n₁+n₃Is an integer of 0 to 40, n₂And n₄Each independently an integer of 0 to 29, and n₂+n₄Is an integer of 0 to 30, and the arrangement of the repeating units of- (A-O) -and- (B-O) -may be random or block. Further, in the case of a block, either one of- (A-O) -and- (B-O) -may be a bisphenyl side. }

For example, from the viewpoint of resolution and adhesion, a dimethacrylate of polyethylene glycol obtained by adding ethylene oxide of 5 moles, on average, to each end of bisphenol a, a dimethacrylate of polyethylene glycol obtained by adding ethylene oxide of 2 moles, on average, to each end of bisphenol a, and a dimethacrylate of polyethylene glycol obtained by adding ethylene oxide of 1 mole, on average, to each end of bisphenol a are preferable.

Further, compounds having hetero atoms and/or substituents on the aromatic ring in the above general formula (I) may also be used.

Examples of the hetero atom include a halogen atom, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, a group containing a heterocyclic ring, and an aryl group substituted by these substituents. These substituents may form a condensed ring, or hydrogen atoms in these substituents may be substituted with hetero atoms such as halogen atoms. When the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

The compound (B) having an ethylenically unsaturated double bond is preferably a (meth) acrylate compound containing an ethylenically unsaturated double bond having 3 or more (i.e., 3 or more functions) from the viewpoint that the adhesiveness when the development is carried out after the exposure and heating can be significantly improved, and particularly, good adhesiveness can be obtained even when the time from the exposure to the development is prolonged. From the same viewpoint, a (meth) acrylate compound having 4 or more ethylenically unsaturated double bonds is more preferable, a (meth) acrylate compound having 5 or more ethylenically unsaturated double bonds is further preferable, and a (meth) acrylate compound having 6 or more ethylenically unsaturated double bonds is particularly preferable. From the same viewpoint, it is preferable that they are methacrylate compounds. It is considered that the compound having an ethylenically unsaturated double bond of 3 or more, 4 or more, 5 or more, and 6 or more has an effect of increasing the crosslinking density when polymerized by exposure, but the desired crosslinking density is not obtained in many cases due to the effect of steric hindrance caused by the large number of functional groups. In the present invention, it has been found that a compound having 3 or more ethylenically unsaturated double bonds, more preferably 4 or more ethylenically unsaturated double bonds, still more preferably 5 or more ethylenically unsaturated double bonds, and particularly preferably 6 or more ethylenically unsaturated double bonds is preferably used, and that even when heat treatment is performed after exposure, the fluidity in the system is improved, whereby the influence of steric hindrance is reduced even if the number of functional groups is large, and high adhesion can be obtained. The content of the compound having preferably 3 or more ethylenically unsaturated double bonds, more preferably 4 or more ethylenically unsaturated double bonds, further preferably 5 or more ethylenically unsaturated double bonds, particularly preferably 6 or more ethylenically unsaturated double bonds is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, particularly preferably 10% by mass or more, based on the solid content of the photosensitive resin composition. The upper limit of the content is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of exhibiting the effect of the heat treatment after exposure.

Examples of the (b1) (meth) acrylate compound having 3 or more ethylenically unsaturated bonds include:

tri (meth) acrylates such as ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolpropane tri (meth) acrylate (for example, tri (meth) acrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane and tri (meth) acrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane are preferable examples from the viewpoint of flexibility, adhesion, and bleed-out suppression);

tetra (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and the like;

penta (meth) acrylates such as dipentaerythritol penta (meth) acrylate and the like;

hexa (meth) acrylates, such as dipentaerythritol hexa (meth) acrylate, and the like.

Among them, tetra-, penta-or hexa- (meth) acrylates are preferred.

(b1) The (meth) acrylate compound having 3 or more ethylenically unsaturated bonds preferably has a weight average molecular weight of 500 or more, more preferably 700 or more, and even more preferably 900 or more, from the viewpoint of suppressing bleeding.

As the tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate is preferable. The pentaerythritol tetra (meth) acrylate is preferably a tetra (meth) acrylate obtained by adding 1 to 40 moles of alkylene oxide to 4 terminals of pentaerythritol in total.

The tetra (meth) acrylate is more preferably a tetra (meth) acrylate compound represented by the following general formula (II):

{ formula (II) wherein R₃～R₆Each independently represents a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m₁、m₂、m₃And m₄Each independently an integer of 0 to 40, m₁+m₂+m₃+m₄1 to 40, and m₁+m₂+m₃+m₄When the number is 2 or more, X's may be the same as or different from each other }.

While not wishing to be bound by theory, it is believed that the tetramethylacrylate compound represented by formula (II) has the group R₃～R₆And has H₂The tetraacrylate having a C ═ CH-CO-O-moiety can inhibit its hydrolyzability in an alkaline solution. The photosensitive resin composition containing the tetramethylacrylate compound represented by the general formula (II) is preferably used from the viewpoint that the adhesion when the development is carried out after the exposure is significantly improved, and particularly, the excellent adhesion is realized even when the time from the exposure to the development is prolonged.

In the general formula (II), the radical R₃～R₆At least one of (A) is preferably methyl, and more preferably a group R₃～R₆All are methyl groups.

In the general formula (II), X is-CH and is preferably selected from the viewpoint of obtaining a desired resolution, curl shape, residual film ratio and the like for a resist pattern₂-CH₂-。

In the general formula (II), m is preferably m in order to obtain a desired resolution, curl shape, residual film ratio and the like for the resist pattern₁、m₂、m₃And m₄Each independently is an integer of 1 to 20, more preferably an integer of 2 to 10. Further preferably in the formula (II), m₁+m₂+m₃+m₄1 to 36 or 4 to 36.

Examples of the compound represented by the general formula (II) include pentaerythritol (poly) alkoxytetramethylacrylate and the like. In the present disclosure, "pentaerythritol (poly) alkoxytetramethylacrylate" includes m in the above general formula (II)₁+m₂+m₃+m₄"pentaerythritol alkoxytetramethylacrylate" and m ═ 1₁+m₂+m₃+m₄2 to 40 of pentaerythritol polyalkoxytetramethacrylate. Examples of the compound represented by the general formula (II) include compounds described in Japanese patent laid-open publication No. 2013-156369, for example pentaerythritol (poly) alkoxytetramethylacrylate.

The hexa (meth) acrylate compound is preferably hexa (meth) acrylate obtained by adding 1 to 24 moles in total of ethylene oxide to 6 terminals of dipentaerythritol, or hexa (meth) acrylate obtained by adding 1 to 10 moles in total of epsilon-caprolactone to 6 terminals of dipentaerythritol.

In the photosensitive resin composition of the present embodiment, it is particularly preferable to contain a (meth) acrylate compound having 4 or more ethylenically unsaturated bonds and having an oxyalkylene chain as the compound (B) having an ethylenically unsaturated bond, from the viewpoint that the adhesiveness when the development is carried out after the exposure and then the heating can be significantly improved, and particularly, good adhesiveness can be achieved even when the time from the exposure to the development is prolonged. At this time, the ethylenic unsaturated bond is more preferably derived from a methacryloyl group, and the oxyalkylene chain is more preferably an oxyethylene chain.

In the present embodiment, the photosensitive resin composition preferably contains a (meth) acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton as the compound (B) having an ethylenically unsaturated bond, from the viewpoint that the adhesiveness when the development is carried out after the exposure is remarkably improved, and particularly, the favorable adhesiveness is realized even when the time from the exposure to the development is prolonged. Examples of the oxyalkylene chain include an oxyethylene chain, an oxypropylene chain, an oxybutylene chain, an oxypentylene chain, and an oxyphexylene chain. When the photosensitive resin composition contains a plurality of oxyalkylene chains, they may be the same or different from each other. From the above viewpoint, as the oxyalkylene chain, an oxyethylene chain, an oxypropylene chain and an oxybutylene chain are more preferable, an oxyethylene chain and an oxypropylene chain are further preferable, and an oxyethylene chain is particularly preferable.

In the photosensitive resin composition, by using (a) an alkali-soluble polymer and a (meth) acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton in combination, a balance of chemical resistance, adhesiveness, and resolution of a resist pattern tends to be maintained.

The (meth) acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton is an ester of a dipentaerythritol compound in which at least one of a plurality of hydroxyl groups is modified with an oxyalkylene group and (meth) acrylic acid. The 6 hydroxyl groups of the dipentaerythritol skeleton may be modified by alkylene oxides. The number of ester bonds in one ester molecule may be 1 to 6, preferably 6.

Examples of the (meth) acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton include hexa (meth) acrylate in which an alkylene oxide is added to dipentaerythritol in an amount of 4 to 30 moles on the average, 6 to 24 moles on the average, or 10 to 14 moles on the average.

Specifically, as the (meth) acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton, a compound represented by the following general formula (III) is preferable from the viewpoint that the adhesion when development is carried out after exposure and heating can be significantly improved, and particularly, good adhesion can be achieved even when the time from exposure to development is prolonged:

{ wherein R each independently represents a hydrogen atom or a methyl group, n is an integer of 0 to 30, and the total of all n is 1 or more }. In the general formula (III), it is preferable that the average value of all n is 4 or more, or each n is 1 or more. As R, methyl is preferred.

From the same viewpoint, the content of the (meth) acrylate compound having an oxyalkylene chain and a dipentaerythritol skeleton in the photosensitive resin composition is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 40% by mass, and still more preferably in the range of 7 to 30% by mass, relative to the total amount of solid components.

The content of the (meth) acrylate compound having 3 or more ethylenically unsaturated bonds (i.e., the compound having 3 or more (meth) acrylate groups) in the (b1) component is preferably more than 0 mass% and 50 mass% or less with respect to the total solid content of the photosensitive resin composition. If the content exceeds 0 mass%, it is more advantageous from the viewpoint of significantly improving the adhesion when the development is carried out after the exposure by heating, particularly from the viewpoint of achieving good adhesion even when the time from the exposure to the development is prolonged, and if it is 50 mass% or less, the flexibility of the cured resist tends to be improved and the peeling time tends to be shortened. The content is more preferably 2% by mass or more and 40% by mass or less, and further preferably 4% by mass or more and 35% by mass or less. In a more preferred embodiment, (B) the compound having an ethylenically unsaturated double bond contains a compound having 3 or more methacrylate groups in the molecule in an amount of preferably 5% by mass or more, more preferably 9% by mass or more, further preferably 13% by mass or more, particularly preferably 20% by mass or more, further preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition.

From the viewpoint of adhesion and from the viewpoint of suppression of foaming of the developing solution, the photosensitive resin composition preferably contains (B2) a compound having an oxetanyl chain or an oxypropylene chain and 1 or 2 (meth) acryloyl groups as the compound having an ethylenically unsaturated bond (B).

(b2) The compound having an oxetanyl chain or an oxetanyl chain and 1 or 2 (meth) acryloyl groups preferably has a molecular weight of 500 or more, more preferably 700 or more, and still more preferably 1000 or more, from the viewpoint of suppressing bleeding.

Examples of the compound (b2) having an oxybutylene chain or an oxypropylene chain and 1 or 2 (meth) acryloyl groups include polypropylene glycol (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and the like. (b2) The compound having an oxybutylene chain or an oxypropylene chain and 1 or 2 (meth) acryloyl groups may contain an oxyethylene chain in addition to the oxybutylene chain or the oxypropylene chain.

Specifically, (b2) the compound having an oxetanyl chain or an oxetanyl chain and 1 or 2 (meth) acryloyl groups preferably has 1 to 20, more preferably 4 to 15, and still more preferably 6 to 12C groups₄H₈O or C₃H₆O (meth) acrylate or di (meth) acrylate.

The content of the compound having an oxybutylene chain or an oxypropylene chain and 1 or 2 (meth) acryloyl group (b2) is preferably more than 0 mass% and 20 mass% or less with respect to the total solid content of the photosensitive resin composition.

In the present embodiment, in order to suppress bleeding of the components constituting the dry film resist and improve the storage stability, the compound having a weight average molecular weight of 500 or more is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass based on the total solid content of the compound having an ethylenically unsaturated bond (B). The weight average molecular weight of the compound having an ethylenically unsaturated bond (B) is preferably 760 or more, more preferably 800 or more, further preferably 830 or more, and particularly preferably 900 or more, from the viewpoint of suppressing bleeding and chemical resistance of the resist pattern. (B) The weight average molecular weight of the compound having an ethylenically unsaturated bond can be determined as a molecular weight calculated from the molecular structure of (B) the compound having an ethylenically unsaturated bond. When there are a plurality of (B) compounds having an ethylenically unsaturated bond, the molecular weight of each compound can be determined by weight-averaging the contents.

The concentration of the methacryloyl group in the compound having an ethylenically unsaturated bond (B) is preferably 0.20 mol/100 g or more, more preferably 0.30 mol/100 g or more, and still more preferably 0.35 mol/100 g or more, from the viewpoint of chemical resistance, adhesion, high resolution, and curl shape of the resist pattern. The upper limit of the concentration of methacryloyl group is not limited as long as polymerizability and alkali developability are ensured, and may be, for example, 0.90 mol/100 g or less or 0.80 mol/100 g or less.

From the same viewpoint, the value of the concentration of methacryloyl group/(concentration of methacryloyl group + concentration of acryloyl group) in the compound having an ethylenically unsaturated bond (B) is preferably 0.50 or more, more preferably 0.60 or more, further preferably 0.80 or more, particularly preferably 0.90 or more, and most preferably 0.95 or more.

The (meth) acrylate compounds described above may be used independently of each other or in combination. The photosensitive resin composition may further contain another compound as (B) the compound having an ethylenically unsaturated bond. Examples of the other compounds include (meth) acrylates having urethane bonds, compounds obtained by reacting a polyhydric alcohol with an α, β -unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α, β -unsaturated carboxylic acid, and 1, 6-hexanediol di (meth) acrylate.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid content of the photosensitive resin composition is preferably 5 to 70% by mass. This ratio is preferably 5% by mass or more from the viewpoint of sensitivity, resolution and adhesion. This ratio is more preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, from the viewpoint of suppressing edge fusion and peeling delay of the cured resist, the ratio is preferably 70% by mass or less. More preferably, the ratio is 50% by mass or less.

(C) Photopolymerization initiator

(C) The photopolymerization initiator is a compound that polymerizes monomers by light. From the viewpoint of significantly improving the adhesion when the development is carried out after the exposure by heating, and particularly obtaining good adhesion even when the time from the exposure to the development is prolonged, the (C) photopolymerization initiator preferably contains 1 or more selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof, more preferably contains anthracene and/or an anthracene derivative, and further preferably contains an anthracene derivative. Anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof, particularly anthracene and/or anthracene derivatives absorb the 1 st active light having a central wavelength of less than 390nm and the 2 nd active light having a central wavelength of 390nm or more, and function well as a polymerization initiator. Therefore, in one embodiment, the photosensitive resin composition may have photosensitivity to the 1 st active light and the 2 nd active light, and may be used for 2-wavelength exposure. (C) The photopolymerization initiator may be selected to have a plurality of absorption maxima in the wavelength ranges of the 1 st active light and the 2 nd active light.

The total content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass, still more preferably in the range of 0.1 to 7% by mass, and particularly preferably in the range of 0.1 to 6% by mass. (C) The total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and is preferably 20% by mass or less from the viewpoint of obtaining good high resolution by sufficiently transmitting light to the bottom surface of the resist.

Anthracene and an anthracene derivative are advantageous from the viewpoint that adhesion when development is performed after exposure by heating can be significantly improved, and particularly, favorable adhesion can be achieved even when the time from exposure to development is prolonged. The anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms which may be substituted and/or an aryl group having 6 to 40 carbon atoms which may be substituted at the 9-and/or 10-positions, more preferably the 9-and 10-positions, from the same viewpoint.

In one embodiment, the anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms which may be optionally substituted at least at the 9-position or 10-position, and more preferably has an alkoxy group having 1 to 30 carbon atoms which may be optionally substituted at least at the 9-position or 10-position, from the viewpoint of remarkably improving the adhesion when the development is performed after the exposure and particularly achieving good adhesion even when the time from the exposure to the development is prolonged. From the viewpoint of obtaining good adhesion and resolution, the alkoxy group having 1 to 40 carbon atoms and optionally having a substituent is preferably present at the 9 and 10 positions, and the alkoxy group having 1 to 30 carbon atoms and optionally having a substituent is more preferably present at the 9 and 10 positions. The carbon numbers of the groups at the 9-and 10-positions may be the same or different.

Examples of the alkoxy group optionally having a substituent include:

methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methylpropoxy, 1-methylpropoxy, n-pentoxy, isopentoxy, n-hexoxy, 2-ethylhexoxy, nonoxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, eicosyloxy, cyclohexyloxy, norborneoxy, tricyclodecyloxy, tetracyclododecyloxy, adamantyloxy, methyladamantoxy, ethyladamantoxy and butyladamantoxy;

alkoxy modified with halogen, such as chlorobutoxy, chloropropoxy;

an alkoxy group to which a hydroxyl group is added, such as a hydroxybutoxy group;

alkoxy groups to which cyano groups are added, such as cyanobutoxy;

an alkoxy group to which an oxyalkylene group is added, such as methoxybutoxy;

an alkoxy group to which an aryl group is added, for example, phenoxybutoxy group. Among them, n-butoxy group is more preferable.

In one embodiment, the anthracene derivative is preferably an aryl group having 6 to 40 carbon atoms and having an optional substituent at least at the 9-position or 10-position, and more preferably an aryl group having 6 to 30 carbon atoms and having an optional substituent at least at the 9-position or 10-position, from the viewpoint of remarkably improving adhesion when development is performed after heating after exposure, and particularly achieving good adhesion even when the time from exposure to development is prolonged.

From the viewpoint of remarkably improving the adhesion when the development is carried out after the exposure by heating, and particularly achieving good adhesion even when the time from the exposure to the development is prolonged, the aryl group having 6 to 40 carbon atoms and optionally having a substituent at the 9 and 10 positions is preferable, and the aryl group having 6 to 30 carbon atoms and optionally having a substituent at the 9 and 10 positions is more preferable. The carbon numbers of the groups at the 9-and 10-positions may be the same or different. In addition, the groups at the 9-position and the 10-position may be the same group or different groups. For example, the group at the 9-position may be an optionally substituted alkoxy group having 1 to 40 carbon atoms, and the group at the 10-position may be an optionally substituted aryl group having 6 to 40 carbon atoms.

Examples of the aryl group having 6 to 40 carbon atoms which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, and an anthracenyl group; an alkoxy-added aryl group such as a methoxyphenyl group or an ethoxyphenyl group; aryl groups to which alkyl groups are added, such as tolyl, xylyl, 2,4, 6-trimethylphenyl, nonylphenyl; an aryl group to which a halogen is added, such as chlorophenyl; examples of the aryl group to which a hydroxyl group is added include hydroxyphenyl groups. Among them, phenyl is more preferable.

The anthracene derivative is preferably represented by the following general formula (IV).

R¹Independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group or N (R')₂Radical, 2 or more R¹May be bonded to each other to form a cyclic structure, and the cyclic structure may contain a hetero atom.

X independently represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, an-N (R') -group, a-CO-O-group, a-CO-S-group, or an-SO₂-O-group, -SO₂-S-group, -SO₂-N (R') -yl, -O-CO-yl, -S-CO-yl, -O-SO₂-radical or S-SO₂-a radical. However, X is a single bond and R¹Except for combinations that are hydrogen atoms (i.e., unsubstituted anthracene).

R 'represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heteroaryl group, and R' may be bonded to each other to form a cyclic structure, and the cyclic structure may contain a heteroatom.

p is an integer of 1 to 10, preferably 2 to 4.

As the above-mentioned R¹Examples of the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms in R' include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-eicosyl, isopropyl, isobutyl, sec-butyl, and tert-butyl.

As the above-mentioned R¹Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in R' include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and bridged alicyclic hydrocarbon groups having 6 to 20 carbon atoms (for example, norbornyl, tricyclodecyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl, and butyladamantyl groups).

As the above-mentioned R¹And C2-C4 alkene in RSpecific examples of the group include a vinyl group and an acryl group.

As the above-mentioned R¹Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in R' include phenyl, biphenyl, naphthyl, anthryl, methoxyphenyl, ethoxyphenyl, tolyl, xylyl, 2,4, 6-trimethylphenyl, nonylphenyl, chlorophenyl and hydroxyphenyl groups.

As the above-mentioned R¹Examples of the substituted or unsubstituted heteroaryl group in R' include a group containing 1 or more heteroatoms such as a sulfur atom, an oxygen atom, and a nitrogen atom in the substituted or unsubstituted aryl group, and examples thereof include a pyridyl group, an imidazolyl group, a morpholinyl group, a piperidyl group, and a pyrrolidinyl group.

In addition, the above R¹And each of the hydrocarbon groups of R' may be substituted with a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a hydroxyalkyl group having 1 to 4 carbon atoms (e.g., a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, etc.), an alkoxy group having 1 to 4 carbon atoms (e.g., a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a t-butoxy group, etc.), a cyano group, a cyanoalkyl group having 2 to 5 carbon atoms (e.g., a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group, etc.), an alkoxycarbonyl group (, Alkoxycarbonylalkoxy (e.g., methoxycarbonylmethoxy, ethoxycarbonylmethoxy, t-butoxycarbonylmethoxy, etc.), halogen atom (e.g., fluorine, chlorine, etc.), fluoroalkyl (e.g., fluoromethyl, trifluoromethyl, pentafluoroethyl, etc.), and the like. R is as defined above¹And each hydrocarbon group of R' is preferably substituted with a halogen atom. Particularly, the anthracene derivative preferably has an alkoxy group substituted with a halogen atom at the 9-position and/or the 10-position.

As the above-mentioned R¹Preferred specific examples of R' include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, cyclopentyl group, cyclohexyl group, camphoryl group, norbornyl group, p-toluene groupAcyl, benzyl, methylbenzyl, phenyl and 1-naphthyl.

Preferred specific examples of X include a single bond, an oxygen atom, a sulfur atom, -N (R') -, -O-CO-group and O-SO₂-a radical. When X is an-N (R ') -group, R' is preferably a hydrogen atom, a methyl group, an ethyl group, an N-propyl group, an isopropyl group, an N-butyl group, a cyclopentyl group, a cyclohexyl group, a camphoryl group, a norbornyl group or a benzyl group.

Examples of the compound represented by the above general formula (IV) include 1-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 9-methylanthracene, 9, 10-dimethylanthracene, 9-vinylanthracene, 9-phenylanthracene, 9, 10-diphenylanthracene, 2-bromo-9, 10-diphenylanthracene, 9- (4-bromophenyl) -10-phenylanthracene, 9- (1-naphthyl) anthracene, 9- (2-naphthyl) anthracene, 2-bromo-9, 10-bis (2-naphthyl) anthracene, 2, 6-dibromo-9, 10-bis (2-naphthyl) anthracene, 9, 10-diethoxyanthracene, 9, 10-dipropoxyanthracene, 9, 10-dibutoxyanthracene, 9, 10-bis (2-ethylhexyloxy) anthracene, 1, 2-benzanthracene, anthraphenol, 1,4,9, 10-tetrahydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene, 9- (methylaminomethyl) anthracene, 9-acetylanthracene, 9-anthracenealdehyde, 10-methyl-9-anthracenealdehyde, 1,8, 9-triacetoxyanthracene, and the like. Among them, 9, 10-dimethylanthracene, 9, 10-diphenylanthracene, 9, 10-diethoxyanthracene, 9, 10-dipropoxyanthracene, 9, 10-dibutoxyanthracene, 9, 10-bis (2-ethylhexyloxy) anthracene, and 9, 10-bis- (3-chloropropyloxy) anthracene are preferable, and particularly, from the viewpoint that adhesion when development is performed after exposure by heating can be significantly improved, and particularly, good adhesion is achieved even when the time from exposure to development is prolonged, 9, 10-diethoxyanthracene, 9, 10-dibutoxyanthracene, 9, 10-diphenylanthracene, 9, 10-bis- (3-chloropropyloxy) anthracene, and particularly, 9, 10-dibutoxyanthracene and 9, 10-diphenylanthracene are more preferable, 9, 10-bis- (3-chloropropoxy) anthracene. The compounds represented by the above general formula (IV) may be used alone or in combination of two or more.

From the viewpoint that the adhesiveness when the development is carried out after the exposure by heating can be significantly improved, and particularly that good adhesiveness can be obtained even when the time from the exposure to the development is prolonged, (C) the photopolymerization initiator preferably (1) contains 9, 10-diphenylanthracene; (2) contains 9, 10-dialkoxyanthracene; (3) an anthracene derivative having a halogen atom; (4) a halogen substituent containing 9, 10-dialkoxyanthracene; (5) a compound in which the alkoxy group at the 9-position and/or 10-position of a 9, 10-dialkoxyanthracene is modified with 1 or more halogen atoms; and/or (6) a compound containing a halogen atom having a direct bond to the anthracene skeleton.

The compound represented by the general formula (IV) is advantageous from the viewpoint that the adhesion in the case of heating and developing after exposure can be significantly improved, and particularly, good adhesion can be obtained even when the time from exposure to development is prolonged, and further, it is advantageous from the viewpoint that a photosensitive resin composition which can be used for 2-wavelength exposure using 1 st active light having a central wavelength of less than 390nm and 2 nd active light having a central wavelength of 390nm or more and exhibits excellent sensitivity, adhesion and resolution can be provided.

In one embodiment, the photopolymerization initiator (C) preferably contains an anthracene derivative having a halogen atom. A preferable example of the anthracene derivative having a halogen atom is a halogen substituent of 9, 10-dialkoxyanthracene. A preferable example of the halogen substituent is a compound in which the alkoxy group at the 9-position and/or 10-position of 9, 10-dialkoxyanthracene is modified with 1 or more halogen atoms. Preferred examples of the alkoxy group include alkoxy groups having 1 to 40 carbon atoms as exemplified above.

In one embodiment, the anthracene derivative is also preferably a compound having a halogen atom directly bonded to an anthracene skeleton. Examples of the anthracene compound include 9-bromo-10-phenylanthracene, 9-chloro-10-phenylanthracene, 9-bromo-10- (2-naphthyl) anthracene, 9-bromo-10- (1-naphthyl) anthracene, 9- (2-biphenyl) -10-bromoanthracene, 9- (4-biphenyl) -10-bromoanthracene, 9-bromo-10- (9-phenanthryl) anthracene, 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, and 9, 10-dibromoanthracene.

The total amount of anthracene and anthracene derivative, or the amount of the compound represented by the general formula (IV) in a preferred embodiment, is preferably in the range of 0.05 to 5% by mass, more preferably in the range of 0.1 to 3% by mass, and particularly preferably in the range of 0.1 to 1.0% by mass, based on the total solid content of the photosensitive resin composition.

Pyrazoline and pyrazoline derivatives are preferable from the viewpoint of the peeling property, sensitivity, resolution and adhesiveness of the photosensitive resin layer.

As pyrazoline derivatives, for example, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline Pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 5-dimethoxystyryl) -5- (3, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 4-dimethoxystyryl) -5- (3, 4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 6-dimethoxystyryl) -5- (2, 6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 5-dimethoxystyryl) -5- (2, from the above viewpoint, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 3-dimethoxystyryl) -5- (2, 3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 4-dimethoxystyryl) -5- (2, 4-dimethoxyphenyl) -pyrazoline, and the like are preferable, and 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is more preferable.

Examples of the coumarin derivative include 7-diethylamino-4-methylcoumarin, 3' -carbonylbis (7-diethylaminocoumarin), and 3-benzoyl-7-diethylaminocoumarin. Among them, 7-diethylamino-4-methylcoumarin is preferable from the viewpoint of sensitivity, resolution and adhesiveness.

Further examples of the photopolymerization initiator (C) include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkyl aminobenzoate esters, oxime esters, acridines (for example, 9-phenylacridine, bisazinylheptane, 9- (p-methylphenyl) acridine, and 9- (m-methylphenyl) acridine are preferable from the viewpoint of sensitivity, resolution, and adhesion), hexaarylbiimidazole, N-arylamino acids or ester compounds thereof (for example, N-phenylglycine is preferable from the viewpoint of sensitivity, resolution, and adhesion), halogen compounds (for example, tribromomethylphenylsulfone), and the like. These can be used alone in 1 or more than 2 kinds of combination. In addition, 2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, triphenylphosphine oxide and the like can also be used.

Examples of the aromatic ketone include benzophenone, michler's ketone [4, 4' -bis (dimethylamino) benzophenone ], 4 '-bis (diethylamino) benzophenone, and 4-methoxy-4' -dimethylamino benzophenone. These can be used alone in 1 or more than 2 kinds of combination. Among them, from the viewpoint of adhesion, 4' -bis (diethylamino) benzophenone is preferable. Further, from the viewpoint of transmittance, the content of the aromatic ketone in the photosensitive resin composition is preferably in the range of 0.01 to 0.5 mass%, and more preferably in the range of 0.02 to 0.3 mass%.

Examples of the hexaarylbiimidazole 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, and 2,2 ' -bis- (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, and the like, and they may be used alone in 1 kind or in combination of 2 or more kinds. From the viewpoint of sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer is preferable.

The content of hexaarylbiimidazole in the photosensitive resin composition is preferably in the range of 0.05 to 8 mass%, more preferably in the range of 0.1 to 7 mass%, and still more preferably in the range of 1 to 6 mass%, from the viewpoint of improving the peeling characteristics and/or sensitivity of the photosensitive resin layer.

(D) Phenol polymerization inhibitor

The photosensitive resin composition contains (D) a phenolic polymerization inhibitor for the purpose of improving thermal stability and storage stability. In the present disclosure, the phenol-based polymerization inhibitor (D) is a compound having 1 or more phenolic hydroxyl groups. The phenol-based polymerization inhibitor has characteristics of inhibiting a polymerization reaction caused by heat or the like and improving storage stability. The phenol-based polymerization inhibitor may have 1 or more substituents selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 40 carbon atoms, alkoxy groups having 1 to 40 carbon atoms, alkenyl groups having 2 to 4 carbon atoms, substituted or unsubstituted alicyclic groups having 3 to 20 carbon atoms, substituted or unsubstituted aryl groups, and substituted or unsubstituted heteroaryl groups. In a preferred embodiment, the phenolic polymerization inhibitor (D) is a 1-valent phenol (i.e., a compound having 1 phenolic hydroxyl group in the molecule). (D) More specific preferable examples of the phenol-based polymerization inhibitor are p-hydroxyanisole, dibutylhydroxytoluene, hydroquinone, pentaerythritol tetrakis (3- (3 ', 5 ' -di-tert-butyl-4 ' -hydroxyphenyl) propionate), stearyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N ' -hexamethylenebis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanamide), octyl-3, 5-di-tert-butyl-4-hydroxy-hydrocinnamic acid, 2,4, 6-tris (3 ', 5 '-di-tert-butyl-4' -hydroxybenzyl) mesitylene, 2, 4-bis (dodecylthiomethyl) -6-methylphenol, 2, 4-bis (octylthiomethyl) -6-methylphenol, bis (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoic acid) (ethylenebis (oxyethylene)) ester, 1, 6-hexanediol bis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoate), 1,3, 5-tris ((3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl) methyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 4- ((4, 6-bis (octylthio) -1,3, 5-triazin-2-yl) amino) -2, 6-di-tert-butylphenol and the like, and p-hydroxyanisole and dibutylhydroxytoluene are particularly preferable from the viewpoint that a difference in the shortest development time between heating and non-heating after exposure is less likely to occur.

The amount of the phenolic polymerization inhibitor (D) is 1ppm or more, preferably 5ppm or more, more preferably 10ppm or more, further preferably 15ppm or more, and particularly preferably 20ppm or more based on the mass of the photosensitive resin composition when the total solid content of the photosensitive resin composition is 100% by mass, from the viewpoint of obtaining a desired effect of inhibiting polymerization for the photosensitive resin composition, and is 300ppm or less, preferably 200ppm or less, more preferably 150ppm or less, further preferably 100ppm or less, further preferably 75ppm or less, further preferably 50ppm, and particularly preferably 40ppm or less, from the viewpoint of achieving good adhesion when development is carried out by heating after exposure, particularly when the time from exposure to development is extended. The photosensitive resin composition contains the phenolic polymerization inhibitor (D), but the amount thereof is small, and is advantageous from the viewpoint of satisfying both the progress of the polymerization reaction in the photosensitive resin composition at the time of exposure in the case of heating after exposure and then developing, and the promotion of the reaction of the polymer (and hence the improvement of the adhesion) by the effect of improving the fluidity by heating of the polymer. For example, in the case of a system in which the polymer has a bulky molecular structure (for example, a relatively large amount of styrene skeleton), when post-exposure heating intended to improve adhesion is performed, the effect of improving fluidity by heating the polymer may be low (and thus the effect of improving adhesion may be low), but according to the photosensitive resin composition of the present embodiment, the effect of improving adhesion by post-exposure heating is favorably obtained even in the case where such a bulky polymer is present, by setting the amount of the (D) phenolic polymerization inhibitor within the above range.

In a particularly preferred embodiment, the content of dibutylhydroxytoluene in the photosensitive resin composition is 1 to 200ppm, or 10 to 150 ppm.

[ optional Components ]

The photosensitive resin composition may contain any component in addition to the components (a) to (D) described above, as necessary. Examples of the optional component include (D) a polymerization inhibitor other than the phenol-based polymerization inhibitor, a dye, a coloring matter, a plasticizer, an antioxidant, a stabilizer, and the like. For example, additives listed in Japanese patent laid-open publication No. 2013-156369 can be used.

(d) additional polymerization inhibitor)

Examples of the additional polymerization inhibitor include radical polymerization inhibitors, benzotriazoles and carboxybenzotriazoles, which are not the above-mentioned phenolic polymerization inhibitors.

Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, 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.

In one embodiment, the total amount of the added polymerization inhibitor is preferably 0.001 to 3% by mass, more preferably 0.01 to 1% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. It is preferable to set the total amount to 0.001 mass% or more from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, it is preferable to set the total amount to 3 mass% or less from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye.

(dyes and coloring matters)

In the present 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, parafuchsine (para magenta), crystal violet, methyl orange, nile blue 2B, victoria blue, malachite GREEN (for example, HODOGAYA chemcal co., ltd. system AIZEN (registered trademark) MALACHITE GREEN), basic blue 20, and DIAMOND GREEN (for example, HODOGAYA chemcal co., ltd. system AIZEN (registered trademark) DIAMOND GREEN GH). 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. The content of 0.001 mass% or more is preferable from the viewpoint of improving handling properties of the photosensitive resin composition. 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 an alignment marker used for exposure is read by an inspection machine or the like, it is easily recognized when the contrast between the exposed portion and the unexposed portion is large. From such a 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 mass% or more, and particularly preferably 0.4 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 the photosensitive resin composition, the leuco dye and the halogen compound described above as the photopolymerization initiator (C) are preferably used in combination from the viewpoint of optimizing the adhesiveness and the contrast. 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, based on 100% by mass of the total solid content of the photosensitive resin composition, from the viewpoint of maintaining the storage stability of the color tone in the photosensitive layer.

In the present 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 the present embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalates (e.g., diethyl phthalate), 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, there may be mentioned compounds having a bisphenol skeleton such as Adekanol SDX-1569, Adekanol SDX-1570, Adekanol SDX-1571, Adekanol 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, UNIOL DA-700 (manufactured by Nippon oil Co., Ltd.), BA-P4U Glycol, and BA-P8Glycol (manufactured by Nippon emulsifier Co., Ltd.).

The content of the plasticizer in the photosensitive resin composition is preferably 1 to 50% by mass, 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 flow, the content is preferably 50% by mass or less.

When the amount of water in the photosensitive resin composition is large, local plasticization of the photosensitive resin composition is rapidly promoted, and edge fusion occurs. From the viewpoint of suppressing the edge fusion, the amount of water in the photosensitive resin composition is preferably 0.7% or less on a mass basis with respect to the photosensitive resin composition after the photosensitive resin composition preparation liquid is applied to the support film and dried. The water content in the photosensitive resin composition is preferably 0.65% or less, preferably 0.6% or less, preferably 0.55% or less, preferably 0.5% or less, preferably 0.45% or less, preferably 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less, preferably 0.2% 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 ketones are represented by Methyl Ethyl Ketone (MEK) and acetone. 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 film at 25 ℃ is from 500 mPas to 4000 mPas in the production of the photosensitive resin laminate.

[ light transmittance of photosensitive resin composition ]

The light transmittance at least one of 375nm and 405nm of the photosensitive resin composition of the present embodiment is 58% to 95% from the viewpoint of providing a photosensitive resin composition which is excellent in sensitivity, adhesion, line width reproducibility and resolution when development is performed after exposure by heating, and particularly realizes excellent adhesion even when the time from exposure to development is long. 375nm and 405nm correspond to typical exposure wavelengths in the photosensitive resin composition of the present embodiment. The light transmittance is 58% or more, preferably 60% or more, more preferably 62% or more, more preferably 64% or more, and further preferably 65% or more from the viewpoint of obtaining good sensitivity, adhesion, line width reproducibility, and resolution by reaching a region deeper than the photosensitive resin composition by exposure light, and is 95% or less, preferably 85% or less, more preferably 80% or less, more preferably 75% or less, and further preferably 70% or less from the viewpoint of obtaining a good curl shape by suppressing diffuse reflection light from the substrate surface.

The means for controlling the light transmittance at least one of 375nm and 405nm within the above range is not limited to these, and examples thereof include control of the amount of a photopolymerization initiator, a dye, and a coloring material to be added.

[ photosensitive resin laminate ]

The present embodiment also provides a photosensitive resin laminate having a photosensitive resin layer formed from the photosensitive resin composition and a support film. The support film 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. As these films, stretched films can also be used as needed.

The haze of the support film is preferably 5% or less, more preferably 2% or less, further preferably 1.5% or less, and particularly preferably 1.0% or less, from the viewpoint of suppressing light scattering at the time of exposure. From the same viewpoint, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30nm or less, more preferably 20nm or less, and particularly preferably 10nm or less. The thinner the film thickness is, the better the image formability and the economical efficiency are, and therefore, it is advantageous to use a film of 10 to 30 μm in order to maintain the strength of the photosensitive resin laminate. The size of fine particles such as lubricant contained in the support film is preferably less than 5 μm.

The support film may have a single-layer structure or a multilayer structure in which a plurality of resin layers having different compositions are stacked. In the case of a multilayer structure, an antistatic layer may also be present. In the case of a multilayer structure such as a 2-layer structure or a 3-layer structure, for example, a structure in which a resin layer containing fine particles is formed on one surface a, and fine particles are (1) contained in the same manner as in the surface a, (2) contained in a smaller amount than in the surface a, (3) contained in a smaller amount than in the surface a, and (4) not contained may be formed on the other surface B. (2) In the case of the structures of (3) and (4), it is preferable to form a photosensitive resin layer on the surface B side. In this case, it is preferable that a resin layer containing fine particles is present on the surface a side from the viewpoint of smoothness of the film. The size of the fine particles at this time is preferably less than 1.5 μm. The size of the fine particles is a value measured by a scanning electron microscope calibrated by using a standard sample.

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

There may be gels known as fish eyes on the surface of the polyethylene film. When 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 cause a defect in the resist pattern. From the viewpoint of preventing fish eyes, stretched polypropylene is preferable as a material of the protective layer. Specific examples thereof include ALPHAN E-200A manufactured by Wangzi paper company.

The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, and is preferably 1 μm to 300 μm, more preferably 3 μm to 100 μm, particularly preferably 5 μm to 60 μm, and most preferably 10 μm to 30 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.

The transmittance at a wavelength of 630nm of the laminate of the support film and the photosensitive resin layer was an index of discoloration of the dye, and a high transmittance at a wavelength of 630nm indicated that the dye was discolored. The light transmittance at a wavelength of 630nm of the laminate of the support film and the photosensitive resin layer is preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 72% or less, preferably 70% or less, preferably 68% or less, preferably 65% or less, preferably 62% or less, preferably 60% or less, preferably 58% or less, preferably 55% or less, preferably 52% or less, preferably 50% or less. The light transmittance is a value of a laminate (i.e., not including a protective layer) of the support film and the photosensitive resin layer.

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 film, a photosensitive resin layer, and, if necessary, a protective layer, a known method can be employed. For example, a photosensitive resin layer formed of a photosensitive resin composition can be laminated on a support film 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 film using a bar coater or a roll coater, and then drying the coating 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 may include an exposure step of exposing the photosensitive resin composition to light, a heating step of heating the exposed photosensitive resin composition, and a development step of developing the photosensitive resin composition.

Examples of the resist pattern include patterns of a printed wiring board, a semiconductor element, a printing plate, a liquid crystal display panel, a touch panel, a flexible substrate, a lead frame substrate, a substrate for COF (chip on film package), a substrate for semiconductor packaging, 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 process

First, in the laminating step, a photosensitive resin layer is formed on a substrate using a laminating apparatus. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heated and pressed against the surface of the substrate by a laminating device to be laminated. Examples of the material of the substrate include copper, stainless steel (SUS), glass, and Indium Tin Oxide (ITO).

In the present embodiment, the photosensitive resin layer may be laminated on only one surface of the substrate surface or on both surfaces as necessary. The heating temperature for lamination is usually 40 to 160 ℃. Further, by performing the heat pressure bonding 2 or more times at the time of lamination, the adhesion of the obtained resist pattern to the substrate can be improved. In the heat pressure bonding, a two-stage laminating apparatus having a twin roller may be used, or the pressure bonding may be performed by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the roller several times.

(2) Exposure Process

In this step, the photosensitive resin layer is exposed by the following method: an exposure method in which a mask film having a desired wiring pattern is closely attached to a support film and an active light source is used; an exposure method by direct writing of a pattern to be written as a desired wiring pattern; or an exposure method using an image projected through a lens onto a photomask.

The exposure step is preferably performed by the following method: an exposure method by direct drawing of a drawing pattern; or an exposure method in which an image of the photomask is projected through a lens, and more preferably, an exposure method in which direct drawing of a drawn pattern is used. The photosensitive resin composition of the present embodiment is advantageous in that it is more remarkable in an exposure method by direct writing of a writing pattern or an exposure method by projection of an image on a photomask through a lens, and is particularly remarkable in an exposure method by direct writing of a writing pattern.

When the exposure step is an exposure method using direct writing, a laser beam having a center wavelength of less than 390nm or a laser beam having a center wavelength of 390nm or more is preferable. More preferably, the center wavelength is 350nm to 380nm, or 400nm to 410 nm. More preferably, the exposure is performed by a method of performing exposure by using a 1 st laser beam having a center wavelength of less than 390nm and a 2 nd laser beam having a center wavelength of 390nm or more. More preferably, the 1 st laser beam has a center wavelength of 350nm to 380nm, and the 2 nd laser beam has a center wavelength of 400nm to 410 nm.

(3) Heating step

In this step, the exposed photosensitive resin composition is preferably subjected to a heating step at about 30 to about 200 ℃, more preferably in the range of 30 to 150 ℃, and still more preferably in the range of 60 to 120 ℃. By performing this heating step, the resolution and adhesion can be improved. The heating may be performed by a heating furnace, a thermostatic bath, a heating plate, a hot air dryer, an infrared dryer, a hot roll, or the like using hot air, infrared rays, or far infrared rays. When the heating method is a heat roll, the heat roll is preferably a duplex or more in view of enabling the treatment in a short time.

In particular, in the present invention, by using (D) a phenol-based polymerization inhibitor in a small amount and controlling the light transmittance at a specific wavelength of the resin composition to fall within a specific range, the fluidity of the polymer improves by heating when the resin composition is heated after exposure and then developed, and even in the case of a system in which the styrene skeleton content is relatively large, for example, the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly satisfied. As a result, sensitivity, adhesion, line width reproducibility and resolution can be remarkably improved. Further, since the adhesion is significantly improved, good adhesion can be obtained even when the time from exposure to development is long. In addition, from the viewpoint of the effect of the present invention, the heating step is preferably performed within 15 minutes, more preferably within 10 minutes after the exposure.

(4) Developing process

In this step, after exposure, the support film on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed using 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, but is preferably Na having a concentration of about 0.2 to about 2% by mass and at a temperature of about 20 to about 40 ℃₂CO₃An aqueous solution.

In an exemplary embodiment, the time from exposure to development (i.e., the time from the end of exposure to the start of development) may be 5 minutes or more, 60 minutes or more, 180 minutes or more, 1440 minutes or less, 720 minutes or less, or 300 minutes or less.

The resist pattern can be obtained through the above-described steps (1) to (4).

In the method for manufacturing a circuit board of the present invention, the circuit board is formed by etching or plating the substrate having the resist pattern manufactured by the above-described method.

(5) 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.

(6) Peeling step

Then, the resist pattern is peeled off from the substrate using an appropriate peeling liquid as necessary. Examples of the stripping liquid include an aqueous alkali solution and an amine-based stripping liquid. However, a resist pattern formed by heating the photosensitive resin composition of the present invention after exposure has the following advantages: the amine-based release liquid exhibits good releasability, and the release sheet is not excessively miniaturized. Therefore, it is preferable to use an amine-based stripping liquid as the stripping liquid because the advantageous effects of the present invention are further exhibited.

The amine contained in the amine-based stripping liquid may be an inorganic amine or an organic amine.

Examples of the inorganic amine include ammonia, hydroxylamine, hydrazine, and the like.

Examples of the organic amine include ethanolamine, propanolamine, alkylamine, cyclic amine, and quaternary ammonium salt. Specific examples thereof are shown separately

As the ethanolamine, for example, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-dimethylethanolamine, N-diethylethanolamine, aminoethoxyethanol, etc.;

as propanolamine, for example, 1-amino-2-propanol, 2-amino-2-methyl-1, 3-propanediol and the like;

as the alkylamine, for example, monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, tetraethylenepentamine and the like;

as the cyclic amine, for example, choline, morpholine, etc.;

examples of the quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N, N, N-triethyl-N- (2-hydroxyethyl) ammonium hydroxide, and N, N-diethyl-N, N-bis (2-hydroxyethyl) ammonium hydroxide.

The amine-based stripping liquid may be an aqueous solution containing 1 or more of the above-exemplified amines. The concentration of the amine in the aqueous solution can be appropriately set according to the purpose, the composition of the photosensitive resin layer, the development conditions, and the like.

The amine-based release liquid may further contain additives generally used in release agents, for example, a surfactant, an antifoaming agent, a pH adjuster, an antiseptic agent, a re-adhesion preventing agent, and the like.

The peeling step is performed at a temperature of, for example, 0 ℃ to 100 ℃, preferably room temperature (23 ℃) to 50 ℃, for a time of, for example, 1 second to 1 hour, preferably 10 seconds to 10 minutes.

After the peeling step, the substrate from which the resist pattern has been removed may be washed with, for example, pure water, if necessary.

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

Unless otherwise specified, the various parameters described above are measured by the measurement methods in the examples described below or by methods understood by those skilled in the art to be equivalent thereto.

Examples

The present embodiment will be described more specifically with reference 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.

The measurement of the physical property values of the polymers and the production methods of the samples for evaluation in examples and comparative examples will be described. The evaluation method of the obtained sample and the evaluation results thereof are shown.

(1) Measurement and calculation of physical Property values

< measurement of weight-average molecular weight or number-average molecular weight of Polymer >

The weight average molecular weight or number average molecular weight of the polymer was determined as a polystyrene equivalent by Gel Permeation Chromatography (GPC) (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K.4 in series, fluidized bed solvent: tetrahydrofuran, and standard curve obtained using polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.) in polystyrene conversion.

Further, the degree of dispersion of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

< acid equivalent >

In the present disclosure, the acid equivalent refers to the mass (g) of the polymer having 1 equivalent of carboxyl group in the molecule. The acid equivalent was measured by a potentiometric titration method using a 0.1 mol/L aqueous sodium hydroxide solution using a Hei Marsh automatic titrator (COM-555) manufactured by Hei Marsh industries, Ltd.

< I/O value >

The I/O value of the alkali-soluble polymer is derived by the following method. First, I and O values of respective constituent comonomers were calculated by a method described in non-patent literature (organic conceptual diagram (Kaumato PHARMACEUTICAL scientific BULLETIN, Sanchu, 1984); KUMAMOTO PHARMACEUTICAL BULLETIN, 1 st to 16 th (1954); chemical field, Vol.11, 10 th, 719-725 (1957); FRAGRANCE JOURNAL, 34 th, 97 th to 111 th (1979); FRAGRANCE JOURNAL, 50 th, 79 th to 82 th (1981)), and the IO and O values were averaged with molar ratios of the comonomers, respectively, to obtain I and O values_averageValue and O_averageThe value is obtained. Then the obtained I_averageValue divided by O_averageValues, thereby deriving I/O values.

< glass transition temperature Tg >

The glass transition temperature Tg of the alkali-soluble polymer is determined by the Fox equation. When the Glass transition temperature Tg is determined, as the Glass transition temperature of a homopolymer comprising a comonomer which forms the corresponding alkali-soluble Polymer, a value shown in non-patent literature (Brandrup, j.immergut, e.h. eds. "Polymer handbook, Third edition, John wires & sons,1989, p.209chapter VI 'Glass transition temperatures of polymers'") is used. In the examples, the glass transition temperatures of the homopolymers containing the respective comonomers used in the calculation are shown in table 1. When the alkali-soluble polymer is composed of 2 or more polymers, the value obtained by the following formula is the glass transition temperature of the alkali-soluble polymer.

{ in formula (II), W_iThe weight of the solid, Tg, of each alkali-soluble polymer_iGlass transition temperature, W, determined by Fox equation for each alkali-soluble polymer_totalIs the total solid weight of each alkali-soluble polymer, and n is the number of types of alkali-soluble polymers contained in the photosensitive resin composition }

(2) Method for producing sample for evaluation

The evaluation samples were prepared as follows.

< production of photosensitive resin laminate >

The components shown in tables 1 to 3 (wherein the numbers of the components indicate the amount of solid components (parts by mass)) and a solvent were sufficiently stirred and mixed to obtain a photosensitive resin composition preparation liquid. The details of the components shown in tables 1 and 2 are shown in table 3. The prepared liquid was uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film (FB-40, manufactured by Toray Industries, Inc.) using a bar coater as a support film, and dried in a 95 ℃ dryer for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 30 μm.

Subsequently, a 19 μm thick polyethylene film (TAMAPOY CO., LTD., GF-18) was laminated as a protective layer on the surface of the photosensitive resin composition layer on the side on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.

The amounts of p-hydroxyanisole and dibutylhydroxytoluene in tables 1 and 2 refer to the concentrations of the respective components based on the total amount of solid components in the photosensitive resin composition.

< entire surface of substrate >

As an evaluation substrate for image quality, a copper-clad laminate having a thickness of 0.4mm and comprising a 35 μm rolled copper foil laminated thereon was subjected to jet-rinsing using a grinding agent (product of Umbelliferal chemical Co., Ltd. #400) at a jet pressure of 0.2MPa, and then subjected to jet-rinsing with 10-gradeAmount% H₂SO₄The aqueous solution washes the substrate surface.

< lamination >

The photosensitive resin laminate was laminated at a roll temperature of 105 ℃ on a copper-clad laminate preheated to 50 ℃ while the polyethylene film (protective layer) of the photosensitive resin laminate was peeled off, 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.

< Exposure >

The substrate for evaluation after 2 hours from the lamination was exposed by a direct exposure machine (manufactured by Orbotech Ltd., Nuvogo Fine 10, light source: 375nm (30%) +405nm (70%)) using a Stauffer 41-stage exposure table. The exposure was carried out with an exposure amount of 14 steps as the maximum residual film number in the development, using the Stauffer 41 step exposure table as a mask.

< heating >

The substrate for evaluation after 7 minutes of exposure was heated by a heat roll laminator (AL-700, manufactured by Asahi Kasei corporation). The roll temperature was 105 ℃, the air pressure was 0.30MPa, and the lamination speed was 1 m/min. Since the heating effect is lost when the time from exposure to development is prolonged, the heating is usually performed for about 1 minute after exposure. Therefore, the heating after 7 minutes of exposure in this example is a very severe condition.

< development >

After peeling off the polyethylene terephthalate film (support film), 1 mass% Na at 30 ℃ was sprayed over a predetermined period of time using an alkali developing machine (FUJI KIKOU co., ltd., system, developing machine for dry film)₂CO₃And developing with an aqueous solution. The time of the development spray was set to 2 times the shortest development time, and the time of the water washing spray after development was set to 3 times the shortest development time. At this time, the shortest time required for the photosensitive resin layer of the unexposed portion to be completely dissolved is defined as the shortest developing time.

(3) Method for evaluating sample

< amount of p-hydroxyanisole >

The amount of p-hydroxyanisole in the photosensitive resin composition was determined by an internal standard method using gas chromatography (hereinafter abbreviated as GC) manufactured by shimadzu corporation. The detector was a hydrogen flame ionization detector (hereinafter abbreviated as FID), and n-docosane was used as an internal standard.

< dibutyl hydroxy toluene amount >

The amount of dibutylhydroxytoluene in the photosensitive resin composition was determined by GC in the same manner as the amount of p-hydroxyanisole. N-octadecane was used as internal standard.

< transmittance >

The light transmittances at 375nm and 405nm of each resin composition were measured by the following methods.

The transmittance at each wavelength of the photosensitive resin laminate from which the polyethylene film (protective layer) was peeled was measured by using a spectrophotometer (Hitachi High-Tech corporation., U-3010). In this case, the measurement was performed by providing the photosensitive resin laminate so as to transmit light in the film thickness direction.

< evaluation of sensitivity >

In the above exposure step, after exposure is performed through a mask of a Stauffer 41-stage step exposure table, development is performed to obtain an exposure amount (mJ/cm) with the highest residual film number of 14 stages²) The sensitivity was obtained as a value.

< reproducibility of line width >

In the exposure step, exposure is performed using drawing data of a line pattern having a ratio of 20 μm to 20 μm in width between an exposed portion and an unexposed portion. Development is performed according to the above-described development conditions to form a cured resist line.

The line width of the cured resist line was determined as a value of line width reproducibility.

< resolution >

In the exposure step, exposure is performed using drawing data of a line pattern having a ratio of 1:1 of the widths of the exposed portion and the unexposed portion. Development is performed according to the above-described development conditions to form a cured resist line.

The minimum line width at which the cured resist line is normally formed is determined as a value of resolution.

< adhesion >

In the exposure step, exposure is performed using drawing data of a line pattern having a ratio of the widths of the exposed portion and the unexposed portion of x μm to 200 μm. Development was performed according to the above development conditions, and the minimum line width at which the cured resist line was normally formed was measured by an optical microscope. This measurement was performed for 4 lines, and the average value of the 4 line widths was determined as the value of adhesion.

Only the evaluation of the adhesion was performed in 2 cases, i.e., the case where heating was performed after 1 minute after the exposure and the case where heating was performed after 7 minutes after the exposure.

< delay of shortest development time >

In the above-described development step, the shortest time required for the photosensitive resin layer at the unexposed portion to be completely dissolved, that is, the shortest development time, was measured in the case of development without heating after exposure and in the case of development with heating after exposure for 7 minutes, and the results were graded by the following criteria.

Good: there is no difference between the minimum developing time when there is heating after exposure and when there is no heating after exposure

Passing: the shortest development time with heating after exposure is delayed within 1 second compared with the time without heating after exposure

Failing to meet the requirements: the shortest development time with heating after exposure is delayed by more than 1 second compared with the time without heating after exposure

The results are shown in tables 1 and 2.

The heating conditions after exposure in this example were very strict because they were heating after 7 minutes of exposure. For example, the compositions of example 3 and comparative example 2 were all 13.8 μm in adhesiveness when developed without heating after exposure. That is, in the composition of comparative example 1, no effect was observed when heating was performed after 7 minutes of exposure, but in example 3, adhesion could be improved even under very severe conditions. In addition, under the condition of heating after exposure for 1 minute, in the compositions of example 7 and comparative example 1, the adhesion of 10.8 μm was obtained. From the above results, it is understood that even when the adhesion is good under the usual heating conditions after exposure, the adhesion is not good under the severe conditions of heating 7 minutes after exposure, but the adhesion can be made good by the present invention even under the severe conditions of heating after exposure. Thus, when a circuit board is manufactured, good adhesion can be obtained even if the time from exposure to development is prolonged, and therefore a high-definition circuit pattern can be stably formed.

[ Table 1]

[ Table 2]

[ Table 3]

Industrial applicability

The photosensitive resin composition provided by the present invention has good sensitivity, adhesion, line width reproducibility and resolution when heated and developed after exposure, and particularly realizes good adhesion even when the time from exposure to development is long, and therefore, the photosensitive resin composition can be widely used as a photosensitive resin composition.

Claims

1. A photosensitive resin composition comprising:

(A) alkali-soluble polymer: 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

2. The photosensitive resin composition according to claim 1, which contains p-hydroxyanisole as the (D) phenolic polymerization inhibitor.

3. The photosensitive resin composition according to claim 1 or 2, which contains dibutylhydroxytoluene as the (D) phenol-based polymerization inhibitor.

4. The photosensitive resin composition according to claim 3, wherein the content of dibutylhydroxytoluene is 1 to 200 ppm.

5. The photosensitive resin composition according to claim 3, wherein the content of the dibutylhydroxytoluene is 10 to 150 ppm.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the I/O value of the alkali-soluble polymer (A) is 0.600 or less.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the photopolymerization initiator (C) contains at least one selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof.

8. The photosensitive resin composition according to claim 7, wherein the (C) photopolymerization initiator contains anthracene and/or an anthracene derivative.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein a structural unit of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 26% by mass or more.

10. The photosensitive resin composition according to any one of claims 1 to 9, wherein the alkali-soluble polymer (a) contains a structural unit of benzyl (meth) acrylate as a monomer component.

11. The photosensitive resin composition according to any one of claims 1 to 10, wherein the glass transition temperature of the alkali-soluble polymer (A) is 120 ℃ or lower.

12. The photosensitive resin composition according to any one of claims 1 to 11, wherein the compound (B) having an ethylenically unsaturated double bond contains a compound having 3 or more methacrylate groups in a molecule in an amount of 5% by mass or more relative to the total solid content of the photosensitive resin composition.

13. The photosensitive resin composition according to any one of claims 1 to 12, which is used for obtaining an exposed cured resin by using a 1 st laser beam having a central wavelength of less than 390nm and a 2 nd laser beam having a central wavelength of 390nm or more.

14. The photosensitive resin composition according to any one of claims 1 to 13, wherein the 1 st laser has a central wavelength of 350nm or more and 380nm or less, and the 2 nd laser has a central wavelength of 400nm or more and 410nm or less.

15. The photosensitive resin composition according to any one of claims 1 to 14, which is capable of forming a pattern by the following steps:

an exposure step of exposing the photosensitive resin composition;

a heating step of heating the exposed photosensitive resin composition; and

16. The photosensitive resin composition according to any one of claims 1 to 15, wherein a heating temperature in the heating step is in a range of 30 ℃ to 150 ℃.

17. The photosensitive resin composition according to any one of claims 1 to 16, wherein the heating step is performed within 15 minutes after the exposure.

18. A method for forming a resist pattern, comprising the steps of:

an exposure step of exposing the photosensitive resin composition according to any one of claims 1 to 17;

a heating step of heating the exposed photosensitive resin composition; and

19. The method of forming a resist pattern according to claim 18, wherein a heating temperature in the heating step is in a range of 30 ℃ to 150 ℃.

20. The method of forming a resist pattern according to claim 18 or 19, wherein the heating step is performed within 15 minutes after the exposure.

21. The method for forming a resist pattern according to any one of claims 18 to 20, 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.

22. The method of forming a resist pattern according to claim 21, wherein the exposure step is performed by an exposure method using direct drawing of a drawn pattern.

23. The method of forming a resist pattern according to claim 22, wherein the exposure step is performed by a method of performing exposure using a 1 st laser beam having a center wavelength of less than 390nm and a 2 nd laser beam having a center wavelength of 390nm or more.

24. The method of forming a resist pattern according to claim 23, wherein the 1 st laser has a central wavelength of 350nm or more and 380nm or less, and the 2 nd laser has a central wavelength of 400nm or more and 410nm or less.

25. A method for manufacturing a circuit board, comprising the steps of:

a resist pattern forming step of forming a resist pattern on a substrate by the method according to any one of claims 18 to 24; and