JP7422664B2 - Photosensitive resin composition and resist pattern formation method - Google Patents

Description

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

2. Description of the Related Art Printed wiring boards and the like are used in electronic devices such as personal computers and mobile phones to mount components, semiconductors, and the like. Conventionally, resists for manufacturing printed wiring boards, etc., have been used to produce photosensitive resin laminates, which are formed by laminating a photosensitive resin layer on a support film, and further laminating a protective film on the photosensitive resin layer as necessary. A so-called dry film photoresist (hereinafter sometimes referred to as DF) is used. Currently, the photosensitive resin layer is generally of an alkali-developable type using a weak alkaline aqueous solution as a developer.

To produce a printed wiring board or the like using DF, for example, the following steps are performed. If the DF has a protective film, first peel off the protective film. Thereafter, the DF is laminated using a laminator or the like on a permanent circuit manufacturing substrate such as a copper-clad laminate or a flexible substrate, and exposed through a wiring pattern mask film or the like. Next, the supporting film is peeled off as necessary, and the photosensitive resin layer in the uncured portion (for example, the unexposed portion in the case of a negative type) is dissolved or dispersed with a developer, and the cured resist pattern (hereinafter simply referred to as (sometimes called a resist pattern) is formed.

After forming a resist pattern, the process of forming a circuit can be broadly divided into two methods. The first method is to remove the substrate surface not covered by the resist pattern (for example, the copper surface of a copper-clad laminate) by etching, and then remove the resist pattern portion with an aqueous alkaline solution stronger than the developer (etching method). It is.
In the second method, after plating the substrate surface with copper, solder, nickel, tin, etc., the resist pattern portion is removed in the same manner as in the first method, and the exposed substrate surface (e.g. This is a method (plating method) of etching the copper surface of a copper-clad laminate. For etching, cupric chloride, ferric chloride, cupric ammonia complex solution, etc. are used.

In recent years, as electronic devices have become smaller and lighter, printed wiring boards have become smaller and more dense. It has been demanded. In order to achieve such high resolution, Patent Document 1 describes a photosensitive resin composition with enhanced resolution using a specific thermoplastic resin, monomer, and photopolymerization initiator. .

Japanese Patent Application Publication No. 2010-249884

After the exposure step, the photosensitive resin layer may be subjected to a heating step and then developed. By performing this heating step, it is possible to further improve the resolution and adhesion (that is, the adhesion between the resist pattern and the substrate). However, even if a heating step is added after exposure, conventional photosensitive resin compositions still have insufficient adhesion and resolution, and if the time from exposure to development is long, good adhesion cannot be obtained. There was a problem.

The present invention has been proposed in view of such conventional circumstances, and an object of one embodiment of the present invention is to improve sensitivity, adhesion, line width reproducibility, and The object of the present invention is to provide a photosensitive resin composition that has good resolution and achieves good adhesion even when the time from exposure to development is long.

The present invention includes the following aspects.
[1] (A) Alkali-soluble polymer: 10% by mass to 90% by mass;
(B) Compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass;
(C) Photopolymerization initiator: 0.01% by mass to 20% by mass; and (D) Phenolic polymerization inhibitor: 1ppm to 300ppm;
A photosensitive resin composition comprising:
The photosensitive resin composition has a light transmittance of 58% to 95% at at least one of 375 nm and 405 nm.
[2] The photosensitive resin composition according to Aspect 1 above, which contains methoquinone as the (D) phenolic polymerization inhibitor.
[3] The photosensitive resin composition according to Aspect 1 or 2 above, which contains dibutylhydroxytoluene as the phenolic 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 Aspects 1 to 5 above, wherein the alkali-soluble polymer (A) has an I/O value of 0.600 or less.
[7] The photopolymerization initiator (C) includes one or more selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof, according to any one of aspects 1 to 6 above. photosensitive resin composition.
[8] The photosensitive resin composition according to aspect 7, wherein the photopolymerization initiator (C) contains anthracene and/or an anthracene derivative.
[9] The photosensitive resin composition according to any one of Aspects 1 to 8 above, wherein the constituent units of styrene and/or styrene derivatives in the alkali-soluble polymer (A) are 26% by mass or more.
[10] The photosensitive resin composition according to any one of Aspects 1 to 9, wherein the alkali-soluble polymer (A) contains a benzyl (meth)acrylate constitutional unit as a monomer component.
[11] The photosensitive resin composition according to any one of Aspects 1 to 10 above, wherein the alkali-soluble polymer (A) has a glass transition temperature of 120° C. or lower.
[12] The compound (B) having an ethylenically unsaturated double bond contains a compound having three or more methacrylate groups in the molecule in an amount of 5% by mass or more based on the solid content of the entire photosensitive resin composition. The photosensitive resin composition according to any one of the above aspects 1 to 11, comprising:
[13] The photosensitive resin according to any one of aspects 1 to 12 above, for obtaining a cured resin product exposed with a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more. Composition.
[14] The photosensitivity according to any one of aspects 1 to 13 above, wherein the first laser beam has a center wavelength of 350 nm or more and 380 nm or less, and the second laser beam has a center wavelength of 400 nm or more and 410 nm or less. Resin composition.
[15] The following steps:
an exposure step of exposing the photosensitive resin composition;
a heating step of heating the exposed photosensitive resin composition; and a developing step of developing the heated photosensitive resin composition;
The photosensitive resin composition according to any one of the above aspects 1 to 14, which can be pattern-formed by.
[16] The photosensitive resin composition according to any one of Aspects 1 to 15 above, wherein the heating temperature in the heating step is in the range of 30°C to 150°C.
[17] The photosensitive resin composition according to any one of Aspects 1 to 16, wherein the heating step is performed within 15 minutes from exposure.
[18] The following steps:
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 a developing step of developing the heated photosensitive resin composition;
A method for forming a resist pattern, including:
[19] The method for forming a resist pattern according to aspect 18, wherein the heating temperature in the heating step is in the range of 30° C. to 150° C.
[20] The method for forming a resist pattern according to Aspect 18 or 19, wherein the heating step is performed within 15 minutes from exposure.
[21] The method for forming a resist pattern according to any one of Aspects 18 to 20, wherein the exposure step is performed by an exposure method by direct drawing of a drawn pattern or by an exposure method in which an image of a photomask is projected through a lens.
[22] The resist pattern forming method according to aspect 21, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern.
[23] The method for forming a resist pattern according to aspect 22, wherein the exposure step is performed by a method of exposing with a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more.
[24] The method for forming a resist pattern according to aspect 23, wherein the first laser beam has a center wavelength of 350 nm or more and 380 nm or less, and the second laser beam has a center wavelength of 400 nm or more and 410 nm or less.
[25] A resist pattern forming step of forming a resist pattern on a substrate by the method according to any one of aspects 18 to 24; and forming a circuit board by etching or plating the substrate having the resist pattern. A method for manufacturing a circuit board, the method comprising: forming a circuit board.

According to the present invention, sensitivity, adhesion, line width reproducibility, and resolution are good when developing after being heated after exposure, and particularly good adhesion is achieved even when the time from exposure to development is long. It is possible to provide a photosensitive resin composition that achieves the desired properties.

Hereinafter, exemplary embodiments (hereinafter abbreviated as "embodiments") for carrying out the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist. In addition, various measured values in this specification are determined according to the method described in the [Examples] section of this disclosure or a method understood by a person skilled in the art to be equivalent thereto, unless otherwise specified. measured.

<Photosensitive resin composition>
In this embodiment, the photosensitive resin composition includes (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a phenolic polymerization inhibitor. Contains agents. Furthermore, in this embodiment, the photosensitive resin composition can be applied to any support to form a photosensitive resin layer. The above composition of the photosensitive resin composition of this embodiment is useful for obtaining a cured resin product by heating and developing after exposure.

The photosensitive resin composition of this embodiment is a photosensitive resin composition for obtaining a cured resin product by exposure with first active light having a center wavelength of less than 390 nm and second active light having a center wavelength of 390 nm or more. can be. The active light is, for example, laser light. In this embodiment, the photosensitive resin composition has photosensitivity to both the first active light having a center wavelength of less than 390 nm and the second active light having a center wavelength of 390 nm or more. The center wavelength of the first active light is preferably 350 to 380 nm, more preferably 355 to 375 nm, particularly preferably 375 nm. The center wavelength of the second active light is preferably 400 to 410 nm, more preferably 402 to 408 nm, particularly preferably 405 nm (h line).
Each component contained in the photosensitive resin composition will be explained below.

(A) Alkali-soluble polymer (A) Alkali-soluble polymer is a polymer that can be dissolved in an alkaline substance. (A) The alkali-soluble polymer preferably has a carboxyl group from the viewpoint of alkali developability, and is more 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 the alkali-soluble polymer (A) from the viewpoint of high resolution of the resist pattern and profile shape. It is particularly preferable that the photosensitive resin composition contains a copolymer having an aromatic group in a side chain as the alkali-soluble polymer (A). Examples of such aromatic groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The proportion of the copolymer having an aromatic group in 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 Preferably it is 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.

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

Examples of the comonomer having an aromatic group include styrene, polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.) , a monomer having an aralkyl group, and the like. Among these, styrene and styrene derivatives are more preferred.

(A) The total ratio of the constituent units of styrene and/or styrene derivatives in the entire alkali-soluble polymer can significantly improve the adhesion when developing after being heated after exposure, especially from exposure to light. From the viewpoint of being able to obtain good adhesion even when the time until development is long, 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. It is at least 35% by mass, more preferably at least 40% by mass. Since the styrene skeleton is hydrophobic, it can suppress swelling in a developer and can exhibit good adhesion. However, when the content of the styrene skeleton is high, the mobility of the polymer tends to be low and the reactivity tends to be low, which tends to lower the adhesion. Furthermore, as the time from exposure to development becomes longer, the radicals within the system are deactivated, and therefore the effect of improving adhesion by heating after exposure is reduced. In the present invention, by heating and developing after exposure, heating improves the mobility of the polymer even in systems with a high styrene skeleton content, and the hydrophobicity of the styrene skeleton and carbon-carbon double bonds are It is thought that both high reactivity can be achieved and, as a result, good adhesion can be achieved. Moreover, it is thought that this makes it possible to obtain good adhesion even when the time from exposure to development becomes long. (A) The total ratio of the structural units of styrene and/or styrene derivatives in the entire alkali-soluble polymer is preferably 90% by mass or less, and more preferably It may preferably be 80% by mass or less, more preferably 70% by mass or less.

Examples of comonomers having an aralkyl group include monomers having a substituted or unsubstituted benzyl group, monomers having a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), and monomers having a substituted or unsubstituted benzyl group. Monomers are preferred.

Comonomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, vinylbenzyl alcohol, etc. can be mentioned.

(A) Alkali-soluble polymers can significantly improve adhesion when developed after being heated after exposure, and in particular achieve good adhesion even when the time from exposure to development is long. From this point of view, it is preferable to include a benzyl (meth)acrylate structural unit as a monomer component. (A) The ratio of the benzyl (meth)acrylate structural unit in the alkali-soluble polymer is preferably 5 to 85% by mass, more preferably 10 to 80% by mass, more preferably 15 to 60% by mass, and more preferably is 20 to 40% by weight, more preferably 20 to 30% by weight. Moreover, from the same viewpoint, it is preferable that the alkali-soluble polymer (A) has both a constitutional unit of styrene and/or a styrene derivative and a constitutional unit of benzyl (meth)acrylate.

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

A copolymer having an aromatic group (preferably a benzyl group) in a side chain includes (i) a monomer having an aromatic group, and (ii) at least one of the first monomers described below and/or the second monomer described below. It is preferable that it is obtained by polymerizing at least one of the following.

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 below, and at least one of the first monomers described below. More preferably, it is obtained by copolymerizing the seed and at least one of the second monomers described below.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester, and the like. Among these, (meth)acrylic acid is preferred.
In addition, in this 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 and controlling edge fusing property. The copolymerization ratio is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably It is 25% by weight or less, particularly preferably 22% by weight or less, most preferably 20% by weight or less.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert - (Meth)acrylates such as butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate; vinyl acetate, etc. Examples include esters of vinyl alcohol; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred.

(A) The alkali-soluble polymer can be prepared by polymerizing the monomer or monomers described above by known polymerization methods, preferably addition polymerization, and more preferably radical polymerization.
It is preferable that the monomer contains a monomer having an aralkyl group and/or styrene from the viewpoint of chemical resistance, adhesion, high resolution, or groove shape of the resist pattern. As the alkali-soluble polymer (A), particularly preferred are copolymers of methacrylic acid, benzyl methacrylate, and styrene, copolymers of methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene, and the like.

(A) The I/O value of the alkali-soluble polymer is preferably 0.600 or less. The I/O value represents the ratio of (inorganic value)/(organic value) and is a value that evaluates the polarity of various organic compounds based on an organic conceptual diagram. This is one of the functional group contribution methods to be set. Regarding I/O values, for example, non-patent literature (Organic Conceptual Diagram (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1-16 (1954); Field of Chemistry, Volume 11, No. 10, Paragraphs 719-725 (1957); Fragrance Journal, No. 34, Paragraphs 97-111 (1979); Fragrance Journal, No. 50, Paragraphs 79-82 (1981) ); and other documents. The concept of I/O value divides the properties of compounds into organic groups representing covalent bonding and inorganic groups representing ionic bonding, and all organic compounds are named organic axis and inorganic axis, respectively. It is shown positioned as a point on the coordinates with respect to the orthogonal axis. The closer the I/O value is to 0, the more non-polar (i.e., hydrophobic or highly organic) organic compound; the larger the I/O value, the more polar (i.e., hydrophilic or inorganic) indicates that it is an organic compound (large).

(A) The I/O value of the alkali-soluble polymer is preferably 0.600 or less, more preferably 0.570 from the viewpoint of adhesion and resolution of the resist pattern when it is heated after exposure and then developed. Below, it is more preferably 0.520 or less, particularly preferably 0.490 or less, and from the viewpoint of resolution and peelability when heated and developed after exposure, preferably 0.300 or more, more Preferably it is 0.400 or more, more preferably 0.450 or more.

(A) The glass transition temperature of the alkali-soluble polymer is the value determined by the Fox equation (if the alkali-soluble polymer (A) contains multiple types of polymers, the glass transition temperature Tg of the entire mixture, that is, The weight average value Tg _total of the glass transition temperature is preferably 130°C or less, 120°C or less, 110°C or less from the viewpoint of chemical resistance, adhesion, high resolution, or groove shape of the resist pattern. , 100°C or less, 95°C or less, 90°C or less, or 80°C or less. (A) The lower limit of the glass transition temperature (Tg) of the alkali-soluble polymer is not limited, but from the viewpoint of controlling edge fuse properties, it is preferably 30°C or higher, more preferably 50°C or higher, and even more preferably 60°C. That's all. The glass transition temperature of a homopolymer made of the same monomer as the one or more monomers constituting the alkali-soluble polymer (A) can be found in a non-patent document (edited by Brandrup, J. Immergut, E. H. "Polymer handbook, Third edition, John Wiley & sons, 1989, p. 209 Chapter VI 'Glass transition temperatures of polymers'") shall be used.

The acid equivalent of the alkali-soluble polymer (A) (if component (A) contains multiple types of copolymers, the acid equivalent of the entire mixture) is determined by the development resistance of the photosensitive resin layer and the resolution of the resist pattern. It is preferably 100 or more from the viewpoint of imageability and adhesion, and preferably 600 or less from the viewpoint of developability and peelability of the photosensitive resin layer. The acid equivalent of the alkali-soluble polymer (A) is more preferably from 200 to 500, even more preferably from 250 to 450.

The weight average molecular weight of the alkali-soluble polymer (A) (if component (A) contains multiple types of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 500,000. . (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 or more from the viewpoint of maintaining a uniform thickness of the dry film resist and obtaining resistance to a developing solution. It is preferable that it is 500,000 or less from the viewpoint of maintaining the high resolution and groove shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern. The weight average molecular weight of the alkali-soluble polymer (A) is more preferably 10,000 to 200,000, still more preferably 20,000 to 100,000, particularly preferably 30,000 to 70,000. (A) The molecular weight dispersity of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. .

The content of the alkali-soluble polymer (A) in the photosensitive resin composition is 10 mass based on the total solid content of the photosensitive resin composition (hereinafter, the same applies to each component unless otherwise specified). % to 90% by weight, preferably 20% to 80% by weight, and more preferably 40% to 60% by weight. (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 the resist pattern formed by exposure has a high performance as a resist material. From the viewpoint of sufficient performance, the high resolution of the resist pattern, the profile of the resist pattern, and the chemical resistance of the resist pattern, the content is preferably 90% by mass or less, and is preferably 80% by mass or less. The content is more preferably 70% by mass or less, and even more preferably 60% by mass or less.

(B) Compounds having ethylenically unsaturated bonds (B) Compounds having ethylenically unsaturated bonds are compounds that have polymerizability due to having ethylenically unsaturated bonds (i.e. double bonds) in their structure. . The ethylenically unsaturated bond is more preferably derived from a methacryloyl group. From the viewpoint of adhesion and suppression of foaming property of the developer, the compound (B) having an ethylenically unsaturated bond preferably has an alkylene oxide structure having 3 or more carbon atoms. The number of carbon atoms in the alkylene oxide structure is more preferably 3 to 6, and even more preferably 3 to 4.

Examples of the compound (B) having one (meth)acryloyl group as an ethylenically unsaturated bond include a compound obtained by adding (meth)acrylic acid to one end of polyalkylene oxide, or one end of polyalkylene oxide. Examples include compounds in which (meth)acrylic acid is added to one end of the ester and the other end is alkyl etherified or allyl etherified, phthalic acid compounds, etc., which are preferable from the viewpoint of releasability and flexibility of the cured film.

Examples of such compounds include phenoxyhexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound in which polyethylene glycol is added to a phenyl group, polypropylene glycol in which an average of 2 mol of propylene oxide is added, and an average of 7 mol of polypropylene glycol. Polyethylene glycol with 1 mol of ethylene oxide added to it, 4-Normalnonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate which is a (meth)acrylate of a compound added to nonylphenol, and polypropylene with an average of 1 mol of propylene oxide added. 4-Normal nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound obtained by adding glycol, polyethylene glycol with an average of 5 moles of ethylene oxide added to nonylphenol, and an average of 8 moles of ethylene. Examples include 4-normal nonylphenoxyoctaethylene glycol (meth)acrylate (for example, M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding oxide-added polyethylene glycol to nonylphenol.
In addition, it is preferable to include γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-о-phthalate from the viewpoints of sensitivity, resolution, and adhesion in addition to the above-mentioned viewpoints.

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

Examples of such compounds include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, and octaethylene glycol di(meth)acrylate. Polyethylene glycol (meth)acrylate such as meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, and compounds having (meth)acryloyl groups at both ends of a 12 mole ethylene oxide chain. Examples include polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, etc. As a polyalkylene oxide di(meth)acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound, for example, polypropylene glycol to which an average of 12 moles of propylene oxide has been added is further added with an average of 3 moles of ethylene oxide to both ends of each polypropylene glycol. FA-023M, FA-024M, FA-027M (product name) , manufactured by Hitachi Chemical), etc. These are preferable from the viewpoints of flexibility, resolution, adhesion, etc.

｛式中、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ_２Ｈ_４であり、ＢはＣ_３Ｈ_６であり、ｎ１及びｎ３は各々独立に０～３９の整数であり、かつｎ１＋ｎ３は０～４０の整数であり、ｎ２及びｎ４は各々独立に０～２９の整数であり、かつｎ２＋ｎ４は０～３０の整数であり、－（Ａ－Ｏ）－及び－（Ｂ－Ｏ）－の繰り返し単位の配列は、ランダムであってもブロックであってもよい。そして、ブロックの場合、－（Ａ－Ｏ）－と－（Ｂ－Ｏ）－とのいずれがビスフェニル基側でもよい。｝で表される化合物を使用することができる。
例えば、ビスフェノ－ルＡの両端にそれぞれ平均５モルずつのエチレンオキサイドを付加したポリエチレングリコ－ルのジメタクリレ－ト、ビスフェノ－ルＡの両端にそれぞれ平均２モルずつのエチレンオキサイドを付加したポリエチレングリコ－ルのジメタクリレ－ト、ビスフェノ－ルＡの両端にそれぞれ平均１モルずつのエチレンオキサイドを付加したポリエチレングリコ－ルのジメタクリレ－トが、解像性、密着性の点で好ましい。
また、上記一般式（Ｉ）中の芳香環が、ヘテロ原子及び／又は置換基を有する化合物を用いてもよい。 As another example of a compound having two (meth)acryloyl groups in the molecule, a compound having (meth)acryloyl groups at both ends by modifying bisphenol A with alkylene oxide has improved resolution and adhesion. It is preferable from this point of view.
Specifically, the following general formula (I):

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , and n1 and n3 are each independently 0 to 39, and n1+n3 is an integer of 0 to 40, n2 and n4 are each independently an integer of 0 to 29, and n2+n4 is an integer of 0 to 30, -(A-O)- The arrangement of repeating units of and -(BO)- may be random or block. In the case of a block, either -(AO)- or -(BO)- may be on the bisphenyl group side. } can be used.
For example, polyethylene glycol dimethacrylate has an average of 5 moles of ethylene oxide added to each end of bisphenol A, and polyethylene glycol has an average of 2 moles of ethylene oxide added to each end of bisphenol A. Dimethacrylate of polyethylene glycol, in which an average of 1 mole of ethylene oxide is added to each end of bisphenol A, is preferred in terms of resolution and adhesion.
Further, a compound in which the aromatic ring in the above general formula (I) has a hetero atom and/or a substituent may be used.

Examples of the heteroatom 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, and a phenacyl group. , amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group , a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having an alkyl group having 1 to 10 carbon atoms, an acyl group having an alkyl group having 1 to 10 carbon atoms, 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, or a group containing a heterocycle; Examples include aryl groups substituted with substituents. These substituents may form a condensed ring, or the hydrogen atoms in these substituents may be substituted with heteroatoms such as halogen atoms. When the aromatic ring in general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

(B) As a compound having an ethylenically unsaturated double bond, it is possible to include a (meth)acrylate compound having three or more ethylenically unsaturated double bonds (that is, trifunctional or higher functional) after heating after exposure. It is preferable from the viewpoint that adhesion upon development can be significantly improved, and good adhesion can be obtained even when the time from exposure to development is particularly long. From the same viewpoint, it is more preferable to include a (meth)acrylate compound having 4 or more ethylenically unsaturated double bonds, and it is more preferable to include a (meth)acrylate compound having 5 or more ethylenically unsaturated double bonds. More preferably, it is particularly preferable to include a (meth)acrylate compound having six or more ethylenically unsaturated double bonds. Moreover, from the same viewpoint, these are preferably methacrylate compounds. Compounds having 3 or more, 4 or more, 5 or more, or 6 or more ethylenically unsaturated double bonds are thought to have the effect of increasing the crosslinking density during polymerization by exposure to light, but the number of functional groups Due to the influence of steric hindrance caused by the presence of a large amount of carbon dioxide, the desired crosslinking density cannot often be obtained. In the present invention, preferably a compound having 3 or more ethylenically unsaturated double bonds, more preferably a compound having 4 or more ethylenically unsaturated double bonds, still more preferably 5 ethylenically unsaturated double bonds. By using a compound having 6 or more ethylenically unsaturated double bonds, particularly preferably a compound having 6 or more ethylenically unsaturated double bonds, and by performing heat treatment after exposure to improve the mobility within the system, even if the number of functional groups is large, steric hindrance can be avoided. It has been found that the influence can be reduced and high adhesion can be obtained. Preferably a compound having three or more ethylenically unsaturated double bonds, more preferably a compound having four or more ethylenically unsaturated double bonds, still more preferably a compound having five or more ethylenically unsaturated double bonds, Particularly preferably, the content of the compound having 6 or more ethylenically unsaturated double bonds is preferably 3% by mass or more, more preferably 5% by mass or more, based on the solid content of the photosensitive resin composition. It is more preferably at least 10% by mass, particularly preferably at least 10% by mass. In addition, the upper limit of the content is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and 15% by mass or less, from the viewpoint of expressing the effect of heat treatment after exposure. is particularly preferred.

(b1) As a (meth)acrylate compound having three or more ethylenically unsaturated bonds:
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 (e.g., flexible, Preferred examples from the viewpoint of adhesion and bleed-out suppression include tri(meth)acrylate, which is prepared by adding an average of 21 moles of ethylene oxide to trimethylolpropane, and tri(meth)acrylate, which is made by adding an average of 30 moles of ethylene oxide to trimethylolpropane. (meth)acrylate) etc.;
Tetra (meth) acrylates, such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate;
Penta(meth)acrylate, such as dipentaerythritol penta(meth)acrylate;
Examples include hexa(meth)acrylate, such as dipentaerythritol hexa(meth)acrylate.
Among these, tetra, penta or hexa(meth)acrylate is preferred.

(b1) The (meth)acrylate compound having three 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 bleedout. .

As the tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferred. As the pentaerythritol tetra(meth)acrylate, a tetra(meth)acrylate in which a total of 1 to 40 moles of alkylene oxide is added to the four terminals of pentaerythritol is preferable.

｛式中、Ｒ₃～Ｒ₆は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２～６のアルキレン基を表し、ｍ₁、ｍ₂、ｍ₃及びｍ₄は、それぞれ独立に、０～４０の整数であり、ｍ₁＋ｍ₂＋ｍ₃＋ｍ₄は、１～４０であり、そしてｍ₁＋ｍ₂＋ｍ₃＋ｍ₄が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい｝で表されるテトラ（メタ）アクリレート化合物であることがより好ましい。 Tetra(meth)acrylate has the following general formula (II):

{In the formula, R ₃ to R ₆ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₁ , m ₂ , m ₃ and m ₄ are Each independently is an integer from 0 to 40, m ₁ + m ₂ + m ₃ + m ₄ is from 1 to 40, and when m ₁ + m ₂ + m ₃ + m ₄ is 2 or more, the plurality of X is , which may be the same or different from each other} are more preferably tetra(meth)acrylate compounds.

Although not wishing to be bound by theory, the tetramethacrylate compound represented by general formula (II) has groups R ₃ to R ₆ to form a H ₂ C=CH-CO-O- moiety. It is thought that the hydrolyzability in an alkaline solution is suppressed compared to that of tetraacrylate. Using a photosensitive resin composition containing a tetramethacrylate compound represented by the general formula (II) can significantly improve the adhesion when developing after exposure, especially from exposure to development. This is preferable from the viewpoint of achieving good adhesion even when the time period becomes long.

In general formula (II), at least one of the groups R ₃ to R ₆ is preferably a methyl group, and more preferably all of the groups R ₃ to R ₆ are methyl groups.

In general formula (II), X is preferably -CH ₂ -CH ₂ - from the viewpoint of obtaining desired resolution, groove shape, and residual film rate for the resist pattern.

In general formula (II), m ₁ , m ₂ , m ₃ and m ₄ are each independently an integer of 1 to 20 from the viewpoint of obtaining desired resolution, groove shape and residual film rate for the resist pattern. It is preferably an integer of 2 to 10, and more preferably an integer of 2 to 10. Further, in the general formula (II), m ₁ +m ₂ +m ₃ +m ₄ is preferably 1 to 36 or 4 to 36.

Examples of the compound represented by general formula (II) include pentaerythritol (poly)alkoxytetramethacrylate. In addition, in the present disclosure, "pentaerythritol (poly)alkoxytetramethacrylate" refers to "pentaerythritol alkoxytetramethacrylate" where m ₁ +m ₂ +m ₃ +m ₄ =1 and m ₁ +m ₂ in the above general formula (II). It includes both "pentaerythritol polyalkoxytetramethacrylate" where +m ₃ +m ₄ =2 to 40. Examples of the compound represented by the general formula (II) include compounds listed in JP-A No. 2013-156369, such as pentaerythritol (poly)alkoxytetramethacrylate.

Examples of hexa(meth)acrylate compounds include hexa(meth)acrylate with a total of 1 to 24 moles of ethylene oxide added to the six ends of dipentaerythritol, and hexa(meth)acrylate with a total of 1 to 10 moles of ethylene oxide added to the six ends of dipentaerythritol. Hexa(meth)acrylate to which ε-caprolactone is added is preferred.

The photosensitive material according to the present embodiment can significantly improve adhesion when developed after being heated after exposure, and from the viewpoint of realizing good adhesion even when the time from exposure to development is particularly long. It is particularly preferable that the (B) compound having an ethylenically unsaturated bond includes a (meth)acrylate compound having four or more ethylenically unsaturated bonds and an alkylene oxide chain. In this case, the ethylenically unsaturated bond is more preferably derived from a methacryloyl group and the alkylene oxide chain is more preferably an ethylene oxide chain.

In this embodiment, it is possible to significantly improve the adhesion when developing after heating after exposure, and from the viewpoint of achieving good adhesion even when the time from exposure to development is particularly long, It is preferable that the (B) compound having an ethylenically unsaturated bond includes a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton. Examples of the alkylene oxide chain include an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentylene oxide chain, and a hexylene oxide chain. When the photosensitive resin composition contains a plurality of alkylene oxide chains, they may be the same or different from each other. From the above viewpoint, the alkylene oxide chain is more preferably an ethylene oxide chain, a propylene oxide chain, or a butylene oxide chain, even more preferably an ethylene oxide chain or a propylene oxide chain, and particularly preferably an ethylene oxide chain.

In the photosensitive resin composition, chemical resistance, adhesion, and resolution of the resist pattern can be improved by using (A) an alkali-soluble polymer together with a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton. Gender balance tends to be maintained.

The (meth)acrylate compound having an alkylene oxide 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 alkyleneoxy group and (meth)acrylic acid. The six hydroxyl groups of the dipentaerythritol skeleton may be modified with alkyleneoxy groups. The number of ester bonds in one ester molecule may be from 1 to 6, preferably 6.

Examples of (meth)acrylate compounds having an alkylene oxide chain and a dipentaerythritol skeleton include hexane, which has an average of 4 to 30 moles, an average of 6 to 24 moles, or an average of 10 to 14 moles of alkylene oxide added to dipentaerythritol. (Meth)acrylates are mentioned.

｛式中、Ｒは、それぞれ独立に、水素原子又はメチル基を表し、かつｎは、０～３０の整数であり、かつ全てのｎの合計値が１以上である｝で表される化合物が好ましい。一般式（ＩＩＩ）において、全てのｎの平均値が４以上であるか、又はｎがそれぞれ１以上であることが好ましい。Ｒとしてはメチル基が好ましい。 Specifically, as a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, it can significantly improve adhesion when heated after exposure and then developed, and in particular, the time from exposure to development can be significantly improved. From the viewpoint of achieving good adhesion even when the length is long, the following general formula (III):

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

From the same viewpoint, the content of the (meth)acrylate compound having an alkylene oxide chain and dipentaerythritol skeleton relative to the total solid content in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 5% by mass. It is within the range of 7% to 30% by weight, more preferably 7% to 30% by weight.

The content of (b1) a (meth)acrylate compound having three or more ethylenically unsaturated bonds (i.e., a compound having three or more (meth)acrylate groups) with respect to the total solid content of the photosensitive resin composition is , preferably more than 0% by mass and 50% by mass or less. If this content exceeds 0% by mass, it will significantly improve adhesion when heated and developed after exposure, and in particular, good adhesion will be achieved even when the time from exposure to development is long. When the content is 50% by mass or less, the flexibility of the cured resist tends to be improved and the peeling time tends to be shortened. This content is more preferably 2% by mass or more and 40% by mass or less, and even more 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 three or more methacrylate groups in the molecule, preferably in an amount of 5% by mass based on the solid content of the entire photosensitive resin composition. Above, more preferably 9% by mass or more, still more preferably 13% by mass or more, particularly preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less. Contain in an amount of

From the viewpoint of adhesion and suppression of developer foaming, the photosensitive resin composition contains (B) a compound having an ethylenically unsaturated bond, (b2) a butylene oxide chain or a propylene oxide chain, and one or more It is preferable to include a compound having two (meth)acryloyl groups.
(b2) The compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups preferably has a molecular weight of 500 or more, more preferably 700 or more, and even more preferably has a molecular weight of 1000 or more.

(b2) Compounds having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups include polypropylene glycol (meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol ( Examples include meth)acrylate, polytetramethylene glycol di(meth)acrylate, and the like. (b2) The compound having a butylene oxide chain or propylene oxide chain and one or two (meth)acryloyl groups may contain an ethylene oxide chain in addition to the butylene oxide chain or propylene oxide chain.

Specifically, (b2) the compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups preferably has 1 to 20, more preferably 4 to 15, and further Preferred are (meth)acrylates or di(meth)acrylates having 6 to 12 C ₄ H ₈ O or C ₃ H ₆ O.

The content of (b2) a compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups is more than 0% by mass with respect to the total solid content of the photosensitive resin composition. , and preferably 20% by mass or less.

In this embodiment, in order to suppress bleed-out of the constituent components of the dry film resist and improve storage stability, preferably 70% by mass is used, based on the total solid content of (B) the compound having an ethylenically unsaturated bond. % or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, particularly preferably 100% by weight, is a compound having a weight average molecular weight of 500 or more. From the viewpoint of suppressing bleed-out and chemical resistance of the resist pattern, the weight average molecular weight of (B) the compound having an ethylenically unsaturated bond is preferably 760 or more, more preferably 800 or more, still more preferably 830 or more, and especially Preferably it is 900 or more. (B) The weight average molecular weight of the compound having an ethylenically unsaturated bond can be determined as the molecular weight calculated from the molecular structure of the compound having (B) an ethylenically unsaturated bond. When there are multiple types of (B) compounds having ethylenically unsaturated bonds, the molecular weight of each compound can be determined by weighted average of the content.

From the viewpoint of chemical resistance, adhesion, high resolution, and groove shape of the resist pattern, the concentration of methacryloyl group in (B) the compound having an ethylenically unsaturated bond is preferably 0.20 mol/100 g or more. , more preferably 0.30 mol/100g or more, still more preferably 0.35 mol/100g or more. The upper limit of the concentration of the methacryloyl group is not limited as long as polymerizability and alkali developability are ensured, but 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 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. It is .60 or more, more preferably 0.80 or more, particularly preferably 0.90 or more, and most preferably 0.95 or more.

The (meth)acrylate compounds described above can be used independently or in combination. The photosensitive resin composition may also contain other compounds as (B) a compound having an ethylenically unsaturated bond. Other compounds include (meth)acrylates with urethane bonds, compounds obtained by reacting polyhydric alcohols with α,β-unsaturated carboxylic acids, and compounds containing glycidyl groups with α,β-unsaturated carboxylic acids. and 1,6-hexanediol di(meth)acrylate.

The ratio of the compound having an ethylenically unsaturated double bond (B) to the total solid mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. It is preferable that this proportion be 5% by mass or more from the viewpoints of sensitivity, resolution, and adhesion. This proportion is more preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more. On the other hand, it is preferable to set this ratio to 70% by mass or less from the viewpoint of suppressing edge fuse and peeling delay of the cured resist. More preferably, this proportion is 50% by mass or less.

(C) Photopolymerization initiator (C) Photopolymerization initiator is a compound that polymerizes monomers with light. (C) The photopolymerization initiator can significantly improve adhesion when developed after being heated after exposure, and in particular, good adhesion can be obtained even when the time from exposure to development is long. From the viewpoint that it is possible to perform includes anthracene derivatives. Furthermore, anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof, particularly anthracene and/or anthracene derivatives, absorb first active light with a center wavelength of less than 390 nm and second active light with a center wavelength of 390 nm or more. It functions well as a polymerization initiator. Therefore, in one embodiment, the photosensitive resin composition can have photosensitivity to the first active light and the second active light, and can also be used for two-wavelength exposure. (C) The photopolymerization initiator can also be selected to have a plurality of absorption maxima in the wavelength range of the first active light and the second active light.

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

Anthracene and anthracene derivatives can significantly improve adhesion when developed after being heated after exposure, and are particularly advantageous in achieving good adhesion even when the time from exposure to development is long. It is. From the same point of view, the anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms and/or a substituent, which may have a substituent, preferably at the 9th and/or 10th positions, more preferably at the 9th and 10th positions. It has an aryl group having 6 to 40 carbon atoms which may have .

In one aspect, the anthracene derivative can significantly improve adhesion when developed after being heated after exposure, and particularly from the viewpoint of achieving good adhesion even when the time from exposure to development is long. Therefore, it is preferable to have an alkoxy group having 1 to 40 carbon atoms, which may have a substituent, at least one of the 9th or 10th positions, and a substituent at least one of the 9th or 10th positions. It is more preferable to have an alkoxy group having 1 to 30 carbon atoms, which may have 1 to 30 carbon atoms. From the viewpoint of obtaining good adhesion and resolution, it is preferable to have an alkoxy group having 1 to 40 carbon atoms, which may have a substituent, at the 9th and 10th positions; It is more preferable to have an alkoxy group having 1 to 30 carbon atoms, which may be an alkoxy group having 1 to 30 carbon atoms. The carbon numbers of the groups at the 9th and 10th positions may be the same or different.

Alkoxy groups that may have substituents include:
Methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, n-pentyloxy group, isoamyloxy group, n- hexyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tetradecyloxy group, hexadecyloxy group, eicosyloxy group, cyclohexyloxy group, norbornyloxy group, Tricyclodecanyloxy group, tetracyclododecyloxy group, adamantyloxy group, methyladamantyloxy group, ethyladamantyloxy group, and butyladamantyloxy group;
Alkoxy groups modified with halogen, such as chlorobutoxy groups, chloropropoxy groups;
an alkoxy group to which a hydroxyl group is attached, such as a hydroxybutyloxy group;
an alkoxy group to which a cyano group is attached, for example, a cyanobutoxy group;
an alkoxy group to which an alkylene oxide group is attached, such as a methoxybutoxy group;
an alkoxy group to which an aryl group is attached, such as a phenoxybutoxy group,
etc. Among these, n-butoxy group is more preferred.

In one aspect, the anthracene derivative can significantly improve adhesion when developed after being heated after exposure, and particularly from the viewpoint of achieving good adhesion even when the time from exposure to development is long. Therefore, it is preferable to have an aryl group having 6 to 40 carbon atoms, which may have a substituent, in at least one of the 9th or 10th positions, and a substituent in at least one of the 9th or 10th positions. It is more preferable to have an aryl group having 6 to 30 carbon atoms, which may have 6 to 30 carbon atoms.

From the viewpoint of being able to significantly improve the adhesion when developing after being heated after exposure, and achieving good adhesion especially when the time from exposure to development is long, it is ranked 9th and 10th. It is preferable to have an aryl group having 6 to 40 carbon atoms which may have a substituent, and it is preferable to have an aryl group having 6 to 30 carbon atoms which may have a substituent at the 9th and 10th positions. More preferred. The carbon numbers of the groups at the 9th and 10th positions may be the same or different. Moreover, the groups at the 9th and 10th positions may be the same group or different groups. For example, the group at the 9th position is an alkoxy group having 1 to 40 carbon atoms which may have a substituent, and the group at the 10th position is an aryl group having 6 to 40 carbon atoms which may have a substituent. There may be.

Examples of the aryl group having 6 to 40 carbon atoms which may have a substituent include phenyl group, biphenyl group, naphthyl group, anthracenyl group; aryl group to which an alkoxy group is added, such as methoxyphenyl group, ethoxyphenyl group; Aryl groups to which an alkyl group is attached, such as tolyl group, xylyl group, mesityl group, nonylphenyl group; Aryl groups to which a halogen is attached, such as chlorophenyl group; Aryl groups to which a hydroxyl group is attached, such as hydroxyphenyl group. It will be done. Among these, phenyl group is more preferred.

Ｒ¹は、独立に水素原子、炭素数１～４０の置換若しくは非置換のアルキル基、炭素数３～２０の置換若しくは非置換の脂環族基、炭素数２～４のアルケニル基、置換若しくは非置換のアリール基、置換若しくは非置換のヘテロアリール基又はＮ（Ｒ’）₂基を示し、２以上のＲ¹が互いに結合して環状構造を形成してもよく、該環状構造はヘテロ原子を含んでもよい。 The anthracene derivative is preferably represented by the following general formula (IV).

R ¹ is independently 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 alkyl group having 1 to 40 carbon atoms; It represents an unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an N(R') ₂ group, and two or more R ¹ may be bonded to each other to form a cyclic structure, and the cyclic structure is a heteroatom. May include.

X is independently a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, -N(R')- group, -CO-O- group, -CO-S- group, -SO ₂ -O- group , -SO ₂ -S- group, -SO ₂ -N(R')- group, -O-CO- group, -S-CO- group, -O-SO ₂ - group or S-SO ₂ - group show. However, combinations in which X is a single bond and R ¹ is a hydrogen atom (ie, unsubstituted anthracene) are excluded.

The above R' is 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, or a C 6 ~40 substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups, R's 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.

Specifically, the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms in R ¹ and R' is methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- -hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-eicosyl group, i -propyl group, i-butyl group, sec-butyl group, t-butyl group, and the like.

Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in R ¹ and R' above include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a bridged group having 6 to 20 carbon atoms. Examples include alicyclic hydrocarbon groups (eg, norbornyl group, tricyclodecanyl group, tetracyclododecyl group, adamantyl group, methyladamantyl group, ethyladamantyl group, butyladamantyl group, etc.).

Specific examples of the alkenyl group having 2 to 4 carbon atoms in R ¹ and R' include vinyl and propenyl groups.

Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in R ¹ and R' are phenyl group, biphenyl group, naphthyl group, anthracenyl group, methoxyphenyl group, ethoxyphenyl group, tolyl group, xylyl group. group, mesityl group, nonylphenyl group, chlorophenyl group, and hydroxyphenyl group.

The substituted or unsubstituted heteroaryl group in R ¹ and R' above includes a group containing one or more heteroatoms such as a sulfur atom, an oxygen atom, or a nitrogen atom in the substituted or unsubstituted aryl group, such as a pyridyl group. , imidazolyl group, morpholinyl group, piperidyl group, pyrrolidyl group, etc.

Furthermore, each of the hydrocarbon groups R ¹ and R' may be substituted with a substituent. Such substituents include hydroxyl group, carboxyl group, hydroxyalkyl group having 1 to 4 carbon atoms (for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2- hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc.), alkoxyl group having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, etc.), cyano group, cyanoalkyl group having 2 to 5 carbon atoms ( For example, cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, etc.), alkoxycarbonylalkoxy group ( For example, methoxycarbonylmethoxy, ethoxycarbonylmethoxy, t-butoxycarbonylmethoxy, etc.), halogen atoms (e.g., fluorine, chlorine, etc.) and fluoroalkyl groups (e.g., fluoromethyl, trifluoromethyl, pentafluoroethyl etc.). Each of the hydrocarbon groups R ¹ and R' is preferably substituted with a halogen atom. In particular, it is preferable that the anthracene derivative has an alkoxy group substituted with a halogen atom at the 9-position and/or the 10-position.

Preferred specific examples of R ¹ and R' are hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group. n-heptyl group, n-octyl group, cyclopentyl group, cyclohexyl group, camphoroyl group, norbornyl group, p-tolyl group, benzyl group, methylbenzyl group, phenyl group and 1-naphthyl group.

Preferred specific examples of the above X include a single bond, an oxygen atom, a sulfur atom, a -N(R')- group, an -O-CO- group, and an O-SO ₂ - group. Here, when the above X is a -N(R')- group, the above R' is a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, cyclopentyl group, cyclohexyl A camphoroyl group, a norbornyl group or a benzyl group are preferred.

Examples of the compound represented by the above general formula (IV) include 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-t-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-diethoxy Anthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di(2-ethylhexyloxy)anthracene, 1,2-benzanthracene, anthrobin, 1,4,9,10-tetra Hydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene, 9-(methylaminomethyl)anthracene, 9-acetylanthracene, 9-anthraaldehyde, 10-methyl-9-anthraaldehyde, 1,8, Examples include 9-triacetoxyanthracene. Among these, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di(2 -Ethylhexyloxy)anthracene and 9,10-bis-(3-chloropropoxy)anthracene are preferred, and can significantly improve adhesion especially when developed after being heated after exposure, especially in the time from exposure to development. 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 9,10-bis-(3-chloro Propoxy)anthracene is more preferred, and 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-bis-(3-chloropropoxy)anthracene are particularly preferred. The compounds represented by the above general formula (IV) may be used alone or in combination of two or more.

From the viewpoint of being able to significantly improve adhesion when developing after being heated after exposure, and in particular obtaining good adhesion even when the time from exposure to development is long, (C) light The polymerization initiator preferably includes (1) 9,10-diphenylanthracene; (2) 9,10-dialkoxyanthracene; (3) anthracene derivative having a halogen atom; (4) 9, Contains a halogen-substituted 10-dialkoxyanthracene; (5) Contains a compound in which the alkoxy group at position 9 and/or 10 of 9,10-dialkoxyanthracene is modified with one or more halogen atoms; and /Or (6) contains a compound having a halogen atom directly bonded to an anthracene skeleton.

The compound represented by the above general formula (IV) can significantly improve the adhesion when developed after being heated after exposure, and in particular has good adhesion even when the time from exposure to development is long. It is advantageous from the viewpoint of being able to obtain It is also advantageous in that it can provide a photosensitive resin composition that exhibits excellent sensitivity, adhesion, and resolution.

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

In one embodiment, as the anthracene derivative, a compound having a halogen atom directly bonded to an anthracene skeleton is also preferable. Such anthracene compounds include 9-bromo-10-phenylanthracene, 9-chloro-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl) Anthracene, 9-(2-biphenylyl)-10-bromoanthracene, 9-(4-biphenylyl)-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 derivatives, or in a preferred embodiment, the amount of the compound represented by the above general formula (IV) is preferably 0.05 to 5% by mass, based on the total solid content of the photosensitive resin composition. The content is more preferably 0.1 to 3% by weight, particularly preferably 0.1 to 1.0% by weight.

Pyrazoline and pyrazoline derivatives are preferable from the viewpoint of release characteristics, sensitivity, resolution, and adhesion of the photosensitive resin layer.

Examples of pyrazoline derivatives include 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-butyl- phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropyl) phenyl)-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-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, The above-mentioned Preferred from this point of view, and more preferred is 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline.

Examples of coumarin derivatives include 7-diethylamino-4-methylcoumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), and 3-benzoyl-7-diethylaminocoumarin. Among these, 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesion.

(C) Further examples of photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters. , oxime esters, and acridines (for example, 9-phenylacridine, bisacridinylheptane, 9-(p-methylphenyl)acridine, and 9-(m-methylphenyl)acridine have excellent sensitivity, resolution, and adhesion. preferred in terms of sensitivity, resolution, and adhesion), hexaarylbiimidazole, N-arylamino acid or its ester compound (for example, N-phenylglycine is preferred in terms of sensitivity, resolution, and adhesion), and halogen compounds (for example, tribromomethylphenyl sulfone) ), etc. These can be used alone or in combination of two or more. Others: 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl -diphenyl-phosphine oxide, triphenylphosphine oxide, etc. may also be used.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Can be done. These can be used alone or in combination of two or more. Among these, 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of adhesion. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3% by mass. It is within the range of mass%.

Examples of hexaarylbiimidazole include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl) -4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl )-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4' , 5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3- methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'- Bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4 , 4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'- Tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)- Biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis -(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4 ',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'- Tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3 -methoxyphenyl)-biimidazole, etc., and these can be used alone or in combination of two or more. From the viewpoints of sensitivity, resolution and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

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

(D) Phenolic polymerization inhibitor The photosensitive resin composition contains (D) a phenolic polymerization inhibitor in order to improve thermal stability and storage stability. In the present disclosure, (D) the phenolic polymerization inhibitor is a compound having one or more phenolic hydroxyl groups. Phenol-based polymerization inhibitors have the property of inhibiting polymerization reactions caused by heat or the like and improving storage stability. The phenolic polymerization inhibitor is a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms. It may have one or more substituents selected from the group consisting of an alicyclic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. In a preferred embodiment, the phenolic polymerization inhibitor (D) is a monohydric phenol (ie, a compound having one phenolic hydroxyl group in the molecule). (D) More specific preferred examples of the phenolic polymerization inhibitor include methoquinone, dibutylhydroxytoluene, hydroquinone, and tetrakis(3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid). ) Pentaerythritol, 2,2'-thiodiethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 3-(3,5-di-tert-butyl-4-hydroxy stearyl)propionate, N,N'-hexamethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide), octyl-3,5-di-tert-butyl-4 -Hydroxy-hydrocinnic 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)propionic acid)(ethylenebis(oxyethylene)), 1 , 6-hexanediol bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 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, etc., especially methoquinone and dibutylhydroxytoluene, from the viewpoint that the difference in the shortest development time with and without post-exposure heating is unlikely to occur. preferred.

(D) The amount of the phenolic polymerization inhibitor on a mass basis when the total solid mass of the photosensitive resin composition is 100% by mass is determined from the viewpoint of obtaining the desired polymerization inhibition effect on the photosensitive resin composition. 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, even more preferably 15 ppm or more, particularly preferably 20 ppm or more, when developing after heating after exposure, especially when the time from exposure to development is long. From the viewpoint of achieving good adhesion, the amount is 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 75 ppm or less, still more preferably 50 ppm, particularly preferably 40 ppm or less. be. Although the photosensitive resin composition contains (D) the phenolic polymerization inhibitor, the fact that the amount thereof is small means that when the photosensitive resin composition is heated and then developed after exposure, the polymerization reaction during exposure in the photosensitive resin composition is prevented. This is advantageous in that it is possible to achieve both good progress and reaction promotion of the polymer (thus improving adhesion) due to the good mobility improving effect of heating the polymer. For example, in systems where the polymer has a bulky molecular structure (e.g., a relatively large amount of styrene skeleton), when performing post-exposure heating with the intention of improving adhesion, the mobility improvement effect of heating the polymer is low (therefore, the adhesion However, according to the photosensitive resin composition of the present embodiment, the amount of (D) phenolic polymerization inhibitor is within the above range, so that such bulky polymers may be present. In this case, the effect of improving adhesion by post-exposure heating can also be obtained satisfactorily.

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

[Optional ingredients]
In addition to the components (A) to (D) above, the photosensitive resin composition may further contain optional components if desired. Optional components include (d) (D) Additional polymerization inhibitors other than the phenolic polymerization inhibitor, dyes, coloring substances, plasticizers, antioxidants, stabilizers, and the like. For example, additives listed in JP-A-2013-156369 may be used.

((d) Additional polymerization inhibitor)
Additional polymerization inhibitors include radical polymerization inhibitors other than the above phenolic polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles.

Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine, and the like. Nitrosophenylhydroxyamine aluminum salt is preferred in order not to impair the sensitivity of the photosensitive resin composition.

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

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

In one embodiment, the total amount of the additional polymerization inhibitor is preferably from 0.001 to 3% by mass, more preferably from 0.01% by mass when the total solid mass of the photosensitive resin composition is 100% by mass. It is 1% by mass. It is preferable that the total amount be 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, it is preferable for the total amount to be 3% by mass or less from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye.

(dyes and coloring substances)
In this embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (for example, leuco dyes, fluoran dyes, etc.) and coloring substances, if desired.

Examples of coloring substances include fuchsin, phthalocyanine green, auramine base, paramazienta, crystal violet, methyl orange, Nile Blue 2B, Victoria blue, malachite green (for example, MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Examples include Basic Blue 20 and Diamond Green (for example, Eisen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). The content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass when the total solid mass of the photosensitive resin composition is 100% by mass. It is preferable that the content be 0.001% by mass or more from the viewpoint of improving the handleability of the photosensitive resin composition. On the other hand, it is preferable that the content be 1% by mass or less from the viewpoint of maintaining the storage stability of the photosensitive resin composition.

The photosensitive resin composition is preferable from the viewpoint of visibility because the exposed area develops color by containing a dye, and when an inspection machine or the like reads a positioning marker for exposure, it is possible to distinguish between the exposed area and the unexposed area. The larger the contrast, the easier it is to recognize and is advantageous. Preferred dyes from this point of view include leuco dyes and fluoran dyes.
Examples of the leuco dye include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green], and the like. In particular, from the viewpoint of good contrast, it is preferable to use leuco crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass based on the total solid mass of the photosensitive resin composition. It is preferable that this content be 0.1% by mass or more from the viewpoint of improving the contrast between exposed and unexposed areas. This content is more preferably 0.2% by mass or more, particularly preferably 0.4% by mass or more. On the other hand, it is preferable to keep this content at 10% by mass or less from the viewpoint of maintaining storage stability. This content is more preferably 5% by mass or less, particularly preferably 2% by mass or less.

Further, it is preferable to use a combination of a leuco dye and the halogen compound described above in the photopolymerization initiator (C) in the photosensitive resin composition from the viewpoint of optimizing adhesion and 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 0.01 mass% when the total solid mass of the photosensitive resin composition is 100 mass%. % to 3% by mass is preferable from the viewpoint of maintaining the storage stability of hue in the photosensitive layer.

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

In this embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of plasticizers include phthalate esters (for example, diethyl frate, etc.), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl triethyl citrate, etc. -n-propyl, tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like. In addition, ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, ADEKA NOL SDX-479 (manufactured by Asahi Denka Co., Ltd.), New Port BP-23P, New Port BP-3P, New Port BP-5P, New Port Pole BPE-20T, NewPole BPE-60, NewPole BPE-100, NewPole BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), UniAll DB-400, Uniall DAB-800, Uniall DA-350F, Uniall DA- Compounds having a bisphenol skeleton such as 400, Uniol DA-700 (manufactured by NOF Corporation), BA-P4U glycol, and BA-P8 glycol (manufactured by Nippon Nyukazai Co., Ltd.) may also be mentioned.

The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, based on the total solid mass of the photosensitive resin composition. It is. It is preferable that the content be 1% by mass or more from the viewpoint of suppressing the delay in development time and imparting flexibility to the cured film. On the other hand, it is preferable to set the content to 50% by mass or less from the viewpoint of suppressing insufficient curing and cold flow.

When the amount of water in the photosensitive resin composition is large, local plasticization of the photosensitive resin composition is rapidly promoted and edge fuse occurs. From the viewpoint of suppressing edge fuse, the water content in the photosensitive resin composition is 0.7% on a mass basis, based on the photosensitive resin composition after coating and drying the photosensitive resin composition preparation on the support film. It is preferable that it is below. The water content in the photosensitive resin composition is preferably 0.65% or less, preferably 0.6% or less, preferably 0.55% or less, and 0.5% or less. It is preferable that it is 0.45% or less, it is preferable that it is 0.4% or less, it is preferable that it is 0.35% or less, it is preferable that it is 0.3% or less, and 0. It is preferably 25% or less, and preferably 0.2% or less.

[solvent]
The photosensitive resin composition can be dissolved in a solvent and used in the form of a photosensitive resin composition preparation for producing a photosensitive resin laminate. Examples of the solvent include ketones and alcohols. The ketones are typified by methyl ethyl ketone (MEK) and acetone. The alcohols are typified by methanol, ethanol, and isopropanol. When producing the photosensitive resin laminate, the solvent is used in an amount such that the viscosity of the photosensitive resin composition formulation applied onto the support film at 25° C. is 500 mPa·s to 4,000 mPa·s. It is preferably added to the resin composition.

[Light transmittance of photosensitive resin composition]
The light transmittance of the photosensitive resin composition of the present embodiment at at least one of 375 nm and 405 nm has good sensitivity, adhesion, line width reproducibility, and resolution when heated after exposure and then developed. , from the viewpoint of providing a photosensitive resin composition that achieves good adhesion, especially when the time from exposure to development is long, is 58% to 95%. 375 nm and 405 nm correspond to typical exposure wavelengths in the photosensitive resin composition of this embodiment. The light transmittance is preferably 58% or more, from the viewpoint of achieving good sensitivity, adhesion, line width reproducibility, and resolution by allowing the exposure light to reach a deeper region of the photosensitive resin composition during exposure. is 60% or more, more preferably 62% or more, more preferably 64% or more, even more preferably 65% or more, and from the viewpoint of obtaining a good groove shape by suppressing diffusely reflected light from the substrate surface, 95% It is preferably 85% or less, more preferably 80% or less, more preferably 75% or less, even more preferably 70% or less.

Examples of means for controlling the light transmittance at least one of 375 nm and 405 nm within the above range include, but are not limited to, controlling the amount of photopolymerization initiator, dye, or coloring substance added.

[Photosensitive resin laminate]
This embodiment also provides a photosensitive resin laminate having a photosensitive resin layer made of the above-described 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 support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, Examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films may also be stretched if necessary.

From the viewpoint of suppressing light scattering during exposure, the haze of the support film is preferably 5% or less, more preferably 2% or less, even more preferably 1.5% or less, and particularly preferably 1.0% or less. From the same viewpoint, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less. The thinner the film is, the more advantageous it is for improving image forming properties and economical efficiency, but in order to maintain the strength of the photosensitive resin laminate, a thickness of 10 μm to 30 μm is preferably used. 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 laminated. In the case of a multilayer structure, there may be an antistatic layer. In the case of a multilayer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing fine particles is formed on one side A, and the other side B is filled with fine particles in the same way as on side A (1). (2) Contains a smaller amount of fine particles than side A; (3) Contains finer particles than side A; (4) Contains no fine particles. In the case of structures (2), (3), and (4), it is preferable to form a photosensitive resin layer on the surface B side. At this time, it is preferable to have a resin layer containing fine particles on the side A from the viewpoint of the slipperiness of the film. The size of the fine particles at this time is preferably less than 1.5 μm. Note that the size of the fine particles is a value obtained by measurement using a scanning electron microscope calibrated using a standard sample.

An important characteristic of the protective layer used in the photosensitive resin laminate is that its adhesion to the photosensitive resin layer is sufficiently smaller than that of the support film, and that it can be easily peeled off. For example, polyethylene films or polypropylene films can preferably be used as protective layers. Furthermore, a film with excellent releasability disclosed in Japanese Patent Application Laid-Open No. 59-202457 can also be used. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

A gel called fisheye may exist on the surface of a polyethylene film. When a polyethylene film having fish eyes is used as a protective layer, the fish eyes may be transferred to the photosensitive resin layer. When fish eyes are transferred to the photosensitive resin layer, air may be drawn in during lamination, creating voids, leading to defects in the resist pattern. From the viewpoint of preventing fish eyes, stretched polypropylene is preferable as the material for the protective layer. A specific example is Alphan E-200A manufactured by Oji Paper Co., Ltd.

The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but 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 thinner the photosensitive resin layer is, the better the resolution is, and the thicker it is, the better the film strength is.

The light transmittance at a wavelength of 630 nm of the laminate of the support film and the photosensitive resin layer is an indicator of bleaching of the dye, and a high light transmittance at a wavelength of 630 nm indicates that the dye is bleached. The light transmittance of the laminate of the support film and the photosensitive resin layer at a wavelength of 630 nm is preferably 80% or less, preferably 78% or less, preferably 75% or less, and 72% or less. It is preferably at most 70%, preferably at most 68%, preferably at most 65%, preferably at most 62%, preferably at most 60%, It is preferably 58% or less, preferably 55% or less, preferably 52% or less, and preferably 50% or less. This light transmittance is the value of the laminate of the support film and the photosensitive resin layer (that is, the protective layer is not included).

Next, a method for manufacturing a photosensitive resin laminate will be described.
A known method can be employed to produce a photosensitive resin laminate by sequentially laminating a support film, a photosensitive resin layer, and, if necessary, a protective layer. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves it to make a uniform solution, first coated on a support film using a bar coater or roll coater, and then dried to remove the solvent. By removing , a photosensitive resin layer made of a photosensitive resin composition can be laminated on the support film. Then, if necessary, a protective layer is laminated on the photosensitive resin layer to produce a photosensitive resin laminate.

<Method for forming resist pattern>
Next, an example of a method for manufacturing a resist pattern using the photosensitive resin laminate of this embodiment will be described. The method can include an exposure step of exposing the photosensitive resin composition, a heating step of heating the exposed photosensitive resin composition, and a developing step of developing the photosensitive resin composition.
Examples of resist patterns include printed wiring boards, semiconductor elements, printing plates, liquid crystal display panels, touch panels, flexible substrates, lead frame substrates, COF (chip-on-film) substrates, semiconductor package substrates, transparent electrodes for liquid crystals, and liquid crystals. Examples include patterns for TFT wiring, electrodes for PDP (plasma display panel), and the like. As an example, a method for manufacturing a printed wiring board will be described as follows.

A printed wiring board is manufactured through the following steps.
(1) Laminating process First, in the laminating process, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated onto the substrate surface using a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO).
In this embodiment, the photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides as necessary. The heating temperature during lamination is generally 40°C to 160°C. Furthermore, by performing heat-pressing at least twice during lamination, the adhesion of the resulting resist pattern to the substrate can be improved. At the time of thermocompression bonding, a two-stage laminator equipped with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the rolls several times.

(2) Exposure process In this process, a mask film having a desired wiring pattern is brought into close contact with a support film and an exposure method is performed using an active light source, an exposure method is performed by direct drawing of a drawing pattern that is a desired wiring pattern, or The photosensitive resin layer is exposed to light by an exposure method in which an image of a photomask is projected through a lens.

The exposure step is preferably carried out by an exposure method by direct drawing of a drawing pattern, or by an exposure method by which an image of a photomask is projected through a lens, and more preferably by an exposure method by direct drawing of a drawing pattern. The advantage of the photosensitive resin composition according to the present embodiment is more remarkable in an exposure method by direct drawing of a drawing pattern, or an exposure method in which an image of a photomask is projected through a lens, and an exposure method by direct drawing of a drawing pattern. This is particularly noticeable.

When the exposure process is an exposure method using direct writing, it is preferable to use a laser beam with a center wavelength of less than 390 nm or a laser beam with a center wavelength of 390 nm or more. It is more preferable to use a laser beam with a center wavelength of 350 nm or more and 380 nm or less, or a laser beam with a center wavelength of 400 nm or more and 410 nm or less. It is more preferable to perform exposure using a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more. Moreover, it is more preferable that the center wavelength of the first laser beam is 350 nm or more and 380 nm or less, and the center wavelength of the second laser beam is 400 nm or more and 410 nm or less.

(3) Heating step In this step, the exposed photosensitive resin composition is preferably subjected to a heating step at about 30°C to about 200°C, more preferably in the range of 30°C to 150°C, More preferably, the temperature is in the range of 60°C to 120°C. By performing this heating step, resolution and adhesion can be improved. For heating, a heating furnace using hot air, infrared rays, or far infrared rays, a constant temperature oven, a hot plate, a hot air dryer, an infrared dryer, a hot roll, etc. can be used. It is preferable that the heating method is a hot roll because it enables short-time processing, and it is more preferable that the heating method is two or more hot rolls.

In particular, in the present invention, by using (D) a phenolic polymerization inhibitor and using a small amount, and by controlling the light transmittance of the resin composition at a specific wavelength to a specific range, it is possible to heat the resin composition after exposure. When developing the polymer, heating improves the mobility of the polymer. For example, even in systems with a relatively high styrene skeleton content, the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be improved. Can be highly compatible. As a result, sensitivity, adhesion, line width reproducibility, and resolution can be significantly improved. Since the adhesion is significantly improved, good adhesion can be obtained even when the time from exposure to development is long. Further, it is preferable from the viewpoint of the effects of the present invention that the heating step is carried out within 15 minutes from exposure, and more preferably carried out within 10 minutes.

(4) Development process In this process, after exposure, the support film on the photosensitive resin layer is peeled off, and the unexposed areas are developed and removed using an alkaline aqueous developer, thereby forming the resist pattern on the substrate. Form.
As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. The alkaline aqueous solution is appropriately selected depending on the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution with a concentration of about 0.2% by mass to about 2% by mass and a temperature of about 20° C. to about 40° C. is preferable.
In exemplary embodiments, the exposure to development time (i.e., the time from the end of exposure to the start of development) can be greater than or equal to 5 minutes, or greater than or equal to 60 minutes, or greater than or equal to 180 minutes, and less than or equal to 1440 minutes, or less than or equal to 720 minutes. It may be less than 300 minutes or less than 300 minutes.
A resist pattern can be obtained through each of the steps (1) to (4) above.

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

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

(6) Peeling process After that, if necessary, the resist pattern is peeled off from the substrate using an appropriate peeling liquid. Examples of the stripping solution include an alkaline aqueous solution and an amine stripping solution. However, the resist pattern formed from the photosensitive resin composition of the present invention through post-exposure heating exhibits good releasability with respect to amine-based stripping solutions, and the peeled pieces do not become excessively fine. It has the advantage of Therefore, it is preferable to use an amine-based stripper as the stripper because the advantageous effects of the present invention are further exhibited.

The amine contained in the amine stripping solution may be an inorganic amine or an organic amine.
Examples of inorganic amines include ammonia, hydroxylamine, hydrazine, and the like.

Examples of the organic amine include ethanolamine, propanolamine, alkylamine, cyclic amine, and quaternary ammonium salt. Specific examples of these are:
Examples of ethanolamine include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, aminoethoxyethanol, etc.;
As propanolamine, for example, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, etc.;
As the alkylamine, for example, monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, tetraethylenepentamine, etc.;
As a cyclic amine, for example, choline, morpholine, etc.;
Examples of quaternary ammonium salts include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N,N,N-triethyl-N-(2-hydroxyethyl)ammonium hydroxide, N,N- diethyl-N,N-di(2-hydroxyethyl)ammonium hydroxide, etc.;
Examples of each can be given.

The amine stripping solution may be an aqueous solution containing one or more of the amines listed above. The concentration of amine in the aqueous solution may be appropriately set depending on the purpose, composition of the photosensitive resin layer, development conditions, etc.
The amine stripping solution may further contain additives commonly used in stripping agents, such as surfactants, antifoaming agents, pH adjusters, preservatives, and anti-redeposition agents.
The peeling step is performed at a temperature of, for example, 0° C. or higher and 100° C. or lower, preferably room temperature (23° C.) or higher and 50° C. or lower, for example, for a period of 1 second or more and 1 hour or less, preferably 10 seconds or more and 10 minutes or less.

After the stripping step, the substrate from which the resist pattern has been removed may be cleaned, for example, with pure water, if desired.

The photosensitive resin laminate of this embodiment can be used for printed wiring boards, flexible substrates, lead frame substrates, touch panel substrates, COF substrates, semiconductor package substrates, transparent electrodes for liquid crystals, wiring for TFTs for liquid crystals, electrodes for PDPs, etc. This is a photosensitive resin laminate suitable for manufacturing conductor patterns.
It should be noted that the various parameters described above are measured according to the measurement method in Examples described later or a method understood by a person skilled in the art to be equivalent thereto, unless otherwise specified.

Next, this embodiment will be described in more detail with reference to Examples and Comparative Examples. However, this embodiment is not limited to the following examples unless it departs from the gist thereof. The physical properties in the examples were measured by the following method.
A method for measuring physical property values of polymers and preparing samples for evaluation in Examples and Comparative Examples will be explained. Also, the evaluation method and evaluation results for the obtained samples 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 is measured using gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 model, column: Shodex (registered trademark) manufactured by Showa Denko K.K. KF-807, KF-806M, KF-806M, KF-802.5) 4 bottles in series, mobile phase solvent: tetrahydrofuran, polystyrene standard sample (Showa Denko K.K.'s Shodex STANDARD SM-105) using a calibration curve) Calculated as polystyrene equivalent.
Furthermore, 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, acid equivalent means the mass (in grams) of a polymer having 1 equivalent of carboxyl groups in the molecule. The acid equivalent was measured by potentiometric titration using a 0.1 mol/L aqueous sodium hydroxide solution using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

<I/O value>
The I/O value of the alkali-soluble polymer was derived by the following method. First, non-patent literature (Organic Conceptual Diagram (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Items 1-16 (1954); Chemistry Area, Volume 11, No. 10 , 719-725 (1957); Fragrance Journal, No. 34, No. 97-111 (1979); Fragrance Journal, No. 50, No. 79-82 (1981)) The I value and O value of each comonomer were calculated, and then each of the IO value and O value was averaged by the molar ratio of the comonomer to obtain an I _average value and an O _average value. Then, the I/O value was derived by dividing the obtained I _average value by the O _average value.

｛式中、Ｗ_ｉは、各々のアルカリ可溶性高分子の固形重量であり、Ｔｇ_ｉは、各々のアルカリ可溶性高分子のＦｏｘ式で求められるガラス転移温度であり、Ｗ_{ｔｏｔａｌ}は、各々のアルカリ可溶性高分子の合計固形重量であり、かつｎは、感光性樹脂組成物に含まれるアルカリ可溶性高分子の種類の数である｝ <Glass transition temperature Tg>
The glass transition temperature Tg of the alkali-soluble polymer was determined using the Fox formula. When determining the glass transition temperature Tg, the glass transition temperature of a homopolymer consisting of a comonomer forming the corresponding alkali-soluble polymer is determined using a non-patent literature (Brandrup, J. Immergut, E.H. ed. "Polymer handbook, Third edition, John Wiley & Sons, 1989, p. 209 Chapter VI "Glass transition temperatures of polymers") were used. Table 1 shows the glass transition temperatures of homopolymers made of each comonomer used in calculations in Examples. When the alkali-soluble polymer is composed of two or more types of polymers, the value determined by the following formula is the glass transition temperature of the alkali-soluble polymer.

{In the formula, W _i is the solid weight of each alkali-soluble polymer, Tg _i is the glass transition temperature determined by the Fox equation of each alkali-soluble polymer, and W _total is the solid weight of each alkali-soluble polymer. is the total solid weight of the polymer, and n is the number of types of alkali-soluble polymer contained in the photosensitive resin composition}

(2) Method for preparing evaluation samples Evaluation samples were prepared as follows.
<Preparation of photosensitive resin laminate>
The components shown in Tables 1 to 3 below (however, the numbers for each component indicate the amount (parts by mass) as solid content) and the solvent are sufficiently stirred and mixed to make a photosensitive resin composition preparation. I got it. Details of the components shown in Tables 1 and 2 are shown in Table 3. A polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB-40) with a thickness of 16 μm was used as a support film, and this mixture was evenly applied to the surface using a bar coater, and the mixture was dried in a dryer at 95°C for 3 hours. It was dried for minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 30 μm.
Next, on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film is not laminated, a 19 μm thick polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) is laminated as a protective layer, and the photosensitive resin is A laminate was obtained.
In addition, the amount of methoquinone and the amount of dibutylhydroxytoluene in Tables 1 and 2 mean the concentration of each component based on the total amount of solid content in the photosensitive resin composition.

<Substrate surface preparation>
As a substrate for evaluating image quality, a 0.4 mm thick copper clad laminate laminated with 35 μm rolled copper foil was jetted using an abrasive (manufactured by Ujiden Chemical Industry Co., Ltd., #400) at a spray pressure of 0.2 MPa. After scrubbing, the substrate surface was cleaned with a 10% by mass H ₂ SO ₄ aqueous solution.

<Laminate>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, apply the photosensitive resin laminate onto a copper-clad laminate preheated to 50°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation). Lamination was carried out at a roll temperature of 105°C. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m/min.

<Exposure>
Two hours after lamination, the evaluation substrate was exposed using a Stouffer 41-step step tablet using a direct writing exposure machine (manufactured by Orbotech Co., Ltd., Nuvogo Fine 10, light source: 375 nm (30%) + 405 nm (70%)). exposed. Exposure was carried out using the Stouffer 41 step tablet as a mask, and the exposure amount was such that the maximum number of remaining film steps was 14 when exposed and developed.

<Heating>
The evaluation substrate 7 minutes after exposure was heated with a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation). The roll temperature was 105° C., the air pressure was 0.30 MPa, and the lamination speed was 1 m/min. Note that if the time from exposure to development is prolonged, the heating effect will be lost, so heating is usually done for about 1 minute after exposure. Therefore, the conditions for heating after 7 minutes of exposure in this example are very severe.

<Development>
After peeling off the polyethylene terephthalate film (supporting film), a 1% by mass Na ₂ CO ₃ aqueous solution at 30°C was sprayed over a predetermined period of time using an alkaline developer (manufactured by Fuji Kiko Co., Ltd., dry film developer). and developed it. The developing spray time was twice as long as the shortest developing time, and the water washing spray time after development was three times as long as the shortest developing time. At this time, the shortest time required for the unexposed portions of the photosensitive resin layer to completely dissolve was determined as the shortest development time.

(3) Sample evaluation method <methoquinone amount>
The amount of methoquinone in the photosensitive resin composition was determined by an internal standard method using a gas chromatography (hereinafter abbreviated as GC) manufactured by Shimadzu Corporation. The detector was a flame ionization detector (hereinafter abbreviated as FID), and n-docosane was used as an internal standard.
<Amount of dibutylhydroxytoluene>
The amount of dibutylhydroxytoluene in the photosensitive resin composition was determined by GC similarly to the amount of methoquinone. n-octadecane was used as an internal standard.
<Light transmittance>
The light transmittance of each resin composition at 375 nm and 405 nm was measured by the following method.
The transmittance at each wavelength of the photosensitive resin laminate from which the polyethylene film (protective layer) was peeled off was measured using a spectrophotometer (U-3010, Hitachi High Technologies Co., Ltd.). At that time, the measurement was performed by installing the photosensitive resin laminate so that the transmitted light passed in the film thickness direction.

<Sensitivity evaluation>
In the above-mentioned exposure process, the film was exposed to light through a mask of a Stouffer 41-stage step tablet, and then developed, and the exposure amount (mJ/cm ² ) at which the maximum number of remaining film stages was 14 was determined as a sensitivity value.

<Line width reproducibility>
In the above-mentioned exposure process, exposure was performed using drawing data having a line pattern in which the width of the exposed area and the unexposed area was 20 μm:20 μm. Development was performed according to the above-mentioned development conditions to form a cured resist line.
The line width of the cured resist line was determined as a line width reproducibility value.

<Resolution>
In the above-described exposure process, exposure was performed using drawing data having a line pattern in which the width of the exposed area and the unexposed area were in a ratio of 1:1. Development was performed according to the above-mentioned development conditions to form a cured resist line.
The minimum line width at which the cured resist line was normally formed was determined as the resolution value.

<Adhesion>
In the above-mentioned exposure process, exposure was performed using drawing data having a line pattern in which the width of the exposed area and the unexposed area was in the ratio of x μm:200 μm. Developing was carried out according to the above-mentioned developing conditions, and the minimum line width at which a cured resist line was normally formed was measured using an optical microscope. This measurement was performed on four lines, and the average value of the four line widths was determined as the adhesion value.
Only the evaluation of adhesion was carried out in two ways: when heating was performed 1 minute after exposure and when heating was performed 7 minutes after exposure.

<Delay in minimum development time>
In the above-mentioned development process, the maximum amount required for the photosensitive resin layer in the unexposed area to completely dissolve is determined when the development is performed without heating after exposure and when the development is performed after heating 7 minutes after exposure. The shortest development time was measured and ranked according to the following criteria.
Good: There is no difference in the shortest development time with post-exposure heating and without post-exposure heating.Good: The shortest development time with post-exposure heating is delayed by within 1 second compared to without post-exposure heating.Not possible : The shortest development time with post-exposure heating was delayed by more than 1 second compared to without post-exposure heating. The results are shown in Tables 1 and 2.

The post-exposure heating conditions of this example are very strict since the heating is performed 7 minutes after exposure. For example, when the compositions of Example 3 and Comparative Example 2 were developed without heating after exposure, the adhesion was both 13.8 μm. In other words, in the composition of Comparative Example 1, no effect was observed by heating after 7 minutes of exposure, but in Example 3, the adhesion could be improved even under very severe conditions. Further, under the condition of heating after 1 minute of exposure, an adhesion of 10.8 μm was obtained for both the compositions of Example 7 and Comparative Example 1. As can be seen from the above results, even if the adhesion is good under typical post-exposure heating conditions, it does not mean that the adhesion will be good under the harsh conditions of heating 7 minutes after exposure. However, the present invention makes it possible for the first time to improve adhesion even under these severe post-exposure heating conditions. Thereby, when manufacturing a circuit board, good adhesion can be obtained even if the time from exposure to development becomes long, so that a high-definition circuit pattern can be stably formed.

The photosensitive resin composition according to the present invention has good sensitivity, adhesion, line width reproducibility, and resolution when developed after being heated after exposure, especially when the time from exposure to development is long. Since it also achieves good adhesion, it can be used in a wide range of applications as a photosensitive resin composition.

Claims (25)

A photosensitive resin laminate comprising a support film and a photosensitive resin layer made of a photosensitive resin composition,
The photosensitive resin composition is based on solid content,
(A) Alkali-soluble polymer: 10% by mass to 90% by mass;
(B) compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) photopolymerization initiator: 0.01% by mass to 20% by mass;
including;
The content of (D) phenolic polymerization inhibitor in the photosensitive resin layer is 20 ppm to 200 ppm,
The (D) phenolic polymerization inhibitor is methoquinone and/or dibutylhydroxytoluene,
The photosensitive resin composition optionally contains (D) a polymerization inhibitor other than a phenolic polymerization inhibitor at 3% by mass or less based on the solid content of the photosensitive resin composition,
The thickness of the photosensitive resin layer is 1 to 300 μm,
The photosensitive resin laminate, wherein the laminate of the support film and the photosensitive resin layer has a light transmittance of 58% to 85% at at least one of 375 nm and 405 nm. The photosensitive resin laminate according to claim 1, wherein the (D) phenolic polymerization inhibitor contains methoquinone. The photosensitive resin laminate according to claim 1 or 2, wherein the (D) phenolic polymerization inhibitor contains dibutylhydroxytoluene. The photosensitive resin laminate according to claim 3, wherein the content of the dibutylhydroxytoluene in the photosensitive resin layer is 1 to 200 ppm. The photosensitive resin laminate according to claim 3, wherein the content of the dibutylhydroxytoluene in the photosensitive resin layer is 10 to 150 ppm. The photosensitive resin laminate according to any one of claims 1 to 5, wherein the alkali-soluble polymer (A) has an I/O value of 0.600 or less. The photosensitive initiator according to any one of claims 1 to 6, wherein the photopolymerization initiator (C) contains one or more selected from the group consisting of anthracene, pyrazoline, triphenylamine, coumarin, and derivatives thereof. Resin laminate. The photosensitive resin laminate according to claim 7, wherein the photopolymerization initiator (C) contains anthracene and/or an anthracene derivative. The photosensitive resin laminate according to any one of claims 1 to 8, wherein the constituent units of styrene and/or styrene derivatives in the alkali-soluble polymer (A) are 26% by mass or more. The photosensitive resin laminate according to any one of claims 1 to 9, wherein the alkali-soluble polymer (A) contains a benzyl (meth)acrylate structural unit as a monomer component. The photosensitive resin laminate according to any one of claims 1 to 10, wherein the alkali-soluble polymer (A) has a glass transition temperature of 120°C or less. The (B) compound having an ethylenically unsaturated double bond contains a compound having three or more methacrylate groups in the molecule in an amount of 5% by mass or more based on the solid content of the entire photosensitive resin composition. The photosensitive resin laminate according to any one of claims 1 to 11. The photosensitive resin laminate according to any one of claims 1 to 12, for obtaining an exposed resin cured product with a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more. The photosensitive resin laminate according to claim 13 , wherein the first laser beam has a center wavelength of 350 nm or more and 380 nm or less, and the second laser beam has a center wavelength of 400 nm or more and 410 nm or less. The following steps:
an exposure step of exposing the photosensitive resin composition;
a heating step of heating the exposed photosensitive resin composition; and a developing step of developing the heated photosensitive resin composition;
The photosensitive resin laminate according to any one of claims 1 to 14, which can be patterned by. The photosensitive resin laminate according to claim 15 , wherein the heating temperature in the heating step is in the range of 30°C to 150°C. The photosensitive resin laminate according to claim 15 or 16 , wherein the heating step is performed within 15 minutes from exposure. The following steps:
An exposure step of exposing the photosensitive resin composition of the photosensitive resin laminate according to any one of claims 1 to 17;
a heating step of heating the exposed photosensitive resin composition; and a developing step of developing the heated photosensitive resin composition;
A method for forming a resist pattern, including: The method for forming a resist pattern according to claim 18, wherein the heating temperature in the heating step is in the range of 30° C. to 150° C. 20. The method for forming a resist pattern according to claim 18, wherein the heating step is performed within 15 minutes from exposure. 21. The method for forming a resist pattern according to claim 18, wherein the exposure step is performed by an exposure method that involves direct drawing of a drawn pattern, or an exposure method that projects an image of a photomask 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 by direct drawing of a drawing pattern. 23. The method for forming a resist pattern according to claim 22, wherein the exposure step is performed by a method of exposing with a first laser beam having a center wavelength of less than 390 nm and a second laser beam having a center wavelength of 390 nm or more. 24. The method for forming a resist pattern according to claim 23, wherein the first laser beam has a center wavelength of 350 nm or more and 380 nm or less, and the second laser beam has a center wavelength of 400 nm or more and 410 nm or less. 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 a circuit forming a circuit board by etching or plating the substrate having the resist pattern. A method for manufacturing a circuit board, comprising: a step of forming a board.