JP7615110B2 - Photosensitive resin composition and method for forming resist pattern - Google Patents

Description

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

Electronic devices such as personal computers and mobile phones use printed wiring boards and the like to mount components, semiconductors, and the like. Conventionally, resists used in the manufacture of printed wiring boards and the like have been photosensitive resin laminates, so-called dry film photoresists (hereinafter sometimes referred to as DF), which are made by laminating a photosensitive resin layer on a support film and then laminating a protective film on the photosensitive resin layer as necessary. Currently, the most common photosensitive resin layer is an alkaline development type that uses a weak alkaline aqueous solution as the developer.

To produce a printed wiring board or the like using DF, for example, the following steps are taken. If the DF has a protective film, the protective film is first peeled off. Then, the DF is laminated onto a substrate for producing permanent circuits, such as a copper-clad laminate or a flexible board, using a laminator or the like, and exposed through a wiring pattern mask film or the like. Next, the support film is peeled off as necessary, and the photosensitive resin layer in the uncured parts (for example, the unexposed parts in the case of a negative type) is dissolved or dispersed and removed using a developer, forming a cured resist pattern (hereinafter sometimes simply referred to as a resist pattern) on the substrate.

After the resist pattern is formed, the process of forming a circuit can be roughly divided into two methods. The first method is to etch away the substrate surface not covered by the resist pattern (e.g., the copper surface of a copper-clad laminate), and then remove the resist pattern portion with an alkaline aqueous solution that is stronger than the developer (etching method).
In the second method, the substrate surface is plated with copper, solder, nickel, tin, or the like, and then the resist pattern is removed in the same manner as in the first method, and the exposed substrate surface (e.g., the copper surface of a copper-clad laminate) is etched (plating method). Cupric chloride, ferric chloride, cuprammonium complex solution, or the like is used for etching.

In recent years, as electronic devices become smaller and lighter, printed wiring boards have become finer and denser, and there is a demand for high-performance DFs that provide high resolution and high adhesion in the manufacturing process described above. As a means of achieving such high resolution, Patent Document 1 describes a photosensitive resin composition that has enhanced resolution due to a specific thermoplastic resin, monomer, and photopolymerization initiator.

JP 2010-249884 A

After the exposure step, the photosensitive resin layer may be subjected to a heating step and then developed in some cases. By carrying out this heating step, it is possible to further improve the high resolution and high adhesion. However, even if a post-exposure heating step is added, there are problems with conventional photosensitive resin compositions in that the improvement in adhesion is insufficient, and good adhesion cannot be obtained if the time elapsed after exposure is long.

The present invention has been proposed in view of the above-mentioned conventional circumstances, and the object of the present invention is to:
To provide a photosensitive resin composition which can remarkably improve adhesion when exposed to light, heated and then developed, and which can realize good adhesion even when a long time has elapsed since exposure.

As a result of intensive research, the inventors have discovered that the above object can be achieved by using a specific amount of a monomer component having a specific structural unit in an alkali-soluble polymer that constitutes a photosensitive resin composition, and have thus completed the present invention.
Furthermore, as a result of continuing intensive research, the inventors have discovered that the above object can be achieved by using a specific photopolymerization initiator in the alkali-soluble polymer that constitutes the photosensitive resin composition, and have thus completed the present invention.
That is, the present invention is as follows.
[1]
A photosensitive resin composition for obtaining a resin cured product by exposure, heating and development, the photosensitive resin composition comprising the following components based on the total solid content mass of the photosensitive resin composition:
(A) alkali-soluble polymer: 10% by mass to 90% by mass;
(B) a compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) a photopolymerization initiator: 0.01% by mass to 20% by mass;
Including,
A photosensitive resin composition comprising (A) the alkali-soluble polymer in which the structural units of styrene and/or a styrene derivative are 15 mass % or more in the entirety of the alkali-soluble polymer.
[2]
The photosensitive resin composition according to [1], wherein the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol/100 g or more as the compound (B) having an ethylenically unsaturated double bond is 0 to 18 mass% based on the solid content of the photosensitive resin composition.
[3]
The photosensitive resin composition according to [1] or [2], further comprising (D) an inhibitor.
[4]
The photosensitive resin composition according to any one of [1] to [3], further comprising (E) a benzotriazole derivative.
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein the (B) compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having three or more ethylenically unsaturated double bonds.
[6]
The photosensitive resin composition according to [5], wherein the (B) compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having four or more ethylenically unsaturated double bonds.
[7]
The photosensitive resin composition according to [6], wherein the (B) compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having six or more ethylenically unsaturated double bonds.
[8]
The photosensitive resin composition according to any one of [1] to [7], wherein the value of [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is 0.94 or more.
[9]
The photosensitive resin composition according to [8], wherein the value of [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is 1.04 or more.
[10]
The photosensitive resin composition according to [9], wherein the value of [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is 1.11 or more.
[11]
The photosensitive resin composition according to [10], wherein the value of [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is 1.21 or more.
[12]
The photosensitive resin composition according to [11], wherein the value of [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is 1.30 or more.
[13]
The photosensitive resin composition according to any one of [1] to [12], wherein the value of [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is 5 or less.
[14]
The photosensitive resin composition according to [13], wherein the value of [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is 4 or less.
[15]
The photosensitive resin composition according to [14], wherein the value of [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is 3 or less.
[16]
The photosensitive resin composition according to [15], wherein the value of [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is 2 or less.
[17]
The photosensitive resin composition according to [16], wherein the value of [(A) the content of the alkali-soluble polymer]/[(B) the content of the compound having an ethylenically unsaturated double bond] is 1.5 or less.
[18]
A photosensitive resin composition for obtaining a resin cured product by exposure, heating, and development, the photosensitive resin composition comprising the following components based on the total solid content mass of the photosensitive resin composition:
(A) alkali-soluble polymer: 10% by mass to 90% by mass;
(B) a compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) a photopolymerization initiator: 0.01% by mass to 20% by mass;
Including,
The photosensitive resin composition, wherein the (C) photopolymerization initiator contains anthracene and/or anthracene derivative.
[19]
The photosensitive resin composition according to [18], wherein the anthracene derivative has an alkoxy group having 1 to 40 carbon atoms which may have a substituent and/or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9-position and/or the 10-position.
[20]
The photosensitive resin composition according to [18] or [19], wherein the anthracene derivative has an alkoxy group having 1 to 40 carbon atoms which may have a substituent and/or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9- and 10-positions.
[21]
The photosensitive resin composition according to [20], wherein the (C) photopolymerization initiator contains 9,10-diphenylanthracene.
[22]
The photosensitive resin composition according to [20], wherein the (C) photopolymerization initiator contains 9,10-dialkoxyanthracene.
[23]
The photosensitive resin composition according to any one of [18] to [22], wherein the (C) photopolymerization initiator contains an anthracene derivative having a halogen atom.
[24]
The photosensitive resin composition according to [23], wherein the (C) photopolymerization initiator contains a halogen-substituted 9,10-dialkoxyanthracene.
[25]
The photosensitive resin composition according to [24], wherein the (C) photopolymerization initiator includes a compound in which an alkoxy group at the 9-position and/or the 10-position of a 9,10-dialkoxyanthracene is modified with one or more halogen atoms.
[26]
The photosensitive resin composition according to any one of [18] to [25], wherein the (C) photopolymerization initiator includes a compound having a halogen atom directly bonded to an anthracene skeleton.
[27]
The photosensitive resin composition according to any one of [18] to [26], wherein the content of structural units of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 15 mass% or more.
[28]
The photosensitive resin composition according to any one of [1] to [27], wherein the content of structural units of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 25 mass% or more.
[29]
The photosensitive resin composition according to [28], wherein the content of structural units of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 30 mass% or more.
[30]
The photosensitive resin composition according to [29], wherein the content of structural units of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 35 mass% or more.
[31]
The photosensitive resin composition according to [30], wherein the content of structural units of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 40 mass% or more.
[32]
The photosensitive resin composition according to any one of [1] to [31], wherein the content of structural units of styrene and/or a styrene derivative in the alkali-soluble polymer (A) is 90 mass% or less.
[33]
The photosensitive resin composition according to any one of [1] to [32], wherein the alkali-soluble polymer (A) further contains benzyl (meth)acrylate as a monomer component.
[34]
A method for forming a resist pattern, comprising: a step of exposing the photosensitive resin composition according to any one of items [1] to [33]; a heating step of heating the exposed photosensitive resin composition; and a developing step of developing the heated photosensitive resin composition.
[35]
The method for forming a resist pattern according to [34], wherein the heating temperature in the heating step is in the range of 30° C. to 150° C.
[36]
The method for forming a resist pattern according to [34] or [35], wherein the exposure step is carried out by an exposure method based on direct writing of a pattern, or an exposure method in which an image of a photomask is projected through a lens.
[37]
The method for forming a resist pattern according to [34] or [35], wherein the exposure step is carried out by an exposure method involving direct writing of a drawing pattern.
[38]
The method for forming a resist pattern according to any one of [34] to [37], wherein the heating step is carried out within 15 minutes after the exposure.
[39]
The method for forming a resist pattern according to any one of [34] to [38], wherein the exposure step is carried out by exposing with a first laser beam having a central wavelength of less than 390 nm and a second laser beam having a central wavelength of 390 nm or more.
[40]
The method for forming a resist pattern according to [39], wherein the first laser beam has a central wavelength of 350 nm or more and 380 nm or less, and the second laser beam has a central wavelength of 400 nm or more and 410 nm or less.
[41]
A method for producing a circuit board, comprising etching or plating a substrate having a resist pattern produced by the method according to any one of [34] to [40] to form a circuit board.
[42]
The photosensitive resin composition according to any one of [1] to [33], which is a photosensitive resin composition for obtaining a resin cured product by exposure to a first laser beam having a central wavelength of less than 390 nm and a second laser beam having a central wavelength of 390 nm or more.
[43]
The photosensitive resin composition according to [42], wherein the first laser beam has a central wavelength of 350 nm or more and 380 nm or less, and the second laser beam has a central wavelength of 400 nm or more and 410 nm or less.

The present invention provides a photosensitive resin composition that can significantly improve adhesion when exposed to light, heated, and then developed, and that achieves good adhesion even when a long time has passed since exposure.

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

[Photosensitive resin composition]
The photosensitive resin composition of the present invention is a photosensitive resin composition for obtaining a resin cured product by exposure, heating, and then developing, and the photosensitive resin composition is The following components, based on the total solid content by mass: (A) an alkali-soluble polymer: 10% by mass to 90% by mass; (B) a 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;
In particular, in the photosensitive resin composition of the present embodiment, when the alkali-soluble polymer (A) is composed of a plurality of types of alkali-soluble polymers, the amount of styrene and/or styrene derivatives in the entire alkali-soluble polymer (A) is The composition is characterized in that the constituent unit is 15% by mass or more.

Dry film resists obtained from photosensitive resin compositions usually do not achieve improved adhesion unless they are heated immediately after exposure, but the dry film resists obtained from the photosensitive resin compositions of the present invention can exhibit good adhesion (i.e., thin resists) even when a long time has passed since exposure. The photosensitive resin compositions of the present invention have a composition suitable for this characteristic.

In the photosensitive resin composition of the present embodiment, when the alkali-soluble polymer (A) contains multiple types of alkali-soluble polymers, the content of structural units of styrene and/or styrene derivatives in the entire alkali-soluble polymer (A) is 15 mass% or more, whereby the adhesion when exposed to light and then heated and developed can be significantly improved, and particularly good adhesion can be obtained even when a long time has elapsed since exposure.
Each component will be described in turn below.

<(A) Alkali-soluble polymer>
In the present disclosure, the (A) alkali-soluble polymer includes a polymer that is easily soluble in an alkaline substance. More specifically, the amount of carboxyl groups contained in the (A) alkali-soluble polymer is 100 to 600, preferably 250 to 450, in terms of acid equivalent. The acid equivalent refers to the mass (unit: grams) of a polymer having one equivalent of carboxyl groups in its molecule. The carboxyl groups in the (A) alkali-soluble polymer are necessary to impart developability and peelability to an alkaline aqueous solution to the photosensitive resin layer. It is preferable to set the acid equivalent to 100 or more from the viewpoint of improving development resistance, resolution, and adhesion. And it is more preferable to set the acid equivalent to 250 or more. On the other hand, it is preferable to set the acid equivalent to 600 or less from the viewpoint of improving developability and peelability. And it is more preferable to set the acid equivalent to 450 or less. In the present disclosure, the acid equivalent is a value measured by a potentiometric titration method using a potentiometric titrator and titrating with a 0.1 mol/L NaOH aqueous solution.

(A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. A weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. A weight average molecular weight of 100,000 or less is more preferable, a weight average molecular weight of 70,000 or less is even more preferable, a weight average molecular weight of 60,000 or less is even more preferable, and a weight average molecular weight of 50,000 or less is particularly preferable. On the other hand, a weight average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of the development aggregate and the properties of the unexposed film such as edge fuse property and cut chip property when the photosensitive resin laminate is formed. A weight average molecular weight of 10,000 or more is more preferable, and a weight average molecular weight of 20,000 or more is even more preferable. Edge fuse property refers to the degree of easiness of protrusion of the photosensitive resin layer (i.e., the layer made of the photosensitive resin composition) from the end face of the roll when the photosensitive resin laminate is wound into a roll. Cut chipping refers to the degree to which chips fly off when an unexposed film is cut with a cutter. If these chips adhere to the top surface of the photosensitive resin laminate, they will be transferred to a mask in a subsequent exposure process, causing defective products. (A) The dispersity of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0.

In this embodiment, the photosensitive resin composition can remarkably improve adhesion when it is heated after exposure and then developed, and in particular, from the viewpoint of exhibiting good adhesion even when the time elapsed after exposure is long, it is preferable that the (A) alkali-soluble polymer contains a monomer component having an aromatic hydrocarbon group. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content ratio of the monomer component having an aromatic hydrocarbon group in this (A) alkali-soluble polymer is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, particularly preferably 55% by mass or more, and most preferably 60% by mass or more, based on the total mass of all monomer components. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 80% by mass or less. In the case where multiple types of (A) alkali-soluble polymers are contained, the content ratio of the monomer component having an aromatic hydrocarbon group was calculated as a weight average value.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative. Among these, a monomer having an aralkyl group or styrene is preferred.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, with a substituted or unsubstituted benzyl group being preferred.
An example of a comonomer having a phenylalkyl group is phenylethyl (meth)acrylate.
Examples of the comonomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; and vinyl monomers having a benzyl group, such as vinylbenzyl chloride, vinylbenzyl alcohol, etc. Among these, benzyl (meth)acrylate is preferred.

The alkali-soluble polymer (A) containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one kind of a first monomer described later and/or at least one kind of a second monomer described later.
The alkali-soluble polymer (A) that does not contain a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one type of first monomer described later, and more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described later.

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, and maleic acid half ester. Among these, (meth)acrylic acid is preferable.
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. A copolymerization ratio of 10% by mass or more is preferable from the viewpoint of achieving good developability and controlling edge fusing properties, and is more preferably 15% by mass or more, and even more preferably 20% by mass or more. A copolymerization ratio of 50% by mass or less is preferable from the viewpoint of high resolution and bottom shape of the resist pattern, and furthermore from the viewpoint of chemical resistance of the resist pattern, and from these viewpoints, 35% by mass or less is more preferable, 32% by mass or less is even more preferable, and 30% by mass or less is particularly preferable.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferred.
It is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer, because this can remarkably improve the adhesion when the film is heated and developed after exposure, and in particular, it is preferable to exhibit good adhesion even when the time after exposure is long. For example, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, or a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene is preferable.

(A) Alkali-soluble polymers may be used alone or in combination of two or more. When using a mixture of two or more, it is preferable to use two types of alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group, or to use a mixture of an alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group and an alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group. In the latter case, the proportion of the alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group used is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 95% by mass or more, based on the total amount of (A) alkali-soluble polymer.

The (A) alkali-soluble polymer of this embodiment preferably contains 3% by mass or more of the alkali-soluble polymer (A-1) containing 52% by mass or more of structural units of styrene and/or a styrene derivative as a monomer component, based on the solid content in the photosensitive resin composition. This can significantly improve the adhesion when heated and developed after exposure, and can provide good adhesion even when the elapsed time after exposure is long. From the same viewpoint, the (A) alkali-soluble polymer more preferably contains 10% by mass or more of the alkali-soluble polymer (A-1) based on the solid content in the photosensitive resin composition, more preferably contains 15% by mass or more, particularly preferably contains 20% by mass or more, and most preferably contains 30% by mass or more.
Examples of styrene derivatives include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer.

In particular, in this embodiment, when the (A) alkali-soluble polymer is composed of multiple types of alkali-soluble polymers, the structural units of styrene and/or styrene derivatives in the entire (A) alkali-soluble polymer are 15% by mass or more. This significantly improves adhesion when exposed to light and then heated and developed, and good adhesion can be obtained even when a long time has passed since exposure. Since the styrene skeleton is hydrophobic, swelling in the developer can be suppressed, and good adhesion can be achieved. The structural units of styrene and/or styrene derivatives in the (A) alkali-soluble polymer are preferably 25% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, and particularly preferably 40% by mass or more.

However, if the styrene skeleton content is high, the mobility of the resin decreases, so the reactivity does not increase sufficiently and the desired adhesion cannot be obtained. In addition, as the time elapsed after exposure increases, the radicals in the system are deactivated, so the effect of improving adhesion by heating after exposure decreases. (A) The upper limit of the structural units of styrene and/or styrene derivatives in the alkali-soluble polymer is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, and particularly preferably 70% by mass or less.

In this way, in the present invention, the structural units of styrene and/or styrene derivatives in the entire alkali-soluble polymer (A) are 15% by mass or more, and by heating after exposure and then developing, the mobility of the resin is improved by heating even in systems with a high content of styrene skeletons, and it is possible to achieve a high degree of compatibility between the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bonds, and as a result, it is believed that the remarkable improvement in adhesion makes it possible to obtain good adhesion even when the time elapsed after exposure is long.

In addition, from the viewpoint of significantly improving adhesion when the film is heated and developed after exposure, and particularly exhibiting good adhesion even when a long time has elapsed since exposure, the alkali-soluble polymer (A-1) preferably contains 25% by mass or more of (meth)acrylic acid structural units as a monomer component, more preferably 26% by mass or more, even more preferably 27% by mass or more, particularly preferably 28% by mass or more, and most preferably 29% by mass or more. From the same viewpoint, it is preferable that the polymer contains 35% by mass or less, more preferably 32% by mass or less, and even more preferably 30% by mass or less.

(A) The synthesis of an alkali-soluble polymer is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring the solution. In some cases, the synthesis is carried out while dropping a portion of the mixture into the reaction solution. After the reaction is completed, further solvent may be added to adjust the concentration to the desired level. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used.

The weight average value Tg ^total of the glass transition temperature Tg of the alkali-soluble polymer (A) is preferably 30° C. or more and 150° C. or less. Tg ^total is calculated by the method described in the examples described later. In the photosensitive resin composition, by using an alkali-soluble polymer (A) having a Tg ^total of 150° C. or less, the adhesion when heated after exposure and then developed can be significantly improved, and good adhesion can be exhibited even when the elapsed time after exposure is long. From this viewpoint, the Tg ^total of the alkali-soluble polymer (A) is more preferably 135° C. or less, even more preferably 130° C. or less, even more preferably 125° C. or less, even more preferably 120° C. or less, and particularly preferably 110° C. or less. In addition, it is preferable to use an alkali-soluble polymer (A) having a Tg ^total of 30° C. or more from the viewpoint of improving edge fuse resistance. From this viewpoint, the Tg ^total of the alkali-soluble polymer (A) is more preferably 40° C. or higher, further preferably 50° C. or higher, and particularly preferably 60° C. or higher.

The ratio of the alkali-soluble polymer (A) to the total solid mass of the photosensitive resin composition is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and even more preferably 40% by mass to 60% by mass. It is preferable to set the ratio of the alkali-soluble polymer (A) to the photosensitive resin composition to 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable to set the ratio of the alkali-soluble polymer (A) to the photosensitive resin composition to 10% by mass or more from the viewpoint of improving edge fuse resistance.

<(B) Compound Having an Ethylenically Unsaturated Double Bond>
From the viewpoints of curability and compatibility with the alkali-soluble polymer (A), the compound having an ethylenically unsaturated double bond (B) preferably contains a compound having a (meth)acryloyl group in the molecule. The number of (meth)acryloyl groups in the compound (B) may be one or more.

The compound having an ethylenically unsaturated bond (B) is a compound that has polymerizability due to having an ethylenically unsaturated group in its structure. The ethylenically unsaturated bond is more preferably derived from a methacryloyl group. From the viewpoint of adhesion and suppression of foaming of the developer, the compound having an ethylenically unsaturated bond (B) 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 (B) compound having one (meth)acryloyl group include a compound in which (meth)acrylic acid is added to one end of a polyalkylene oxide, a compound in which (meth)acrylic acid is added to one end of a polyalkylene oxide and the other end is alkyl- or allyl-etherified, and a phthalic acid-based compound, which are preferred in terms of peelability and cured film flexibility.

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; 4-normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound in which polypropylene glycol to which an average of 2 moles of propylene oxide has been added and polyethylene glycol to which an average of 7 moles of ethylene oxide has been added are added to nonylphenol; 4-normal nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound in which polypropylene glycol to which an average of 1 mole of propylene oxide has been added and polyethylene glycol to which an average of 5 moles of ethylene oxide has been added are added to nonylphenol; and 4-normal nonylphenoxyoctaethylene glycol (meth)acrylate (e.g., M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound in which polyethylene glycol to which an average of 8 moles of ethylene oxide has been added is added to nonylphenol.
Furthermore, inclusion of γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate is preferable from the viewpoints of sensitivity, resolution and adhesion in addition to the above 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, and compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain in which ethylene oxide chains and propylene oxide chains are bonded randomly or in blocks.

Examples of such compounds include polyethylene glycol (meth)acrylates such as tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, and compounds having (meth)acryloyl groups at both ends of a 12-mol ethylene oxide chain, as well as polypropylene glycol di(meth)acrylate and polybutylene glycol di(meth)acrylate. Examples of polyalkylene oxide di(meth)acrylate compounds containing ethylene oxide groups and propylene oxide groups include dimethacrylates of glycols in which an average of 3 moles of ethylene oxide have been added to both ends of polypropylene glycol to which an average of 12 moles of propylene oxide have been added, dimethacrylates of glycols in which an average of 18 moles of propylene oxide have been added, and dimethacrylates of glycols in which an average of 15 moles of ethylene oxide have been added to both ends of polypropylene glycol to which an average of 18 moles of propylene oxide have been added, FA-023M, FA-024M, FA-027M (product names, manufactured by Hitachi Chemical Co., Ltd.). These are preferred in terms 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１～３９の整数であり、かつｎ１＋ｎ３は２～４０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）－とのいずれか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 obtained by modifying bisphenol A with an alkylene oxide is preferred from the viewpoints of resolution and adhesion.
Specifically, the compound represented by the following general formula (I):

{wherein R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n1 and n3 each independently represent an integer from 1 to 39, and n1+n3 is an integer from 2 to 40, n2 and n4 each independently represent an integer from 0 to 29, and n2+n4 is an integer from 0 to 30, and the arrangement of the repeating units -(A-O)- and -(B-O)- may be random or block. In the case of a block, either -(A-O)- or -(B-O)- may be on the bisphenyl group side.} can be used.
For example, dimethacrylate of polyethylene glycol having an average of 5 moles of ethylene oxide added to each end of bisphenol A, dimethacrylate of polyethylene glycol having an average of 2 moles of ethylene oxide added to each end of bisphenol A, and dimethacrylate of polyethylene glycol having an average of 1 mole of ethylene oxide added to each end of bisphenol A are preferred in terms of resolution and adhesion.
Furthermore, a compound in which the aromatic ring in the above general formula (I) has a heteroatom and/or a substituent may be used.

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

A compound having three or more (meth)acryloyl groups in the molecule has three or more moles of a group to which an alkylene oxide group can be added in the molecule as a central skeleton, and is obtained by adding an alkyleneoxy group such as an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group to this to obtain an alcohol, which is then made into a (meth)acrylate. In this case, examples of compounds that can become the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings. As these compounds, tri(meth)acrylates, for example, ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate (for example, trimethacrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane, and trimethacrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane) are suitable for softening. Examples of suitable (meth)acrylates include tetra(meth)acrylate, such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, and hexa(meth)acrylate. Compounds having three or more (meth)acryloyl groups can significantly improve adhesion when developed after heating following exposure, and are particularly preferred from the viewpoint of exhibiting good adhesion even when the time elapsed after exposure is long, and compounds having three or more methacrylic groups are even more preferred.

The tetra(meth)acrylate is preferably pentaerythritol tetra(meth)acrylate, which may be a tetra(meth)acrylate having 1 to 40 moles of alkylene oxide added to the four terminals of pentaerythritol.
As the hexa(meth)acrylate, a hexa(meth)acrylate having 1 to 40 moles of ethylene oxide added in total to six terminals of dipentaerythritol, or a hexa(meth)acrylate having 1 to 20 moles of ε-caprolactone added in total to six terminals of dipentaerythritol is preferred.

The compound (B) having an ethylenically unsaturated double bond preferably contains a (meth)acrylate compound having three or more ethylenically unsaturated double bonds, since this can significantly improve adhesion when the compound is heated after exposure and then developed, and can provide good adhesion even when the time elapsed after exposure is long. From the same viewpoint, it is more preferable to contain a (meth)acrylate compound having four or more ethylenically unsaturated double bonds, even more preferable to contain a (meth)acrylate compound having five or more ethylenically unsaturated double bonds, and particularly preferable to contain a (meth)acrylate compound having six or more ethylenically unsaturated double bonds. 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 crosslink density during polymerization by exposure, but the desired crosslink density is often not obtained due to the influence of steric hindrance caused by the large number of functional groups. In the present invention, it has been found that by improving the mobility in the system by subjecting a compound having preferably 3 or more ethylenically unsaturated double bonds, more preferably a compound having 4 or more ethylenically unsaturated double bonds, even more preferably a compound having 5 or more ethylenically unsaturated double bonds, and particularly preferably a compound having 6 or more ethylenically unsaturated double bonds, to a heat treatment after exposure, it is possible to reduce the influence of steric hindrance and obtain high adhesion even if the number of functional groups is large.

The content of the compound having preferably 3 or more ethylenically unsaturated double bonds, more preferably 4 or more ethylenically unsaturated double bonds, even more preferably 5 or more ethylenically unsaturated double bonds, and particularly preferably 6 or more ethylenically unsaturated double bonds is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more, based on the solid content of the photosensitive resin composition. 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 particularly preferably 15% by mass or less, from the viewpoint of expressing the effect of the heat treatment after exposure.

(b1) Examples of the (meth)acrylate compound having three or more ethylenically unsaturated bonds include:
tri(meth)acrylates, for example, ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate (for example, as preferred examples from the viewpoints of flexibility, adhesion, and bleed-out suppression, tri(meth)acrylate in which an average of 21 moles of ethylene oxide are added to trimethylolpropane, and tri(meth)acrylate in which an average of 30 moles of ethylene oxide are added to trimethylolpropane);
Tetra(meth)acrylates, for example, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.;
Penta(meth)acrylates, for example, dipentaerythritol penta(meth)acrylate;
Hexa(meth)acrylates, for example, dipentaerythritol hexa(meth)acrylate, and the like.
Of these, tetra-, penta- or hexa(meth)acrylates are preferred.

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

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 are added to the four terminals of pentaerythritol is preferred.

｛式中、Ｒ₃～Ｒ₆は、それぞれ独立に、炭素数１～４のアルキル基を表し、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クリレート化合物であることがより好ましい。 The tetra(meth)acrylate is represented by the following general formula (II):

{wherein R ₃ to R ₆ each independently represent an alkyl group having 1 to 4 carbon atoms; X represents an alkylene group having 2 to 6 carbon atoms; m ₁ , m ₂ , m ₃ and m ₄ each independently represent an integer from 0 to 40; m ₁ + m ₂ + m ₃ + m ₄ is 1 to 40; and when m ₁ + m ₂ + m ₃ + m ₄ is 2 or greater, multiple Xs may be the same or different.} is more preferable.

Without wishing to be bound by theory, it is believed that the tetramethacrylate compound represented by general formula (II) has groups R ₃ to R ₆ and is therefore less hydrolyzable in an alkaline solution than a tetraacrylate having an H ₂ C═CH—CO—O— moiety. The use of a photosensitive resin composition containing a tetramethacrylate compound represented by general formula (II) can significantly improve adhesion when exposed to light and then heated and developed, and is particularly preferred from the viewpoint of realizing good adhesion even when a long time has elapsed since exposure.

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

From the viewpoint of obtaining the desired resolution, foot shape and remaining film ratio for the resist pattern, in formula (II), X is preferably --CH ₂ --CH ₂ --.

From the viewpoint of obtaining the desired resolution, foot shape and remaining film ratio for the resist pattern, in general formula (II), _m1 , _m2 , _m3 and _m4 are each preferably independently an integer from 1 to 20, and more preferably an integer from 2 to 10. Furthermore, in general formula (II), _m1 + _m2 + _m3 + _m4 is preferably 1 to 36 or 4 to 36.

Examples of the compound represented by the general formula (II) include pentaerythritol (poly) alkoxy tetramethacrylate. In the present disclosure, "pentaerythritol (poly) alkoxy tetramethacrylate" includes both "pentaerythritol alkoxy tetramethacrylate" in which m ₁ + m ₂ + m ₃ + m ₄ = 1 in the above general formula (II) and "pentaerythritol polyalkoxy tetramethacrylate" in which m ₁ + m ₂ + m ₃ + m ₄ = 2 to 40. Examples of the compound represented by the general formula (II) include the compounds listed in JP 2013-156369 A, such as pentaerythritol (poly) alkoxy tetramethacrylate.

Preferred hexa(meth)acrylate compounds are hexa(meth)acrylates in which a total of 1 to 24 moles of ethylene oxide are added to the six terminals of dipentaerythritol, and hexa(meth)acrylates in which a total of 1 to 10 moles of ε-caprolactone are added to the six terminals of dipentaerythritol.

From the viewpoint of significantly improving adhesion when exposed to light and then heated and then developed, and particularly realizing good adhesion even when a long time has elapsed since exposure, it is particularly preferable that the photosensitive resin composition according to this embodiment contains, as the compound (B) having an ethylenically unsaturated bond, 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, the adhesion can be significantly improved when the composition is developed after heating after exposure, and in particular, from the viewpoint of realizing good adhesion even when the time elapsed after exposure is long, the photosensitive resin composition preferably contains, as a compound having an ethylenically unsaturated bond (B), 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 preferably an ethylene oxide chain, a propylene oxide chain, or a butylene oxide chain, more preferably an ethylene oxide chain or a propylene oxide chain, and particularly preferably an ethylene oxide chain.

In the photosensitive resin composition, the use of (A) an alkali-soluble polymer in combination with a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton tends to maintain a balance between the chemical resistance, adhesion, and resolution of the resist pattern.

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 the multiple hydroxyl groups is modified with an alkyleneoxy group, and (meth)acrylic acid. Six hydroxyl groups in the dipentaerythritol skeleton may be modified with an alkyleneoxy group. The number of ester bonds in one ester molecule may be 1 to 6, and is preferably 6.

Examples of (meth)acrylate compounds having an alkylene oxide chain and a dipentaerythritol skeleton include hexa(meth)acrylates in which 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 are added to dipentaerythritol.

｛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, the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton is a (meth)acrylate compound represented by the following general formula (III):

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

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

It is preferable that the content of (b1) the (meth)acrylate compound having three or more ethylenically unsaturated bonds is more than 0% by mass and less than 40% by mass, based on the total solid content of the photosensitive resin composition. If this content exceeds 0% by mass, the adhesion when heated and developed after exposure can be significantly improved, and there is a tendency to achieve good adhesion even when the time elapsed after exposure is long, and if it is less than 40% by mass, the flexibility of the cured resist is improved and the peeling time is shortened. This content is more preferably 2% by mass or more and 30% by mass or less, and even more preferably 4% by mass or more and 25% by mass or less.

From the viewpoint of adhesion and suppression of foaming property of the developer, the photosensitive resin composition preferably contains, as the compound (B) having an ethylenically unsaturated bond, (b2) a compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups.
(b2) The compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups has a molecular weight of preferably 500 or more, more preferably 700 or more, and even more preferably 1,000 or more, from the viewpoint of suppressing bleed-out.

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

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

It is preferable that the content of (b2) the compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups is more than 0 mass% and is 20 mass% or less, based on the total solid content of the photosensitive resin composition.

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

From the viewpoint of chemical resistance, adhesion, high resolution, and foot shape of the resist pattern, the concentration of methacryloyl groups in the compound having an ethylenically unsaturated bond (B) is preferably 0.20 mol/100 g or more, more preferably 0.30 mol/100 g or more, and even more preferably 0.35 mol/100 g or more. The upper limit of the concentration of methacryloyl groups is not limited as long as the polymerizability and alkaline 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 the concentration of methacryloyl groups/(concentration of methacryloyl groups+concentration of acryloyl groups) in the compound having an ethylenic unsaturated bond (B) is preferably 0.50 or more, more preferably 0.60 or more, even 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 the compound (B) having an ethylenically unsaturated bond. Examples of other compounds include (meth)acrylates having a urethane bond, compounds obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid, and 1,6-hexanediol di(meth)acrylate.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. A ratio of 5% by mass or more is preferable from the viewpoints of sensitivity, resolution, and adhesion. A ratio of 20% by mass or more is more preferable, and a ratio of 30% by mass or more is even more preferable. On the other hand, a ratio of 70% by mass or less is preferable from the viewpoints of suppressing edge fuse and peeling delay of the cured resist. A ratio of 50% by mass or less is more preferable.

(B) As a compound having an ethylenically unsaturated double bond, the content of compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol/100 g or more is preferably 0 to 18 mass % based on the solid content of the photosensitive resin composition. This significantly improves adhesion when exposed to light and then heated and developed, and can provide good adhesion even when a long time has passed since exposure. Compounds having ethylenically unsaturated double bonds and a high concentration of bisphenol A skeletons generally have improved adhesion due to their hydrophobicity.

In the present invention, it was found that due to the rigid skeleton of bisphenol A, the mobility does not improve even when heating is performed after exposure, and the effect of improving adhesion is small. Therefore, in the present invention, from the above viewpoint, the content of compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol/100 g or more as a compound having an ethylenically unsaturated double bond (B) is preferably 18% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 6% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less, based on the solid content of the photosensitive resin composition. From the same viewpoint, the content of compound (B-1) having a bisphenol A skeleton concentration of 0.20 mol/100 g or more as a compound having an ethylenically unsaturated double bond (B) is preferably 18% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 6% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less, based on the solid content of the photosensitive resin composition.

In particular, in this embodiment, the value of [(A) content of alkali-soluble polymer]/[(B) content of compound having ethylenically unsaturated double bond] is preferably 0.94 or more. This can significantly improve the adhesion when the film is heated and developed after exposure, and can provide good adhesion even when the time after exposure is long. From the same viewpoint, the value of [(A) content of alkali-soluble polymer]/[(B) content of compound having ethylenically unsaturated double bond] is more preferably 1.04 or more, even more preferably 1.11 or more, particularly preferably 1.21 or more, even more preferably 1.30 or more, and most preferably 1.35 or more.
Increasing the value of [content of (A) alkali-soluble polymer]/[content of (B) compound having ethylenically unsaturated double bond] generally increases the amount of alkali-soluble, i.e., hydrophilic components, and increases the Tg in the system, lowering the mobility, lowering the double bond reaction rate, and as a result, lowering the adhesion. However, in the present invention, by increasing the value of [content of (A) alkali-soluble polymer]/[content of (B) compound having ethylenically unsaturated double bond] and also carrying out heat treatment after exposure, the mobility in the system is improved and the double bond reaction rate is improved even if the value of [content of (A) alkali-soluble polymer]/[content of (B) compound having ethylenically unsaturated double bond] is large, and further, the effect of improving adhesion due to the interaction between the carboxyl group of the alkali-soluble polymer and copper is added, and it is considered that the effect of the present invention has been realized.

The value of [(A) content of alkali-soluble polymer]/[(B) content of compound having ethylenically unsaturated double bonds] is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, particularly preferably 2 or less, and most preferably 1.5 or less.

<(C) Photopolymerization initiator>
(C) The photopolymerization initiator is a compound that polymerizes a monomer by the action of light.
(C-1) Photopolymerization Initiator The photosensitive resin composition of this embodiment contains a compound generally known in the technical field as (C-1) a photopolymerization initiator ((C) photopolymerization initiator).

The total content of the (C-1) photopolymerization initiator in the photosensitive resin composition is preferably within the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, even more preferably 0.1 to 7% by mass, and particularly preferably 0.1 to 6% by mass. The total content of the (C-1) photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and is preferably 20% by mass or less from the viewpoint of allowing sufficient light transmission to the bottom surface of the resist and obtaining good high resolution.

(C-1) 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 are preferred in terms of sensitivity, resolution, and adhesion), and further include hexaarylbiimidazole, biphenylsulfonyl ethers, and phenylsulfonyl ethers. Examples of the photosensitive dye include lazoline compounds, anthracene compounds (for example, 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene are preferred in terms of sensitivity, resolution, and adhesion), coumarin compounds (for example, 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesion), N-arylamino acids or ester compounds thereof (for example, N-phenylglycine is preferred in terms of sensitivity, resolution, and adhesion), and halogen compounds (for example, tribromomethylphenylsulfone). These may be used alone or in combination of two or more. Other examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and triphenylphosphine oxide.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. 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 within the range of 0.01% by mass to 0.5% by mass, and more preferably 0.02% by mass to 0.3% by 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, and 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', Examples of the biimidazole include 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. These may be used alone or in combination of two or more. From the viewpoints of high sensitivity, resolution, and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

In this embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably within the range of 0.05% by mass to 7% by mass, more preferably 0.1% by mass to 6% by mass, and even more preferably 1% by mass to 5% by mass, from the viewpoint of improving the peeling properties and/or sensitivity of the photosensitive resin layer.

From the viewpoints of the release characteristics or sensitivity, resolution, and adhesion of the photosensitive resin layer, it is preferable that the photosensitive resin composition also contains a pyrazoline compound or an anthracene compound as a photosensitizer (for example, sialic acid anthracenes such as 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene are preferable in terms of sensitivity, resolution, and adhesion).
Examples of pyrazoline compounds 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-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)- From the above viewpoints, 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-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, and the like are preferred. Among these, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

In this embodiment, the content of the photosensitizer in the photosensitive resin composition is preferably within the range of 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, even more preferably 0.1% by mass to 1% by mass, and particularly preferably 0.1% by mass to 0.7% by mass, from the viewpoint of transmittance and from the viewpoint of improving the peeling properties and/or sensitivity of the photosensitive resin layer.

(C-2) Photopolymerization Initiator In the present embodiment, the photosensitive resin composition can use, as the (C-2) photopolymerization initiator ((C) photopolymerization initiator), one containing anthracene and/or anthracene derivative.

(C-2) Using at least anthracene and/or anthracene derivatives as the photopolymerization initiator can significantly improve adhesion when exposed to light, heated and then developed, and is particularly advantageous in terms of being able to obtain good adhesion even when a long time has passed since exposure. In addition, anthracene and/or anthracene derivatives can absorb a first active light having a central wavelength of less than 390 nm and a second active light having a central wavelength of 390 nm or more, and function as a polymerization initiator. The active light is, for example, laser light.

Therefore, in one embodiment, the photosensitive resin composition can have photosensitivity to the first and second active light, and can also be used for two-wavelength exposure. The anthracene and/or anthracene derivative can also be selected to have multiple absorption maxima in the wavelength range of the first and second active light. The central wavelength of the first active light is preferably 350 to 380 nm, more preferably 355 to 375 nm, and particularly preferably 375 nm. The central wavelength of the second active light is preferably 400 to 410 nm, more preferably 402 to 408 nm, and particularly preferably 405 nm (h-line).

The total content of the (C-2) photopolymerization initiator in the photosensitive resin composition is preferably within the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, even more preferably 0.1 to 7% by mass, and particularly preferably 0.1 to 6% by mass. The total content of the (C-2) photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and is preferably 20% by mass or less from the viewpoint of allowing sufficient light transmission to the bottom surface of the resist and obtaining good high resolution.

Anthracene and anthracene derivatives can significantly improve adhesion when exposed to light, heated and then developed, and are particularly advantageous in that they achieve good adhesion even when a long time has passed since exposure. From the same viewpoint, the anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms, which may have a substituent, and/or an aryl group having 6 to 40 carbon atoms, which may have a substituent, at the 9th and/or 10th positions, and more preferably at the 9th and 10th positions.

In one embodiment, the anthracene derivative can remarkably improve adhesion when exposed to light and then heated and developed, and from the viewpoint of realizing good adhesion even when a long time has elapsed since exposure, it is preferable that at least one of the 9th or 10th positions has an alkoxy group having 1 to 40 carbon atoms which may have a substituent, and it is more preferable that at least one of the 9th or 10th positions has an alkoxy group having 1 to 30 carbon atoms which may have a substituent. From the viewpoint of obtaining good adhesion and resolution, it is preferable that at the 9th and 10th positions, it is preferable that at least one of the 9th and 10th positions has an alkoxy group having 1 to 40 carbon atoms which may have a substituent, and it is more preferable that at least one of the 9th and 10th positions has an alkoxy group having 1 to 30 carbon atoms which may have a substituent. The number of carbon atoms of the groups at the 9th and 10th positions may be the same or different.
The optionally substituted alkoxy group is:
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;
Halogen-modified alkoxy groups, for example, chlorobutoxy and chloropropoxy groups;
an alkoxy group having a hydroxyl group added thereto, for example, a hydroxybutyloxy group;
an alkoxy group to which a cyano group has been added, for example, a cyanobutoxy group;
an alkoxy group having an alkylene oxide group added thereto, for example, a methoxybutoxy group;
Aryl-added alkoxy groups, for example, phenoxybutoxy groups;
Among these, an n-butoxy group is more preferable.

In one embodiment, the anthracene derivative can significantly improve adhesion when exposed to light and then heated and developed, and from the viewpoint of realizing good adhesion even when a long time has passed since exposure, it is preferable that at least one of the 9th or 10th positions has an aryl group having 6 to 40 carbon atoms, which may have a substituent, and it is more preferable that at least one of the 9th or 10th positions has an aryl group having 6 to 30 carbon atoms, which may have a substituent.

In order to significantly improve adhesion when developed after exposure and heating, and in particular to achieve good adhesion even when a long time has passed since exposure, it is preferable to have an aryl group having 6 to 40 carbon atoms, which may have a substituent, at the 9th and 10th positions, and more preferable to have an aryl group having 6 to 30 carbon atoms, which may have a substituent, at the 9th and 10th positions. The number of carbon atoms in the groups at the 9th and 10th positions may be the same or different. Furthermore, the groups at the 9th and 10th positions may be the same or different. For example, the group at the 9th position may be an alkoxy group having 1 to 40 carbon atoms, which may have a substituent, and the group at the 10th position may be an aryl group having 6 to 40 carbon atoms, which may have a substituent.

Aryl groups having 6 to 40 carbon atoms, which may have a substituent, include phenyl, biphenyl, naphthyl, and anthracenyl groups; aryl groups to which an alkoxy group has been added, such as a methoxyphenyl group and an ethoxyphenyl group; aryl groups to which an alkyl group has been added, such as a tolyl group, a xylyl group, a mesityl group, and a nonylphenyl group; aryl groups to which a halogen has been added, such as a chlorophenyl group; and aryl groups to which a hydroxyl group has been added, such as a hydroxyphenyl group. Of these, the 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 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or 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 may contain a heteroatom.

X independently represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, a -N(R')- group, a -CO-O- group, a -CO-S- group, a -SO ₂ -O- group, a -SO ₂ -S- group, a -SO ₂ -N(R')- group, a -O-CO- group, a -S-CO- group, a -O-SO ₂ - group or a S-SO ₂ - group, except for a combination in which X is a single bond and R ¹ is a hydrogen atom (i.e. unsubstituted anthracene).

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

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

Specific examples of the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms in ^R1 and R' include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tetradecyl group, an n-hexadecyl group, an n-eicosyl group, an i-propyl group, an i-butyl group, a sec-butyl group, and a t-butyl group.

Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in ^R1 and R' include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a bridged alicyclic hydrocarbon group having 6 to 20 carbon atoms (for example, a norbornyl group, a tricyclodecanyl group, a tetracyclododecyl group, an adamantyl group, a methyladamantyl group, an ethyladamantyl group, a 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 ^R1 and R' include a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, an ethoxyphenyl group, a tolyl group, a xylyl group, a mesityl group, a nonylphenyl group, a chlorophenyl group, and a hydroxyphenyl group.

The substituted or unsubstituted heteroaryl group in ^R1 and R' includes a substituted or unsubstituted aryl group containing one or more heteroatoms such as a sulfur atom, an oxygen atom, or a nitrogen atom, such as a pyridyl group, an imidazolyl group, a morpholinyl group, a piperidyl group, or a pyrrolidyl group.

Each of the hydrocarbon groups ^R1 and R' may be substituted with a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a hydroxyalkyl group having 1 to 4 carbon atoms (e.g., a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, etc.), an alkoxyl group having 1 to 4 carbon atoms (e.g., a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a t-butoxy group, etc.), a sialic acid group, a cyclic alkyl ... Examples of the aryl group include a cyano group, a cyanoalkyl group having 2 to 5 carbon atoms (e.g., a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group, etc.), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, etc.), an alkoxycarbonylalkoxy group (e.g., a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group, a t-butoxycarbonylmethoxy group, etc.), a halogen atom (e.g., a fluorine atom, a chlorine atom, etc.), and a fluoroalkyl group (e.g., a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, etc.). Each of the hydrocarbon groups ^R1 and R' is preferably substituted with a halogen atom. In particular, the anthracene derivative preferably has an alkoxy group substituted with a halogen atom at the 9th and/or 10th positions.

Preferred specific examples of ^R1 and R' include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a cyclopentyl group, a cyclohexyl group, a camphoroyl group, a norbornyl group, a p-toluyl group, a benzyl group, a methylbenzyl group, a phenyl group, and a 1-naphthyl group.

Preferred specific examples of X include a single bond, an oxygen atom, a sulfur atom, an -N(R')- group, an -O-CO- group, and an O- _SO2- group. When X is an -N(R')- group, R' is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, a camphoroyl group, a norbornyl group, or a benzyl group.

Examples of compounds 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-9,1 0-bis(2-naphthyl)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di(2-ethylhexyloxy)anthracene, 1,2-benzanthracene, anthrobin, 1,4,9,10-tetrahydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene, 9-(methylaminomethyl)anthracene, 9-acetylanthracene, 9-anthraldehyde, 10-methyl-9-anthraldehyde, 1,8,9-triacetoxyanthracene, and the like. 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 from the viewpoint of significantly improving adhesion when heated and then developed after exposure, and realizing good adhesion even when a long time has elapsed since exposure, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-bis-(3-chloropropoxy)anthracene are more preferred, and 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-bis-(3-chloropropoxy)anthracene are particularly preferred. The compound represented by the above general formula (IV) may be used alone or in combination of two or more types.

In terms of being able to significantly improve adhesion when developed after exposure and heating, and in particular being able to obtain good adhesion even when a long time has passed since exposure, the photopolymerization initiator (C-2) preferably contains (1) 9,10-diphenylanthracene; (2) 9,10-dialkoxyanthracene; (3) anthracene derivative having a halogen atom; (4) a halogen-substituted 9,10-dialkoxyanthracene; (5) a compound in which the alkoxy groups at the 9th and/or 10th positions of 9,10-dialkoxyanthracene are modified with one or more halogen atoms; and/or (6) a compound having a halogen atom directly bonded to the anthracene skeleton.

The compound represented by the above general formula (IV) can significantly improve adhesion when developed after heating after exposure, and is particularly advantageous in that it can provide good adhesion even when a long time has elapsed since exposure.Furthermore, it is advantageous in that it can be used for two-wavelength exposure using a first active light having a central wavelength of less than 390 nm and a second active light having a central wavelength of 390 nm or more, and can provide a photosensitive resin composition that exhibits excellent sensitivity, adhesion, and resolution.

In one embodiment, the photopolymerization initiator (C-2) preferably contains an anthracene derivative having a halogen atom. A suitable example of an anthracene derivative having a halogen atom is a halogen-substituted 9,10-dialkoxyanthracene. A suitable example of the halogen-substituted anthracene is a compound in which the alkoxy groups at the 9th and/or 10th positions of 9,10-dialkoxyanthracene are 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, the anthracene derivative is preferably a compound having a halogen atom directly bonded to the anthracene skeleton. Examples of 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 in the range of 0.05 to 5 mass%, more preferably 0.1 to 3 mass%, and particularly preferably 0.1 to 1.0 mass%, based on the total solid content of the photosensitive resin composition.

(C-2) The photopolymerization initiator may further contain compounds other than anthracene and anthracene derivatives. Examples of such compounds include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters, acridines (for example, 9-phenylacridine, bisacridinylheptane, 9-(p-methylphenyl)acridine, and 9-(m-methylphenyl)acridine are preferred in terms of sensitivity, resolution, and adhesion), hexaarylbiimidazole, pyrazoline compounds, coumarin compounds (for example, 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesion), N-arylamino acids or ester compounds thereof (for example, N-phenylglycine is preferred in terms of sensitivity, resolution, and adhesion), and halogen compounds (for example, tribromomethylphenyl sulfone). These can be used alone or in combination of two or more. Other examples include 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and triphenylphosphine oxide.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. 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 within the range of 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3% by 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, and 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', Examples of suitable imidazoles include 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. These may 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 the hexaarylbisimidazole compound in the photosensitive resin composition is preferably within the range of 0.05% by mass to 8% by mass, more preferably 0.1% by mass to 7% by mass, and even more preferably 1% by mass to 6% by mass, from the viewpoint of improving the peeling properties and/or sensitivity of the photosensitive resin layer.

From the viewpoint of the peeling characteristics, sensitivity, resolution, and adhesion of the photosensitive resin layer, it is preferable that the photosensitive resin composition contains one or more pyrazoline compounds as a photopolymerization initiator (C-2).

Examples of pyrazoline compounds 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-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxyphenyl)-pyrazoline, From the above viewpoints, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is preferred, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

<(D) Inhibitor>
In this embodiment, it is preferable that the photosensitive resin composition further contains an inhibitor (D) from the viewpoint that the shortest development time of the unexposed portion is not extended even if heating is performed after exposure. From the same viewpoint, the inhibitor (D) is preferably a radical polymerization inhibitor or a phenol derivative, and more preferably a phenol derivative. The inhibitor (D) may be originally contained in the raw material components used, or may be added during preparation of the photosensitive resin composition preparation. When the inhibitor is originally contained in the raw material components used, the inhibitor content can be quantified by GC-MS analysis or the like after the photosensitive resin laminate is produced.

Examples of radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine, etc. Nitrosophenylhydroxyamine aluminum salt is preferred so as not to impair the sensitivity of the photosensitive resin composition.

Examples of phenol derivatives include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,2'-methylenebis( 4-Methyl-6-tert-butylphenol), bis(2-hydroxy-3-t-butyl-5-ethylphenyl)methane, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl -4-hydroxybenzyl)-isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrenated phenol (e.g., Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.), tribenzylphenol (e.g., TBP, a phenol having 1 to 3 benzyl groups, manufactured by Kawaguchi Chemical Industry Co., Ltd.), biphenol, etc.

The ratio of the inhibitor (D) to the total solid mass of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass. This ratio is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more, from the viewpoint of preventing an extension of the shortest development time of the unexposed portion even when heating is performed after exposure. On the other hand, this ratio is preferably 10% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.3% by mass or less, from the viewpoint of less sensitivity reduction and improved resolution.

<(E) Benzotriazole Derivative>
It is preferable that the composition further contains a benzotriazole derivative (E) from the viewpoint that no discoloration is observed on the copper surface after the photosensitive resin composition layer is developed and removed even when the composition is heated after exposure to light. The benzotriazole derivative (E) preferably contains at least one compound selected from the group consisting of benzotriazoles and carboxybenzotriazoles.
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, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.
Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole.
Among these, carboxybenzotriazoles are particularly preferred.

The content of the (E) benzotriazole derivative is preferably 0.001% by mass to 3% by mass when the total solid mass of the photosensitive resin composition is taken as 100% by mass. A content of 0.001% by mass or more is preferable from the viewpoint that no discoloration is observed on the copper surface after the photosensitive resin composition layer is developed and removed even when heating is performed after exposure, and 0.02% by mass or more is more preferable, and 0.05% by mass or more is even more preferable. On the other hand, a content of 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye, and 2% by mass or less is more preferable, 1% by mass or less is even more preferable, 0.5% by mass or less is particularly preferable, and 0.3% by mass or less is most preferable.

The decolorization of the dye can be measured by the transmittance at a wavelength of 630 nm. A high transmittance at a wavelength of 630 nm indicates that the dye is decolorized. The transmittance at a wavelength of 630 nm of the laminate of the support film and the photosensitive resin composition layer is preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 72% or less, preferably 70% or less, preferably 68% or less, preferably 65% or less, preferably 62% or less, preferably 60% or less, preferably 58% or less, preferably 55% or less, preferably 52% or less, preferably 50% or less. This transmittance is the transmittance of the laminate of the support film and the photosensitive resin composition layer, and does not include the protective layer.

<Additives>
If desired, the photosensitive resin composition may contain additives such as dyes, plasticizers, antioxidants, stabilizers, etc. For example, the additives listed in JP 2013-156369 A may be used.
(Dyes and Coloring Materials)
In this embodiment, the photosensitive resin composition may further contain, if desired, at least one selected from the group consisting of dyes (for example, leuco dyes, fluoran dyes, etc.) and coloring substances.

Examples of coloring substances include fuchsine, phthalocyanine green, auramine base, paramagienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (e.g., Aizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue 20, and diamond green (e.g., Aizen (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 content mass of the photosensitive resin composition is taken as 100% by mass. It is preferable to set the content at 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 to set the content at 1% by mass or less from the viewpoint of maintaining the storage stability of the photosensitive resin composition.

The photosensitive resin composition contains a dye, which is preferable in terms of visibility since the exposed portion develops a color, and when an inspection machine or the like reads the alignment marker for exposure, it is advantageous in that the greater the contrast between the exposed portion and the unexposed portion, the easier it is to recognize. Preferred dyes from this viewpoint include leuco dyes and fluoran dyes.
Examples of the leuco dye include tris(4-dimethylaminophenyl)methane [leuco crystal violet] and bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green]. In particular, from the viewpoint of improving the 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 with respect to the total solid content mass of the photosensitive resin composition. It is preferable to set this content to 0.1% by mass or more from the viewpoint of improving the contrast between the exposed portion and the unexposed portion. It is more preferable to set this content to 0.2% by mass or more, and particularly preferable to set this content to 0.4% by mass or more. On the other hand, it is preferable to set this content to 10% by mass or less from the viewpoint of maintaining storage stability. It is more preferable to set this content to 5% by mass or less, and particularly preferable to set this content to 2% by mass or less.

In addition, it is preferable to use a leuco dye in combination with 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 preferably 0.01% by mass to 3% by mass when the total solid content mass of the photosensitive resin composition is taken as 100% by mass, from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer.

(Other additives)
In the present embodiment, the photosensitive resin composition may further contain an epoxy compound of bisphenol A. Examples of the epoxy compound of bisphenol A include a compound in which bisphenol A is modified with polypropylene glycol and the terminal is epoxidized.
In the present embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalates (e.g., diethyl phthalate, etc.), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether. Further examples include compounds having a bisphenol skeleton, such as ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, ADEKA NOL SDX-479 (all manufactured by Asahi Denka Co., Ltd.), NEWPOL BP-23P, NEWPOL BP-3P, NEWPOL BP-5P, NEWPOL BPE-20T, NEWPOL BPE-60, NEWPOL BPE-100, NEWPOL BPE-180 (all manufactured by Sanyo Chemical Industries, Ltd.), UNIOL DB-400, UNIOL DAB-800, UNIOL DA-350F, UNIOL DA-400, UNIOL DA-700 (all manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U glycol, and BA-P8 glycol (all manufactured by Nippon Nyukazai Co., Ltd.).

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 content mass of the photosensitive resin composition. A content of 1% by mass or more is preferable from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film. On the other hand, a content of 50% by mass or less is preferable from the viewpoint of suppressing insufficient curing and cold flow.
If the water content in the photosensitive resin composition is high, local plasticization of the photosensitive resin composition is rapidly promoted, and edge fuse occurs. In order to suppress edge fuse, the water content in the photosensitive resin composition is preferably 0.7% or less, based on the photosensitive resin composition after applying the photosensitive resin composition preparation liquid to a support film and drying. The water content in the photosensitive resin composition is preferably 0.65% or less, preferably 0.6% or less, preferably 0.55% or less, preferably 0.5% or less, preferably 0.45% or less, preferably 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less, and preferably 0.2% or less.

[solvent]
The photosensitive resin composition can be dissolved in a solvent to prepare a photosensitive resin composition liquid, which can be used in the production of a photosensitive resin laminate. Examples of the solvent include ketones and alcohols. Representative examples of the ketones include methyl ethyl ketone (MEK) and acetone. Representative examples of the alcohols include methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin composition in an amount such that the viscosity of the photosensitive resin composition liquid to be applied to the support layer at 25° C. is 500 mPa·s to 4,000 mPa·s when producing the photosensitive resin laminate.

[Photosensitive resin laminate]
The support film is preferably a transparent support film that transmits the 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, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can also be stretched as necessary.
The support film preferably has a haze of 5% or less from the viewpoint of suppressing light scattering during exposure, 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, the more advantageous it is for improving image forming properties and economic efficiency, but in order to maintain the strength of the photosensitive resin laminate, a film having a thickness of 10 μm to 30 μm is preferably used. The size of the fine particles of a lubricant or the like 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 resin layers formed from a plurality of compositions are laminated. In the case of a multilayer structure, an antistatic layer may be present. 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 can have a structure in which (1) the same fine particles as side A are contained, (2) a smaller amount of fine particles than side A are contained, (3) finer fine particles than side A are contained, or (4) no fine particles are contained. In the case of structures (2), (3), and (4), it is preferable to form a photosensitive resin layer on the side B side. In this case, it is preferable to have a resin layer containing fine particles on the side A side from the viewpoint of the slipperiness of the film. In this case, the size of the fine particles is preferably less than 1.5 μm from the viewpoint of the effect of the present invention.

An important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesion to the photosensitive resin layer is sufficiently smaller than that of the support layer, and that it can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Also, a film with excellent peelability as shown in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

Gels called fisheyes may be present on the surface of polyethylene film. When a polyethylene film with fisheyes is used as a protective layer, the fisheyes may be transferred to the photosensitive resin layer. If the fisheyes are transferred to the photosensitive resin layer, they may trap air during lamination, causing voids and leading to defects in the resist pattern. From the viewpoint of preventing fisheyes, oriented polypropylene is preferred 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, the higher the resolution, and the thicker the layer, the higher the film strength.

Next, a method for producing the photosensitive resin laminate will be described.
A known method can be used to prepare a photosensitive resin laminate by sequentially laminating a support layer, a photosensitive resin layer, and, if necessary, a protective layer. For example, the photosensitive resin composition used in the photosensitive resin layer is mixed with a solvent that dissolves it to prepare a homogeneous solution, which is then applied to the support layer using a bar coater or roll coater, and then dried to remove the solvent, thereby laminating a photosensitive resin layer made of the photosensitive resin composition on the support layer. Next, if necessary, a protective layer is laminated on the photosensitive resin layer to prepare a photosensitive resin laminate.

<Method of forming a resist pattern>
Next, an example of a method for producing a resist pattern using the photosensitive resin laminate of the present embodiment will be described. The method can include an exposure step of exposing a photosensitive resin composition to light, a heating step of heating the exposed photosensitive resin composition, and a development step of developing the photosensitive resin composition.
Examples of resist patterns include patterns of printed wiring boards, semiconductor elements, printing plates, liquid crystal display panels, touch panels, flexible substrates, lead frame substrates, substrates for COF (chip on film), substrates for semiconductor packages, transparent electrodes for liquid crystals, wiring for TFTs for liquid crystals, electrodes for PDPs (plasma display panels), etc. As an example, a method for producing a printed wiring board will be described below.

A printed wiring board is manufactured through the following steps.
(1) Lamination process First, in the lamination 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 laminated on the substrate surface by heating and pressing using a laminator. Examples of materials for the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc.
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. In addition, by performing the thermocompression bonding at the time of lamination two or more times, the adhesion of the obtained resist pattern to the substrate can be improved. During the 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 to bond the laminate.

(2) Exposure Step In this step, the photosensitive resin layer is exposed to light by an exposure method using an active light source in which a mask film having a desired wiring pattern is closely attached to the support layer, an exposure method by direct drawing of a drawing pattern which is the desired wiring pattern, or an exposure method by projecting an image of a photomask through a lens.

The exposure step is preferably performed by an exposure method using direct drawing of a drawing pattern or an exposure method using a photomask image projected through a lens, and more preferably by an exposure method using direct drawing of a drawing pattern. The advantages of the photosensitive resin composition according to this embodiment are more prominent in an exposure method using direct drawing of a drawing pattern or an exposure method using a photomask image projected through a lens, and are particularly prominent in an exposure method using direct drawing of a drawing pattern.

When the exposure step is an exposure method by direct writing, it is preferable that the laser light has a central wavelength of less than 390 nm or a central wavelength of 390 nm or more. It is more preferable that the laser light has a central wavelength of 350 nm or more and 380 nm or less, or a central wavelength of 400 nm or more and 410 nm or less. It is preferable to perform the exposure method using a first laser light with a central wavelength of less than 390 nm and a second laser light with a central wavelength of 390 nm or more. It is also more preferable that the first laser light has a central wavelength of 350 nm or more and 380 nm or less, and the second laser light has a central wavelength of 400 nm or more and 410 nm or less.

(3) Heating step In this step, the exposed photosensitive resin composition is preferably heated at about 30°C to about 200°C, more preferably in the range of 30°C to 150°C, and even more preferably in the range of 60°C to 120°C. By carrying out this heating step, it is possible to improve the resolution and adhesion. For heating, a hot air, infrared, or far infrared heating furnace, a thermostatic chamber, a hot plate, a hot air dryer, an infrared dryer, a hot roll, or the like can be used. If the heating method is a hot roll, it is preferable because it allows for short-time processing, and more preferably, the number of hot rolls is two or more.

In particular, in the present invention, by containing 15% by mass or more of structural units of styrene and/or styrene derivatives and by heating after exposure and then developing, the mobility of the resin is improved by heating even in systems with a high content of styrene skeletons, and it is possible to achieve a high degree of compatibility between the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bonds.

In addition, in the present invention, at least anthracene and/or anthracene derivatives are used as the (C-2) photopolymerization initiator ((C) photopolymerization initiator), and the resin is heated after exposure and then developed, so that the mobility of the resin is improved by heating, and for example, even in a system with a relatively high content of styrene skeletons, the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bonds can be highly compatible.

As a result, adhesion can be significantly improved. Furthermore, the significantly improved adhesion makes it possible to obtain good adhesion even when a long time has elapsed since exposure. From the viewpoint of the effects of the present invention, it is preferable to carry out the heating step within 15 minutes of exposure, more preferably within 10 minutes, and even more preferably within 5 minutes.

(4) Development Step In this step, after exposure, the support layer on the photosensitive resin layer is peeled off, and then the unexposed areas are developed and removed using an alkaline aqueous developer, thereby forming a resist pattern on the substrate.
The alkaline aqueous solution used is an aqueous solution of Na ₂ CO ₃ or K ₂ CO _3. The alkaline aqueous solution is appropriately selected according to 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 at a temperature of about 20° C. to about 40° C. is preferred.
A resist pattern can be obtained through the above steps (1) to (4).

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 or Plating Step 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) Stripping Step Thereafter, the resist pattern is stripped from the substrate using an appropriate stripping solution.
The stripping solution used here may be, for example, an alkaline aqueous solution, an amine-based stripping solution, etc. However, the resist pattern formed from the photosensitive resin composition of the present invention through post-exposure heating exhibits good stripping properties with respect to the amine-based stripping solution, and has the characteristic that the stripped pieces are not excessively miniaturized. Therefore, it is preferable to use an amine-based stripping solution as the stripping solution, since the advantageous effects of the present invention can be maximized.

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

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

The amine-based stripping agent used in the present invention may be an aqueous solution containing one or more of the amines listed above. The concentration of the amine in the aqueous solution may be appropriately set depending on the purpose, the composition of the photosensitive resin layer, the development conditions, etc.
The amine-based stripping agent used in the present invention 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 carried out at a temperature of, for example, 0° C. to 100° C., preferably room temperature (23° C.) to 50° C., for example, 1 second to 1 hour, preferably 10 seconds to 10 minutes.

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

The photosensitive resin laminate of the present embodiment is a photosensitive resin laminate suitable for producing conductor patterns such as printed wiring boards, flexible substrates, lead frame substrates, touch panel substrates, COF substrates, semiconductor package substrates, transparent electrodes for liquid crystal, wiring for TFTs for liquid crystal, and electrodes for PDPs.
Unless otherwise specified, the various parameters described above are measured according to the measurement methods in the Examples described below or methods that will be understood by those skilled in the art to be equivalent thereto.

Next, the present embodiment will be described in more detail with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples as long as it does not deviate from the gist of the present embodiment. The physical properties in the examples were measured by the following methods.
The measurement of the physical properties of the polymer and the preparation of evaluation samples for the examples and comparative examples are described below. The evaluation methods and results of the obtained samples are also shown.

<<First embodiment>>
In the first example, (A) a photosensitive resin composition in which the structural units of styrene and/or a styrene derivative in the entire alkali-soluble polymer accounted for 15 mass % or more was evaluated.

(1) Measurement of physical properties <Measurement of weight average molecular weight or number average molecular weight of polymer>
The weight average molecular weight or number average molecular weight of the polymer was determined in terms of polystyrene by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: four Shodex (registered trademark) columns (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K. in series, mobile phase solvent: tetrahydrofuran, using a calibration curve based on a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.)).
Furthermore, the dispersity 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).

(2) Method for Preparing Evaluation Samples Evaluation samples were prepared as follows.
<Preparation of Photosensitive Resin Laminate>
The components shown in Table 1-1 (Table 2-1, Table 3-1) below (wherein the number of each component indicates the amount (parts by mass) of solid content) and the solvent were thoroughly stirred and mixed to obtain a photosensitive resin composition preparation. The names of the components represented by abbreviations in Table 1-1 (Table 2-1, Table 3-1) are shown in Table 1-2 (Table 2-2, Table 3-2) below. A 16 μm thick polyethylene terephthalate film (Toray Industries, Inc., FB-40) was used as a support film, and the preparation was uniformly applied to the surface of the film using a bar coater, followed by drying in a dryer at 95° C. for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 25 μm.
Next, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) was laminated as a protective layer on the surface of the photosensitive resin composition layer on the side on which the polyethylene terephthalate film was not laminated, to obtain a photosensitive resin laminate.

<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 jet scrubbed and polished with an abrasive (Ujiden Chemical Industry Co., Ltd., #400) at a spray pressure of 0.2 MPa, and then the substrate surface was washed with a 10 mass % H ₂ SO ₄ aqueous solution.
<Lamination>
While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was laminated onto a copper-clad laminate preheated to 50° C. using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) at a roll temperature of 105° C. The air pressure was 0.35 MPa and the lamination speed was 1.5 m/min.

<Exposure>
The evaluation substrate 2 hours after lamination was exposed using a Stouffer 41-step step tablet by a direct imaging exposure machine IP-8 8000H. The exposure was performed at an exposure dose that resulted in a maximum remaining film step number of 15 steps when exposed and developed using the Stouffer 41-step step tablet as a mask.

The evaluation substrate was heated 7 minutes after exposure using 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 0.5 m/min. Note that heating is usually performed about 1 minute after exposure, since the effect of heating decreases if the time after exposure is extended. Therefore, the heating conditions 7 minutes after exposure in this example are very strict.

<Developing>
After peeling off the polyethylene terephthalate film (support layer), development was performed by spraying a 1% by mass _{Na2CO3 aqueous} solution at 30°C for a predetermined time using an alkaline developer (manufactured by Fuji Kiko, a dry film developer). The development spray time was twice the shortest development time, and the water washing spray time after development was four times the shortest development time. In this case, the shortest development time was determined to be the time required for the photosensitive resin layer in the unexposed area to completely dissolve.

<Adhesion evaluation>
The minimum line width at which a mask pattern L/S=X μm/200 μm was normally formed was measured using an optical microscope. This measurement was performed for eight lines, and the average value of the eight line widths was calculated as the value of adhesion.

<Discoloration of copper surface>
The same steps as above were carried out up to the development, and in the unexposed area where the photosensitive resin composition layer was laminated, the copper surface after the photosensitive resin composition layer was developed and removed was visually observed.
〇: No discoloration △: Slight discoloration

<Delay in minimum development time>
The shortest development time was measured under the following two conditions.
(A) Shortest Normal Development Time A photosensitive resin laminate was laminated on a substrate, and the support film was peeled off, after which the shortest time required for the photosensitive resin layer in the unexposed area to completely dissolve was measured.
(B) Shortest Development Time After Heating After laminating the photosensitive resin laminate on the substrate, the laminate was heated by a hot roll laminator (AL-700, manufactured by Asahi Kasei Corp.). The roll temperature was 105° C., the air pressure was 0.30 MPa, and the lamination speed was 0.1 m/min.
○: (B) and (A) have the same shortest development time (no delay)
△: The shortest development time of (B) is 1 to 3 seconds longer than the shortest development time of (A) (there is a delay)

The above evaluation results are shown in Table 1-1 along with the components of the photosensitive resin compositions of the examples and comparative examples. The names of the components represented by abbreviations in Table 1-1 are also shown in Table 1-2.

The results in Tables 1-1 and 1-2 confirm that the examples falling within the scope of the constituent elements of the present invention have better image quality evaluation results than the comparative examples that are outside the scope of the present invention.

The results in Tables 1-1 and 1-2 confirm that the examples falling within the scope of the constituent elements of the present invention have better image quality evaluation results than the comparative examples that are outside the scope of the present invention.

The post-exposure heating conditions in this example are very strict conditions since heating is performed 7 minutes after exposure. For example, the adhesion was 12.0 μm when the compositions of Example 1 and Comparative Example 1 were developed without heating after exposure. In other words, no effect was observed when heating 7 minutes after exposure was observed in the composition of Comparative Example 1, but adhesion can be improved in Example 1 even under very strict conditions. In addition, under conditions of heating 1 minute after exposure, adhesion of 10.0 μm was obtained for both the compositions of Example 1 and Comparative Example 1.

The above results show that even if adhesion is good under typical post-exposure heating conditions, it does not necessarily mean that adhesion will be good under the harsh conditions of heating 7 minutes after exposure in this example. However, the photosensitive resin composition of the present invention, which has a specific composition, was the first to be able to improve adhesion even under these harsh post-exposure heating conditions. This makes it possible to obtain good adhesion even if a long time has passed since exposure when manufacturing circuit boards, making it possible to stably form high-definition circuit patterns.

<<Second embodiment>>
In the second example, a photosensitive resin composition in which the compound having an ethylenically unsaturated double bond (B) contains a (meth)acrylate compound having three or more ethylenically unsaturated double bonds was evaluated.
Evaluation samples were prepared using the components shown in Table 2-1 below in the same manner as in the first example described above.
<Exposure>
The evaluation substrate 2 hours after lamination was exposed to light using a direct imaging exposure machine (Nuvogo1000, manufactured by Orbotech, Inc., light source: 375 nm (30%) + 405 nm (70%)) with a Stouffer 41-step tablet. The exposure was performed with an exposure amount that resulted in a maximum remaining film step number of 19 steps when exposed and developed using the Stouffer 41-step tablet as a mask.

<Heating>
The evaluation substrate 7 minutes after exposure was heated using 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, since the heating effect is lost if the time after exposure is extended, heating is usually performed about 1 minute after exposure. Therefore, the heating condition 7 minutes after exposure in this example is very strict.

<Developing>
After peeling off the polyethylene terephthalate film (support layer), development was performed by spraying a 1% by mass _{Na2CO3 aqueous} solution at 30°C for a predetermined time using an alkaline developer (manufactured by Fuji Kiko, a dry film developer). The development spray time was twice the shortest development time, and the water washing spray time after development was three times the shortest development time. In this case, the shortest development time was the time required for the photosensitive resin layer in the unexposed area to completely dissolve.

Except for carrying out the steps from exposure to development as described above, evaluation was carried out in the same manner as in the first example.
The above evaluation results are shown in Table 2-1 together with the components of the photosensitive resin compositions of the Examples and Comparative Examples. The names of the components shown by abbreviations in Table 2-1 are shown in Table 2-2.

The results in Tables 2-1 and 2-2 confirm that the examples falling within the scope of the constituent elements of the present invention have better image quality evaluation results than the comparative examples that are outside the scope of the present invention.

The post-exposure heating conditions in this example are very strict conditions since heating is performed 7 minutes after exposure. For example, the adhesion was 11.8 μm when the compositions of Example 1 and Comparative Example 1 were developed without heating after exposure. In other words, no effect was observed when heating 7 minutes after exposure was observed in the composition of Comparative Example 1, but adhesion can be improved in Example 1 even under very strict conditions. In addition, under conditions of heating 1 minute after exposure, adhesion of 9.6 μm was obtained for both the compositions of Example 1 and Comparative Example 1.

The above results show that even if adhesion is good under typical post-exposure heating conditions, it does not necessarily mean that adhesion will be good under the harsh conditions of heating 7 minutes after exposure in this example. However, the present invention is the first to be able to improve adhesion even under these harsh post-exposure heating conditions. This makes it possible to obtain good adhesion even if a long time has passed since exposure when manufacturing circuit boards, making it possible to stably form high-definition circuit patterns.

<<Third Example>>
In the third example, (C-2) a photosensitive resin composition in which the photopolymerization initiator contains anthracene and/or anthracene derivative was evaluated.
Evaluation samples were prepared using the components shown in Table 3-1 below in the same manner as in the first example described above.
<Exposure>
The evaluation substrate 2 hours after lamination was exposed to light using a direct imaging exposure machine (Nuvogo1000, manufactured by Orbotech Corp., light source: 375 nm (30%) + 405 nm (70%)) with a Stouffer 41-step tablet. The exposure was performed with an exposure amount that resulted in a maximum remaining film step number of 21 steps when exposed and developed using the Stouffer 41-step tablet as a mask.

<Heating>
The evaluation substrate 7 minutes after exposure was heated using 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, since the heating effect is lost if the time after exposure is extended, heating is usually performed about 1 minute after exposure. Therefore, the heating condition 7 minutes after exposure in this example is very strict.

<Developing>
After peeling off the polyethylene terephthalate film (support layer), development was performed by spraying a 1% by mass _{Na2CO3 aqueous} solution at 30°C for a predetermined time using an alkaline developer (manufactured by Fuji Kiko, a dry film developer). The development spray time was twice the shortest development time, and the water washing spray time after development was three times the shortest development time. In this case, the shortest development time was the time required for the photosensitive resin layer in the unexposed area to completely dissolve.

Except for carrying out the steps from exposure to development as described above, evaluation was carried out in the same manner as in the first example.
The above evaluation results are shown in Table 3-1 together with the components of the photosensitive resin compositions of the Examples and Comparative Examples. The names of the components shown by abbreviations in Table 3-1 are shown in Table 3-2.

From the results of Tables 3-1 and 3-2, it was confirmed that the image quality evaluation results were superior in the examples that fell within the scope of the present invention's constituent elements compared to the comparative examples that fell outside the scope of the present invention. The post-exposure heating conditions in this example were very severe conditions, since heating was performed 7 minutes after exposure. For example, the adhesion was 12.8 μm when the compositions of Example 7 and Comparative Example 1 were developed without post-exposure heating. In other words, no effect was observed when heating was performed 7 minutes after exposure in the composition of Comparative Example 1, but the adhesion of Example 7 could be improved even under very severe conditions. Furthermore, under conditions of heating 1 minute after exposure, an adhesion of 9.6 μm was obtained for both the compositions of Example 7 and Comparative Example 1.

The above results show that even if adhesion is good under typical post-exposure heating conditions, it does not necessarily mean that adhesion will be good under the harsh conditions of heating 7 minutes after exposure, and that the present invention is the first to be able to improve adhesion even under these harsh post-exposure heating conditions. In other words, when manufacturing circuit boards, the composition of the present invention can provide good adhesion even if a long time has passed since exposure, making it possible to stably form high-definition circuit patterns.

The above describes an embodiment of the present invention, but the present invention is not limited to this and can be modified as appropriate without departing from the spirit of the invention.

By using the photosensitive resin composition of the present invention, it is possible to significantly improve adhesion when the composition is exposed to light, heated, and then developed. In particular, good adhesion is achieved even when a long time has passed since exposure, and the composition can be widely used as a photosensitive resin composition.

Claims (23)

A photosensitive resin composition for obtaining a resin cured product by exposure, heating and development, the photosensitive resin composition comprising the following components based on the total solid content mass of the photosensitive resin composition:
(A) alkali-soluble polymer: 10% by mass to 90% by mass;
(B) a compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) a photopolymerization initiator: 0.01% by mass to 20% by mass;
Including,
the (A) alkali-soluble polymer includes a copolymer containing (meth)acrylic acid and a monomer having an aromatic hydrocarbon group,
the monomer having an aromatic hydrocarbon group includes styrene and/or a styrene derivative,
The content of styrene and/or styrene derivative in the entire alkali-soluble polymer (A) is 40 mass% or more,
The compound (B) having an ethylenically unsaturated double bond is a (meth)acrylate compound having four or more ethylenically unsaturated double bonds , and is represented by the following general formula (III):
{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's is 1 or more} ,
The photosensitive resin composition, wherein the (C) photopolymerization initiator contains anthracene and/or anthracene derivative. The photosensitive resin composition according to claim 1, wherein the anthracene derivative has an alkoxy group having 1 to 40 carbon atoms, which may have a substituent, and/or an aryl group having 6 to 40 carbon atoms, which may have a substituent, at the 9th and/or 10th positions. The photosensitive resin composition according to claim 1 or 2, wherein the anthracene derivative has an alkoxy group having 1 to 40 carbon atoms, which may have a substituent, and/or an aryl group having 6 to 40 carbon atoms, which may have a substituent, at the 9th and 10th positions. The photosensitive resin composition according to claim 3, wherein the photopolymerization initiator (C) contains 9,10-diphenylanthracene. The photosensitive resin composition according to claim 3, wherein the photopolymerization initiator (C) includes 9,10-dialkoxyanthracene. The photosensitive resin composition according to any one of claims 1 to 5, wherein the (C) photopolymerization initiator includes an anthracene derivative having a halogen atom. The photosensitive resin composition according to claim 6, wherein the photopolymerization initiator (C) contains a halogen-substituted 9,10-dialkoxyanthracene. The photosensitive resin composition according to claim 7, wherein the photopolymerization initiator (C) includes a compound in which the alkoxy groups at the 9th and/or 10th positions of 9,10-dialkoxyanthracene are modified with one or more halogen atoms. The photosensitive resin composition according to any one of claims 1 to 8, wherein the (C) photopolymerization initiator includes a compound having a halogen atom directly bonded to the anthracene skeleton. The photosensitive resin composition according to any one of claims 1 to 9, wherein the constituent units of styrene and/or styrene derivatives in the alkali-soluble polymer (A) are 90 mass% or less. The photosensitive resin composition according to any one of claims 1 to 10, wherein the (A) alkali-soluble polymer further contains benzyl (meth)acrylate as a monomer component. A method for forming a resist pattern comprising a step of exposing the photosensitive resin composition according to any one of claims 1 to 11, a heating step of heating the exposed photosensitive resin composition, and a developing step of developing the heated photosensitive resin composition. The method for forming a resist pattern according to claim 12, wherein the heating temperature in the heating step is in the range of 30°C to 150°C. The method for forming a resist pattern according to claim 12 or 13, wherein the exposure step is performed by an exposure method using direct drawing of a drawing pattern or an exposure method using a photomask image projected through a lens. The method for forming a resist pattern according to claim 12 or 13, wherein the exposure step is performed by an exposure method involving direct drawing of a drawing pattern. The method for forming a resist pattern according to any one of claims 12 to 15, wherein the heating step is carried out within 15 minutes of exposure. The method for forming a resist pattern according to any one of claims 12 to 16, wherein the exposure step is performed by exposing to a first laser beam having a central wavelength of less than 390 nm and a second laser beam having a central wavelength of 390 nm or more. The method for forming a resist pattern according to claim 17, wherein the central wavelength of the first laser light is 350 nm or more and 380 nm or less, and the central wavelength of the second laser light is 400 nm or more and 410 nm or less. The method for forming a resist pattern according to any one of claims 12 to 18, wherein the layer of the photosensitive resin composition is not placed in a reduced pressure atmosphere or a low oxygen concentration atmosphere between the exposure and the heating. The method for forming a resist pattern according to any one of claims 12 to 19, wherein the resist pattern is a resist pattern for manufacturing a circuit board. A method for manufacturing a circuit board, comprising the steps of: etching or plating a substrate having a resist pattern manufactured by the method according to any one of claims 12 to 20 to form a circuit board. The photosensitive resin composition according to any one of claims 1 to 11, which is a photosensitive resin composition for obtaining a resin cured product by exposure to a first laser beam having a central wavelength of less than 390 nm and a second laser beam having a central wavelength of 390 nm or more. The photosensitive resin composition according to claim 22, wherein the central wavelength of the first laser light is 350 nm or more and 380 nm or less, and the central wavelength of the second laser light is 400 nm or more and 410 nm or less.