Photosensitive resin composition and resist pattern formation method

Abstract

To provide a photosensitive resin composition which is suitable for heating after exposure and achieves higher resolution.SOLUTION: A photosensitive resin composition for obtaining a resin cured product by exposing, heating and developing contains, on a mass basis of the total solid content of the photosensitive resin composition, the following components: (A) 10-90 mass% of an alkali-soluble polymer; (B) 5-70 mass% of a compound having an ethylenically unsaturated double bond; and (C) 0.01-20 mass% of a photopolymerization initiator, wherein a structural unit of styrene and / or a styrene derivative in the whole of (A) the alkali-soluble polymer is 15 mass% or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a method for forming a resist pattern, and the like. [Background technology]

[0002] Printed wiring boards and the like are used in electronic devices such as personal computers and mobile phones to mount components, semiconductors, and the like. Conventionally, resists for manufacturing printed wiring boards and the like have been used in the form of photosensitive resin laminates, so-called dry film photoresists (hereinafter sometimes referred to as DF), which are formed by laminating a photosensitive resin layer on a support film and further laminating a protective film on the photosensitive resin layer as necessary. At present, the photosensitive resin layer is generally of the alkaline development type, which uses a weak alkaline aqueous solution as the developer.

[0003] To produce a printed wiring board or the like using a 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 substrate, 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 portion (for example, the unexposed portion 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.

[0004] After forming the resist pattern, the process of forming the circuit can be roughly divided into two methods. The first method is to etch away the board surface not covered by the resist pattern (for example, 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). The second method is a method (plating method) in which the above-mentioned substrate surface is plated with copper, solder, nickel, tin, etc., and then the resist pattern portion is removed in the same manner as the first method, and the exposed substrate surface (e.g., the copper surface of a copper-clad laminate) is etched. Cupric chloride, ferric chloride, cuprammonium complex solution, etc. are used for etching.

[0005] In recent years, with the miniaturization and weight reduction of electronic devices, printed wiring boards have become finer and denser, and there is a demand for high-performance DF that provides high resolution and high adhesion in the above-mentioned manufacturing process. As a material that realizes such high resolution, Patent Document 1 describes a photosensitive resin composition that has enhanced resolution by using a specific thermoplastic resin, monomer, and photopolymerization initiator. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2010-249884 A Summary of the Invention [Problem to be solved by the invention]

[0007] After the exposure step, the photosensitive resin layer may be subjected to a heating step and then developed. By carrying out this heating step, it is possible to further improve high resolution and high adhesion. However, even if the post-exposure heating step is added, there is a problem that the improvement in adhesion is insufficient in the conventional photosensitive resin composition, or good adhesion cannot be obtained when the time elapsed after exposure is long.

[0008] 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. [Means for solving the problem]

[0009] 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) photopolymerization initiator: 0.01% by mass to 20% by mass; Including, A photosensitive resin composition, characterized in that the (A) alkali-soluble polymer as a whole contains structural units of styrene and / or a styrene derivative of 15 mass % or more. [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) photopolymerization initiator: 0.01% by mass to 20% by mass; Including, A 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. [twenty one] The photosensitive resin composition according to

[20] , wherein the (C) photopolymerization initiator contains 9,10-diphenylanthracene. [twenty two] The photosensitive resin composition according to

[20] , wherein the (C) photopolymerization initiator contains 9,10-dialkoxyanthracene. [twenty three] 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. [twenty four] The photosensitive resin composition according to

[23] , wherein the (C) photopolymerization initiator contains a halogen-substituted 9,10-dialkoxyanthracene. [twenty five] The photosensitive resin composition according to

[24] , wherein the (C) photopolymerization initiator comprises 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 contains 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 [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 involving direct drawing of a drawing 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 exposing 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] above, 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. Effect of the Invention

[0010] According to the present invention, it is possible to provide a photosensitive resin composition that can remarkably improve adhesion when exposed to light, heated, and then developed, and that can achieve good adhesion even when a long time has elapsed since exposure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, exemplary embodiments for carrying out the present invention (hereinafter, abbreviated as "embodiments") will be described in detail. 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, 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, unless otherwise specified.

[0012] [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 development, and contains, based on the total solids mass of the photosensitive resin composition, the following components: (A) alkali-soluble polymer: 10% by mass to 90% by mass; (B) compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) photopolymerization initiator: 0.01% by mass to 20% by mass. In particular, the photosensitive resin composition of this embodiment is characterized in that when the (A) alkali-soluble polymer is composed of multiple types of alkali-soluble polymers, the content of structural units of styrene and / or styrene derivatives in the entire (A) alkali-soluble polymer is 15 mass% or more.

[0013] A dry film resist obtained from a photosensitive resin composition usually cannot improve adhesion unless it is heated immediately after exposure, but a dry film resist obtained from the photosensitive resin composition of the present invention can exhibit good adhesion (i.e., a thin resist) even when the time elapsed after exposure is long. The photosensitive resin composition of the present invention has a composition suitable for this characteristic.

[0014] 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.

[0015] <(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: gram) 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 in which a potentiometric titrator is used to titrate with a 0.1 mol / L NaOH aqueous solution.

[0016] The weight average molecular weight of the (A) alkali-soluble polymer is preferably 5,000 to 500,000. The weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, the weight average molecular weight of 5,000 or more is preferable from the viewpoint of controlling the properties of the development aggregates and the properties of the unexposed film such as edge fuse property and cut chip property when the photosensitive resin laminate is formed. The weight average molecular weight is more preferably 10,000 or more, and even more preferably 20,000 or more. The edge fuse property refers to the degree of easiness of the photosensitive resin layer (i.e., the layer made of the photosensitive resin composition) to protrude from the end face of the roll when the photosensitive resin laminate is wound into a roll. The cut chip property refers to the degree of ease with which chips fly off when an unexposed film is cut with a cutter. If these chips adhere to the upper surface of the photosensitive resin laminate, they will be transferred to a mask in a subsequent exposure step, causing defective products. The dispersity of (A) 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.

[0017] In this embodiment, the photosensitive resin composition can remarkably improve adhesion when it is developed after heating after exposure, 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 the (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 a plurality of 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.

[0018] Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative. Among them, a monomer having an aralkyl group or styrene is preferable.

[0019] 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.

[0020] 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 type of first monomer described below and / or at least one type of second monomer described below. 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.

[0021] 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 preferred. 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".

[0022] 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 foot shape of the resist pattern, and furthermore from the viewpoint of chemical resistance of the resist pattern, and from these viewpoints, a copolymerization ratio of 35% by mass or less is more preferable, a copolymerization ratio of 32% by mass or less is even more preferable, and a copolymerization ratio of 30% by mass or less is particularly preferable.

[0023] 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 them, 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 elapsed 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.

[0024] The (A) alkali-soluble polymer may be used alone or in a mixture of two or more. When using in 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 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 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 the (A) alkali-soluble polymer.

[0025] 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 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 obtain good adhesion even when the time elapsed 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.

[0026] In particular, in this embodiment, when the (A) alkali-soluble polymer is composed of a plurality of types of alkali-soluble polymers, the structural unit of styrene and / or styrene derivative in the entire (A) alkali-soluble polymer is 15% by mass or more. This can significantly improve the adhesion when heated and developed after exposure, and can provide good adhesion even when a long time has passed since exposure. Since the styrene skeleton is hydrophobic, it can suppress swelling in the developer, and can provide good adhesion. The structural unit of styrene and / or styrene derivative in the (A) alkali-soluble polymer is 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.

[0027] However, if the content of the styrene skeleton 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. The upper limit of the structural units of styrene and / or styrene derivatives in (A) 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.

[0028] Thus, in the present invention, the content of styrene and / or styrene derivative structural units in the entire alkali-soluble polymer (A) is 15% by mass or more, and by heating after exposure and then developing, the mobility of the resin is improved by heating even in a system with a high content of styrene skeleton, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly compatible, which is believed to result in a significant improvement in adhesion. It is also believed that the significant improvement in adhesion allows good adhesion to be obtained even when the time elapsed after exposure is long.

[0029] In addition, from the viewpoint of significantly improving the adhesion when developed after heating after exposure, and particularly exhibiting good adhesion even when the time elapsed after exposure is long, 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 preferably contains 35% by mass or less, more preferably 32% by mass or less, and even more preferably 30% by mass or less.

[0030] (A) The synthesis of the alkali-soluble polymer is preferably carried out by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting 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 part of the mixture into the reaction solution. In some cases, after the reaction is completed, further solvent is added to adjust the concentration to the desired level. As a synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

[0031] (A) Weight average value of glass transition temperature Tg of alkali-soluble polymers total is preferably 30°C or higher and 150°C or lower. total In the photosensitive resin composition, Tg total By using the alkali-soluble polymer (A) having the above Tg, it is possible to significantly improve the adhesion when the film is exposed to light and then heated and developed. In particular, good adhesion can be achieved even when a long time has elapsed since exposure. total 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. total From the viewpoint of improving edge fuse resistance, it is preferable to use the alkali-soluble polymer (A) having the Tg total It is more preferable that the temperature is 40° C. or higher, further preferably 50° C. or higher, and particularly preferably 60° C. or higher.

[0032] The proportion of the alkali-soluble polymer (A) relative 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 proportion of the alkali-soluble polymer (A) relative 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 proportion of the alkali-soluble polymer (A) relative to the photosensitive resin composition to 10% by mass or more from the viewpoint of improving edge fuse resistance.

[0033] <(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.

[0034] The compound having an ethylenically unsaturated bond (B) is a compound having polymerizability due to the presence of 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 a 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.

[0035] Examples of the compound (B) 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-etherified or allyl-etherified, and a phthalic acid-based compound, which are preferred from the viewpoints of releasability and flexibility of the cured film.

[0036] 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.

[0037] 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.

[0038] Examples of such compounds include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, polyethylene glycol (meth)acrylates such as compounds having (meth)acryloyl groups at both ends of a 12-mol ethylene oxide chain, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, and the like. Examples of polyalkylene oxide di(meth)acrylate compounds containing an ethylene oxide group and a propylene oxide group in the compound include dimethacrylates of glycols in which an average of 3 moles of ethylene oxide are added to both ends of polypropylene glycols to which an average of 12 moles of propylene oxide are added, dimethacrylates of glycols in which an average of 15 moles of ethylene oxide are added to both ends of polypropylene glycols to which an average of 18 moles of propylene oxide are added, FA-023M, FA-024M, FA-027M (product names, manufactured by Hitachi Chemical Co., Ltd.), etc. These are preferred in terms of flexibility, resolution, adhesion, etc.

[0039] 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): [ka] In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group; A is C 2 H 4 and B is C 3 H 6where n1 and n3 are each independently an integer of 1 to 39, and n1+n3 is an integer of 2 to 40, n2 and n4 are each independently an integer of 0 to 29, and n2+n4 is an integer of 0 to 30, and the arrangement of the repeating units of -(AO)- and -(BO)- may be random or block. In the case of block, either -(AO)- or -(BO)- may be on the bisphenyl group side. A compound represented by the formula { 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.

[0040] Examples of the heteroatom include a halogen atom, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group in which the alkyl group has 1 to 10 carbon atoms, an acyl group in which the alkyl group has 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, or a group containing a heterocycle, or an aryl group substituted with these substituents. These substituents may form a condensed ring, or a hydrogen atom in these substituents may be replaced by a heteroatom such as a halogen atom. When the aromatic ring in the general formula (I) has multiple substituents, the multiple substituents may be the same or different.

[0041] The 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 can be obtained by adding an alkyleneoxy group such as an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group to the central skeleton to obtain an alcohol, which can be made into a (meth)acrylate. In this case, examples of the compound that can become the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and an isocyanurate ring. Examples of these compounds include tri(meth)acrylates, such as ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate (e.g., 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), which are soft. Examples of suitable acrylates include tetra(meth)acrylates, such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and the like; penta(meth)acrylates, such as dipentaerythritol penta(meth)acrylate, and the like; and hexa(meth)acrylates, such as dipentaerythritol hexa(meth)acrylate. Compounds having three or more (meth)acryloyl groups can significantly improve adhesion when developed after heating after 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 more preferred.

[0042] 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 a total of 1 to 40 moles of ethylene oxide added to six terminals of dipentaerythritol, or a hexa(meth)acrylate having a total of 1 to 20 moles of ε-caprolactone added to six terminals of dipentaerythritol is preferred.

[0043] The (B) compound 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 the adhesion when the compound is heated after exposure and then developed, and can obtain 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, more preferably to contain a (meth)acrylate compound having five or more ethylenically unsaturated double bonds, and particularly preferably to contain a (meth)acrylate compound having six or more ethylenically unsaturated double bonds. From the same viewpoint, these are preferably methacrylate compounds.

[0044] Compounds having 3 or more, 4 or more, 5 or more, or 6 or more ethylenically unsaturated double bonds are considered to have the effect of increasing the crosslink density during polymerization by exposure, but due to the influence of steric hindrance caused by the large number of functional groups, the desired crosslink density is often not obtained.In the present invention, it has been found that by carrying out heat treatment after exposure to improve the mobility in the system, preferably a compound having 3 or more ethylenically unsaturated double bonds, more preferably a compound having 4 or more ethylenically unsaturated double bonds, and particularly preferably a compound having 5 or more ethylenically unsaturated double bonds, and particularly preferably a compound having 6 or more ethylenically unsaturated double bonds, it is possible to reduce the influence of steric hindrance and obtain high adhesion even if the number of functional groups is large, by improving the mobility in the system by carrying out heat treatment after exposure.

[0045] 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. 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 exhibiting the effect of heat treatment after exposure.

[0046] (b1) As the (meth)acrylate compound having three or more ethylenically unsaturated bonds, 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 in terms 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, such as 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.

[0047] (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.

[0048] The tetra(meth)acrylate is preferably pentaerythritol tetra(meth)acrylate. The pentaerythritol tetra(meth)acrylate is preferably a tetra(meth)acrylate having 1 to 40 moles of alkylene oxide added to the four terminals of pentaerythritol.

[0049] The tetra(meth)acrylate is represented by the following general formula (II): [ka] {where, R 3 ~R 6 each independently represents 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 are each independently an integer of 0 to 40, 1 +m 2 +m 3 +m 4 is 1 to 40, and m 1 +m 2 +m 3 +m 4 In the case where X is 2 or more, the multiple Xs may be the same or different from each other.

[0050] Without wishing to be bound by theory, the tetramethacrylate compound represented by the general formula (II) is 3 ~R 6 By having 2It is considered that the hydrolysis in an alkaline solution is suppressed compared with tetraacrylates having a C=CH-CO-O- portion. The use of a photosensitive resin composition containing a tetramethacrylate compound represented by general formula (II) can significantly improve the adhesion when the composition is exposed to light and then heated and developed, and is particularly preferable from the viewpoint of realizing good adhesion even when a long time has elapsed since exposure.

[0051] In the general formula (II), the group R 3 ~R 6 At least one of the groups R 3 ~R 6 It is more preferable that all of are methyl groups.

[0052] From the viewpoint of obtaining the desired resolution, foot shape and remaining film ratio of the resist pattern, in general formula (II), X is -CH 2 -CH 2 - is preferred.

[0053] From the viewpoint of obtaining the desired resolution, foot shape and remaining film ratio of the resist pattern, it is preferable that m 1 , m 2 , m 3 and m 4 are each independently preferably an integer of 1 to 20, more preferably an integer of 2 to 10. Furthermore, in the general formula (II), m 1 +m 2 +m 3 +m 4 is preferably 1-36 or 4-36.

[0054] Examples of the compound represented by the general formula (II) include pentaerythritol (poly)alkoxy tetramethacrylate. In the present disclosure, the term "pentaerythritol (poly)alkoxy tetramethacrylate" refers to the compound represented by the general formula (II) above, m 1 +m 2 +m 3 +m 4"Pentaerythritol alkoxytetramethacrylate" where m = 1 and 1 +m 2 +m 3 +m 4 = 2 to 40. Examples of the compound represented by general formula (II) include the compounds listed in JP-A-2013-156369, such as pentaerythritol (poly)alkoxytetramethacrylate.

[0055] As the hexa(meth)acrylate compound, a hexa(meth)acrylate having a total of 1 to 24 moles of ethylene oxide added to six terminals of dipentaerythritol, or a hexa(meth)acrylate having a total of 1 to 10 moles of ε-caprolactone added to six terminals of dipentaerythritol is preferred.

[0056] From the viewpoint of significantly improving the adhesion when the composition is developed after heating following exposure, and particularly realizing good adhesion even after a long time has elapsed since exposure, the photosensitive resin composition according to this embodiment particularly preferably 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.

[0057] In this embodiment, the photosensitive resin composition can remarkably improve the adhesion when the composition is heated and developed after exposure, and from the viewpoint of realizing good adhesion even when the time elapsed after exposure is long, the photosensitive resin composition preferably contains a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton as a compound having an ethylenically unsaturated bond (B). Examples of the alkylene oxide chain include an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentylene oxide chain, and a hexylene oxide chain. When the photosensitive resin composition contains a plurality of alkylene oxide chains, they may be the same or different from each other. From the above viewpoint, the alkylene oxide chain is more preferably an ethylene oxide chain, a propylene oxide chain, and a butylene oxide chain, more preferably an ethylene oxide chain and a propylene oxide chain, and particularly preferably an ethylene oxide chain.

[0058] In the photosensitive resin composition, by using in combination the (A) alkali-soluble polymer and the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, the chemical resistance, adhesion, and resolution of the resist pattern tend to be well balanced.

[0059] The (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton is an ester of a dipentaerythritol compound in which at least one of a plurality of hydroxyl groups is modified with an alkyleneoxy group, and (meth)acrylic acid. Six hydroxyl groups of 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.

[0060] Examples of the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton include hexa(meth)acrylate 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 is added to dipentaerythritol.

[0061] Specifically, as a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, from the viewpoint of being able to significantly improve adhesion when exposed to light and then heated and then developed, and in particular to realizing good adhesion even when a long time has elapsed since exposure, a (meth)acrylate compound represented by the following general formula (III): [ka] A compound represented by the formula: {wherein R each independently represents a hydrogen atom or a methyl group, n is an integer of 0 to 30, and the total value of all n's is 1 or more} is preferred. In the 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.

[0062] 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 mass % to 50 mass %, more preferably 5 mass % to 40 mass %, and even more preferably 7 mass % to 30 mass %.

[0063] It is preferable that the content of (b1) (meth)acrylate compound having 3 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 can be significantly improved when the photosensitive resin composition is heated and developed after exposure, and there is a tendency to realize good adhesion even when the time elapsed after exposure is long, and if this content 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.

[0064] From the viewpoint of adhesion and suppression of foaming property of the developer, the photosensitive resin composition preferably contains, as the (B) compound 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.

[0065] (b2) Examples of the compound 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) The compound 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.

[0066] Specifically, (b2) a compound having a butylene oxide chain or a propylene oxide chain and one or two (meth)acryloyl groups preferably has 1 to 20, more preferably 4 to 15, and even more preferably 6 to 12 C 4 H 8 O or C 3 H 6 O-containing (meth)acrylate or di(meth)acrylate.

[0067] 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 20 mass% or less, based on the total solid content of the photosensitive resin composition.

[0068] In this embodiment, in order to suppress bleeding out of the components of the dry film resist and improve storage stability, based on the total solid content of the compound having an ethylenically unsaturated bond (B), 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 is a compound having a weight average molecular weight of 500 or more. From the viewpoint of suppressing bleeding out and chemical resistance of the resist pattern, the weight average molecular weight of the compound having an ethylenically unsaturated bond (B) 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 compound having an ethylenically unsaturated bond (B) can be calculated as a molecular weight calculated from the molecular structure of the compound having an ethylenically unsaturated bond (B). When multiple types of compounds having an ethylenically unsaturated bond (B) are present, it can be calculated by weighting the molecular weight of each compound by the content.

[0069] From the viewpoint of chemical resistance, adhesion, high resolution, and foot shape of the resist pattern, the concentration of the methacryloyl group in the compound having an ethylenic 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 the methacryloyl group 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.

[0070] From a similar 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.

[0071] The (meth)acrylate compounds described above can be used independently or in combination. The photosensitive resin composition may also contain other compounds as the (B) compound having an ethylenically unsaturated bond. Examples of the 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.

[0072] The ratio of the compound having (B) an ethylenically unsaturated double bond to the total solid mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. It is preferable to set this ratio at 5% by mass or more from the viewpoints of sensitivity, resolution, and adhesion. It is more preferable to set this ratio at 20% by mass or more, and even more preferable to set this ratio at 30% by mass or more. On the other hand, it is preferable to set this ratio at 70% by mass or less from the viewpoints of suppressing edge fuse and delayed peeling of the cured resist. It is more preferable to set this ratio at 50% by mass or less.

[0073] As the compound having (B) an ethylenically unsaturated double bond, the content of the 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 can significantly improve the adhesion when the composition is heated and developed after exposure, and can obtain good adhesion even when the time after exposure is long. In general, a compound having an ethylenically unsaturated double bond with a high concentration of bisphenol A skeleton may improve adhesion due to its hydrophobicity.

[0074] In the present invention, it was found that the rigid skeleton of bisphenol A does not improve mobility 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 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 preferably 18 mass % or less, more preferably 15 mass % or less, even more preferably 10 mass % or less, even more preferably 6 mass % or less, particularly preferably 3 mass % or less, and most preferably 1 mass % or less, based on the solid content of the photosensitive resin composition. From a similar viewpoint, the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.20 mol / 100 g or more as the compound (B) having an ethylenically unsaturated double bond is preferably 18 mass % or less, more preferably 15 mass % or less, even more preferably 10 mass % or less, still more preferably 6 mass % or less, particularly preferably 3 mass % or less, and most preferably 1 mass % or less, relative to the solid content of the photosensitive resin composition.

[0075] In particular, in this embodiment, the value of [content of (A) alkali-soluble polymer] / [content of (B) 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 [content of (A) alkali-soluble polymer] / [content of (B) 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 and lowering the double bond reaction rate, resulting in lower 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 performing 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 believed that the effect of the present invention has been realized.

[0076] The value of [(A) content of alkali-soluble polymer] / [(B) content of compound having ethylenically unsaturated double bond] 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.

[0077] <(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 the present embodiment contains a compound generally known in the technical field as a (C-1) photopolymerization initiator ((C) photopolymerization initiator).

[0078] The total content of the (C-1) photopolymerization initiator in the photosensitive resin composition is preferably within the range of 0.01 to 20 mass%, more preferably 0.05 to 10 mass%, further preferably 0.1 to 7 mass%, and particularly preferably 0.1 to 6 mass%. The total content of the (C-1) photopolymerization initiator is preferably 0.01 mass% or more from the viewpoint of obtaining sufficient sensitivity, and is preferably 20 mass% or less from the viewpoint of allowing sufficient light transmission to the bottom surface of the resist and obtaining good high resolution.

[0079] Examples of the photopolymerization initiator (C-1) 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, bisacridinyl heptane, cyclohexaaryl biimidazole, and cyclohexaaryl biimidazole. Examples of the photosensitive dye include lazoline compounds, anthracene compounds (e.g., 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene are preferred in terms of sensitivity, resolution, and adhesion), coumarin compounds (e.g., 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesion), N-arylamino acids or ester compounds thereof (e.g., N-phenylglycine is preferred in terms of sensitivity, resolution, and adhesion), and halogen compounds (e.g., tribromomethylphenylsulfone). These may be used alone or in combination of two or more. In addition, 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 may also be used.

[0080] 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.

[0081] 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.

[0082] Examples of hexaarylbiimidazoles include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole , 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,Examples of the imidazole include 5'-tetrakis-(3-methoxyphenyl)-biimidazole and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 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.

[0083] 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.

[0084] From the viewpoints of the peeling 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 preferred 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, preferred examples include 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, and 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline. Among these, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

[0085] 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.

[0086] (C-2) Photopolymerization initiator In the present embodiment, the photosensitive resin composition may contain anthracene and / or anthracene derivative as the (C-2) photopolymerization initiator ((C) photopolymerization initiator).

[0087] (C-2) The use of at least anthracene and / or anthracene derivative as the photopolymerization initiator can remarkably improve the adhesion when the film is heated and developed after exposure, 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 derivative can absorb the first active light having a central wavelength of less than 390 nm and the 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.

[0088] Therefore, in one embodiment, the photosensitive resin composition can have photosensitivity to the first and second active rays, and can also be used for two-wavelength exposure. The anthracene and / or anthracene derivative can also be selected so as to have a plurality of absorption maxima in the wavelength range of the first and second active rays. 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).

[0089] The total content of the (C-2) photopolymerization initiator in the photosensitive resin composition is preferably 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.

[0090] Anthracene and anthracene derivatives can remarkably improve adhesion when exposed to light and then heated and developed, and are particularly advantageous in that they achieve good adhesion even when a long time has elapsed since exposure. From the same viewpoint, the anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms and / or an aryl group having 6 to 40 carbon atoms, which may have a substituent, at the 9-position and / or 10-position, more preferably at the 9-position and 10-position.

[0091] In one embodiment, the anthracene derivative can remarkably improve adhesion when developed after heating after exposure, and in particular 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 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. From the viewpoint of obtaining good adhesion and resolution, it is preferable that at 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 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, such as chlorobutoxy and chloropropoxy groups; an alkoxy group to which a hydroxyl group has been added, 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.

[0092] 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 preferably has an aryl group having 6 to 40 carbon atoms which may have a substituent at at least one of the 9th or 10th positions, and more preferably has an aryl group having 6 to 30 carbon atoms which may have a substituent at at least one of the 9th or 10th positions.

[0093] In order to remarkably improve the adhesion when the film is developed after heating following exposure, and in particular to realize good adhesion even after a long time has elapsed since exposure, it is preferable that the film has an aryl group having 6 to 40 carbon atoms, which may have a substituent, at the 9th and 10th positions, and more preferable that the film has 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. In addition, 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.

[0094] Examples of the aryl group having 6 to 40 carbon atoms which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, an aryl group having an alkoxy group added thereto, such as a methoxyphenyl group, an ethoxyphenyl group, an aryl group having an alkyl group added thereto, such as a tolyl group, a xylyl group, a mesityl group, a nonylphenyl group, an aryl group having a halogen added thereto, such as a chlorophenyl group, an aryl group having a hydroxyl group added thereto, such as a hydroxyphenyl group, etc. Among these, a phenyl group is more preferred.

[0095] The anthracene derivative is preferably represented by the following general formula (IV). [ka] R 1 are independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or N(R') 2 represents a group, and is 2 or more R 1 may be linked together to form a cyclic structure, which may include heteroatoms.

[0096] 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, or a -SO 2 -O- group, -SO 2 -S- group, -SO 2 -N(R')- group, -O-CO- group, -S-CO- group, -O-SO 2 - group or S-SO 2 - group, where X is a single bond and R 1 except for combinations of hydrogen atoms (i.e., unsubstituted anthracene).

[0097] 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, and the cyclic structure may contain a heteroatom.

[0098] p is an integer of 1 to 10, and preferably 2 to 4.

[0099] Above R 1 Specific examples of the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms for 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.

[0100] Above R 1 Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms for 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.).

[0101] Above R 1 Specific examples of the alkenyl group having 2 to 4 carbon atoms in R' include vinyl and propenyl groups.

[0102] Above R 1Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in 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.

[0103] Above R 1 Examples of the substituted or unsubstituted heteroaryl group in R' include 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, and a pyrrolidyl group.

[0104] In addition, the above R 1 Each of the hydrocarbon groups of R 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 alkoxy group having 1 to 4 carbon atoms (e.g., a methoxy group, an ethoxy group, a n-propoxy group, a i-propoxy group, a n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a t-butoxy group, etc.), a cyano group, a phenyl ... Examples of the R 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.). 1Each of the hydrocarbon groups of R 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 9-position and / or the 10-position.

[0105] Above R 1 Preferred specific examples of 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.

[0106] Preferred examples of X include a single bond, an oxygen atom, a sulfur atom, a -N(R')- group, a -O-CO- group, and an O-SO 2 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.

[0107] Examples of the compound represented by the above general formula (IV) include 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-t-butylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 9-vinylanthracene, 9-phenylanthracene, 9,10-diphenylanthracene, 2-bromo-9,10-diphenylanthracene, 9-(4-bromophenyl)-10-phenylanthracene, 9-(1-naphthyl)anthracene, 9-(2-naphthyl)anthracene, 2-bromo-9,10-bis(2-naphthyl)anthracene, 2,6-di ... Examples of the anthracene include 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, and 1,8,9-triacetoxyanthracene. Among these, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di(2-ethylhexyloxy)anthracene, and 9,10-bis-(3-chloropropoxy)anthracene are preferred, and from the viewpoint of significantly improving adhesion when heated and then developed after exposure, and particularly 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 compounds represented by the above general formula (IV) may be used alone or in combination of two or more kinds.

[0108] From the viewpoint 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 elapsed since exposure, the (C-2) photopolymerization initiator 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 9- and / or 10-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.

[0109] The compound represented by the above general formula (IV) is advantageous in that it can remarkably improve adhesion when exposed to light and then heated and developed, and 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 actinic ray having a central wavelength of less than 390 nm and a second actinic ray having a central wavelength of 390 nm or more, and can provide a photosensitive resin composition that exhibits excellent sensitivity, adhesion and resolution.

[0110] In one embodiment, the photopolymerization initiator (C-2) preferably contains an anthracene derivative having a halogen atom. A suitable example of the anthracene derivative having a halogen atom is a halogen-substituted 9,10-dialkoxyanthracene. A suitable example of the halogen-substituted 9,10-dialkoxyanthracene is a compound in which the alkoxy groups at the 9-position and / or 10-position of the 9,10-dialkoxyanthracene are modified with one or more halogens. Preferred examples of the alkoxy group include those exemplified above as an alkoxy group having 1 to 40 carbon atoms.

[0111] In one embodiment, the anthracene derivative is also preferably a compound having a halogen atom directly bonded to the anthracene skeleton.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.

[0112] 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.

[0113] The (C-2) photopolymerization initiator may further contain a compound 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 may be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, triphenylphosphine oxide, etc. may also be used.

[0114] 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.

[0115] Examples of hexaarylbiimidazoles include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole , 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,Examples of the photosensitive dye include 5'-tetrakis-(3-methoxyphenyl)-biimidazole and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 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.

[0116] 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.

[0117] From the viewpoints of the peeling properties, sensitivity, resolution, and adhesion of the photosensitive resin layer, the photosensitive resin composition preferably contains one or more pyrazoline compounds as the photopolymerization initiator (C-2).

[0118] 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-dimethy ... From the above viewpoints, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is preferred, and 1-phenyl-3-(4-tert-butyl-phenyl)-pyrazoline is more preferred.

[0119] <(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.

[0120] Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine, etc. In order not to impair the sensitivity of the photosensitive resin composition, nitrosophenylhydroxyamine aluminum salt is preferred.

[0121] 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-diethylene bis[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 4,4'-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, phenol having 1 to 3 benzyl groups, manufactured by Kawaguchi Chemical Industry Co., Ltd.), and biphenol.

[0122] The ratio of the (D) inhibitor to the total solid mass of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass. From the viewpoint of preventing the shortest development time of the unexposed portion from being extended even when heating is performed after exposure, 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. On the other hand, from the viewpoint of less sensitivity reduction and improved resolution, 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.

[0123] <(E) Benzotriazole derivatives> 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 if the composition is heated after exposure. 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.

[0124] The content of the (E) benzotriazole derivative is preferably 0.001% by mass to 3% by mass when the total solid content mass of the photosensitive resin composition is taken as 100% by mass. The content is preferably 0.001% by mass or more 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, more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more. On the other hand, the content is preferably 3% by mass or less from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye, 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.

[0125] 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, and 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.

[0126] <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 the present 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.

[0127] 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 to 0.001% by mass or more from the viewpoint of improving the handling property of the photosensitive resin composition. On the other hand, it is preferable to set the content to 1% by mass or less from the viewpoint of maintaining the storage stability of the photosensitive resin composition.

[0128] 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 based on 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.

[0129] In addition, it is preferable to use a leuco dye in combination with the halogen compound described above in the (C) photopolymerization initiator in the photosensitive resin composition from the viewpoint of optimizing adhesion and contrast. When the 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.

[0130] (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, such as phthalic acid esters (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, polypropylene glycol alkyl ether, etc. 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.).

[0131] 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 of the photosensitive resin composition. A content of 1% by mass or more is preferable from the viewpoint of suppressing a 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.

[0132] [solvent] The photosensitive resin composition can be dissolved in a solvent to prepare a photosensitive resin composition liquid for use 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.

[0133] [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.

[0134] 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 such as (1) containing fine particles in the same manner as side A, (2) containing a smaller amount of fine particles than side A, (3) containing finer particles than side A, or (4) not containing fine particles. In the case of the structures (2), (3), and (4), it is preferable to form a photosensitive resin layer on the side B. In this case, if there is a resin layer containing fine particles on the side A side, it is preferable 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.

[0135] An important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesive strength with the photosensitive resin layer is sufficiently smaller than that of the support layer, and the layer 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 disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

[0136] Gels called fisheyes may be present on the surface of the polyethylene film. When a polyethylene film having 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, air may be trapped during lamination to form voids, leading to defects in the resist pattern. From the viewpoint of preventing fisheyes, oriented polypropylene is preferable as the material for the protective layer. A specific example is Alphan E-200A manufactured by Oji Paper Co., Ltd.

[0137] 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 photosensitive resin layer, the higher the film strength.

[0138] 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.

[0139] <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 is described below.

[0140] 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, if 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 with a laminator. Examples of materials for the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). In this embodiment, the photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides as necessary. The heating temperature during lamination is generally 40°C to 160°C. In addition, by performing the thermocompression bonding at the time of lamination twice or more, the adhesion of the obtained resist pattern to the substrate can be improved. During the thermocompression bonding, a two-stage laminator equipped with two consecutive 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.

[0141] (2) Exposure process In this process, the photosensitive resin layer is exposed to light by an exposure method in which a mask film having a desired wiring pattern is adhered to the support layer and an active light source is used, an exposure method in which a drawing pattern, which is the desired wiring pattern, is directly drawn, or an exposure method in which an image of a photomask is projected through a lens.

[0142] The exposure step is preferably performed by an exposure method by direct drawing of a pattern or an exposure method by projecting an image of a photomask through a lens, and more preferably by an exposure method by direct drawing of a pattern. The advantages of the photosensitive resin composition according to the present embodiment are more prominent in the exposure method by direct drawing of a pattern or an exposure method by projecting an image of a photomask through a lens, and are particularly prominent in the exposure method by direct drawing of a pattern.

[0143] When the exposure step is an exposure method by direct writing, it is preferable to use a laser light having a central wavelength of less than 390 nm or a laser light having a central wavelength of 390 nm or more. It is more preferable to use a laser light having a central wavelength of 350 nm or more and 380 nm or less, or a laser light having a central wavelength of 400 nm or more and 410 nm or less. It is preferable to perform exposure using a first laser light having a central wavelength of less than 390 nm and a second laser light having 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.

[0144] (3)Heating process In this step, the exposed photosensitive resin composition is preferably subjected to a heating step at about 30°C to about 200°C, more preferably in the range of 30°C to 150°C, 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 bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, or the like can be used. The heating method using a hot roll is preferable because it allows for short-time treatment, and it is more preferable to use two or more hot rolls.

[0145] In particular, in the present invention, by containing 15 mass % or more of structural units of styrene and / or a styrene derivative and by heating after exposure and then developing, the mobility of the resin is improved by heating even in a system with a high content of styrene skeleton, and it is possible to achieve a high degree of both the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bonds.

[0146] 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 development is performed after heating following exposure, so that the mobility of the resin is improved by heating, 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 even in a system having a relatively high content of the styrene skeleton.

[0147] As a result, the adhesion can be significantly improved. Furthermore, the significantly improved adhesion makes it possible to obtain good adhesion even when the time elapsed after the exposure is long. From the viewpoint of the effects of the present invention, the heating step is preferably performed within 15 minutes, more preferably within 10 minutes, and even more preferably within 5 minutes after the exposure.

[0148] (4)Developing process In this process, after exposure, the support layer on the photosensitive resin layer is peeled off, and then the unexposed areas are developed and removed using an aqueous alkaline developer, thereby forming a resist pattern on the substrate. The alkaline solution is 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 is preferably a Na solution having a concentration of about 0.2% by mass to about 2% by mass and at about 20° C. to about 40° C. 2 CO 3 An aqueous solution is preferred. A resist pattern can be obtained through the above steps (1) to (4).

[0149] In the method for producing a circuit board of the present invention, a circuit board is formed by etching or plating the substrate having the resist pattern produced by the above-mentioned method.

[0150] (5) Etching or plating process The substrate surface exposed by development (for example, the copper surface of a copper-clad laminate) is etched or plated to produce a conductor pattern. (6) Peeling process The resist pattern is then 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.

[0151] 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.

[0152] Examples of organic amines include ethanolamine, propanolamine, alkylamine, cyclic amine, and quaternary ammonium salt. Specific examples of these include: Ethanolamines include, for example, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, aminoethoxyethanol, and the like; Propanolamines include, for example, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, and the like; Examples of alkylamines include monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, and tetraethylenepentamine; Cyclic amines, such as choline, morpholine, etc.; As quaternary ammonium salts, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N,N,N-triethyl-N-(2-hydroxyethyl)ammonium hydroxide, N,N-diethyl-N,N-di(2-hydroxyethyl)ammonium hydroxide, etc.; Examples of each can be given.

[0153] 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.

[0154] After the stripping step, the substrate from which the resist pattern has been removed may be washed, for example, with pure water, if desired.

[0155] 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. EXAMPLES

[0156] 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.

[0157] <<First Example>> 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.

[0158] (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 using 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, and a calibration curve using 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).

[0159] (2) Method for preparing evaluation samples The 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 (GF-818, manufactured by Tamapoly Co., Ltd.) 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.

[0160] <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 used. After jet scrubbing polishing with an abrasive (Ujiden Chemical Industry Co., Ltd., #400) at a spray pressure of 0.2 MPa, the laminate was sprayed with 10 mass% H 2 SO 4 The surface of the substrate was washed with an 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.

[0161] <Exposure> The evaluation substrate 2 hours after lamination was exposed using a Stouffer 41-step step tablet with 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.

[0162] 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 condition 7 minutes after exposure in this example is very strict.

[0163] <Development> After peeling off the polyethylene terephthalate film (support layer), the film was exposed to an alkaline developer (manufactured by Fuji Kiko, a dry film developer) at 30°C with 1% by weight Na 2 CO 3 The aqueous solution was sprayed for a predetermined time to perform development. The development spray time was twice the shortest development time, and the post-development water spray time was four times the shortest development time. In this case, the shortest development time was determined to be the time required for the unexposed photosensitive resin layer to completely dissolve.

[0164] <Adhesion evaluation> The minimum line width at which the mask pattern L / S=Xμm / 200μm was normally formed was measured using an optical microscope. This measurement was performed for eight lines, and the average of the eight line widths was calculated as the adhesion value.

[0165] <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 is observed

[0166] <Delay in minimum development time> The shortest development time was measured under the following two conditions. (A) Normal shortest development time The 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 substrate was heated with 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).

[0167] The above evaluation results are shown in Table 1-1 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 1-1 are shown in Table 1-2.

[0168] [Table 1-1]

[0169] [Table 1-2]

[0170] From the results in Tables 1-1 and 1-2, it was confirmed that the Examples falling within the scope of the constituent elements of the present invention had better image quality evaluation results than the Comparative Examples falling outside the scope of the present invention.

[0171] From the results in Tables 1-1 and 1-2, it was confirmed that the examples falling within the scope of the constituent elements of the present invention had better image quality evaluation results than the comparative examples which are outside the scope of the present invention.

[0172] In addition, the post-exposure heating conditions in this embodiment are very severe 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 post-exposure heating. That is, no effect was observed when heating was performed 7 minutes after exposure in the composition of Comparative Example 1, but the adhesion can be improved in Example 1 even under very severe conditions. In addition, under the condition of heating 1 minute after exposure, an adhesion of 10.0 μm was obtained in both the compositions of Example 1 and Comparative Example 1.

[0173] From the above results, even if the adhesion is good under general post-exposure heating conditions, it does not necessarily mean that the adhesion is good under the severe condition of heating 7 minutes after exposure in this embodiment. However, the photosensitive resin composition of the present invention having a specific composition was the first to improve the adhesion even under such severe post-exposure heating conditions. As a result, when manufacturing a circuit board, good adhesion can be obtained even if the elapsed time after exposure is long, so that a high-definition circuit pattern can be stably formed.

[0174] <<Second Example>> In the second example, a photosensitive resin composition in which the (B) compound having an ethylenically unsaturated double bond 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 dose 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.

[0175] <Heating> 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 1 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.

[0176] <Development> After peeling off the polyethylene terephthalate film (support layer), the film was exposed to an alkaline developer (manufactured by Fuji Kiko, a dry film developer) at 30°C with 1% by weight Na 2 CO 3 The aqueous solution was sprayed for a predetermined time to perform development. The development spray time was twice the shortest development time, and the post-development water spray time was three times the shortest development time. In this case, the shortest development time was determined to be the time required for the unexposed photosensitive resin layer to completely dissolve.

[0177] 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.

[0178] [Table 2-1]

[0179] [Table 2-2]

[0180] From the results in Tables 2-1 and 2-2, it was confirmed that the Examples falling within the scope of the constituent elements of the present invention had better image quality evaluation results than the Comparative Examples falling outside the scope of the present invention.

[0181] The post-exposure heating conditions in this embodiment are very severe conditions since the 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 post-exposure heating. That is, the composition of Comparative Example 1 showed no effect when heated 7 minutes after exposure, but the adhesion of Example 1 can be improved even under very severe conditions. Moreover, under the condition of heating 1 minute after exposure, both the compositions of Example 1 and Comparative Example 1 obtained an adhesion of 9.6 μm.

[0182] From the above results, even if the adhesion is good under typical post-exposure heating conditions, it does not necessarily mean that the adhesion is good under the severe condition of heating 7 minutes after exposure in this embodiment. However, the present invention has made it possible to improve the adhesion even under such severe post-exposure heating conditions for the first time. As a result, when manufacturing a circuit board, good adhesion can be obtained even if the time elapsed after exposure is long, making it possible to stably form a high-definition circuit pattern.

[0183] <<Third Example>> In the third example, a photosensitive resin composition in which the photopolymerization initiator (C-2) 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, Inc., light source: 375 nm (30%) + 405 nm (70%)) with a Stouffer 41-step tablet. The exposure was performed with an exposure dose 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.

[0184] <Heating> 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 1 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.

[0185] <Development> After peeling off the polyethylene terephthalate film (support layer), the film was exposed to an alkaline developer (manufactured by Fuji Kiko, a dry film developer) at 30°C with 1% by weight Na 2 CO 3 The aqueous solution was sprayed for a predetermined time to perform development. The development spray time was twice the shortest development time, and the post-development water spray time was three times the shortest development time. In this case, the shortest development time was determined to be the time required for the unexposed photosensitive resin layer to completely dissolve.

[0186] 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.

[0187] [Table 3-1]

[0188] [Table 3-2]

[0189] From the results of Tables 3-1 and 3-2, it was confirmed that the image quality evaluation results were better in the examples that were within the scope of the present invention than in the comparative examples that were 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 in the composition of Comparative Example 1 when heated 7 minutes after exposure, but the adhesion of Example 7 could be improved even under very severe conditions. In addition, under the condition of heating 1 minute after exposure, both the compositions of Example 7 and Comparative Example 1 obtained an adhesion of 9.6 μm.

[0190] From the above results, it can be seen that even if the adhesion is good under typical post-exposure heating conditions, the adhesion is not necessarily good under the severe condition of heating 7 minutes after exposure, and the present invention is the first to improve the adhesion even under such severe post-exposure heating conditions. In other words, when manufacturing a circuit board, the composition according to the present invention can obtain good adhesion even if the time elapsed after exposure is long, so that a high-definition circuit pattern can be stably formed.

[0191] Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be modified as appropriate without departing from the spirit of the invention. [Industrial Applicability]

[0192] 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 can be achieved even when a long time has elapsed since exposure, and the composition can be widely used as a photosensitive resin composition.

Claims

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) 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. 2. The photosensitive resin composition according to claim 1, wherein the content of a 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 claim 1 or 2, further comprising (D) an inhibitor.

4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (E) a benzotriazole derivative.

5. The photosensitive resin composition according to any one of claims 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 claim 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 claim 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 claims 1 to 7, wherein the value of [content of (A) alkali-soluble polymer] / [content of (B) compound having an ethylenically unsaturated double bond] is 0.94 or more.

9. 9. The photosensitive resin composition according to claim 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. 10. The photosensitive resin composition according to claim 9, wherein the value of [content of (A) the alkali-soluble polymer] / [content of (B) the compound having an ethylenically unsaturated double bond] is 1.11 or more.

11. The photosensitive resin composition according to claim 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 claim 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 claims 1 to 12, wherein the value of [content of (A) alkali-soluble polymer] / [content of (B) compound having an ethylenically unsaturated double bond] is 5 or less.

14. The photosensitive resin composition according to claim 13, wherein the value of [content of (A) the alkali-soluble polymer] / [content of (B) the compound having an ethylenically unsaturated double bond] is 4 or less.

15. The photosensitive resin composition according to claim 14, wherein the value of [content of (A) the alkali-soluble polymer] / [content of (B) the compound having an ethylenically unsaturated double bond] is 3 or less.

16. The photosensitive resin composition according to claim 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 claim 16, wherein the value of [content of (A) the alkali-soluble polymer] / [content of (B) 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) 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 claim 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 claim 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 claim 20, wherein the (C) photopolymerization initiator contains 9,10-diphenylanthracene.

22. The photosensitive resin composition according to claim 20, wherein the (C) photopolymerization initiator contains 9,10-dialkoxyanthracene.

23. The photosensitive resin composition according to any one of claims 18 to 22, wherein the (C) photopolymerization initiator includes an anthracene derivative having a halogen atom.

24. The photosensitive resin composition according to claim 23, wherein the (C) photopolymerization initiator contains a halogen-substituted 9,10-dialkoxyanthracene.

25. The photosensitive resin composition according to claim 24, wherein the (C) photopolymerization initiator comprises 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 claims 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 claims 18 to 26, wherein the content of structural units of styrene and / or styrene derivatives in the alkali-soluble polymer (A) is 15 mass% or more.

28. The photosensitive resin composition according to any one of claims 1 to 27, wherein the content of structural units of styrene and / or styrene derivatives in the alkali-soluble polymer (A) is 25 mass% or more.

29. 29. The photosensitive resin composition according to claim 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. 30. The photosensitive resin composition according to claim 29, wherein the alkali-soluble polymer (A) contains 35 mass% or more of structural units of styrene and / or a styrene derivative.

31. The photosensitive resin composition according to claim 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 claims 1 to 31, wherein the content of structural units of styrene and / or styrene derivatives in the alkali-soluble polymer (A) is 90 mass% or less.

33. The photosensitive resin composition according to any one of claims 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 claims 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 claim 34, wherein the heating temperature in the heating step is in the range of 30°C to 150°C.

36. 36. The method for forming a resist pattern according to claim 34 or 35, wherein the exposure step is carried out by an exposure method based on direct drawing of a drawing pattern, or an exposure method in which an image of a photomask is projected through a lens.

37. 36. The method for forming a resist pattern according to claim 34, 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 claims 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 claims 34 to 38, wherein the exposure step is carried out by a method of exposing with a first laser light having a central wavelength of less than 390 nm and a second laser light having a central wavelength of 390 nm or more.

40. 40. The method for forming a resist pattern according to claim 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 claims 34 to 40, to form a circuit board.

42. The photosensitive resin composition according to any one of claims 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. 43. The photosensitive resin composition according to claim 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.

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