Photosensitive resin composition and method for forming resist pattern

Abstract

The invention relates to a photosensitive resin composition and a method for forming a resist pattern. Provided is a photosensitive resin composition which is suitable for heating after exposure and achieves higher resolution. A photosensitive resin composition for obtaining a cured resin product by heating after exposure and then developing, the photosensitive resin composition comprising the following components based on the total solid content mass of the photosensitive resin composition: (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% by mass of a photopolymerization initiator, wherein the content of structural units of styrene and / or styrene derivatives in the entire alkali-soluble polymer (A) is 15% by mass or more.

Description

[0001] This application is a divisional application of a Chinese patent application with an application date of June 18, 2019, an application number of 201980041666.2, and an invention title of "Photosensitive Resin Composition and Method for Forming Resist Pattern". Technical Field

[0002] The present invention relates to a photosensitive resin composition, a method for forming a resist pattern, and the like. Background Art

[0003] In electronic devices such as personal computers and mobile phones, printed circuit boards and the like are used for mounting components, semiconductors, etc. As a resist used for manufacturing printed circuit boards and the like, a photosensitive resin laminate in which a photosensitive resin layer is laminated on a support film and, if necessary, a protective film is further laminated on the photosensitive resin layer, so-called dry film photoresist (hereinafter sometimes also referred to as DF) has been conventionally used. As the photosensitive resin layer, an alkali-developable resin layer using a weak alkali aqueous solution as a developer is currently commonly used.

[0004] For manufacturing a printed circuit board or the like using DF, for example, the following steps are involved. When DF has a protective film, first, the protective film is peeled off. Thereafter, DF is laminated on a substrate for permanent circuit formation such as a copper-clad laminate or a flexible substrate using a laminator or the like, and exposure is performed through a wiring pattern mask film or the like. Then, if necessary, the support film is peeled off, and the un-cured portion (for example, the un-exposed portion in the case of a negative type) of the photosensitive resin layer is dissolved or dispersed and removed using a developer, thereby forming a cured resist pattern (hereinafter sometimes also simply referred to as a resist pattern) on the substrate.

[0005] After forming the resist pattern, the process of forming a circuit is roughly divided into two methods. The first method is a method (etching method) in which the substrate surface not covered by the resist pattern (for example, the copper surface of a copper-clad laminate) is etched away and then the resist pattern portion is removed using an alkali aqueous solution stronger than the developer.

[0006] The second method is a method (plating method) in which after the above-mentioned substrate surface is plated with copper, solder, nickel, tin, etc., the resist pattern portion is removed in the same manner as the first method, and then the exposed substrate surface (for example, the copper surface of a copper-clad laminate) is etched. Etching is performed using copper chloride, ferric chloride, copper ammonia complex solution, etc.

[0007] In recent years, with the miniaturization and light weight of electronic devices, the miniaturization and high density of printed circuit boards have been developed. In the manufacturing process as described above, it is required to provide a high-performance DF with high resolution and high adhesion. As a substance for achieving such high resolution, Patent Document 1 describes a photosensitive resin composition that improves resolution through a specific thermoplastic resin, monomer, and photopolymerization initiator.

[0008] Prior art documents

[0009] Patent documents

[0010] Patent document 1: Japanese Patent Application Laid-Open No. 2010-249884 Summary of the invention

[0011] Problems to be Solved by the Invention

[0012] After the exposure step, depending on the circumstances, the photosensitive resin layer is sometimes subjected to a heating step, followed by development. By carrying out this heating step, further improvement in high resolution and high adhesion can be achieved. However, even when a heating step is applied after exposure, the conventional photosensitive resin compositions have the following problems: the improvement in adhesion becomes insufficient, or good adhesion cannot be obtained when the elapsed time after exposure becomes long.

[0013] The present invention has been made in view of such an actual situation, and an object of the present invention is

[0014] To provide a photosensitive resin composition capable of significantly improving the adhesion when heating is carried out after exposure and then development, and in particular, capable of achieving good adhesion even when the elapsed time after exposure becomes long.

[0015] Solutions for Solving the Problems

[0016] As a result of continuous and in-depth research by the present inventors, it has been found that by using a monomer component having a specific structural unit in a specific amount in an alkali-soluble polymer constituting the photosensitive resin composition, the above object can be achieved, and thus the present invention has been completed.

[0017] In addition, as a result of continuous and in-depth research by the present inventors, it has been found that by using a specific photopolymerization initiator in an alkali-soluble polymer constituting the photosensitive resin composition, the above object can be achieved, and thus the present invention has been completed.

[0018] That is, the present invention is as follows.

[0019] [1] A photosensitive resin composition for obtaining a resin cured product by heating after exposure and then development, characterized in that the photosensitive resin composition contains the following components based on the mass of the total solid content of the photosensitive resin composition:

[0020] (A) An alkali-soluble polymer: 10% by mass to 90% by mass;

[0021] (B) A compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and

[0022] (C) Photoinitiator: 0.01% to 20% by mass,

[0023] The structural unit of styrene and / or styrene derivative in the whole of the aforementioned (A) alkali-soluble polymer is 15% by mass or more.

[0024] [2] The photosensitive resin composition according to [1], wherein, as the aforementioned (B) compound having an ethylenically unsaturated double bond, the content of the compound (B-1) having a concentration of the bisphenol A skeleton of 0.18 mol / 100 g or more is 0% to 18% by mass based on the solid content of the photosensitive resin composition.

[0025] [3] The photosensitive resin composition according to [1] or [2], which further contains (D) inhibitor.

[0026] [4] The photosensitive resin composition according to any one of [1] to [3], which further contains (E) benzotriazole derivative.

[0027] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the aforementioned (B) compound having an ethylenically unsaturated double bond contains a (meth)acrylate compound having 3 or more ethylenically unsaturated double bonds.

[0028] [6] The photosensitive resin composition according to [5], wherein the aforementioned (B) compound having an ethylenically unsaturated double bond contains a (meth)acrylate compound having 4 or more ethylenically unsaturated double bonds.

[0029] [7] The photosensitive resin composition according to [6], wherein the aforementioned (B) compound having an ethylenically unsaturated double bond contains a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds.

[0030] [8] The photosensitive resin composition according to any one of [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.

[0031] [9] The photosensitive resin composition according to [8], wherein the value of [(content of (A) alkali-soluble polymer)] / [(content of (B) compound having an ethylenically unsaturated double bond)] is 1.04 or more.

[0032]

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

[0033]

[11] The photosensitive resin composition according to

[10] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 1.21 or more.

[0034]

[12] The photosensitive resin composition according to

[11] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 1.30 or more.

[0035]

[13] The photosensitive resin composition according to any one of [1] to

[12] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 5 or less.

[0036]

[14] The photosensitive resin composition according to

[13] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 4 or less.

[0037]

[15] The photosensitive resin composition according to

[14] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 3 or less.

[0038]

[16] The photosensitive resin composition according to

[15] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 2 or less.

[0039]

[17] The photosensitive resin composition according to

[16] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 1.5 or less.

[0040]

[18] A photosensitive resin composition which is a photosensitive resin composition for obtaining a resin cured product by heating after exposure and then developing, characterized in that the photosensitive resin composition contains the following components based on the total solid content mass of the photosensitive resin composition:

[0041] (A) An alkali-soluble polymer: 10% by mass to 90% by mass;

[0042] (B) A compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and

[0043] (C) A photopolymerization initiator: 0.01% by mass to 20% by mass,

[0044] The aforementioned (C) photopolymerization initiator contains anthracene and / or anthracene derivatives.

[0045]

[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 10-position.

[0046]

[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 9,10-positions.

[0047]

[21] The photosensitive resin composition according to

[20] , wherein the (C) photoinitiator contains 9,10-diphenylanthracene.

[0048]

[22] The photosensitive resin composition according to

[20] , wherein the (C) photoinitiator contains 9,10-dialkoxyanthracene.

[0049]

[23] The photosensitive resin composition according to any one of

[18] to

[22] , wherein the (C) photoinitiator contains an anthracene derivative having a halogen atom.

[0050]

[24] The photosensitive resin composition according to

[23] , wherein the (C) photoinitiator contains a halogenated product of 9,10-dialkoxyanthracene.

[0051]

[25] The photosensitive resin composition according to

[24] , wherein the (C) photoinitiator contains a compound obtained by modifying the alkoxy group at the 9-position and / or 10-position of 9,10-dialkoxyanthracene with one or more halogen atoms.

[0052]

[26] The photosensitive resin composition according to any one of

[18] to

[25] , wherein the (C) photoinitiator contains a compound having a halogen atom directly bonded to the anthracene skeleton.

[0053]

[27] The photosensitive resin composition according to any one of

[18] to

[26] , wherein the structural unit of styrene and / or styrene derivative in the (A) alkali-soluble polymer is 15% by mass or more.

[0054]

[28] The photosensitive resin composition according to any one of [1] to

[27] , wherein the structural unit of styrene and / or styrene derivative in the (A) alkali-soluble polymer is 25% by mass or more.

[0055]

[29] The photosensitive resin composition according to

[28] , wherein the structural unit of styrene and / or styrene derivative in the (A) alkali-soluble polymer is 30% by mass or more.

[0056]

[30] The photosensitive resin composition according to

[29] , wherein the structural unit of styrene and / or styrene derivative in the aforementioned (A) alkali-soluble polymer is 35% by mass or more.

[0057]

[31] The photosensitive resin composition according to

[30] , wherein the structural unit of styrene and / or styrene derivative in the aforementioned (A) alkali-soluble polymer is 40% by mass or more.

[0058]

[32] The photosensitive resin composition according to any one of [1] to

[31] , wherein the structural unit of styrene and / or styrene derivative in the aforementioned (A) alkali-soluble polymer is 90% by mass or less.

[0059]

[33] The photosensitive resin composition according to any one of [1] to

[32] , wherein the aforementioned (A) alkali-soluble polymer further contains benzyl (meth)acrylate as a monomer component.

[0060]

[34] A method for forming a resist pattern, which includes the following steps:

[0061] 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.

[0062]

[35] The method for forming a resist pattern according to

[34] , wherein the heating temperature in the aforementioned heating step is in the range of 30°C to 150°C.

[0063]

[36] The method for forming a resist pattern according to

[34] or

[35] , wherein the aforementioned exposure step is performed by an exposure method of direct drawing based on a drawn pattern or an exposure method of projecting an image of a photomask through a lens.

[0064]

[37] The method for forming a resist pattern according to

[34] or

[35] , wherein the aforementioned exposure step is performed by an exposure method of direct drawing based on a drawn pattern.

[0065]

[38] The method for forming a resist pattern according to any one of

[34] to

[37] , wherein the aforementioned heating step is performed within 15 minutes after exposure.

[0066]

[39] The method for forming a resist pattern according to any one of

[34] to

[38] , wherein the aforementioned exposure step is performed by an exposure method of using a first laser with a center wavelength less than 390 nm and a second laser with a center wavelength of 390 nm or more.

[0067]

[40] The method for forming a resist pattern according to

[39] , wherein the central wavelength of the first laser is 350 nm or more and 380 nm or less, and the central wavelength of the second laser is 400 nm or more and 410 nm or less.

[0068]

[41] A method for manufacturing a circuit board, wherein etching or plating is performed on a substrate having a resist pattern manufactured by the method according to any one of

[34] to

[40] , thereby forming a circuit board.

[0069]

[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 using a first laser having a central wavelength less than 390 nm and a second laser having a central wavelength of 390 nm or more.

[0070]

[43] The photosensitive resin composition according to

[42] , wherein the central wavelength of the first laser is 350 nm or more and 380 nm or less, and the central wavelength of the second laser is 400 nm or more and 410 nm or less.

[0071] Effects of the Invention

[0072] According to the present invention, a photosensitive resin composition can be provided that can significantly improve the adhesion during heating after exposure and then development, and in particular, can achieve good adhesion even when the elapsed time after exposure becomes long. Detailed Description

[0073] Hereinafter, exemplary embodiments for implementing the present invention (hereinafter abbreviated as "embodiments") will be described in detail. In addition, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of its gist. In addition, for various measured values in this specification, unless otherwise specified, they are measured according to the method described in the [Examples] section of this application or a method considered equivalent by those skilled in the art.

[0074] [Photosensitive Resin Composition]

[0075] The photosensitive resin composition of the present invention is a photosensitive resin composition for obtaining a resin cured product by heating after exposure and then developing. The photosensitive resin composition contains the following components based on the mass of the total solid content of the photosensitive resin composition: (A) an alkali-soluble polymer: 10% by mass to 90% by mass; (B) a compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) a photopolymerization initiator: 0.01% by mass to 20% by mass.

[0076] Further, in particular, the photosensitive resin composition of the present embodiment is characterized in that, when the (A) alkali-soluble polymer contains a plurality of alkali-soluble polymers, the structural unit of styrene and / or styrene derivative in the whole of the (A) alkali-soluble polymer is 15% by mass or more.

[0077] In general, for a dry film resist obtained from a photosensitive resin composition, if it is not heated immediately after exposure, the effect of improving the adhesion cannot be obtained. However, the dry film resist obtained from the photosensitive resin composition of the present invention can exhibit good adhesion even when the elapsed time after exposure becomes long (in other words, a fine resist). The photosensitive resin composition of the present invention has a composition suitable for this property.

[0078] In the photosensitive resin composition of the present embodiment, when the (A) alkali-soluble polymer contains a plurality of alkali-soluble polymers, by making the structural unit of styrene and / or styrene derivative in the whole of the (A) alkali-soluble polymer 15% by mass or more, the adhesion during heating after exposure and then development can be significantly improved, and in particular, good adhesion can be obtained even when the elapsed time after exposure becomes long.

[0079] Hereinafter, each component will be described in turn.

[0080] <(A) Alkali-soluble polymer>

[0081] In the present application, 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 in terms of acid equivalent, preferably 250 to 450. The acid equivalent refers to the mass (unit: g) of a polymer having 1 equivalent of carboxyl groups in its molecule. The carboxyl groups in the (A) alkali-soluble polymer are required to impart developability and peelability with respect to an aqueous alkali solution to the photosensitive resin layer. From the viewpoints of improving the development tolerance, resolution, and adhesion, it is preferable that the acid equivalent is 100 or more. And more preferably, the acid equivalent is 250 or more. On the other hand, from the viewpoints of improving the developability and peelability, it is preferable that the acid equivalent is 600 or less. And more preferably, the acid equivalent is 450 or less. In the present application, the acid equivalent is a value measured by a potentiometric titration method using a potentiometric titration apparatus and titrating with a 0.1 mol / L aqueous NaOH solution.

[0082] (A) The weight-average molecular weight of the alkali-soluble polymer is preferably from 5,000 to 500,000. From the viewpoint of improving the resolution and developability, it is preferred that the weight-average molecular weight is 500,000 or less. More preferably, the weight-average molecular weight is 100,000 or less, still more preferably 70,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoints of controlling the properties of the developed aggregates and the properties of the unexposed film such as the edge fuse and cut chip properties when forming the photosensitive resin laminate, it is preferred that the weight-average molecular weight is 5,000 or more. More preferably, the weight-average molecular weight is 10,000 or more, still more preferably 20,000 or more. The edge fuse property refers to the degree of ease with which the photosensitive resin layer (i.e., the layer formed from the photosensitive resin composition) is exposed from the end face of the roll when wound in the form of a photosensitive resin laminate. The cut chip property refers to the degree of ease with which chips fly when cutting the unexposed film with a cutting machine. If such chips adhere to the upper surface of the photosensitive resin laminate, etc., they are transferred to the mask in subsequent exposure processes, etc., and become a cause of defective products. The dispersity of the (A) alkali-soluble polymer is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, still more preferably from 1.0 to 4.0, still more preferably from 1.0 to 3.0.

[0083] In the present embodiment, for the photosensitive resin composition, from the viewpoint of being able to significantly improve the adhesion during heating after exposure and then developing, especially showing good adhesion even when the elapsed time after exposure becomes long, as the (A) alkali-soluble polymer, it is preferred to contain a monomer component having an aromatic hydrocarbon group. It should be noted that as such an aromatic hydrocarbon group, for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group can be cited. 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, still 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. As the upper limit, there is no particular limitation, and it is preferably 95% by mass or less, more preferably 80% by mass or less. It should be noted that the content ratio of the monomer component having an aromatic hydrocarbon group when containing a plurality of (A) alkali-soluble polymers is determined in the form of a weight average value.

[0084] As the aforementioned monomer having an aromatic hydrocarbon group, for example, a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative can be cited. Among them, a monomer having an aralkyl group or styrene is preferred.

[0085] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl (excluding benzyl), substituted or unsubstituted benzyl, etc., and preferably substituted or unsubstituted benzyl.

[0086] Examples of the comonomer having a phenylalkyl group include phenethyl (meth)acrylate, etc.

[0087] Examples of the comonomer having a benzyl group include (meth)acrylate having a benzyl group, such as benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group, such as vinylbenzyl chloride, vinylbenzyl alcohol, etc. Among them, benzyl (meth)acrylate is preferred.

[0088] The (A) alkali-soluble polymer 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 of the following-described first monomers and / or at least one of the following-described second monomers.

[0089] The (A) alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the following-described first monomers, and more preferably obtained by copolymerizing at least one first monomer with at least one of the following-described second monomers.

[0090] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include, for example, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid semiester, etc. Among these, (meth)acrylic acid is preferred.

[0091] It should be noted that in this specification, “(meth)acrylic acid” means acrylic acid or methacrylic acid, “(meth)acryloyl” means acryloyl or methacryloyl, and “(meth)acrylate” means “acrylate” or “methacrylate”.

[0092] The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. From the viewpoints of exhibiting good developability and controlling edge fusion properties, etc., it is preferred that the copolymerization ratio is 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. From the viewpoints of high resolution of the resist pattern and the shape of the undercut, and further from the viewpoint of chemical resistance of the resist pattern, it is preferred that the copolymerization ratio is 50% by mass or less, and from these viewpoints, more preferably 35% by mass or less, further preferably 32% by mass or less, and particularly preferably 30% by mass or less.

[0093] The second monomer is a non-acidic monomer having at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylate esters 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, 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.

[0094] From the viewpoint of being able to significantly improve the adhesion when heating is performed after exposure and then development, especially showing good adhesion even when the elapsed time after exposure becomes longer, it is preferred to contain a monomer having an aralkyl group and / or styrene as the monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene, etc. are preferred.

[0095] (A) The alkali-soluble polymer can be used alone in 1 kind, or 2 or more kinds can be used in combination. When 2 or more kinds are used in combination, it is preferred to use in combination two alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group; or to mix an alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group with an alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group. In the latter case, the use ratio 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, preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 95% by mass or more relative to the total of (A) the alkali-soluble polymer.

[0096] In the (A) alkali-soluble polymer of the present embodiment, it is preferred to contain an alkali-soluble polymer (A-1) of 3% by mass or more based on the solid content in the photosensitive resin composition, and the alkali-soluble polymer (A-1) contains a structural unit of styrene and / or a styrene derivative of 52% by mass or more as a monomer component. Thereby, the adhesion when heating is performed after exposure and then development can be significantly improved, especially good adhesion can be obtained even when the elapsed time after exposure becomes longer. From the same viewpoint, the (A) alkali-soluble polymer more preferably contains an alkali-soluble polymer (A-1) of 10% by mass or more based on the solid content in the photosensitive resin composition, further preferably contains 15% by mass or more, particularly preferably contains 20% by mass or more, and most preferably contains 30% by mass or more.

[0097] Examples of the styrene derivative include, for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, and the like.

[0098] In particular, in the present embodiment, when the (A) alkali-soluble polymer contains a plurality of alkali-soluble polymers, the structural unit of styrene and / or styrene derivative in the whole (A) alkali-soluble polymer is 15% by mass or more. Thereby, the adhesion during heating after exposure followed by development can be significantly improved. In particular, good adhesion can be obtained even when the elapsed time after exposure becomes long. Since the styrene skeleton is hydrophobic, the swelling property with respect to the developer can be suppressed, and good adhesion can be exhibited. 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, further preferably 35% by mass or more, and particularly preferably 40% by mass or more.

[0099] However, if the content of the styrene skeleton is large, the fluidity of the resin decreases, and thus the reactivity cannot be sufficiently improved, and the desired adhesion cannot be obtained. In addition, as the elapsed time after exposure becomes long, the free radicals in the system are gradually inactivated, and thus the effect of improving the adhesion by heating after exposure gradually decreases. The upper limit of the structural unit of styrene and / or styrene derivative in the (A) alkali-soluble polymer is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and particularly preferably 70% by mass or less.

[0100] In this way, in the present invention, by making the structural unit of styrene and / or styrene derivative in the whole (A) alkali-soluble polymer 15% by mass or more and heating after exposure followed by development, even in a system with a large content of the styrene skeleton, the fluidity of the resin is increased by heating, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly balanced. As a result, it is considered that the adhesion can be significantly improved. And it is considered that: by significantly improving the adhesion, good adhesion can be obtained even when the elapsed time after exposure becomes long.

[0101] In addition, from the viewpoint of significantly improving the adhesion during heating after exposure and then development, especially showing good adhesion even when the elapsed time after exposure becomes longer, in the alkali-soluble polymer (A-1), it preferably contains 25% by mass or more of structural units of (meth)acrylic acid as monomer components, more preferably 26% by mass or more, further preferably 27% by mass or more, particularly preferably 28% by mass or more, and most preferably 29% by mass or more. From the same viewpoint, it is preferably 35% by mass or less, more preferably 32% by mass or less, and further preferably 30% by mass or less.

[0102] (A) The synthesis of the alkali-soluble polymer is preferably carried out by appropriately adding a radical polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile to a solution obtained by diluting the above-described single or multiple monomers with a solvent such as acetone, methyl ethyl ketone, or isopropyl alcohol, and heating and stirring. Sometimes, a part of the mixture is added dropwise to the reaction solution while carrying out the synthesis. Sometimes, after the reaction is completed, a solvent is further added to adjust to a desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used.

[0103] (A) The weight-average Tg of the glass transition temperature Tg of the alkali-soluble polymer total is preferably 30 °C or higher and 150 °C or lower. Tg total is calculated by the method described in the examples below. In the photosensitive resin composition, by using an (A) alkali-soluble polymer having a Tg of 150 °C or lower total the adhesion during heating after exposure and then development can be significantly improved, especially showing good adhesion even when the elapsed time after exposure becomes longer. From this viewpoint, the Tg of the (A) alkali-soluble polymer total is more preferably 135 °C or lower, further preferably 130 °C or lower, most preferably 125 °C or lower, further preferably 120 °C or lower, and particularly preferably 110 °C or lower. In addition, from the viewpoint of improving the edge fusion resistance, it is preferable to use an (A) alkali-soluble polymer having a Tg of 30 °C or higher total From this viewpoint, the Tg of the (A) alkali-soluble polymer total is more preferably 40 °C or higher, further preferably 50 °C or higher, and particularly preferably 60 °C or higher.

[0104] (A) The proportion of the alkali-soluble polymer relative to the total solid content 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 still more preferably 40% by mass to 60% by mass. From the viewpoint of controlling the development time, it is preferable that the proportion of (A) the alkali-soluble polymer relative to the photosensitive resin composition is 90% by mass or less. On the other hand, from the viewpoint of improving the edge fusion resistance, it is preferable that the proportion of (A) the alkali-soluble polymer relative to the photosensitive resin composition is 10% by mass or more.

[0105] <(B) Compound having an ethylenically unsaturated double bond>

[0106] From the viewpoints of curability and compatibility with (A) the alkali-soluble polymer, the (B) compound having an ethylenically unsaturated double bond preferably contains a compound having a (meth)acryloyl group in the molecule. The number of (meth)acryloyl groups in the (B) compound may be 1 or more.

[0107] (B) The compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated group in its structure. The ethylenically unsaturated bond more preferably originates from a methacryloyl group. From the viewpoints of adhesion and suppression of the foaming property of the developer, the (B) compound having an ethylenically unsaturated bond preferably has an alkylene oxide structure having 3 or more carbon atoms. The number of carbon atoms in the alkylene oxide structure is more preferably 3 to 6, and still more preferably 3 to 4.

[0108] Examples of the (B) compound having 1 (meth)acryloyl group include a compound obtained by adding (meth)acrylic acid to a single terminal of a polyalkylene oxide, or a compound obtained by adding (meth)acrylic acid to a single terminal of a polyalkylene oxide and subjecting the other terminal to alkyl etherification or allyl etherification, and phthalic acid-based compounds, etc., which are preferable from the viewpoints of peelability and flexibility of the cured film.

[0109] Examples of such compounds include (meth)acrylates of compounds obtained by adding polyethylene glycol to phenyl, i.e., phenoxyhexaethylene glycol mono(meth)acrylate; (meth)acrylates of compounds obtained by adding polypropylene glycol with an average addition of 2 moles of propylene oxide and polyethylene glycol with an average addition of 7 moles of ethylene oxide to nonylphenol, i.e., 4-nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate; (meth)acrylates of compounds obtained by adding polypropylene glycol with an average addition of 1 mole of propylene oxide and polyethylene glycol with an average addition of 5 moles of ethylene oxide to nonylphenol, i.e., 4-nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate; acrylates of compounds obtained by adding polyethylene glycol with an average addition of 8 moles of ethylene oxide to nonylphenol, i.e., 4-nonylphenoxyoctaethylene glycol (meth)acrylate (e.g., manufactured by Toagosei Co., Ltd., M-114), etc.

[0110] In addition, if γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl phthalate is included, it is preferable not only from the above viewpoints but also from the viewpoints of sensitivity, resolution, and adhesion.

[0111] Examples of compounds having two (meth)acryloyl groups in the molecule include compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain, or compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain obtained by randomly or block-bonding an ethylene oxide chain and a propylene oxide chain.

[0112] 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, poly(ethylene glycol) (meth)acrylates such as compounds having (meth)acryloyl groups at both ends of a 12-mole ethylene oxide chain, and poly(propylene glycol) di(meth)acrylate, poly(butylene glycol) di(meth)acrylate, etc. Examples of poly(alkylene oxide) di(meth)acrylate compounds containing ethylene oxide groups and propylene oxide groups in the compound include dimethyl acrylates of diols obtained by further adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol with an average addition of 12 moles of propylene oxide, dimethyl acrylates of diols obtained by further adding an average of 15 moles of ethylene oxide to both ends of polypropylene glycol with an average addition of 18 moles of propylene oxide, FA-023M, FA-024M, FA-027M (product names, manufactured by Hitachi Chemical Co., Ltd.). They are preferable from the viewpoints of flexibility, resolution, adhesion, etc.

[0113] As another example of a compound having two (meth)acryloyl groups in the molecule, from the viewpoints of resolution and adhesion, a compound having (meth)acryloyl groups at both ends obtained by modifying bisphenol A with an alkylene oxide is preferred.

[0114] Specifically, a compound represented by the following general formula (I) can be used.

[0115]

[0116] {In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is C3H6, 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. The arrangement of the repeating units of -(A-O)- and -(B-O)- can be random or block. And, in the case of a block, either -(A-O)- or -(B-O)- can be on the biphenyl side.}

[0117] For example, from the viewpoints of resolution and adhesion, poly(ethylene glycol) dimethacrylate obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A, poly(ethylene glycol) dimethacrylate obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A, and poly(ethylene glycol) dimethacrylate obtained by adding an average of 1 mole of ethylene oxide to both ends of bisphenol A are preferred.

[0118] In addition, for the aromatic ring in the above general formula (I), a compound having a heteroatom and / or a substituent can be used.

[0119] Examples of the heteroatom include a halogen atom, etc. 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, benzoylmethyl, 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 alkylthio group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms or a group containing a heterocycle, or an aryl group substituted with these substituents, etc. These substituents can form a condensed ring or a hydrogen atom in these substituents is optionally substituted with a heteroatom such as a halogen atom. When the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents can be the same or different.

[0120] As a compound having three or more (meth)acryloyl groups in the molecule, it is obtained by converting an alcohol obtained by adding three or more moles of a group capable of adding an alkylene oxide group in the molecule as a central skeleton and adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide thereto into a (meth)acrylate. At this time, as the compound capable of forming the central skeleton, for example, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanurate ring, etc. can be cited. As these compounds, tri(meth)acrylates such as ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate (for example, from the viewpoints of flexibility, adhesiveness, and suppression of bleeding, preferably a trimethacrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane, a trimethacrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane), etc.; tetra(meth)acrylates such as di(trimethylolpropane) tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.; penta(meth)acrylates such as dipentaerythritol penta(meth)acrylate, etc.; hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylate, etc. From the viewpoint of being able to significantly improve the adhesiveness when heating is performed after exposure and then development is performed, particularly, even when the elapsed time after exposure becomes long, a good adhesiveness is exhibited, a compound having three or more (meth)acryloyl groups is preferred, and a compound having three or more methacryloyl groups is more preferred.

[0121] As the tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferred. The pentaerythritol tetra(meth)acrylate may be a tetra(meth)acrylate obtained by adding a total of 1 to 40 moles of alkylene oxide to the four terminals of pentaerythritol, etc.

[0122] As the hexa(meth)acrylate, a hexa(meth)acrylate obtained by adding a total of 1 to 40 moles of ethylene oxide to the six terminals of dipentaerythritol and a hexa(meth)acrylate obtained by adding a total of 1 to 20 moles of ε-caprolactone to the six terminals of dipentaerythritol are preferred.

[0123] As the compound (B) having an ethylenically unsaturated double bond, from the viewpoint of being able to significantly improve the adhesion when heated after exposure and then developed, especially being able to obtain good adhesion even when the elapsed time after exposure becomes longer, a (meth)acrylate compound having 3 or more ethylenically unsaturated double bonds is preferably included. From the same viewpoint, a (meth)acrylate compound having 4 or more ethylenically unsaturated double bonds is more preferably included, a (meth)acrylate compound having 5 or more ethylenically unsaturated double bonds is further preferably included, and a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds is particularly preferably included. In addition, from the same viewpoint, they are preferably methacrylate compounds.

[0124] It is considered that compounds having 3 or more, 4 or more, 5 or more, 6 or more ethylenically unsaturated double bonds have the effect of increasing the crosslinking density during polymerization based on exposure, but in many cases, the desired crosslinking density cannot be obtained due to the influence of steric hindrance caused by the large number of functional groups. The present invention has found that by subjecting a compound preferably having 3 or more ethylenically unsaturated double bonds, more preferably having 4 or more ethylenically unsaturated double bonds, further preferably having 5 or more ethylenically unsaturated double bonds, and particularly preferably having 6 or more ethylenically unsaturated double bonds to a heat treatment after exposure, the fluidity in the system is increased, so that even when the number of functional groups is large, the influence of steric hindrance is reduced, and high adhesion can be obtained.

[0125] As the content of the compound preferably having 3 or more ethylenically unsaturated double bonds, more preferably having 4 or more ethylenically unsaturated double bonds, further preferably having 5 or more ethylenically unsaturated double bonds, and particularly preferably having 6 or more ethylenically unsaturated double bonds, based on the solid content of the aforementioned photosensitive resin composition, it is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, and particularly preferably 10% by mass or more. In addition, as the upper limit value of the content, from the viewpoint of showing the effect of the heat treatment after exposure, it is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0126] Examples of the (meth)acrylate compound (b1) having 3 or more ethylenically unsaturated bonds include:

[0127] Tri(meth)acrylates, such as ethoxylated glycerol tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate (for example, as suitable examples from the viewpoints of flexibility, adhesion, and suppression of exudation, tri(meth)acrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane, and tri(meth)acrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane), etc.;

[0128] Tetra(meth)acrylates, such as bis(trimethylolpropane) tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.;

[0129] Penta(meth)acrylates, such as dipentaerythritol penta(meth)acrylate, etc.;

[0130] Hexa(meth)acrylates, such as dipentaerythritol hexa(meth)acrylate, etc.

[0131] Among these, tetra-, penta-, or hexa-(meth)acrylates are preferred.

[0132] From the viewpoint of suppressing exudation, the (meth)acrylate compound having 3 or more ethylenically unsaturated bonds preferably has a weight average molecular weight of 500 or more, more preferably 700 or more, and still more preferably 900 or more.

[0133] As the tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferred. As pentaerythritol tetra(meth)acrylate, tetra(meth)acrylate obtained by adding a total of 1 to 40 moles of alkylene oxide to the 4 terminals of pentaerythritol, etc. are preferred.

[0134] The tetra(meth)acrylate is more preferably a tetramethacrylate compound represented by the following general formula (II).

[0135]

[0136] {In the formula, R3 to R6 each independently represent an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, m1, m2, m3, and m4 are each independently an integer of 0 to 40, m1 + m2 + m3 + m4 is 1 to 40, and when m1 + m2 + m3 + m4 is 2 or more, the plurality of Xs may be the same or different}

[0137] Although not wishing to be bound by theory, it is considered that the tetramethacrylate compound represented by the general formula (II) has R3 to R6 groups, and therefore, the hydrolyzability in an alkaline solution is suppressed compared to a tetraacrylate having an H2C=CH-CO-O- moiety. From the viewpoint of being able to significantly improve the adhesion during heating after exposure and then development, particularly achieving good adhesion even when the elapsed time after exposure becomes long, a photosensitive resin composition containing the tetramethacrylate compound represented by the general formula (II) is preferably used.

[0138] In the general formula (II), it is preferred that at least one of the R3 to R6 groups is a methyl group, and more preferably, the R3 to R6 groups are all methyl groups.

[0139] Regarding the resist pattern, from the viewpoint of obtaining desired resolution, undercut shape, and residual film ratio, in the general formula (II), X is preferably -CH2-CH2-.

[0140] Regarding the resist pattern, from the viewpoint of obtaining desired resolution, undercut shape, and residual film ratio, in the general formula (II), m1, m2, m3, and m4 are each independently preferably an integer of 1 to 20, more preferably an integer of 2 to 10. Further, in the general formula (II), m1 + m2 + m3 + m4 is preferably 1 to 36 or 4 to 36.

[0141] Examples of the compound represented by the general formula (II) include pentaerythritol (poly)alkoxy tetramethacrylate. In addition, in the present application, "pentaerythritol (poly)alkoxy tetramethacrylate" includes both "pentaerythritol alkoxy tetramethacrylate" in which m1 + m2 + m3 + m4 = 1 in the above general formula (II) and "pentaerythritol polyalkoxy tetramethacrylate" in which m1 + m2 + m3 + m4 = 2 to 40. Examples of the compound represented by the general formula (II) include the compounds listed in JP-A-2013-156369, such as pentaerythritol (poly)alkoxy tetramethacrylate.

[0142] As the hexa(meth)acrylate compound, preferably, a hexa(meth)acrylate obtained by adding 1 to 24 moles of ethylene oxide in total to the 6 terminals of dipentaerythritol, or a hexa(meth)acrylate obtained by adding 1 to 10 moles of ε-caprolactone in total to the 6 terminals of dipentaerythritol.

[0143] From the viewpoint of being able to significantly improve the adhesion during heating after exposure and then development, especially achieving good adhesion even when the elapsed time after exposure becomes longer, in the photosensitive resin composition described in this embodiment, as the compound (B) having an ethylenically unsaturated bond, it is particularly preferred to contain a (meth)acrylate compound having 4 or more ethylenically unsaturated bonds and an alkylene oxide chain. At this time, the ethylenically unsaturated bond is more preferably derived from a methacryloyl group, and the alkylene oxide chain is more preferably an ethylene oxide chain.

[0144] In this embodiment, from the viewpoint of being able to significantly improve the adhesion during heating after exposure and then development, especially achieving good adhesion even when the elapsed time after exposure becomes longer, in the photosensitive resin composition, as the compound (B) having an ethylenically unsaturated bond, it is preferred to contain a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton. Examples of the alkylene oxide chain include an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentylene oxide chain, a hexylene oxide chain, etc. 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, as the alkylene oxide chain, ethylene oxide chain, propylene oxide chain, and butylene oxide chain are more preferred, ethylene oxide chain and propylene oxide chain are further preferred, and ethylene oxide chain is particularly preferred.

[0145] In the photosensitive resin composition, by using the combination of (A) an alkali-soluble polymer and a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, there is a tendency to maintain a balance among chemical resistance, adhesion, and resolution of the resist pattern.

[0146] The (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton is an ester formed by a dipentaerythritol compound obtained by modifying at least one of the plurality of hydroxyl groups with an alkylene oxide and (meth)acrylic acid. The 6 hydroxyl groups of the dipentaerythritol skeleton are optionally modified with an alkylene oxide. The number of ester bonds in one molecule of the ester can be 1 to 6, preferably 6.

[0147] Examples of the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton include hexa(meth)acrylate obtained by adding 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 to dipentaerythritol.

[0148] Specifically, as the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, from the viewpoint of being able to significantly improve the adhesion during heating after exposure and then development, especially achieving good adhesion even when the elapsed time after exposure becomes longer, the compound represented by the following general formula (III) is preferred.

[0149]

[0150] {In the formula, each R 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}. In general formula (III), it is preferable that the average value of all n's is 4 or more or each n is 1 or more. As R, a methyl group is preferable.

[0151] From the same viewpoint, the content of the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton is preferably in the range of 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and still more preferably 7% by mass to 30% by mass with respect to the total amount of the solid components in the photosensitive resin composition.

[0152] With respect to the total amount of the solid components of the photosensitive resin composition, the content of the (meth)acrylate compound (b1) having 3 or more ethylenically unsaturated bonds is preferably more than 0% by mass and 40% by mass or less. When the content exceeds 0% by mass, there is a tendency that the adhesion during heating after exposure and then development can be significantly improved, particularly good adhesion can be achieved even when the elapsed time after exposure becomes long. When it is 40% by mass or less, there is a tendency that the flexibility of the cured resist is improved and the peeling time is shortened. The content is more preferably 2% by mass or more and 30% by mass or less, and still more preferably 4% by mass or more and 25% by mass or less.

[0153] From the viewpoints of adhesion and suppression of the foaming property of the developer, in the photosensitive resin composition, as the compound (B) having an ethylenically unsaturated bond, it is preferable to contain a compound (b2) having an epoxybutane chain or an epoxypropane chain and having 1 or 2 (meth)acryloyl groups.

[0154] From the viewpoint of suppressing bleeding, the compound (b2) having an epoxybutane chain or an epoxypropane chain and having 1 or 2 (meth)acryloyl groups preferably has a molecular weight of 500 or more, more preferably 700 or more, and still more preferably 1000 or more.

[0155] Examples of the compound (b2) having an epoxybutane chain or an epoxypropane chain and having 1 or 2 (meth)acryloyl groups include polypropylene glycol (meth)acrylate, polypropylene glycol di(meth)acrylate, poly-1,4-butanediol (meth)acrylate, poly-1,4-butanediol di(meth)acrylate, etc. The compound (b2) having an epoxybutane chain or an epoxypropane chain and having 1 or 2 (meth)acryloyl groups may contain an ethylene oxide chain in addition to the epoxybutane chain or the epoxypropane chain.

[0156] Specifically, the compound having an epoxybutane chain or an epoxypropane chain and having one or two (meth)acryloyl groups is a (meth)acrylate or di(meth)acrylate having preferably 1 to 20, more preferably 4 to 15, and still more preferably 6 to 12 C4H8O or C3H6O.

[0157] With respect to the total amount of the solid components of the photosensitive resin composition, the content of the compound having an epoxybutane chain or an epoxypropane chain and having one or two (meth)acryloyl groups is preferably more than 0% by mass and 20% by mass or less.

[0158] In the present embodiment, in order to suppress the bleeding of the components constituting the dry film resist and improve the storage stability, based on the total amount of the solid components of the compound (B) having an ethylenically unsaturated bond, preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% is a compound having a weight average molecular weight of 500 or more. From the viewpoints of suppressing bleeding and chemical resistance of the resist pattern, the weight average molecular weight of the compound (B) having an ethylenically unsaturated bond is preferably 760 or more, more preferably 800 or more, still more preferably 830 or more, and particularly preferably 900 or more. The weight average molecular weight of the compound (B) having an ethylenically unsaturated bond can be determined in the form of the molecular weight calculated from the molecular structure of the compound (B) having an ethylenically unsaturated bond. When there are a plurality of compounds (B) having an ethylenically unsaturated bond, it can be determined by weighted-averaging the molecular weights of the respective compounds by their contents.

[0159] From the viewpoints of chemical resistance, adhesion, high resolution, and undercut shape of the resist pattern, the concentration of methacryloyl groups in the compound (B) having an ethylenically unsaturated bond is preferably 0.20 mol / 100 g or more, more preferably 0.30 mol / 100 g or more, and still more preferably 0.35 mol / 100 g or more. The upper limit value of the concentration of methacryloyl groups is not limited as long as the polymerizability and alkali developability are ensured. For example, it can be 0.90 mol / 100 g or less or 0.80 mol / 100 g or less.

[0160] From the same viewpoints, the value of the concentration of methacryloyl groups in the compound (B) having an ethylenically unsaturated bond / (the concentration of methacryloyl groups + the concentration of acryloyl groups) is preferably 0.50 or more, more preferably 0.60 or more, still more preferably 0.80 or more, particularly preferably 0.90 or more, and most preferably 0.95 or more.

[0161] The above-described (meth)acrylate compounds can be used independently or in combination. In the photosensitive resin composition, as the compound (B) having an ethylenically unsaturated bond, other compounds can also be included. Examples of other compounds include (meth)acrylates having a urethane bond, compounds obtained by reacting a polyol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a compound containing a glycidyl group with an α,β-unsaturated carboxylic acid, 1,6-hexanediol di(meth)acrylate, and the like.

[0162] (B) The proportion of the compound having an ethylenically unsaturated double bond relative to the total solid content mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. From the viewpoints of sensitivity, resolution, and adhesion, it is preferred that this proportion is 5% by mass or more. More preferably, this proportion is 20% by mass or more, and still more preferably 30% by mass or more. On the other hand, from the viewpoints of suppressing edge fusion and delaying the peeling of the cured resist, it is preferred that this proportion is 70% by mass or less. More preferably, this proportion is 50% by mass or less.

[0163] As the compound (B) having 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 relative to the solid content of the photosensitive resin composition is preferably 0% or more and 18% by mass or less. Thereby, the adhesion during heating after exposure followed by development can be significantly improved, and in particular, good adhesion can be obtained even when the elapsed time after exposure becomes long. Compounds having an ethylenically unsaturated double bond with a high bisphenol A skeleton concentration usually have improved adhesion due to their hydrophobicity.

[0164] The present invention has found that due to the rigid skeleton of bisphenol A, even when heated after exposure, the fluidity does not increase, and the effect of improving adhesion is small. Therefore, in the present invention, from the above viewpoints, as the compound (B) having 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 relative to the solid content of the photosensitive resin composition is preferably 18% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, most preferably 6% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less. From the same viewpoints, as the compound (B) having an ethylenically unsaturated double bond, the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.20 mol / 100 g or more relative to the solid content of the photosensitive resin composition is preferably 18% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, most preferably 6% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less.

[0165] In particular, in the present embodiment, the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is preferably 0.94 or more. Thereby, the adhesion during heating after exposure followed by development can be significantly improved. In particular, good adhesion can be obtained even when the elapsed time after exposure becomes long. From the same viewpoint, as [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond], it is more preferably 1.04 or more, further preferably 1.11 or more, particularly preferably 1.21 or more, most preferably 1.30 or more, and most preferably 1.35 or more.

[0166] When the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is increased, generally the alkali solubility, in other words, the hydrophilic component becomes more, and the Tg in the system also rises, and the fluidity decreases. As a result, the double bond reaction rate decreases, and as a result, the adhesion generally decreases. However, it is considered that in the present invention, since the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is large and heat treatment is also performed after exposure, even if the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is large, the fluidity in the system will increase, the double bond reaction rate will also increase, and further, there is an effect of improving the adhesion by the interaction between the carboxyl group of the alkali-soluble polymer and copper, and the effects of the present invention can be achieved.

[0167] [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is preferably 5 or less, more preferably 4 or less, further preferably 3 or less, particularly preferably 2 or less, and most preferably 1.5 or less.

[0168] <(C) Photoinitiator>

[0169] (C) The photoinitiator is a compound that polymerizes monomers using light.

[0170] (C-1) Photoinitiator

[0171] In the photosensitive resin composition of the present embodiment, as the (C-1) photoinitiator ((C) photoinitiator), compounds generally known in the art are included.

[0172] The total content of the (C-1) photoinitiator in the photosensitive resin composition is preferably in the range of 0.01 to 20% by mass, more preferably 0.05% to 10% by mass, still more preferably 0.1% to 7% by mass, and particularly preferably 0.1% to 6% by mass. From the viewpoint of obtaining sufficient sensitivity, the total content of the (C-1) photoinitiator is preferably 0.01% by mass or more, and from the viewpoint of allowing light to sufficiently penetrate to the bottom surface of the resist and obtaining good high resolution, it is preferably 20% by mass or less.

[0173] Examples of the (C-1) photoinitiator include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoates, oxime esters, acridines (for example, from the viewpoints of sensitivity, resolution, and adhesion, 9-phenylacridine, bisacridylheptane, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine are preferred), and furthermore, hexaphenylbiimidazole, dihydropyrazole compounds, anthracene compounds (for example, from the viewpoints of sensitivity, resolution, and adhesion, 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene are preferred), coumarin compounds (for example, from the viewpoints of sensitivity, resolution, and adhesion, 7-diethylamino-4-methylcoumarin is preferred), N-aryl amino acids or their ester compounds (for example, from the viewpoints of sensitivity, resolution, and adhesion, N-phenylglycine is preferred), and halides (for example, tribromomethylphenyl sulfone), etc. They can be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-oxide, and triphenylphosphine oxide can also be used.

[0174] Examples of the aromatic ketones include, for example, benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. They can be used alone or in combination of two or more. Among these, from the viewpoint of adhesion, 4,4'-bis(diethylamino)benzophenone is preferred.

[0175] Furthermore, from the viewpoint of transmittance, the content of the aromatic ketones in the photosensitive resin composition is preferably in the range of 0.01% to 0.5% by mass, and more preferably 0.02% to 0.3% by mass.

[0176] Examples of the hexaarylbiimidazole include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,5-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,6-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, and 2,2'-bis(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, etc. They can 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.

[0177] In the present embodiment, from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably in the range of 0.05% by mass to 7% by mass, more preferably in the range of 0.1% by mass to 6% by mass, and still more preferably in the range of 1% by mass to 5% by mass.

[0178] From the viewpoints of the peeling property, sensitivity, resolution, and adhesion of the photosensitive resin layer, the photosensitive resin composition preferably further contains a dihydropyrazole compound and an anthracene compound (for example, from the viewpoints of sensitivity, resolution, and adhesion, dialkoxyanthracenes such as 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene) as photosensitizers.

[0179] As the dihydropyrazole compound, from the above viewpoints, for example, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-(4-(benzoxazol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-dihydropyrazole, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-dihydropyrazole, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-dihydropyrazole, etc. can be preferably cited. Among these, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole is more preferred.

[0180] In the present embodiment, from the viewpoint of transmittance and from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer, the content of the photosensitizer in the photosensitive resin composition is preferably in the range of 0.05% by mass to 5% by mass, more preferably in the range of 0.1% by mass to 3% by mass, further preferably in the range of 0.1% by mass to 1% by mass, and particularly preferably in the range of 0.1% by mass to 0.7% by mass.

[0181] (C-2) Photoinitiator

[0182] In addition, in the present embodiment, as the (C-2) photoinitiator ((C) photoinitiator) in the photosensitive resin composition, a photoinitiator containing anthracene and / or an anthracene derivative can be used.

[0183] When at least anthracene and / or an anthracene derivative is used as the (C-2) photopolymerization initiator, it is advantageous from the viewpoint of being able to significantly improve the adhesion during heating after exposure and then development, particularly being able to obtain good adhesion even when the elapsed time after exposure becomes long. In addition, anthracene and / or an anthracene derivative absorbs the first active light having a center wavelength of less than 390 nm and the second active light having a center wavelength of 390 nm or more and can function as a polymerization initiator. The active light is, for example, a laser.

[0184] Therefore, in one aspect, the photosensitive resin composition can have photosensitivity to the first active light and the second active light and can also be used for two-wavelength exposure. Anthracene and / or an anthracene derivative can also be selected so as to have multiple maximum absorptions in the wavelength ranges of the first active light and the second active light. The center wavelength of the first active light is preferably 350 to 380 nm, more preferably 355 to 375 nm, and particularly preferably 375 nm. The center wavelength of the second active light is preferably 400 to 410 nm, more preferably 402 to 408 nm, and particularly preferably 405 nm (h-ray).

[0185] The total content of the (C-2) photopolymerization initiator in the photosensitive resin composition is preferably in the range of 0.01 to 20% by mass, more preferably 0.05% by mass to 10% by mass, still more preferably 0.1% by mass to 7% by mass, and particularly preferably 0.1% by mass to 6% by mass. From the viewpoint of obtaining sufficient sensitivity, the total content of the (C-2) photopolymerization initiator is preferably 0.01% by mass or more, and from the viewpoint of allowing light to sufficiently transmit to the bottom surface of the resist and obtaining good high resolution, the total content of the (C-2) photopolymerization initiator is preferably 20% by mass or less.

[0186] Anthracene and anthracene derivatives are advantageous from the viewpoint of being able to significantly improve the adhesion during heating after exposure and then development, particularly achieving good adhesion even when the elapsed time after exposure becomes long. From the same viewpoint, the anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms which may have a substituent and / or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9-position and / or 10-position, more preferably at the 9,10-positions.

[0187] In one embodiment, from the perspective of significantly improving the adhesion during heating after exposure and then development, especially achieving good adhesion even when the elapsed time after exposure is prolonged, the anthracene derivative preferably has an alkoxy group with 1 to 40 carbon atoms, optionally having a substituent, at least at one of the 9-position or 10-position, and more preferably has an alkoxy group with 1 to 30 carbon atoms, optionally having a substituent, at least at one of the 9-position or 10-position. From the perspective of obtaining good adhesion and resolution, it is preferred to have an alkoxy group with 1 to 40 carbon atoms, optionally having a substituent, at the 9,10-positions, and more preferably have an alkoxy group with 1 to 30 carbon atoms, optionally having a substituent, at the 9,10-positions. The number of carbon atoms of the groups at the 9-position and 10-position may be the same or different.

[0188] Examples of the alkoxy group optionally having a substituent include:

[0189] methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methylpropoxy, 1-methylpropoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, eicosyloxy, cyclohexyloxy, norbornyloxy, tricyclodecyloxy, tetracyclododecyloxy, adamantyloxy, methyladamantyloxy, ethyladamantyloxy, and butyladamantyloxy;

[0190] alkoxy groups modified with halogen, such as chlorobutoxy and chloropropoxy;

[0191] alkoxy groups added with a hydroxyl group, such as hydroxybutoxy;

[0192] alkoxy groups added with a cyano group, such as cyanobutoxy;

[0193] alkoxy groups added with an epoxyalkylene group, such as methoxybutoxy;

[0194] alkoxy groups added with an aryl group, such as phenoxybutoxy, etc.

[0195] Among them, n-butoxy is more preferred.

[0196] In one embodiment, from the perspective of significantly improving the adhesion during heating after exposure and then development, especially achieving good adhesion even when the elapsed time after exposure is prolonged, the anthracene derivative preferably has an aryl group with 6 to 40 carbon atoms, optionally having a substituent, at least at one of the 9-position or 10-position, and more preferably has an aryl group with 6 to 30 carbon atoms, optionally having a substituent, at least at one of the 9-position or 10-position.

[0197] From the viewpoint of significantly improving the adhesion during heating after exposure and then development, especially achieving good adhesion even when the elapsed time after exposure becomes longer, it is preferable to have an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9- and 10-positions, and more preferably an aryl group having 6 to 30 carbon atoms which may have a substituent at the 9- and 10-positions. The number of carbon atoms of the groups at the 9- and 10-positions may be the same or different. In addition, the groups at the 9- and 10-positions may be the same group or different groups. For example, the group at the 9-position may be an alkoxy group having 1 to 40 carbon atoms which may have a substituent, and the group at the 10-position may be an aryl group having 6 to 40 carbon atoms which may have a substituent.

[0198] Examples of the aryl group having 6 to 40 carbon atoms which may have a substituent include phenyl, biphenyl, naphthyl, anthryl; an aryl group to which an alkoxy group is added, such as methoxyphenyl, ethoxyphenyl; an aryl group to which an alkyl group is added, such as tolyl, xylyl, mesityl, nonylphenyl; an aryl group to which a halogen is added, such as chlorophenyl; an aryl group to which a hydroxyl group is added, such as hydroxyphenyl, etc. Among them, phenyl is more preferable.

[0199] The anthracene derivative is preferably represented by the following general formula (IV).

[0200]

[0201] R 1 independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group or an N(R')2 group, and two or more Rs 1 optionally bond to each other to form a cyclic structure, and the cyclic structure optionally contains a heteroatom.

[0202] X independently represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, a -N(R')- group, a -CO-O- group, a -CO-S- group, a -SO2-O- group, a -SO2-S- group, a -SO2-N(R')- group, an -O-CO- group, a -S-CO- group, an -O-SO2- group or an S-SO2- group. Among them, the combination where X is a single bond and R 1 is a hydrogen atom (i.e., unsubstituted anthracene) is excluded.

[0203] 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 optionally bond to each other to form a cyclic structure, and the cyclic structure optionally contains a heteroatom.

[0204] p is an integer from 1 to 10, preferably from 2 to 4.

[0205] As the above-mentioned R 1 and the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms in R', specifically, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-icosyl, isopropyl, isobutyl, sec-butyl, tert-butyl, etc. can be cited.

[0206] As the above-mentioned R 1 Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in R' include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and bridged alicyclic hydrocarbon groups having 6 to 20 carbon atoms (such as norbornyl, tricyclodecyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl, butyladamantyl, etc.).

[0207] As the above-mentioned R 1 Specific examples of the alkenyl group having 2 to 4 carbon atoms in R' include vinyl and propenyl.

[0208] As the above-mentioned R 1 Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in R' include phenyl, biphenyl, naphthyl, anthryl, methoxyphenyl, ethoxyphenyl, tolyl, xylyl, mesityl, nonylphenyl, chlorophenyl, hydroxyphenyl.

[0209] As the above-mentioned R 1 The substituted or unsubstituted heteroaryl group in R' includes groups containing one or more heteroatoms such as sulfur atoms, oxygen atoms, nitrogen atoms, etc. in the substituted or unsubstituted aryl group, such as pyridyl, imidazolyl, morpholinyl, piperidyl, pyrrolidinyl, etc.

[0210] In addition, the above-mentioned R 1Each of the hydrocarbon groups of R and R' is optionally 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 (such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.), an alkoxy group having 1 to 4 carbon atoms (such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy, etc.), a cyano group, a cyanoalkyl group having 2 to 5 carbon atoms (such as cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, etc.), an alkoxycarbonyl group (such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, etc.), an alkoxycarbonylalkoxy group (such as methoxycarbonylmethoxy, ethoxycarbonylmethoxy, tert-butoxycarbonylmethoxy, etc.), a halogen atom (such as fluorine, chlorine, etc.), and a fluoroalkyl group (such as fluoromethyl, trifluoromethyl, pentafluoroethyl, etc.). The above R 1 Each 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 10-position.

[0211] Examples of the preferred R 1 and R' include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-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-toluoyl group, a benzyl group, a methylbenzyl group, a phenyl group, and a 1-naphthyl group.

[0212] Examples of the preferred X include a single bond, an oxygen atom, a sulfur atom, a -N(R')- group, a -O-CO- group, and an O-SO2- group. Here, when the above X is a -N(R')- group, the above R' is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, a camphoroyl group, a norbornyl group, or a benzyl group.

[0213] Examples of the compound represented by the above general formula (IV) include, for example, 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 9-vinylanthracene, 9-phenylanthracene, 9,10-diphenylanthracene, 2-bromo-9,10-diphenylanthracene, 9-(4-bromophenyl)-10-phenylanthracene, 9-(1-naphthyl)anthracene, 9-(2-naphthyl)anthracene, 2-bromo-9,10-bis(2-naphthyl)anthracene, 2,6-dibromo-9,10-bis(2-naphthyl)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 1,2-benzanthracene, dihydroxyanthraquinone, 1,4,9,10-tetrahydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene, 9-(methylaminomethyl)anthracene, 9-acetylanthracene, 9-anthracenecarbaldehyde, 10-methyl-9-anthracenecarbaldehyde, 1,8,9-triacetoxyanthracene, etc. Among these, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9,10-bis(3-chloropropoxy)anthracene are preferred. In particular, from the viewpoint of being able to significantly improve the adhesion when heated after exposure and then developed, especially achieving good adhesion even when the elapsed time after exposure becomes longer, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-bis(3-chloropropoxy)anthracene are more preferred. 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-bis(3-chloropropoxy)anthracene are particularly preferred. The compound represented by the above general formula (IV) can be used alone or in combination of two or more kinds.

[0214] From the viewpoint of being able to significantly improve the adhesion when heated after exposure and then developed, especially achieving good adhesion even when the elapsed time after exposure becomes longer, the (C-2) photoinitiator preferably (1) includes 9,10-diphenylanthracene; (2) includes 9,10-dialkoxyanthracene; (3) includes an anthracene derivative having a halogen atom; (4) includes a halide of 9,10-dialkoxyanthracene; (5) includes a compound in which the alkoxy group at the 9-position and / or 10-position of 9,10-dialkoxyanthracene is modified with one or more halogen atoms; and / or, (6) includes a compound having a halogen atom directly bonded to the anthracene skeleton.

[0215] The compound represented by the above general formula (IV) is advantageous from the viewpoint of being able to significantly improve the adhesion when heated after exposure and then developed, especially being able to obtain good adhesion even when the elapsed time after exposure becomes long. Further, it is also advantageous from the viewpoint of being usable for two-wavelength exposure using a first actinic light having a central wavelength of less than 390 nm and a second actinic light having a central wavelength of 390 nm or more, and being able to provide a photosensitive resin composition exhibiting excellent sensitivity, adhesion, and resolution.

[0216] In one aspect, the (C-2) photopolymerization initiator preferably contains an anthracene derivative having a halogen atom. Suitable examples of the anthracene derivative having a halogen atom are halogenated products of 9,10-dialkoxyanthracene. Suitable examples of the halogenated product are compounds in which the alkoxy group at the 9-position and / or 10-position of 9,10-dialkoxyanthracene is modified with one or more halogen atoms. As the preferred alkoxy group, the alkoxy groups exemplified above as alkoxy groups having 1 to 40 carbon atoms can be mentioned.

[0217] In one aspect, as the anthracene derivative, a compound having a halogen atom directly bonded to the anthracene skeleton is also preferred. Examples of such anthracene compounds include 9-bromo-10-phenylanthracene, 9-chloro-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenyl)-10-bromoanthracene, 9-(4-biphenyl)-10-bromoanthracene, 9-bromo-10-(9-phenanthryl)anthracene, 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, 9,10-dibromoanthracene.

[0218] In 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% by mass, more preferably 0.1 to 3% by mass, and particularly preferably 0.1 to 1.0% by mass, based on the total solid content of the photosensitive resin composition.

[0219] (C-2) The photoinitiator may further contain compounds other than anthracene and anthracene derivatives. Examples of such compounds include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoates, oxime esters, acridines (for example, from the viewpoints of sensitivity, resolution, and adhesion, 9-phenylacridine, bisacridylheptane, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine are preferred), hexarylbisimidazole, dihydropyrazole compounds, coumarin compounds (for example, from the viewpoints of sensitivity, resolution, and adhesion, 7-diethylamino-4-methylcoumarin is preferred), N-aryl amino acids or their ester compounds (for example, from the viewpoints of sensitivity, resolution, and adhesion, N-phenylglycine is preferred), and halides (for example, tribromomethylphenyl sulfone). They may be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-oxide phosphine, triphenylphosphine oxide, etc. may also be used.

[0220] Examples of the aromatic ketones include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. They may be used alone or in combination of two or more. Among these, from the viewpoint of adhesion, 4,4'-bis(diethylamino)benzophenone is preferred. Further, from the viewpoint of transmittance, the content of the aromatic ketones in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3% by mass.

[0221] Examples of the hexaarylbiimidazole include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,4-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,5-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,6-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, and 2,2'-bis(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, etc. They can be used alone or in combination of two or more. From the viewpoints of sensitivity, resolution, and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

[0222] From the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably in the range of 0.05% by mass to 8% by mass, more preferably in the range of 0.1% by mass to 7% by mass, and further preferably in the range of 1% by mass to 6% by mass.

[0223] From the viewpoints of the peeling characteristics, sensitivity, resolution, and adhesion of the photosensitive resin layer, in the photosensitive resin composition, as the (C-2) photopolymerization initiator, it is preferably to contain one or more dihydropyrazole compounds.

[0224] From the above viewpoints, as the dihydropyrazole compound, it is preferably, for example, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-(4-(benzoxazol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-dihydropyrazole, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-dihydropyrazole, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-dihydropyrazole, etc., and more preferably 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole.

[0225] <(D) inhibitor>

[0226] In this embodiment, from the viewpoint that even after heating after exposure, the shortest development time of the unexposed portion is not prolonged, it is preferred that the photosensitive resin composition further contains a (D) inhibitor. From the same viewpoint, as the (D) inhibitor, a radical polymerization inhibitor or a phenol derivative is preferred, and a phenol derivative is more preferred. The (D) inhibitor may be originally contained in the raw material components used, or may be added when formulating the photosensitive resin composition formulation. In the case of being originally contained in the raw material components used, the content of the inhibitor can be quantified by GC-MS analysis, etc. after producing the photosensitive resin laminate.

[0227] Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, aluminum salt of nitrosophenylhydroxylamine, diphenylnitrosamine, etc. Aluminum salt of nitrosophenylhydroxylamine is preferred in order not to impair the sensitivity of the photosensitive resin composition.

[0228] Examples of the phenol derivative 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-tertamylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis(2-hydroxy-3-tert-butyl-5-ethylphenyl)methane, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrenated phenol (e.g., manufactured by Kawaguchi Chemical Industry Co., Ltd., ANTAGE SP), tribenzylphenol (e.g., manufactured by Kawaguchi Chemical Industry Co., Ltd., TBP, phenol having 1 to 3 benzyl groups), biphenol, etc.

[0229] (D) The proportion of the inhibitor relative to the total solid content mass of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass. From the viewpoint that the shortest development time of the unexposed portion is not prolonged even after heating after exposure, this proportion is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, further preferably 0.01% by mass or more, most preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, from the viewpoints of less reduction in sensitivity and improvement in resolution, this proportion is preferably 10% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.3% by mass or less.

[0230] <(E) Benzotriazole derivative>

[0231] Furthermore, from the viewpoint that no discoloration is observed on the copper surface even after heating after exposure and after developing and removing the photosensitive resin composition layer, it is preferable to contain an (E) benzotriazole derivative. As the (E) benzotriazole derivative, it is preferable to contain at least one compound selected from the group consisting of benzotriazoles and carboxybenzotriazoles.

[0232] Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylidene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylidene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylidene-1,2,3-benzotriazole, and the like.

[0233] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylidene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylidene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylidene carboxybenzotriazole, and the like.

[0234] Among these, carboxybenzotriazoles are particularly preferred.

[0235] When the total solid content mass of the photosensitive resin composition is 100% by mass, the content of the (E) benzotriazole derivative is preferably 0.001% by mass to 3% by mass. From the viewpoint that no discoloration is observed on the copper surface even after heating after exposure and after developing and removing the photosensitive resin composition layer, it is preferable that the content is 0.001% by mass or more, more preferably 0.02% by mass or more, and further preferably 0.05% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing dye decolorization, it is preferable that the content is 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.3% by mass or less.

[0236] The decolorization of the dye can be measured at the transmittance at a wavelength of 630 nm. A high transmittance at a wavelength of 630 nm indicates that the dye has been decolorized. The transmittance of the laminate of the support film and the photosensitive resin composition layer at a wavelength of 630 nm is preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 72% or less, preferably 70% or less, preferably 68% or less, preferably 65% or less, preferably 62% or less, preferably 60% or less, preferably 58% or less, preferably 55% or less, preferably 52% or less, preferably 50% or less. This transmittance is the transmittance of the laminate of the support film and the photosensitive resin composition layer and does not include the protective layer.

[0237] <Additive>

[0238] The photosensitive resin composition may contain additives such as dyes, plasticizers, antioxidants, and stabilizers as desired. For example, the additives listed in Japanese Patent Laid-Open No. 2013-156369 can be used.

[0239] (Dye and coloring matter)

[0240] In the present embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (such as leuco dyes and fluoran dyes) and coloring matters as desired.

[0241] Examples of the coloring matter include magenta, phthalocyanine green, basic sophor yellow, pararosaniline, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green (for example, manufactured by Hodogaya Chemical Co., Ltd., Aizen (registered trademark) MALACHITEGREEN), basic blue 20, diamond green (for example, manufactured by Hodogaya Chemical Co., Ltd., Aizen (registered trademark) DIAMOND GREEN GH). When the total solid content mass of the photosensitive resin composition is 100% by mass, the content of the coloring matter in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass. From the viewpoint of improving the processability of the photosensitive resin composition, it is preferable that the content is 0.001% by mass or more. On the other hand, from the viewpoint of maintaining the storage stability of the photosensitive resin composition, it is preferable that the content is 1% by mass or less.

[0242] Since the photosensitive resin composition develops color in the exposed portion by containing a dye, it is preferable from the viewpoint of visual observability. In addition, when reading the alignment marks for exposure with an inspection machine or the like, it is easy to identify when the contrast between the exposed portion and the unexposed portion is large, which is advantageous. From this viewpoint, preferred dyes include leuco dyes and fluoran dyes.

[0243] Examples of the leuco dye include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], etc. In particular, from the viewpoint of obtaining good contrast, leuco crystal violet is preferably used as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass with respect to the total solid content mass of the photosensitive resin composition. From the viewpoint of obtaining good contrast between the exposed portion and the unexposed portion, it is preferred that the content is 0.1% by mass or more. More preferably, the content is 0.2% by mass or more, and particularly preferably 0.4% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, it is preferred that the content is 10% by mass or less. More preferably, the content is 5% by mass or less, and particularly preferably 2% by mass or less.

[0244] In addition, from the viewpoint of optimizing the adhesion and contrast, it is preferred to use a leuco dye and the halide described in (C) the photopolymerization initiator in combination in the photosensitive resin composition. When the leuco dye and the halide are used in combination, from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer, when the total solid content mass of the photosensitive resin composition is 100% by mass, the content of the halide in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass.

[0245] (Other additives)

[0246] In this embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. Examples of the epoxy compounds of bisphenol A include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminals, etc.

[0247] In the present embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalic acid esters (e.g., diethyl phthalate, etc.), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetylcitrate, tri-n-propyl acetylcitrate, tri-n-butyl acetylcitrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc. In addition, ADEKANOL SDX-1569, ADEKANOL SDX-1570, ADEKANOL SDX-1571, ADEKANOL SDX-479 (the above are 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 (the above are manufactured by Sanyo Chemical Industries, Ltd.); UNIOL DB-400, UNIOL DAB-800, UNIOL DA-350F, UNIOL DA-400, UNIOL DA-700 (the above are manufactured by NOF Corporation); BA-P4UGLYCOL, BA-P8 GLYCOL (the above are manufactured by Nippon Emulsion Co., Ltd.) and other compounds having a bisphenol skeleton can also be cited.

[0248] The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, based on the total solid content mass of the photosensitive resin composition. From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, it is preferable that the content is 1% by mass or more. On the other hand, from the viewpoint of suppressing insufficient curing and cold flow, it is preferable that the content is 50% by mass or less.

[0249] If the water content in the photosensitive resin composition is high, the local plasticization of the photosensitive resin composition is rapidly promoted, and edge fusion occurs. From the viewpoint of suppressing edge fusion, based on the photosensitive resin composition after coating the photosensitive resin composition formulation on a support film and drying, the water content in the photosensitive resin composition is preferably 0.7% or less. The water content in the photosensitive resin composition is preferably 0.65% or less, preferably 0.6% or less, preferably 0.55% or less, preferably 0.5% or less, preferably 0.45% or less, preferably 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less, preferably 0.2% or less.

[0250] [Solvent]

[0251] The photosensitive resin composition can be dissolved in a solvent and used in the form of a photosensitive resin composition preparation liquid for manufacturing a photosensitive resin laminate. Examples of the solvent include ketones and alcohols. The aforementioned ketones are represented by methyl ethyl ketone (MEK) and acetone. The aforementioned alcohols are represented by methanol, ethanol, and isopropyl alcohol. When manufacturing the photosensitive resin laminate, the solvent is preferably added to the photosensitive resin composition in such an amount that the viscosity of the photosensitive resin composition preparation liquid coated on the support layer reaches 500 mPa·s to 4,000 mPa·s at 25°C.

[0252] [Photosensitive resin laminate]

[0253] As the support film, a transparent support film that transmits the light emitted from the exposure light source is preferred. Examples of such support films include polyethylene terephthalate films, polyvinyl alcohol films, polyvinyl chloride films, vinyl chloride copolymer films, polyvinylidene chloride films, vinylidene chloride copolymer films, polymethyl methacrylate copolymer films, polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. These films can also be stretched films as needed.

[0254] As the support film, from the viewpoint of suppressing light scattering during exposure, a film with a haze of 5% or less is preferred, more preferably 2% or less, further 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 thickness of the film, the more advantageous it is in terms of image formability and economy, but in order to maintain the strength of the photosensitive resin laminate, a film with a thickness of 10 μm to 30 μm is preferably used. The size of the fine particles such as lubricants contained in the support film is preferably less than 5 μm.

[0255] In addition, the support film can have a single-layer structure or a multilayer structure obtained by laminating resin layers formed of multiple components. In the case of a multilayer structure, an antistatic layer can be provided. In the case of a multilayer structure such as a two-layer structure or a three-layer structure, for example, the following structure can be adopted: a resin layer containing fine particles is formed on one surface A, and on the other surface B, (1) it contains fine particles in the same manner as surface A, (2) it contains fewer fine particles than surface A, (3) it contains finer fine particles than surface A, or (4) it does not contain fine particles. In the case of the structures (2), (3), and (4), it is preferred to form the photosensitive resin layer on the surface B side. At this time, if a resin layer containing fine particles is provided on the surface A side, it is preferred from the viewpoints of the slidability of the film, etc. From the viewpoint of the effects of the present invention, the size of the fine particles at this time is also preferably less than 1.5 μm.

[0256] An important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesion to the photosensitive resin layer is sufficiently small compared to the support layer, and it can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. In addition, a film with excellent peelability shown in Japanese Patent Laid-Open No. 59-202457 can also be used. The film thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

[0257] Gels called fisheyes sometimes exist on the surface of the polyethylene film. When a polyethylene film with fisheyes is used as the protective layer, the fisheyes are sometimes transferred to the photosensitive resin layer. If the fisheyes are transferred to the photosensitive resin layer, air may be involved during lamination to form voids, resulting in defects in the resist pattern. From the viewpoint of preventing fisheyes, stretched polypropylene is preferably used as the material of the protective layer. As a specific example, ALPHAN E-200A manufactured by Oji Paper Co., Ltd. can be cited.

[0258] The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the use, and is preferably 1 μm to 300 μm, more preferably 3 μm to 100 μm, particularly preferably 5 μm to 60 μm, and most preferably 10 μm to 30 μm. The thinner the thickness of the photosensitive resin layer, the higher the resolution, and the thicker the layer, the higher the film strength.

[0259] Next, the manufacturing method of the photosensitive resin laminate will be described.

[0260] As a method of sequentially laminating a support layer, a photosensitive resin layer, and a protective layer as needed to produce a photosensitive resin laminate, a known method can be adopted. For example, by mixing a photosensitive resin composition used for the photosensitive resin layer with a solvent that dissolves it to form a uniform solution, first, it is coated on the support layer using a bar coater or a roll coater, and then dried to remove the aforementioned solvent. Thus, a photosensitive resin layer formed from the photosensitive resin composition can be laminated on the support layer. Next, if necessary, a protective layer is laminated on the photosensitive resin layer to produce a photosensitive resin laminate.

[0261] <Method for forming a resist pattern>

[0262] Next, an example of a method for producing a resist pattern using the photosensitive resin laminate of the present embodiment will be described. This method may include the following steps: an exposure step of exposing the photosensitive resin composition; a heating step of heating the exposed photosensitive resin composition; and a developing step of developing the photosensitive resin composition.

[0263] Examples of the resist pattern include patterns such as printed circuit 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, wirings for TFTs for liquid crystals, and electrodes for PDP (plasma display panels). As an example, the manufacturing method of a printed circuit board will be described as follows.

[0264] The printed circuit board is manufactured through the following respective processes.

[0265] (1) Lamination process

[0266] First, in the lamination process, a photosensitive resin layer is formed on the substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, after peeling off the protective layer, the photosensitive resin layer is heat-pressed onto the substrate surface using a laminator for lamination. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc.

[0267] In the present embodiment, the photosensitive resin layer can be laminated only on one side of the substrate surface or on both sides as needed. The heating temperature during lamination is usually 40°C to 160°C. In addition, by performing the heat-pressing during lamination two or more times, the adhesion of the obtained resist pattern to the substrate can be improved. During heat-pressing, the pressing can be performed by using a two-stage laminator equipped with two rollers or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the rollers multiple times.

[0268] (2) Exposure process

[0269] In this process, the photosensitive resin layer is exposed by an exposure method in which a mask film having a desired wiring pattern is closely attached to the support layer and an active light source is used, an exposure method based on direct drawing of a drawing pattern as the desired wiring pattern, or an exposure method based on projecting an image of a photomask through a lens.

[0270] The exposure process is preferably performed by an exposure method based on direct drawing of a drawing pattern or an exposure method of projecting an image of a photomask through a lens, and more preferably by an exposure method based on direct drawing of a drawing pattern. The advantages of the photosensitive resin composition described in the present embodiment are more remarkable in the exposure method based on direct drawing of a drawing pattern or the exposure method of projecting an image of a photomask through a lens, and are particularly remarkable in the exposure method based on direct drawing of a drawing pattern.

[0271] When the exposure process is an exposure method based on direct drawing, it is preferable to use a laser with a center wavelength less than 390 nm or a laser with a center wavelength of 390 nm or more. More preferably, it is a laser with a center wavelength of 350 nm or more and 380 nm or less, or a laser with a center wavelength of 400 nm or more and 410 nm or less. It is preferably carried out by an exposure method using a first laser with a center wavelength less than 390 nm and a second laser with a center wavelength of 390 nm or more. In addition, more preferably, the center wavelength of the first laser is 350 nm or more and 380 nm or less, and the center wavelength of the second laser is 400 nm or more and 410 nm or less.

[0272] (3) Heating process

[0273] In this process, it is preferable to perform a heating process on the exposed photosensitive resin composition at about 30°C to about 200°C, more preferably in the range of 30°C to 150°C, and further preferably in the range of 60°C to 120°C. By performing this heating process, the resolution and adhesion can be improved. Heating can be carried out using a heating furnace, constant temperature bath, hot plate, hot air dryer, infrared dryer, hot roller, etc. in the form of hot air, infrared rays or far-infrared rays. If the heating method is a hot roller, it is preferable from the aspect of being able to process in a short time, and more preferably there are two or more hot rollers.

[0274] In particular, in the present invention, by including a structural unit of 15% by mass or more of styrene and / or styrene derivative, and performing heating after exposure and then development, even in a system with a large content of styrene skeleton, the fluidity of the resin is increased due to heating, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly balanced.

[0275] In addition, in the present invention, by using at least anthracene and / or anthracene derivative as the (C-2) photopolymerization initiator ((C) photopolymerization initiator), and performing heating after exposure and then development, the fluidity of the resin is increased due to heating. For example, even in a system with a relatively large content of styrene skeleton, the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly balanced.

[0276] As a result, the adhesion can be significantly improved. And, due to the significant improvement in adhesion, good adhesion can be obtained even when the elapsed time after exposure becomes long. In addition, from the viewpoint of the effects of the present invention, the aforementioned heating process is preferably carried out within 15 minutes after exposure, more preferably within 10 minutes, and further preferably within 5 minutes.

[0277] (4) Development process

[0278] In this process, after exposing, the support layer on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution, thereby forming a resist pattern on the substrate.

[0279] As the alkaline aqueous solution, an aqueous solution of Na2CO3 or K2CO3 is used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, and preferably an aqueous solution of Na2CO3 with a concentration of about 0.2% by mass to about 2% by mass and at about 20°C to about 40°C.

[0280] The resist pattern can be obtained through the above steps (1) to (4).

[0281] In the method for manufacturing a circuit board of the present invention, a circuit board is formed by subjecting the substrate having the resist pattern manufactured by the above method to etching or plating.

[0282] (5) Etching process or plating process

[0283] The surface of the substrate exposed by development (for example, the copper surface of a copper-clad laminate) is etched or plated to manufacture a conductor pattern.

[0284] (6) Stripping process

[0285] Thereafter, using an appropriate stripping solution, the resist pattern is peeled off from the substrate.

[0286] As the stripping solution used here, for example, an alkaline aqueous solution, an amine-based stripping solution, etc. can be cited. However, the resist pattern formed by heating the photosensitive resin composition of the present invention after exposure has the following characteristics: it shows good peelability to the amine-based stripping solution, and the peeled pieces do not become overly fine. Therefore, if an amine-based stripping solution is used as the stripping solution, the advantageous effects of the present invention are maximally exerted, and thus it is preferred.

[0287] The amine contained in the amine-based stripping solution can be an inorganic amine or an organic amine.

[0288] As the inorganic amine, for example, ammonia, hydroxylamine, hydrazine, etc. can be cited.

[0289] As the organic amine, for example, ethanolamine, propanolamine, alkylamine, cyclic amine, quaternary ammonium salt, etc. can be cited. As these specific examples, respectively

[0290] As ethanolamine, for example, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, aminoethoxyethanol, etc. can be exemplified;

[0291] As the propanolamine, for example, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, etc. can be exemplified;

[0292] As the alkylamine, for example, monomethylamine, dimethylamine, trimethylamine, ethylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, tetraethylenepentamine, etc. can be exemplified;

[0293] As the cyclic amine, for example, choline, morpholine, etc. can be exemplified;

[0294] As the quaternary ammonium salt, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N,N,N-triethyl-N-(2-hydroxyethyl)ammonium hydroxide, N,N-diethyl-N,N-bis(2-hydroxyethyl)ammonium hydroxide, etc. can be exemplified.

[0295] The amine-based stripper used in the present invention may be an aqueous solution containing one or more of the above-exemplified amines. The amine concentration in the aqueous solution can be appropriately set according to the purpose, the composition of the photosensitive resin layer, the development conditions, etc.

[0296] The amine-based stripper used in the present invention may further contain additives commonly used in strippers, such as surfactants, defoamers, pH adjusters, preservatives, anti-reattachment agents, etc.

[0297] The stripping step is carried out at a temperature of, for example, 0°C or higher and 100°C or lower, preferably at a temperature of room temperature (23°C) or higher and 50°C or lower, for a time of, for example, 1 second or longer and 1 hour or shorter, preferably 10 seconds or longer and 10 minutes or shorter.

[0298] After the stripping step, if desired, the substrate after removing the resist pattern can be washed with, for example, pure water.

[0299] The photosensitive resin laminate of the present embodiment is a photosensitive resin laminate suitable for manufacturing conductor patterns such as printed circuit boards, flexible substrates, lead frame substrates, touch panel substrates, substrates for COF, substrates for semiconductor packages, transparent electrodes for liquid crystals, wirings for TFTs for liquid crystals, and electrodes for PDPs.

[0300] It should be noted that for the above various parameters, as long as there is no special description, the measurement is carried out according to the measurement method in the following examples or a method considered equivalent by those skilled in the art.

[0301] Examples

[0302] Next, examples and comparative examples are listed to more specifically illustrate the present embodiment. However, the present embodiment is not limited to the following examples as long as it does not exceed its gist. The physical properties in the examples were measured by the following methods.

[0303] Describes the measurement of the physical property values of polymers and the method for producing evaluation samples for Examples and Comparative Examples. In addition, shows the relevant evaluation methods and evaluation results of the obtained samples.

[0304] <<First Embodiment>>

[0305] In the first embodiment, evaluation is performed on a photosensitive resin composition in which the structural unit of styrene and / or styrene derivative in the (A) alkali-soluble polymer is 15% by mass or more.

[0306] (1) Measurement of Physical Property Values

[0307] ><Measurement of the Weight-Average Molecular Weight or Number-Average Molecular Weight of the Polymer>

[0308] The weight-average molecular weight or number-average molecular weight of the polymer is determined in terms of polystyrene conversion by a gel permeation chromatograph (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, columns: four Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) columns in series manufactured by Showa Denko K.K., mobile phase solvent: tetrahydrofuran, using a standard curve based on a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.)).

[0309] Furthermore, the dispersity of the polymer is calculated in the form of the ratio of the weight-average molecular weight to the number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0310] (2) Method for Producing Evaluation Samples

[0311] The evaluation samples are produced as follows.

[0312] ><Production of Photosensitive Resin Laminate>

[0313] The components shown in Table 1-1 (Table 2-1, Table 3-1) below (where the numbers of the respective components represent the compounding amounts (parts by mass) based on the solid content) and a solvent are sufficiently stirred and mixed to obtain a photosensitive resin composition formulation liquid. The names of the components abbreviated 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 (FB-40 manufactured by Toray Industries, Inc.) is used as the support film, and the formulation liquid is uniformly coated on its surface using a bar coater and dried 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 is 25 μm.

[0314] Next, on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film is not laminated, a 19-μm-thick polyethylene film (manufactured by TAMAPOLY Co., Ltd., GF-818) was pasted as a protective layer to obtain a photosensitive resin laminate.

[0315] <Substrate leveling>

[0316] As an image evaluation substrate, a copper-clad laminate with a 35-μm rolled copper foil laminated on a 0.4-mm-thick substrate was sprayed and washed with a grinding agent (manufactured by Uji Electrochemical Industry Co., Ltd., #400) at a spraying pressure of 0.2 MPa, and then the surface of the substrate was cleaned with a 10% by mass aqueous H2SO4 solution.

[0317] <Lamination>

[0318] While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was laminated on the copper-clad laminate preheated to 50°C at a roll temperature of 105°C using a hot roll laminator (manufactured by Asahi Kasei Corporation, AL-700). The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m / min.

[0319] <Exposure>

[0320] For the evaluation substrate after 2 hours of lamination, exposure was performed using a direct drawing exposure machine IP-88000H and a Stouffer 41-step exposure meter. The exposure was performed at an exposure amount at which the maximum remaining film step number reached 15 steps when the Stouffer 41-step exposure meter was used as a mask for exposure and development.

[0321] The evaluation substrate after 7 minutes of exposure was heated using a hot roll laminator (manufactured by Asahi Kasei Corporation, AL-700). The roll temperature was set to 105°C, the air pressure was set to 0.30 MPa, and the lamination speed was set to 0.5 m / min. It should be noted that if the elapsed time after exposure is extended, the heating effect gradually disappears. Therefore, heating is usually performed about 1 minute after exposure. Therefore, the heating 7 minutes after exposure in this example is a very severe condition.

[0322] <Development>

[0323] After peeling off the polyethylene terephthalate film (support layer), development was performed by spraying a 1% by mass aqueous Na2CO3 solution at 30°C for a specified time using an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., dry film developing machine). The development spraying time was set to twice the shortest development time, and the water washing spraying time after development was set to four times the shortest development time. At this time, the shortest time required to completely dissolve the photosensitive resin layer in the unexposed part was set as the shortest development time.

[0324] <Evaluation of Conformity>

[0325] Use an optical microscope to measure the minimum line width of a pattern with a normally formed mask pattern of L / S = X μm / 200 μm. This measurement is performed on 8 lines, and the average value of these 8 line widths is obtained as the conformity value.

[0326] <Discoloration of Copper Surface>

[0327] Perform the same processes as above until development. For the unexposed portion of the layer laminated with the photosensitive resin composition layer, visually observe the copper surface after developing and removing the photosensitive resin composition layer.

[0328] 〇: No discoloration

[0329] △: Slight discoloration is observed

[0330] <Delay in Shortest Development Time>

[0331] Measure the shortest development time using the following two conditions.

[0332] (A) Normal shortest development time

[0333] Laminate the photosensitive resin laminate on the substrate. After peeling off the support film, measure the shortest time required for the photosensitive resin layer of the unexposed portion to completely dissolve.

[0334] (B) Shortest development time after heating

[0335] After laminating the photosensitive resin laminate on the substrate, heat it using a hot roll laminator (manufactured by Asahi Kasei Corporation, AL-700). Set the roll temperature to 105 °C, the air pressure to 0.30 MPa, and the laminating speed to 0.1 m / min.

[0336] 〇: The shortest development time of (B) is the same as that of (A) (no delay)

[0337] △: The shortest development time of (B) is 1 - 3 seconds longer than that of (A) (with delay)

[0338] Show the above evaluation results together with the components of the photosensitive resin compositions in Examples and Comparative Examples in Table 1-1. In addition, show the component names abbreviated in Table 1-1 in Table 1-2.

[0339] [Table 1-1]

[0340]

[0341] [Table 1-2]

[0342]

[0343] It can be confirmed from the results of Tables 1-1 and 1-2 that the imageability evaluation results of the examples falling within the technical feature scope of the present invention are excellent compared with the comparative examples outside the scope of the present invention.

[0344] It can be confirmed from the results of Tables 1-1 and 1-2 that the imageability evaluation results of the examples falling within the technical feature scope of the present invention are excellent compared with the comparative examples outside the scope of the present invention.

[0345] It should be noted that the heating condition after exposure in this example is heating after 7 minutes of exposure, so it is a very harsh condition. For example, the adhesiveness when developing the compositions of Example 1 and Comparative Example 1 without heating after exposure is 12.0 μm for both. In other words, in the composition of Comparative Example 1, no effect was observed with heating after 7 minutes of exposure, but Example 1 was able to improve the adhesiveness even under very harsh conditions. In addition, under the condition of heating after 1 minute of exposure, the compositions of Example 1 and Comparative Example 1 were both able to obtain an adhesiveness of 10.0 μm.

[0346] Based on the above results, even when the adhesiveness is good under normal heating conditions after exposure, it does not mean that the adhesiveness is also improved under the harsh condition of heating 7 minutes after exposure in this example. However, with the photosensitive resin composition of the present invention having a specific composition, the adhesiveness can be improved for the first time even under this harsh heating condition after exposure. Thus, when manufacturing a circuit board, good adhesiveness can be obtained even when the elapsed time after exposure becomes longer. Therefore, a highly fine circuit pattern can be stably formed.

[0347] <<Second Embodiment>>

[0348] In the second embodiment, a photosensitive resin composition in which the compound (B) having an ethylenically unsaturated double bond contains a (meth)acrylate compound having 3 or more ethylenically unsaturated double bonds was evaluated.

[0349] Using the components shown in Table 2-1 described later, in the same operation as the above first embodiment, samples for evaluation were prepared.

[0350] <Exposure>

[0351] Using a direct drawing exposure machine (manufactured by ORBOTECH, Nuvogo1000, light source: 375 nm (30%) + 405 nm (70%)), a Stouffer 41-step exposure meter was used to expose the evaluation substrate after 2 hours of lamination. The exposure was performed at an exposure amount at which the maximum remaining film step number reached 19 steps when performing exposure and development with the aforementioned Stouffer 41-step exposure meter as a mask.

[0352] <Heating>

[0353] The evaluation substrate after 7 minutes of exposure was heated using a hot roll laminator (manufactured by Asahi Kasei Corporation, AL-700). The roll temperature was set at 105°C, the air pressure was set at 0.30 MPa, and the lamination speed was set at 1 m / min. It should be noted that if the elapsed time after exposure is extended, the heating effect gradually disappears. Therefore, heating is usually performed about 1 minute after exposure. Therefore, the heating 7 minutes after exposure in this example is a very severe condition.

[0354] <Development>

[0355] After peeling off the polyethylene terephthalate film (support layer), a soda developer (manufactured by Fuji Kiko Co., Ltd., a developer for dry film) was used to spray a 1 mass% Na2CO3 aqueous solution at 30°C for a specified time for development. The development spraying time was set to twice the shortest development time, and the water washing spraying time after development was set to three times the shortest development time. At this time, the shortest time required to completely dissolve the photosensitive resin layer in the unexposed portion was defined as the shortest development time.

[0356] Except that the exposure to development process was operated as above, the same operations as in the first example were performed for evaluation.

[0357] The above evaluation results are shown in Table 2-1 together with the compositions of the photosensitive resin compositions of the examples and comparative examples. In addition, the component names abbreviated in Table 2-1 are shown in Table 2-2.

[0358] [Table 2-1]

[0359]

[0360] [Table 2-2]

[0361]

[0362] From the results of Tables 2-1 and 2-2, it can be confirmed that the image property evaluation results of the examples falling within the technical feature range of the present invention are excellent compared to the comparative examples outside the scope of the present invention.

[0363] It should be noted that the heating condition after exposure in this example is heating 7 minutes after exposure, so it is a very severe condition. For example, when the compositions of Example 1 and Comparative Example 1 were developed without heating after exposure, the adhesion was 11.8 μm in both cases. In other words, in the composition of Comparative Example 1, no effect was observed with heating 7 minutes after exposure, but Example 1 was able to improve the adhesion even under very severe conditions. In addition, under the condition of heating 1 minute after exposure, the compositions of Example 1 and Comparative Example 1 both achieved an adhesion of 9.6 μm.

[0364] From the above results, it can be seen that even when the adhesion is good under the normal heating conditions after exposure, the adhesion does not improve under the severe conditions of heating 7 minutes after exposure in this embodiment. However, according to the present invention, for the first time, the adhesion can be improved even under such severe post-exposure heating conditions. Thus, when manufacturing a circuit board, good adhesion can be obtained even when the elapsed time after exposure is long. Therefore, a highly fine circuit pattern can be stably formed.

[0365] <<Third Embodiment>>

[0366] In the third embodiment, a photosensitive resin composition in which the (C-2) photoinitiator contains anthracene and / or an anthracene derivative is evaluated.

[0367] Using the components shown in Table 3-1 described later, samples for evaluation were produced in the same manner as in the first embodiment above.

[0368] <Exposure>

[0369] Using a direct drawing exposure machine (manufactured by ORBOTECH, Nuvogo1000, light source: 375nm (30%) + 405nm (70%)), a substrate for evaluation that had been laminated for 2 hours was exposed using a Stouffer 41-step exposure table. The exposure was carried out at an exposure amount such that the maximum remaining film step number during exposure and development reached 21 steps with the aforementioned Stouffer 41-step exposure table used as a mask.

[0370] <Heating>

[0371] The substrate for evaluation 7 minutes after exposure was heated using a hot roll laminator (manufactured by Asahi Kasei, AL-700). The roll temperature was set to 105°C, the air pressure was set to 0.30 MPa, and the lamination speed was set to 1 m / min. It should be noted that if the elapsed time after exposure is extended, the heating effect gradually disappears. Therefore, heating is usually carried out about 1 minute after exposure. Therefore, the heating 7 minutes after exposure in this embodiment is a very severe condition.

[0372] <Development>

[0373] After peeling off the polyethylene terephthalate film (support layer), a soda developer (manufactured by Fuji Kiko Co., Ltd., a developer for dry film) was used to spray a 1 mass% Na2CO3 aqueous solution at 30°C for a specified time for development. The development spraying time was set to 2 times the shortest development time, and the post-development water washing spraying time was set to 3 times the shortest development time. At this time, the shortest time required to completely dissolve the unexposed part of the photosensitive resin layer was set as the shortest development time.

[0374] Except that the exposure - development process is operated as described above, the same operations as in the first embodiment are performed for evaluation.

[0375] The above evaluation results and the components of the photosensitive resin compositions of the examples and comparative examples are shown together in Table 3 - 1. In addition, the component names represented by abbreviations in Table 3 - 1 are shown in Table 3 - 2.

[0376] [Table 3 - 1]

[0377]

[0378] [Table 3 - 2]

[0379]

[0380] From the results of Tables 3 - 1 and 3 - 2, it can be confirmed that: compared with the comparative examples outside the scope of the present invention, the image property evaluation results of the examples falling within the technical feature scope of the present invention are excellent. It should be noted that the heating condition after exposure in this embodiment is heating 7 minutes after exposure, so it is a very severe condition. For example, the adhesiveness when developing the compositions of Example 7 and Comparative Example 1 without heating after exposure is 12.8 μm for both. In other words, in the composition of Comparative Example 1, no effect was observed with heating 7 minutes after exposure, but Example 7 can improve the adhesiveness even under very severe conditions. In addition, under the condition of heating 1 minute after exposure, the compositions of Example 7 and Comparative Example 1 can both obtain an adhesiveness of 9.6 μm.

[0381] From the above results, it can be seen that: even when the adhesiveness is good under normal heating conditions after exposure, it does not mean that the adhesiveness is also improved under the severe condition of heating 7 minutes after exposure. However, according to the present invention, for the first time, the adhesiveness can be improved even under this severe heating condition after exposure. That is, according to the composition of the present invention, when manufacturing a circuit board, good adhesiveness can be obtained even when the elapsed time after exposure becomes longer. Therefore, a highly fine circuit pattern can be stably formed.

[0382] The above describes the embodiments of the present invention, but the present invention is not limited thereto and can be appropriately changed within the scope not exceeding the gist of the invention.

[0383] Industrial Applicability

[0384] By using the photosensitive resin composition of the present invention, the adhesiveness during development after heating after exposure can be significantly improved. In particular, good adhesiveness can be achieved even when the elapsed time after exposure becomes longer, and it can be widely used as a photosensitive resin composition.

Claims

1. A photosensitive resin composition which is a photosensitive resin composition for obtaining a resin cured product by heating after exposure and then developing, characterized in that, The photosensitive resin composition contains the following components based on the mass of the total solid components of the photosensitive resin composition: (A) An alkali-soluble polymer: 10% by mass to 90% by mass; (B) A compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) A photopolymerization initiator: 0.01% by mass to 20% by mass, The structural unit of styrene and / or styrene derivative in the whole of the (A) alkali-soluble polymer is 15% by mass or more.

2. The photosensitive resin composition according to claim 1, wherein, As the (B) compound having an ethylenically unsaturated double bond, the content of the compound (B-1) having a concentration of bisphenol A skeleton of 0.18 mol / 100 g or more is 0 or more and 18% by mass or less based on the solid components of the photosensitive resin composition.

3. The photosensitive resin composition according to claim 1 or 2, which further comprises (D) an inhibitor.

4. The photosensitive resin composition according to any one of claims 1 to 3, which further comprises (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 contains a (meth)acrylate compound having 3 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 contains a (meth)acrylate compound having 4 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 contains a (meth)acrylate compound having 6 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. The photosensitive resin composition according to claim 8, wherein, The value of [(content of (A) alkali-soluble polymer)] / [(content of (B) compound having an ethylenically unsaturated double bond)] is 1.04 or more.

10. The photosensitive resin composition according to claim 9, wherein, The value of [(content of (A) alkali-soluble polymer)] / [(content of (B) 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 [(content of (A) alkali-soluble polymer)] / [(content of (B) 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 [(content of (A) alkali-soluble polymer)] / [(content of (B) 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) alkali-soluble polymer)] / [(content of (B) 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) alkali-soluble polymer)] / [(content of (B) compound having an ethylenically unsaturated double bond)] is 3 or less.

16. The photosensitive resin composition according to claim 15, wherein, The value of [(content of (A) alkali-soluble polymer)] / [(content of (B) 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) alkali-soluble polymer)] / [(content of (B) compound having an ethylenically unsaturated double bond)] is 1.5 or less.

18. A photosensitive resin composition, which is a photosensitive resin composition for obtaining a resin cured product by heating after exposure and then developing, and is characterized in that, The photosensitive resin composition contains the following components based on the mass of the total solid components of the photosensitive resin composition: (A) An alkali-soluble polymer: 10% by mass to 90% by mass; (B) A compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) A photopolymerization initiator: 0.01% by mass to 20% by mass, The (C) photopolymerization initiator contains anthracene and / or anthracene derivatives.

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 optionally have a substituent and / or an aryl group having 6 to 40 carbon atoms which may optionally have a substituent at the 9-position and / or 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 optionally have a substituent and / or an aryl group having 6 to 40 carbon atoms which may optionally have a substituent at the 9,10-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 contains an anthracene derivative having a halogen atom.

24. The photosensitive resin composition according to claim 23, wherein, The (C) photopolymerization initiator contains a halogenated product of 9,10-dialkoxyanthracene.

25. The photosensitive resin composition according to claim 24, wherein, The (C) photopolymerization initiator contains a compound obtained by modifying the alkoxy group at the 9-position and / or 10-position of 9,10-dialkoxyanthracene 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 contains a compound having a halogen atom directly bonded to the anthracene skeleton.

27. The photosensitive resin composition according to any one of claims 18 to 26, wherein, The structural unit of styrene and / or styrene derivative in the (A) alkali-soluble polymer is 15% by mass or more.

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

29. The photosensitive resin composition according to claim 28, wherein, The structural unit of styrene and / or styrene derivative in the (A) alkali-soluble polymer is 30% by mass or more.

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

31. The photosensitive resin composition according to claim 30, wherein, The structural unit of styrene and / or styrene derivative in the (A) alkali-soluble polymer is 40% by mass or more.

32. The photosensitive resin composition according to any one of claims 1 to 31, wherein, The structural unit of styrene and / or styrene derivative in the (A) alkali-soluble polymer is 90% by mass or less.

33. The photosensitive resin composition according to any one of claims 1 to 32, wherein, The (A) alkali-soluble polymer further contains benzyl (meth)acrylate as a monomer component.

34. A method for forming an etching pattern, comprising the following steps: 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 an etching pattern according to claim 34, wherein, The heating temperature in the heating step is in the range of 30°C to 150°C.

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

37. The method for forming an etching pattern according to claim 34 or 35, wherein, The exposure step is carried out by an exposure method of direct drawing based on a drawn pattern.

38. The method for forming an etching pattern according to any one of claims 34 to 37, wherein, The heating step is carried out within 15 minutes after exposure.

39. The method for forming an etching pattern according to any one of claims 34 to 38, wherein, The exposure step is carried out by a method of exposing using a first laser having a center wavelength less than 390 nm and a second laser having a center wavelength of 390 nm or more.

40. The method for forming an etching pattern according to claim 39, wherein, The center wavelength of the first laser is 350 nm or more and 380 nm or less, and the center wavelength of the second laser is 400 nm or more and 410 nm or less.

41. A method for manufacturing a circuit board, wherein, Etching or plating is performed on a substrate having a resist pattern manufactured by the method according to any one of claims 34 to 40, thereby forming 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 using a first laser having a center wavelength of less than 390 nm and a second laser having a center wavelength of 390 nm or more.

43. The photosensitive resin composition according to claim 42, wherein, The center wavelength of the first laser is 350 nm or more and 380 nm or less, and the center wavelength of the second laser is 400 nm or more and 410 nm or less.

Images