Photosensitive resin laminate and resist pattern forming method

Abstract

Provided is a photosensitive resin laminate provided with a support film and a resist layer containing a photosensitive resin composition, the photosensitive resin composition containing the following components: (A) a compound having an ethylenically unsaturated bond; and (B) an alkali-soluble resin, the component (A) comprising: (A1) general formula (I) [in the formula, n is 2-20, each i is a natural number of 1-n, k, each li and m are each independently 0-30, each R1, R2i and R3 independently represent a hydrogen atom or a methyl group, each R4, R5i and R6 are each independently selected from the group consisting of alkylene groups having 1-10 carbon atoms, and formula (II) [in the formula, each R7 and R8 are each independently an alkylene group having 1-10 carbon atoms. ] and a group represented by formula (III) [In the formula, R9 represents an alkylene group having 1-10 carbon atoms. ], and a method for producing the same. ] a polyglycerol-based (meth) acrylate represented by formula (1); and (A2) a compound that does not have a carboxyl group and has an ethylenically unsaturated bond.

Description

Technical Field

[0001] This invention relates to photosensitive resin laminates and methods for forming resist patterns. Background Technology

[0002] Printed circuit boards are typically manufactured using photolithography. Photolithography refers to a method of forming a desired wiring pattern on a substrate through the following steps: First, a layer containing a photosensitive resin composition is formed on the substrate. This coating is then exposed to a pattern and developed to form a resist pattern. Next, a conductor pattern is formed through etching or plating. Finally, the desired wiring pattern is formed on the substrate by removing the resist pattern.

[0003] Typically, the formation of resist patterns in photolithography processes is achieved by methods such as: coating a solution of a photosensitive resin composition onto a substrate and drying it; or laminating a dry film resist layer (a photosensitive resin laminate comprising a resist layer and a supporting film) onto a substrate.

[0004] In the manufacture of printed circuit boards, photosensitive resin laminates are mostly used. In the production and use of photosensitive resin laminates, the properties such as developability, flexibility, resolution, adhesion, and peelability, as well as productivity, are important, as they are determined by the types and combinations of compounds with olefinic unsaturated bonds and the setting of their content.

[0005] For example, Patent Document 1 discloses that by using glyceryl triacrylate, the developability and peelability are improved.

[0006] Patent document 2 discloses that resolution and adhesion are improved by using (meth)acrylate compounds with a backbone derived from pentaerythritol.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 10-198031

[0010] Patent Document 2: Japanese Patent Application Publication No. 2013-92693 Summary of the Invention

[0011] The problem the invention aims to solve

[0012] However, although the photosensitive resin composition described in Patent Document 1 has the specified developability and peelability, there is still room for further improvement in terms of resolution and adhesion.

[0013] Furthermore, while the curable resin composition described in Patent Document 2 has specified resolution and adhesion, there is still room for further improvement in terms of developability and flexibility.

[0014] The purpose of this invention is to provide a photosensitive resin laminate with excellent developability, flexibility, resolution and adhesion, as well as a method for forming resist patterns.

[0015] Solution for solving the problem

[0016] The present invention is as follows. [1]

[0018] A photosensitive resin laminate comprising a supporting film and a resist layer containing a photosensitive resin composition.

[0019] The aforementioned photosensitive resin composition comprises the following components:

[0020] (A) Compounds containing olefinic unsaturated bonds; and

[0021] (B) Alkali-soluble resin,

[0022] The aforementioned component (A) includes:

[0023] (A1) Polyglycerol-based (meth)acrylates represented by the following general formula (I); and

[0024] (A2) Compounds that do not have a carboxyl group but have olefinic unsaturated bonds.

[0025]

[0026] [In the formula, n is 2~20,]

[0027] Each i is a natural number from 1 to n.

[0028] k, each li, and m are independently 0~30.

[0029] R1, R 2i R and R3 each independently represent a hydrogen atom or a methyl group.

[0030] R4, R 5i R6 and R6 are each independently selected from one of the following groups consisting of an alkylene group having 1 to 10 carbon atoms, a group represented by formula (II) below, and a group represented by formula (III) below.

[0031]

[0032] [In the formula, R7 and R8 are each independently an alkylene group having 1 to 10 carbon atoms.]

[0033]

[0034] [In the formula, R9 is an alkylene group having 1 to 10 carbon atoms.] [2]

[0036] According to the photosensitive resin laminate described in [1], the total content of the aforementioned component (A) and component (B) in the aforementioned photosensitive resin composition is 80% by mass or more and 98% by mass or less, based on the total mass of all solid components of the aforementioned photosensitive resin composition. [3]

[0038] According to the photosensitive resin laminate described in [1] or [2], the content of the aforementioned component (B) is 70% by mass or less, based on the total content of the aforementioned component (A) and the aforementioned component (B). [4]

[0040] The photosensitive resin laminate according to any one of [1] to [3], wherein the aforementioned component (B) comprises structural units derived from styrene and benzyl methacrylate. [5]

[0042] The photosensitive resin laminate according to any one of [1] to [4], wherein the aforementioned component (B) comprises a structural unit derived from styrene, and the styrene content in the aforementioned component (B) is 35% by mass or more and 80% by mass or less. [6]

[0044] The photosensitive resin laminate according to any one of [1] to [5], wherein the aforementioned photosensitive resin composition further comprises a photopolymerization initiator as component (C). [7]

[0046] According to the photosensitive resin laminate described in [6], the content of the aforementioned component (C) in the aforementioned photosensitive resin composition is 25% by mass or less, based on the content of the aforementioned component (A). [8]

[0048] According to the photosensitive resin laminate described in [6] or [7], wherein the aforementioned component (C) comprises a hexaaryl biimidazole compound. [9]

[0050] The photosensitive resin laminate according to any one of [1] to [8], wherein the aforementioned photosensitive resin composition further comprises (D) a polymerization inhibitor.

[10]

[0052] The photosensitive resin laminate according to any one of [1] to [9], wherein the aforementioned (A2) component is a compound having 2 to 6 olefinic unsaturated bonds.

[11]

[0054] The photosensitive resin laminate according to any one of [1] to [9], wherein the aforementioned (A2) component comprises a compound having two olefinic unsaturated bonds.

[12]

[0056] The photosensitive resin laminate according to any one of [1] to [9], wherein the aforementioned (A2) component comprises a compound having one olefinic unsaturated bond.

[13]

[0058] The photosensitive resin laminate according to any one of [1] to

[12] , wherein the aforementioned (A2) component comprises a di(meth)acrylate compound having a bisphenol A structure.

[14]

[0060] The photosensitive resin laminate according to any one of [1] to

[13] , wherein R1, R2, R3 in the aforementioned general formula (I) 2i R3 is a methyl group.

[15]

[0062] The photosensitive resin laminate according to any one of [1] to

[14] , wherein R4O and R in the aforementioned general formula (I) are used. 5i O and R6O in formula R j When expressed in the form of O{where j=4, 5i, 6 (where i=1, 2, ..., n)}, the number of (meth)acryloyl groups relative to the aforementioned R j The ratio of the total number of O is less than 20.

[16]

[0064] The photosensitive resin laminate according to any one of [1] to

[15] , wherein n in the aforementioned general formula (I) is an integer from 2 to 15.

[17]

[0066] The photosensitive resin laminate according to any one of [1] to

[15] , wherein n in the aforementioned general formula (I) is 2 to 15 in number mean.

[18]

[0068] The photosensitive resin laminate according to any one of [1] to

[17] , wherein the aforementioned R4, R 5i R6 is an alkylene group.

[19]

[0070] The photosensitive resin laminate according to any one of [1] to

[18] , wherein the aforementioned R4, R 5i R6 contains ethylene and / or propylene.

[20]

[0072] The photosensitive resin laminate according to any one of [1] to

[18] , wherein the aforementioned R4, R 5i R6 is ethylene and / or propylene. [twenty one]

[0074] The photosensitive resin laminate according to any one of [1] to

[18] , wherein the aforementioned R4, R 5i R6 is ethylene. [twenty two]

[0076] The photosensitive resin laminate according to any one of [1] to

[21] further comprises a protective film. [twenty three]

[0078] A photosensitive resin laminate comprising a supporting film and a resist layer containing a photosensitive resin composition.

[0079] The aforementioned photosensitive resin composition comprises the following components:

[0080] (A) Compounds containing olefinic unsaturated bonds; and

[0081] (B) Alkali-soluble resin,

[0082] The aforementioned component (A) includes:

[0083] (A3) Compounds that do not have a quaternary carbon and / or an aromatic ring, and have more than four olefinic unsaturated bonds in one molecule; and

[0084] (A4) A compound having a quaternary carbon and / or an aromatic ring but no carboxyl group and having an olefinic unsaturated bond. [twenty four]

[0086] According to the photosensitive resin laminate described in

[23] , wherein the aforementioned (A4) compound comprises a compound having one or two olefinic unsaturated bonds.

[25]

[0088] According to the photosensitive resin laminate described in

[23] or

[24] , the amount of olefinic unsaturated bonds in each 100g of the aforementioned (A4) compound is less than 0.25mol.

[26]

[0090] The photosensitive resin laminate according to any one of

[23] to

[25] , wherein, based on the total mass of all solid components of the aforementioned photosensitive resin composition, the content of the aforementioned component (A) is 20% by mass or more.

[27]

[0092] The photosensitive resin laminate according to any one of

[23] to

[26] , wherein the aforementioned component (B) contains a copolymer comprising structural units derived from (meth)acrylic acid as a monomer component,

[0093] The content of the aforementioned structural units derived from (meth)acrylic acid in component (B) is less than 27% by mass.

[28]

[0095] The photosensitive resin laminate according to any one of

[23] to

[26] , wherein the aforementioned component (B) contains a copolymer comprising structural units derived from (meth)acrylic acid as a monomer component,

[0096] The content of the aforementioned structural units derived from (meth)acrylic acid in component (B) is less than 25% by mass.

[29]

[0098] A method for forming a resist pattern, which is a method for forming a resist pattern using any one of the photosensitive resin laminates [1] to

[28] , comprising the following steps:

[0099] The process of laminating a resist layer on a substrate;

[0100] The exposure process for exposing the anti-etching layer; and

[0101] The developing process involves developing and removing the unexposed portions of the resist layer.

[30]

[0103] A method for manufacturing a wiring board, which is a method for manufacturing a wiring board using any one of the photosensitive resin laminates described in [1] to

[28] , comprising the following steps:

[0104] The process of laminating a resist layer on a substrate;

[0105] An exposure process that exposes an anti-corrosion layer;

[0106] The developing process that removes the unexposed portions of the resist layer to form the resist pattern;

[0107] A conductor pattern forming process involves etching or plating a substrate with the resist pattern to form a conductor pattern; and

[0108] The peeling process that removes the aforementioned resist pattern from the substrate.

[0109] The effects of the invention

[0110] According to the present invention, a photosensitive resin laminate having a resist layer comprising a photosensitive resin composition having excellent developability, flexibility, resolution, adhesion and peelability, and a method for forming a resist pattern can be provided. Detailed Implementation

[0111] Hereinafter, exemplary embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to this embodiment, and various modifications and implementations can be made within its scope. In this specification, the upper and lower limits of each numerical range can be arbitrarily combined. Furthermore, in this embodiment, the upper or lower limit value recorded in a certain numerical range can also be replaced with the value shown in the embodiment.

[0112] It should be noted that in this specification, the numerical range represented by "~" is considered to include both the upper and lower limits.

[0113] Regarding the term "process" in the following explanation, it goes without saying that it refers to an independent process. However, if it cannot be clearly distinguished from other processes, it can also be included in the term as long as the function of the process can be achieved.

[0114] In addition, in this specification, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, "(meth)acryloyl" refers to acryloyl or methacryloyl, and "(meth)acrylate" refers to acrylate or methacrylate.

[0115] <Photosensitive resin laminate>

[0116] In one embodiment, the photosensitive resin laminate includes a support film and a resist layer comprising a photosensitive resin composition.

[0117] Furthermore, the photosensitive resin composition constituting the photosensitive resin laminate provided in one particular embodiment comprises:

[0118] (A) Compounds containing olefinic unsaturated bonds; and

[0119] (B) Alkali-soluble resin.

[0120] In particular, in the photosensitive resin laminate of this embodiment, the photosensitive resin composition of this embodiment includes (A1) a polyglycerol (meth) acrylate and (A2) a compound that does not have a carboxyl group but has an olefinic unsaturated bond as (A1) a compound having an olefinic unsaturated bond.

[0121] The inventors have discovered that, as a component of the photosensitive resin composition of this embodiment, by combining polyglycerol-based (meth)acrylate (A1) and a compound (A2) that does not have a carboxyl group but has an olefinic unsaturated bond, the developability, softness, resolution, adhesion and peelability become good.

[0122] That is, according to this embodiment, a photosensitive resin composition with excellent developability, flexibility, resolution, adhesion and peelability, as well as a method for forming a resist pattern, can be provided.

[0123] In addition, in the photosensitive resin laminates of other embodiments, the photosensitive resin composition of this embodiment includes, as (A) the compound having olefin unsaturated bonds, the following compounds are included: (A3) the compound that does not have a quaternary carbon and / or an aromatic ring and has four or more olefin unsaturated bonds in one molecule; and (A4) the compound that has a quaternary carbon and / or an aromatic ring, does not have a carboxyl group, and has olefin unsaturated bonds.

[0124] <Supporting Thin Film>

[0125] The supporting film in this embodiment is a layer or film used to support the resist layer, preferably a transparent substrate film that allows active light to pass through.

[0126] As transparent substrate films, examples include films containing synthetic resins such as polyethylene, polypropylene, polycarbonate, polyethylene terephthalate (PET), cellulose triacetate, and cyclic olefin polymers.

[0127] Among them, high-quality films with fewer internal foreign objects are preferred.

[0128] Specifically, as a high-quality film, polyethylene terephthalate (PET) film, cellulose triacetate film, cyclic olefin polymer film, etc. are preferred, and polyethylene terephthalate (PET) film with moderate flexibility and strength is more preferred.

[0129] Among PET films, the following are more preferred: PET films synthesized using Ti-based catalysts, PET films with small diameters and low lubricant content, PET films containing lubricant only on one side of the film, thin-film PET films, PET films that have undergone smoothing treatment on at least one side, and PET films that have undergone roughening treatment such as plasma treatment on at least one side.

[0130] Therefore, the light being exposed can reach the resist layer without being blocked by internal foreign matter, thereby improving the resolution of the photosensitive resin composition.

[0131] The thickness of the support film is preferably 5 μm or more and 25 μm or less, more preferably 6 μm or more and 20 μm or less. The thinner the support film, the fewer foreign objects there are inside, which can prevent a decrease in resolution. However, if the film thickness is too thin, it can cause tensile deformation in the winding direction caused by tension during the coating / winding manufacturing process, breakage caused by minor damage, or wrinkles during lamination due to insufficient film strength.

[0132] At least one side of the support film can be smoothed using a calendering apparatus or the like. This reduces the surface roughness of one side of the support film, particularly the side in contact with the photosensitive resin composition layer described later, thus improving the performance of this embodiment.

[0133] From the viewpoint of improving the parallelism of the light irradiating the resist layer and obtaining higher resolution after exposure and development of the photosensitive resin laminate, the haze of the support film is preferably 0.01% to 1.5%, more preferably 0.01% to 1.2%, and even more preferably 0.01% to 0.95%.

[0134] <Anti-corrosion layer>

[0135] The resist layer of this embodiment comprises a photosensitive resin composition. Alternatively, in another embodiment, the resist layer is a photosensitive resin composition layer.

[0136] In this embodiment, the thickness of the resist layer is preferably 3 to 100 μm, more preferably 3 to 50 μm. The closer the thickness of the resist layer is to 3 μm, the higher the resolution; the closer it is to 100 μm, the stronger the film strength. Therefore, it can be appropriately selected according to the application.

[0137] The thickness of the resist layer in this embodiment can be greater than 100 μm and less than 500 μm. By making the thickness of the resist layer within the above range, it can also be suitable for bump forming and copper pillar forming.

[0138] <Photosensitive Resin Composition>

[0139] The photosensitive resin composition of this embodiment comprises (A) a compound having olefinic unsaturated bonds and (B) an alkali-soluble resin.

[0140] • (A) Compounds containing olefinic unsaturated bonds

[0141] In this embodiment, (A) the compound having an olefinic unsaturated bond (hereinafter referred to as (A) component) includes (A1) a polyglycerol (meth) acrylate and (A2) a compound that does not have a carboxyl group but has an olefinic unsaturated bond as a component.

[0142] In one embodiment, component (A) comprises a polyglycerol-based (meth)acrylate (A1) represented by general formula (I) described below and a compound (A2) that does not have a carboxyl group and has an olefinic unsaturated bond.

[0143] As component (A) in the photosensitive resin composition of this embodiment, by combining polyglycerol-based (meth)acrylate (A1) and a compound (A2) that does not have a carboxyl group but has an olefinic unsaturated bond, the developability, softness, resolution, adhesion and peelability become good.

[0144] (A1) Polyglycerol-based (meth)acrylates

[0145] In this embodiment, (A1) polyglycerol-based (meth)acrylate refers to a compound having a polyglycerol backbone and a (meth)acryloyl group, and refers to a compound having the following structural formula (I) (in one embodiment, general formula (I) or formula (I)).

[0146]

[0147] [In the formula, n is 2~20,]

[0148] Each i is a natural number from 1 to n.

[0149] k, each li, and m are independently 0~30.

[0150] R1, R 2i R and R3 each independently represent a hydrogen atom or a methyl group.

[0151] R4, R 5i R6 and R6 are each independently selected from one of the following groups consisting of an alkylene group having 1 to 10 carbon atoms, a group represented by formula (II) below, and a group represented by formula (III) below.

[0152]

[0153] [In the formula, R7 and R8 are each independently an alkylene group having 1 to 10 carbon atoms.]

[0154]

[0155] [In the formula, R9 is an alkylene group having 1 to 10 carbon atoms.]

[0156] In addition, (A1) polyglycerol-based (meth)acrylates can be used alone or in combination with two or more compounds.

[0157] It has R4O, R 5iThe polyglycerol (meth)acrylate of the repeating units shown in O and R6O can be synthesized, for example, by the following methods, but the synthesis method of the (A1) polyglycerol (meth)acrylate of this embodiment is not limited to this.

[0158] R4 and R can be obtained by reacting the hydroxyl groups of polyglycerol with epoxides, followed by reacting the terminal hydroxyl groups with acrylic acid or methacrylic acid. 5i R6 is an alkylene polyglycerol-based (meth)acrylate.

[0159] By replacing alkyl epoxides with compounds such as epichlorohydrin that have leaving groups and epoxy groups in the reaction, the aforementioned R4 and R can be obtained. 5i And R6 as shown in chemical formula (II) polyglycerol (meth)acrylate.

[0160] By using lactone compounds instead of epoxides in the reaction, R4 and R can be obtained. 5i And R6 as shown in chemical formula (III) polyglycerol (meth)acrylate.

[0161] These reactions can be freely combined; alternatively, R4O and R can be omitted. 5i The repeating units shown in O and R6O, and the hydroxyl groups of polyglycerol react with acrylic acid or methacrylic acid.

[0162] Specifically, as polyglycerol-based (meth)acrylates, SA-TE6 and SA-TE60 manufactured by Sakamoto Pharmaceutical Chemical Co., Ltd. can be used.

[0163] From the viewpoint of flexibility and tightness, k, each li, and m in formula (I) are each preferably 2 to 20, more preferably 2 to 15, further preferably 2 to 12, even more preferably 2 to 10, particularly preferably 2 to 8, and most preferably 2 to 6.

[0164] It should be noted that in this disclosure, when the (A1) polyglycerol-based (meth)acrylate represented by formula (I) is composed of a single type of molecule, k, each li and m can be represented by integer values.

[0165] In addition, when the (A1) polyglycerol-based (meth)acrylate shown in formula (I) is composed of multiple molecules, k, each li and m can be represented by the mean value.

[0166] From the viewpoint of flexibility and peelability, n in structural formula (I) is preferably an integer from 2 to 15, more preferably from 2 to 10, even more preferably from 2 to 8, even more preferably from 2 to 6, and particularly preferably from 2 to 4.

[0167] In addition, when the (A1) polyglycerol (meth)acrylate represented by general formula (I) is composed of multiple molecules, n can be represented by the number mean.

[0168] In one embodiment, n in formula (I) is a numerical mean, preferably 2 to 15, more preferably 2 to 10, further preferably 2 to 8, even more preferably 2 to 6, and particularly preferably 2 to 4.

[0169] In this disclosure, regarding the structure (I) (k+l1+l2+…+l…), n The value of +m) / (n+2), that is, the value of R4O and R in equation (I). 5i O and R6O in formula R j When expressed in the form O{where j=4, 5i, 6 (where i=1, 2, ..., n)}, the number of (meth)acryloyl groups relative to R j From the viewpoint of resolution and tightness, the ratio of the total number of O is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and particularly preferably 6 or less.

[0170] In another embodiment, the value of (k+l+m) / (n+2) in structural formula (I) is preferably 2 or more. It should be noted that, in this disclosure, k, each li, and m in the formula (I) of the (Al) polyglycerol-based (meth)acrylate are referred to as repeating units.

[0171] From the perspective of fit and resolution, R1 and R of structural formula (I) 2i R3 is preferably methyl.

[0172] From the perspective of fit and resolution, R4 and R of structural formula (I) 5i R6 is preferably an alkylene group.

[0173] More preferably, it is an alkylene group having 1 to 10 carbon atoms.

[0174] More preferably, it comprises one or more alkylene groups selected from the group consisting of ethylene, propylene, and tetramethylene.

[0175] More preferably, it contains ethylene and / or propylene.

[0176] Particularly preferred are ethylene and / or propylene,

[0177] Ethylene is the most preferred.

[0178] Based on the total solid content of the photosensitive resin composition, the content of (A1) polyglycerol-based (meth)acrylate in the photosensitive resin composition of this embodiment is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further more preferably 7% by mass or more, particularly preferably 10% by mass or more, and most preferably 12% by mass or more.

[0179] Furthermore, based on the total solid content of the photosensitive resin composition, the content of (A1) polyglycerol-based (meth)acrylate in the photosensitive resin composition of this embodiment is preferably 50% by mass or less, more preferably 48% by mass or less, even more preferably 45% by mass or less, even more preferably 43% by mass or less, and particularly preferably 40% by mass or less.

[0180] • (A2) Compounds that do not have a carboxyl group but have an olefinic unsaturated bond

[0181] In this embodiment, (A2) is a compound that does not have a carboxyl group but has an olefinic unsaturated bond (hereinafter referred to as (A2) compound or (A2) component) other than (A1), and there are no particular restrictions as long as it is a compound that does not have a carboxyl group but has one or more olefinic unsaturated bonds. As (A2) compound, it is preferable to include a compound having two or more olefinic unsaturated bonds.

[0182] In addition, (A2) compound can be used alone or in combination with two or more compounds.

[0183] By including compound (A2) in component (A), the adhesion of the photosensitive resin composition of this embodiment to the substrate and the peelability of the resist pattern are improved.

[0184] (A2) The compound preferably has a (meth)acryloyl group, more preferably a methacryloyl group.

[0185] (A2) The compound preferably has two olefinic unsaturated bonds.

[0186] Examples of compounds having two olefinic unsaturated bonds include alkyl di(meth)acrylates, 1,3-bis(meth)acryloyloxy-2-propanol, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, tricyclodecyl di(meth)acrylate, ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, tetramethylene glycol oxylated (hydrogenated) bisphenol A di(meth)acrylate, fluorene di(meth)acrylate, etc.

[0187] From the viewpoint of excellent adhesion to the substrate, the compound having olefinic unsaturated bonds preferably includes a di(meth)acrylate compound having a bisphenol A structure, and preferably includes a compound represented by the following general formula (IV):

[0188]

[0189] (where R) 10、 R 11 Each can be independently a hydrogen atom or a methyl group.

[0190] R 12 O, R 13 O, R 14 O and R 15 Each of the O atoms is an oxoalkylene group.

[0191] p, q, r, and s are each independent integers from 0 to 40, p+q is from 1 to 40, and r+s is from 0 to 20.

[0192] R 12 O, R 13 O, R 14 O and R 15 O is preferably oxoethylidene and oxopropylidene, each independently.

[0193] As a compound having a bisphenol A structure, from the viewpoint of resolution and tightness, the average value of p+q+r+s is preferably 20 or less, more preferably 16 or less, further preferably 12 or less, and particularly preferably 10 or less. The average value of p+q+r+s can be 2 or more.

[0194] p, q, r and s are each preferably 0 to 10, more preferably 2 to 8.

[0195] Commercially available examples of compounds having two olefinic unsaturated bonds include, for example, NK ESTER (registered trademark) A-HD-N, related series A-NOD-N, related series A-DOD-N, related series A-NPG, related series 701A, related series A-200, related series A-400, related series A-600, related series A-1000, related series APG-200, related series APG-400, related series APG-700, related series A-PTMG65, related series A-DCP, related series ABE-2, related series ABE-2.2, related series ABE-300, related series A-BPE-4, related series A-BPE-10, and related series... A-BPE-20, A-ABE-30 (same series), A-BPP-3 (same series), HD-N (same series), NOD-N (same series), DOD-N (same series), NPG (same series), 701 (same series), 2G (same series), 3G (same series), 4G (same series), 9G (same series), 14G (same series), 23G (same series), 9PG (same series), DCP (same series), BPE-80N (same series), BPE-100 (same series), BPE-200 (same series), BPE-300 (same series), BPE-500 (same series), BPE-900 (same series), BPE-1300N (same series), NK Oligo (registered trademark) UA-4200, UA-160TM (same series), UA-290TM (same series), UA-W2A (same series), UA-4400 (same series), UA-122P (same series), U-200PA (same series) (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0196] LIGHT ACRYLATE (registered trademark) 3EG-A, 4EG-A (same series), 9EG-A (same series), 14EG-A (same series), PTMGA-250 (same series), NP-A (same series), MPD-A (same series), 1.6HX-A (same series), 1.9ND-A (same series), DCP-A (same series), BP-4EAL (same series), BP-4PA (same series), HPP-A (same series), LIGHT ESTER G-201P (all manufactured by Kyoei Chemical Co., Ltd.)

[0197] FANCRYL (registered trademark) FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-129AS, FA-137M, FA-220M, FA-222A, FA-240A, FA-240M, FA-320M, FA-3218M, FA-321A, FA-321M, FA-324A, FA-731A, FA-P240A, FA-P270A, FA-PTG9A, FA-PTG9M, FA-PTG28A, FA-PTG49A (all manufactured by Showa Denko Materials Co., Ltd.)

[0198] DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (above Daicel Allnex, SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036 (all manufactured by Arkema).

[0199] KAYARAD (registered trademark) NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, R-684 (all manufactured by Nippon Kayaku Co., Ltd.) and other related products.

[0200] (A2) The compound may contain compounds having more than three olefinic unsaturated bonds.

[0201] As a (A2) compound, it can be, for example, a compound having 3 to 6 olefinic unsaturated bonds. That is, the (A2) compound can include compounds having 3 to 6 olefinic unsaturated bonds.

[0202] Examples of compounds having three or more olefinic unsaturated bonds include trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, 4,4',4”-ethide triphenol tri(meth)acrylate, isocyanurate tri(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, bis(trimethylolpropane (tetra / penta / hexa)(meth)acrylate, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0203] In addition, compounds with three or more olefinic unsaturated bonds can also be listed as follows: trimethylolpropane-modified tri(meth)acrylate, glycerol-modified tri(meth)acrylate, 4,4',4”-ethimide triphenol tri(meth)acrylate, epoxide-modified isocyanuric acid tri(meth)acrylate, epoxide-modified pentaerythritol (tri / tetra)(meth)acrylate, epoxide-modified bis(trimethylolpropane)(tetra / penta / hexa)(meth)acrylate, epoxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate, etc.

[0204] From the viewpoint of excellent developability and softness, the (A2) compound preferably contains glycerol tri(meth)acrylate or epoxide-modified glycerol tri(meth)acrylate.

[0205] Commercially available products containing compounds with three or more olefinic unsaturated bonds include, for example, NK ESTER (registered trademark) A-TMPT, A-TMPT-9EO, AT-20E, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-9300, A-9200YN, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMMT, ATM-35E, AD-TMP, A-DPH, A-9550, A-DPH-12E, TPOA-50, and NK. Oligo (registered trademark) UA-7100, UA-1100H, U-6LPA, UA-33H, U-10HA, U-10PA, and U-15HA (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0206] LIGHT ACRYLATE (registered trademark) TMP-A, CPE-3A, PE-4A (same series), DPE-6A (same series) (manufactured by Kyoei Chemical Co., Ltd.), FA-731A (manufactured by Resonac Co., Ltd.)

[0207] TMPTA, EBECRYL 160S, OTA480, PETIA, PETRA, EBECRYL 40, PETA, EBECRYL 140, EBECRYL 1140, EBECRYL 1142, DPHA, EBECRYL 895, EBECRYL 896, EBECRYL TMPTMA (all manufactured by Daicel Allnex)

[0208] SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (all manufactured by Arkema)

[0209] KAYARAD (registered trademark) GPO-303, TMPTA (same series), THE-330 (same series), TPA-330 (same series), PET-30 (same series), T-1420(T) (same series), RP-1040 (same series), DPHA (same series), DPEA-12 (same series), D-310 (same series), DPCA-20 (same series) (all manufactured by Nippon Kayaku Co., Ltd.), etc.

[0210] From the viewpoint of improving resolution, (A2) component is preferably a compound having 2 to 6 olefinic unsaturated bonds, and more preferably a compound having 2 olefinic unsaturated bonds.

[0211] From the perspective of improving peelability, component (A2) may contain compounds with one olefinic unsaturated bond.

[0212] For example, compounds having one olefinically unsaturated bond include epoxide-modified phenol (meth)acrylate, epoxide-modified nonylphenol (meth)acrylate, epoxide-modified 2-ethylhexyl (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ω-carboxy-polycaprolactone mono(meth)acrylate, phthalic acid monohydroxyethyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, 1-naphthyl (meth)acrylate, methylphenoxyethyl (meth)acrylate, and methpropylene (meth)acrylate. Isoamyl acrylate, hexyl acrylate, isodecanyl acrylate, dodecyl acrylate, tetradecyl acrylate, stearyl acrylate, isostearyl acrylate, behenyl acrylate, 2-decyl-1-tetradecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, 1H,1H,5H-octafluoropentyl acrylate, and 3,3,4,4,5,5,6,6,7,7,8,8-dodecyl octyl acrylate, etc.

[0213] The upper limit of the ratio of component (A1) to component (A2) (i.e., the ratio of the content of component (A1) to the content of component (A2)) is preferably 4 or less, more preferably 3.5 or less, further preferably 3 or less, even more preferably 2.75 or less, particularly preferably 2.5 or less, and most preferably 2 or less. The lower limit of the ratio of component (A1) to component (A2) is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.12 or more, even more preferably 0.15 or more, and particularly preferably 0.20 or more.

[0214] In particular, the upper limit of the ratio of the total amount of compounds having one or two olefinic unsaturated bonds in component (A1) to the total amount of compounds having one or two olefinic unsaturated bonds in component (A2) (i.e., the ratio of the content of component (A1) to the total amount of compounds having one or two olefinic unsaturated bonds in component (A2)) is preferably 4 or less, more preferably 3.5 or less, further preferably 3 or less, further more preferably 2.75 or less, particularly preferably 2.5 or less, and most preferably 2 or less. The lower limit of the ratio of the total amount of compounds having one or two olefinic unsaturated bonds in component (A1) to the total amount of compounds having one or two olefinic unsaturated bonds in component (A2) is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.12 or more, even more preferably 0.15 or more, and particularly preferably 0.20 or more.

[0215] From the viewpoints of sensitivity, viscosity, and followability, based on the total solid content of the photosensitive resin composition, the content of the compound (A) having an olefinic unsaturated bond in the photosensitive resin composition of this embodiment is preferably 30% by mass or more, preferably 35% by mass or more. Furthermore, from the viewpoints of edge melting, viscosity, and resolution, based on the total solid content of the photosensitive resin composition, the content of the compound (A) having an olefinic unsaturated bond in the photosensitive resin composition is preferably 50% by mass or less, preferably 45% by mass or less, preferably 43% by mass or less.

[0216] In one embodiment, from the viewpoints of resolution, adhesion, and peelability, based on the total solid components of the photosensitive resin composition, the content of (A) of the compound having an olefinic unsaturated bond in the photosensitive resin composition of this embodiment is preferably 20% by mass or more and 60% by mass or less.

[0217] Furthermore, from the viewpoints of flexibility, resolution, and adhesion, the ratio of the content of compounds having three or more olefinic unsaturated groups in the photosensitive resin composition of this embodiment to the content of compounds having olefinic unsaturated bonds in (A) (i.e., the ratio of the content of compounds having three or more olefinic unsaturated groups to the content of compounds having olefinic unsaturated bonds in (A)) is preferably 0.95 or less, more preferably 0.90 or less.

[0218] Furthermore, from the viewpoints of edge melting, viscosity, and resolution, the upper limit of the ratio of the content of (A) the compound having olefinic unsaturated bonds to the content of (B) the alkali-soluble resin contained in the photosensitive resin composition of this embodiment (i.e., the ratio of the content of (A) the compound having olefinic unsaturated bonds to the content of (B) the alkali-soluble resin) is preferably 1.4 or less, more preferably 1.3 or less, further preferably 1.2 or less, even more preferably 1.1 or less, particularly preferably 1.0 or less, and most preferably 0.9 or less.

[0219] The lower limit of the ratio of (A) the content of the compound having olefinic unsaturated bonds to (B) the content of the alkali-soluble resin is preferably 0.50 or more, more preferably 0.60 or more, further preferably 0.70 or more, further more preferably 0.75 or more, and particularly preferably 0.80 or more.

[0220] In this embodiment, the number of olefinic unsaturated bonds per 100g of solid component of the photosensitive resin composition is preferably set to 0.10 mol to 0.30 mol.

[0221] By setting the concentration to 0.10 mol or higher, contamination during the post-development washing process can be prevented from the photosensitive resin composition leaching out of the cured resist pattern.

[0222] By setting the concentration to below 0.30 mol, contamination during the post-development washing process can be prevented from occurring due to defects in the cured resist pattern or its detachment.

[0223] The amount of olefinic unsaturated bonds per 100g of solid component in the photosensitive resin composition of this embodiment is preferably 0.10 mol or more, more preferably 0.11 mol or more, even more preferably 0.12 mol or more, and even more preferably 0.13 mol or more.

[0224] Furthermore, the amount of olefinic unsaturated bonds per 100g of solid component in the photosensitive resin composition of this embodiment is preferably 0.30 mol or less, more preferably 0.28 mol or less, even more preferably 0.25 mol or less, even more preferably 0.22 mol or less, particularly preferably 0.20 mol or less, even more preferably 0.18 mol or less, and extremely preferably 0.15 mol or less.

[0225] The amount of olefinic unsaturated bonds per 100g of solid component in the photosensitive resin composition of this embodiment is more preferably 0.10 mol to 0.25 mol, further preferably 0.10 mol to 0.20 mol, even more preferably 0.11 mol to 0.20 mol, and extremely preferably 0.11 mol to 0.15 mol.

[0226] (B) Alkali-soluble resin

[0227] In this embodiment, the alkali-soluble resin (hereinafter referred to as component (B)) is preferably obtained by polymerizing at least one of the first monomers described later, and more preferably by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0228] The first monomer is a monomer that has a carboxyl group in its molecule.

[0229] Examples of first monomers include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic half ester. Among these, (meth)acrylic acid is preferred from the viewpoint of excellent adhesion and resolution, and methacrylic acid is more preferred.

[0230] Based on the total mass of all monomer components, the copolymerization ratio of the first monomer is preferably in the range of 10 to 50% by mass.

[0231] From the viewpoint of excellent adhesion and resolution, it is preferable to set the copolymerization ratio to 10% by mass or more, more preferably 15% by mass or more, even more preferably 18% by mass or more, and even more preferably 21% by mass or more.

[0232] From the viewpoint of excellent adhesion and resolution, it is preferable to set the copolymerization ratio to 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 27% by mass or less.

[0233] When two or more monomers are used as the first monomer for polymerization, it is preferable that the total copolymerization ratio of each monomer falls within the above range.

[0234] The second monomer is a monomer that has at least one olefinic unsaturated bond in its molecule and does not have a carboxyl group.

[0235] Examples of second monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenoxyethyl methacrylate, isobornyl methacrylate, nonylphenoxy polyethylene glycol (meth)acrylate, pentamethylpiperidinium methacrylate, and tetramethyl methacrylate. Piperidine esters, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane acetal (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, and other (meth)acrylate esters; styrene derivatives such as styrene, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, N-phenylmaleimide, styrene dimers, and styrene trimers; vinyl acetate and other vinyl alcohol esters; and (meth)acrylonitrile, etc.

[0236] (B) The weight-average molecular weight Mw of the alkali-soluble resin is preferably 10,000 to 60,000.

[0237] From the viewpoint of balancing the flexibility and resolution of the resist pattern, it is preferable to set the weight-average molecular weight Mw to 60,000 or less, and from the same viewpoint, it is more preferable to set it to 55,000 or less, and even more preferably to set it to 50,000 or less.

[0238] From the same point of view, it is preferable to set the weight-average molecular weight Mw to 10,000 or more, more preferably to 12,000 or more, and even more preferably to 14,000 or more.

[0239] (B) The polydispersity (Mw / Mn: weight average molecular weight / number average molecular weight) of the alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0240] (B) Alkali-soluble resins can be used alone or in combination of two or more.

[0241] When using two or more (B) components in combination, the content of monomers in the multiple (B) components is preferably selected in such a way that the content ratio of each (B) component is set to fall within the following range by weight, weight-average molecular weight and polydispersity.

[0242] It should be noted that the weighted average means refers to the value obtained by multiplying the weight ratio of each alkali-soluble resin relative to the total weight of the mixed (B) components by the weight-average molecular weight or polydispersity of each alkali-soluble resin, and then adding them together when two or more (B) components are used in this disclosure.

[0243] (B) The weighted average molecular weight of the component is preferably 10,000 or more, or 15,000 or more, or 20,000 or more, and preferably 60,000 or less, or 55,000 or less, or 50,000 or less.

[0244] (B) The weighted average of the polydispersity of the component is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0245] (B) The synthesis of alkali-soluble resin is preferably carried out by adding appropriate amounts of free radical polymerization initiators such as benzoyl peroxide and azoisobutyronitrile to a solution prepared by diluting one or more monomers described above with solvents such as acetone, methyl ethyl ketone and isopropanol, and heating and stirring.

[0246] Sometimes, synthesis is carried out while a portion of a mixture containing monomers and solvents is added dropwise to a reaction solution such as a free radical polymerization initiator. After the polymerization reaction is complete, solvent can be added further and adjusted to the desired concentration.

[0247] In addition to solution polymerization, other synthetic methods for component (B) include living radical polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization.

[0248] Based on the total solid content of the photosensitive resin composition, the content of (B) alkali-soluble resin in the photosensitive resin composition of this embodiment may be 10% by mass or more, or 20% by mass or more, or 25% by mass or more, or 30% by mass or more, or 35% by mass or more, or 40% by mass or more, or 45% by mass or more, or 50% by mass or more, or 55% by mass or more, or 60% by mass or more.

[0249] Furthermore, based on the total solid content of the photosensitive resin composition, the content of (B) alkali-soluble resin in the photosensitive resin composition of this embodiment may be 90% by mass or less, or 80% by mass or less, or 70% by mass or less, or 60% by mass or less, or 50% by mass or less.

[0250] Based on the total solid content of the photosensitive resin composition of this embodiment, from the viewpoint of controlling the development time, it is preferable to set the content of (B) alkali-soluble resin to 90% by mass or less, and from the viewpoint of suppressing the resist layer from overflowing from the end face of the film, it is preferable to set it to 10% by mass or more.

[0251] From the viewpoint of excellent adhesion to the substrate, it is preferable to include either or both of styrene and benzyl (meth)acrylate in component (B). That is, it is preferable that component (B) contains structural units derived from styrene and / or benzyl (meth)acrylate.

[0252] (B) When the alkali-soluble resin contains multiple alkali-soluble resins, it may contain an alkali-soluble resin containing styrene and an alkali-soluble resin containing benzyl methacrylate.

[0253] Furthermore, from the viewpoints of softness, resolution, and adhesion, based on the total mass of all solid components of the photosensitive resin composition, the total content of component (A) and component (B) contained in the photosensitive resin composition of this embodiment is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.

[0254] From the viewpoints of sensitivity, resolution, and adhesion, based on the total mass of all solid components in the photosensitive resin composition, the total content of component (A) and component (B) contained in the photosensitive resin composition of this embodiment is preferably 98% by mass or less, more preferably 96% by mass or less.

[0255] When component (B) contains structural units derived from styrene, from the viewpoint of tightness, the styrene content in component (B) is preferably 25% by mass or more, or 30% by mass or more, or 35% by mass or more.

[0256] In addition, the styrene content in component (B) may be less than 80% by mass, or less than 75% by mass, or less than 70% by mass, or less than 65% by mass, or less than 60% by mass.

[0257] In the case where component (B) contains structural units derived from styrene, from the point of view of tightness, the styrene content in component (B) may be 25% by mass or more and 80% by mass or less, or 30% by mass or more and 80% by mass or less, or 35% by mass or more and 80% by mass or less.

[0258] Furthermore, from the viewpoints of developability, resolution, and adhesion, based on the total content of component (A) and component (B), the content of component (B) in the photosensitive resin composition is preferably 70% by mass or less, more preferably 65% ​​by mass or less, further preferably 63% by mass or less, and particularly preferably 60% by mass or less.

[0259] Furthermore, relative to the total content of component (A) and component (B), the content of component (B) in the photosensitive resin composition is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more.

[0260] Photosensitive resin laminates in other embodiments

[0261] In one embodiment of the photosensitive resin laminate, a support film and a resist layer comprising a photosensitive resin composition are provided.

[0262] Furthermore, a photosensitive resin composition constituting a photosensitive resin laminate provided in one of other embodiments comprises:

[0263] (A) Compounds containing olefinic unsaturated bonds; and

[0264] (B) Alkali-soluble resin (hereinafter, component (B)).

[0265] The supporting film provided in the photosensitive resin laminate of other embodiments is the same as described above.

[0266] In other embodiments of the photosensitive resin laminate, the photosensitive resin composition preferably includes (A) a compound having an olefinic unsaturated bond (in one embodiment, component (A)) and (A3) a compound that does not have a quaternary carbon and / or an aromatic ring and has four or more olefinic unsaturated bonds per molecule (hereinafter, (A3) compound or (A3) component).

[0267] In other embodiments of the photosensitive resin laminate, the photosensitive resin composition preferably includes (A4) a compound having a quaternary carbon and / or an aromatic ring, without a carboxyl group, and having an olefinic unsaturated bond (hereinafter, (A4) compound or (A4) component).

[0268] In other embodiments of the photosensitive resin laminate, component (A) of the photosensitive resin composition more preferably includes:

[0269] (A3) Compounds that do not have a quaternary carbon and / or an aromatic ring, and have more than four olefinic unsaturated bonds in one molecule; and

[0270] (A4) A compound having a quaternary carbon and / or an aromatic ring, but not a carboxyl group, and having an olefinic unsaturated bond.

[0271] (A3) Compounds that do not have a quaternary carbon and / or an aromatic ring, and have more than four olefinic unsaturated bonds in one molecule.

[0272] (A3) The compound is a compound that does not have a quaternary carbon and / or an aromatic ring and has more than four olefinic unsaturated bonds in one molecule.

[0273] As an example of compound (A3), compound (A1) can be listed. The same applies to compound (A1). Furthermore, as compound (A3), di(meth)acrylate compounds having a bisphenol A structure are preferred, especially those shown in general formula (IV) below.

[0274] It is speculated that by eliminating the quaternary carbon and / or aromatic rings from the (A3) compound, the resist pattern formed using a photosensitive resin composition containing the (A3) compound as component (A) exhibits high flexibility. Furthermore, it is speculated that by having more than four olefinic unsaturated bonds in one molecule of the (A3) compound, the structure within the (A3) compound is complexly bonded during exposure-based curing, thereby making the resist pattern robust. Therefore, it is speculated that the resist pattern formed using a photosensitive resin composition containing the (A3) compound exhibits excellent toughness, thus demonstrating excellent flexibility, resolution, and adhesion.

[0275] By ensuring that the content of structural units derived from (meth)acrylic acid, styrene, and benzyl (meth)acrylate in component (B) is within the range specified above, when using a photosensitive resin composition containing compound (A3), a good balance between developability and flexibility and rigidity can be achieved, easily resulting in excellent flexibility, resolution, and adhesion.

[0276] (A4) Compounds having a quaternary carbon and / or aromatic ring, but lacking a carboxyl group, and having an olefinic unsaturated bond.

[0277] (A4) The compound is a compound having a quaternary carbon and / or an aromatic ring, but no carboxyl group, and having an olefinic unsaturated bond.

[0278] In other embodiments of the photosensitive resin laminate, the photosensitive resin composition preferably includes (A4) a compound having a quaternary carbon and / or an aromatic ring, without a carboxyl group, and having an olefinic unsaturated bond, as (A) the compound having an olefinic unsaturated bond.

[0279] It is speculated that by giving the (A4) compound a quaternary carbon and / or aromatic ring, the resist pattern formed using a photosensitive resin composition containing the (A4) compound as component (A) is rigid. Therefore, it is speculated that by using a photosensitive resin composition containing both (A3) and (A4) compounds, a balance between softness and rigidity can be achieved, resulting in excellent toughness and the formation of a robust resist pattern. Therefore, the resist pattern obtained using a photosensitive resin composition containing both (A3) and (A4) compounds exhibits particularly excellent resolution and adhesion.

[0280] As an example of compound (A4), compounds listed as components (A2) can be given. The same applies to compounds (A2).

[0281] As compounds (A4), examples of compounds listed as components (A2) include: epoxy-modified phenol (meth) acrylate, epoxy-modified nonylphenol (meth) acrylate, bisphenol A di(meth) acrylate, bisphenol diF (meth) acrylate, ethoxylated (hydrogenated) bisphenol A di(meth) acrylate, propoxylated (hydrogenated) bisphenol A di(meth) acrylate, tetramethylene glycol oxygenated (hydrogenated) bisphenol A di(meth) acrylate, naphthalene di(meth) acrylate, fluorene di(meth) acrylate, and trimethylolpropane tri(meth)propylene. Ester, tri(meth)acrylate of isocyanurate, pentaerythritol (tri / tetra)meth acrylate, bis(trimethylolpropane) (tetra / penta / hexa)meth acrylate, dipentaerythritol (tetra / penta / hexa)meth acrylate, trimethylolpropane-modified tri(meth)acrylate, epoxide-modified tri(meth)acrylate of isocyanurate, epoxide-modified pentaerythritol (tri / tetra)meth acrylate, epoxide-modified bis(trimethylolpropane) (tetra / penta / hexa)meth acrylate, epoxide-modified dipentaerythritol (tetra / penta / hexa)meth acrylate, etc.

[0282] Among them, bisphenol A di(meth)acrylate is preferred as the (A4) compound.

[0283] Commercially available products that can be used as (A4) compounds include, for example, A-1000, A-BPE-20, A-BPE-30, 23G, BPE-900, and BPE-1300N (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0284] 25PDC-900B, 30PDC-950B-H, 40PDC-1700B (the above made by NOF Corporation),

[0285] BP-1206A (manufactured by Toho Chemical Industry Co., Ltd.)

[0286] FA-2100A, FA-2200A, FA-P2200M, FA-P2300M, FA-P2200A, FA-P2300A, FA-3218A, FA-027M (all manufactured by Resonac), etc.

[0287] The (A4) compound preferably comprises a compound having one or two olefinic unsaturated bonds. Furthermore, it is preferred that the amount of olefinic unsaturated bonds in 100g of the (A4) compound is 0.25mol or less.

[0288] Therefore, when forming a resist pattern using a photosensitive resin composition containing both (A3) and (A4) compounds, it is easy to achieve a balance between softness and rigidity, and it is easy to form a resist pattern with excellent toughness and firmness, thus exhibiting excellent softness and adhesion.

[0289] Based on the above viewpoint, the amount of olefinic unsaturated bonds in 100g of (A4) compound is more preferably 0.22 mol or less, and even more preferably 0.20 mol or less. Alternatively, the amount of olefinic unsaturated bonds in 100g of (A4) compound may be 0.10 mol or more.

[0290] The photosensitive resin composition contained in the photosensitive resin laminate of other embodiments includes component (B). Regarding component (B), it is the same as described above.

[0291] In component (B), as a monomer component, it is preferable to contain a copolymer comprising structural units derived from (meth)acrylic acid. In one embodiment, the content of structural units derived from (meth)acrylic acid in the copolymer of component (B) is preferably 27% by mass or less, more preferably 25% by mass or less, and even more preferably 23% by mass or less. The content of structural units derived from (meth)acrylic acid in the copolymer of component (B) may be 10% by mass or more, or 15% by mass or more.

[0292] (C) Polymerization initiator

[0293] In this embodiment, the photosensitive resin composition preferably contains (C) a photopolymerization initiator (hereinafter referred to as (C) component).

[0294] Examples of photopolymerization initiators (C) include hexaaryl biimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketals, thioxanone compounds, dialkylaminobenzoate compounds, oxime esters, acridine compounds, pyrazoline derivatives, esters of N-aryl-α-amino acids, and halogen compounds.

[0295] In one embodiment, as component (C), a hexaaryl biimidazole compound is preferably included.

[0296] Examples of hexaaryl biimidazole compounds include pyrophenone dimers, namely, dimers of 2,4,5-triarylimidazole.

[0297] Examples of dimers of phenanthrene, namely 2,4,5-triarylimidazole, include the dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)biimidazole, 2-(p-methoxyphenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, and 2,4-bis(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenyl Biimidazole, 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'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetra- -(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4 ,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, etc.

[0298] From the viewpoints of high sensitivity, resolution and tightness, component (C) preferably contains phenanthrene dimer, wherein 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer is preferred.

[0299] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0300] N-phenylglycine has a high sensitization effect and is therefore preferred.

[0301] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthroquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0302] Examples of aromatic ketone compounds include benzophenone compounds. Examples of benzophenone compounds include benzophenone, milchone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. From the viewpoint of sensitization effect and binding affinity, 4,4'-bis(diethylamino)benzophenone can also be listed as an aromatic ketone compound.

[0303] In this disclosure, the term "anthracene derivative" includes both anthracene and compounds derived from anthracene.

[0304] Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, and 10-phenyl-9-anthraboronic acid.

[0305] From the viewpoint of sensitization effect and adhesion, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.

[0306] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)one, 1-hydroxycyclohexylphenylone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1, etc.

[0307] Commercially available acetophenone compounds include, for example, the Irgacure series (manufactured by Ciba Speciality Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0308] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0309] Commercially available acylphosphine oxide compounds include, for example, Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Speciality Chemicals).

[0310] Examples of benzoin compounds and benzoin ether compounds include, for example, benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, etc.

[0311] Examples of dialkyl ketal compounds include benzoyl dimethyl ketal and benzoyl diethyl ketal.

[0312] Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0313] Examples of dialkylaminobenzoate compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0314] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime.

[0315] Commercially available oxime ester compounds include, for example, CGI-325, Irgacure-OXE01 and Irgacure-OXE02 (all manufactured by Ciba Speciality Chemicals).

[0316] As acridine compounds, 1,7-bis(9,9'-acridyl)heptane or 9-phenylacridinium are preferred in terms of sensitivity, resolution and availability.

[0317] From the viewpoint of tightness and the rectangularity of the anti-corrosion pattern, 1-phenyl-3-(4-tert-butyl-styrene)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyrene)-5-(4-methoxyphenyl)-pyrazoline are preferred as pyrazoline derivatives.

[0318] Examples of ester compounds of N-aryl amino acids include: methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0319] Examples of halogenated compounds include bromopentane, bromoisopentane, bromoisobutene, bromoethylene, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, triazine chloride compounds, and diallyl iodonium compounds.

[0320] Tribromomethylphenyl sulfone is preferred.

[0321] Based on the total solid components of the photosensitive resin composition, the content of (C) photopolymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass.

[0322] By adjusting the content of (C) photopolymerization initiator to the above range, sufficient sensitivity can be easily obtained, thus allowing light to pass through sufficiently to the bottom of the photosensitive resin composition layer, thereby easily achieving improved resolution.

[0323] From the viewpoints of high sensitivity, resolution, and adhesion, pyrophenone dimer is preferably included as the (C) photopolymerization initiator. In this case, based on the total solid content of the photosensitive resin composition, the content of pyrophenone dimer in the photosensitive resin composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.

[0324] As a (C) photopolymerization initiator, anthracene derivatives and hexaaryl biimidazole compounds are preferably used in combination.

[0325] At this time, based on the total solid component mass of the photosensitive resin composition, the content of anthracene derivative contained in the (C) photopolymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.5% by mass or less, more preferably 0.01% by mass to 0.4% by mass.

[0326] Furthermore, based on the total solid components of the photosensitive resin composition, the content of the hexaaryl biimidazole compound contained in the (C) photopolymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass.

[0327] Based on the content of (A) compounds having olefinic unsaturated bonds, the content of (C) photopolymerization initiator in the photosensitive resin composition of this embodiment is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less.

[0328] Furthermore, based on the content of (A) compounds having olefinic unsaturated bonds, the content of (C) photopolymerization initiator in the photosensitive resin composition of this embodiment is preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, and particularly preferably 5% by mass or more.

[0329] (D) Polymerization inhibitor

[0330] In this embodiment, the photosensitive resin composition may contain (D) a polymerization inhibitor.

[0331] Examples of (D) polymerization inhibitors include free radical inhibitors, phenolic inhibitors, hydroquinone, quinone, nitrobenzene, phenothiazine, phenoxazine, catechol, or their derivatives.

[0332] Examples of free radical polymerization inhibitors include nitroso compounds such as p-nitrosophenol, nitrosobenzene, N-nitrosodiphenylamine, isononyl nitrite, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, N,N'-dinitrosophenylenediamine, and their salts; hindered amine compounds such as 2,2,6,6-tetramethylpiperidine-1-oxo radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo radical, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxo radical, and 4-oxo-2,2,6,6-tetramethyl-1-oxopiperidine.

[0333] Examples of phenolic polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-pentylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,2'- Methylene bis(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-Thio-diethylethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 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., Antage SP manufactured by Kawaguchi Chemical Industry Co., Ltd.), tribenzylphenol (e.g., TBP manufactured by Kawaguchi Chemical Industry Co., Ltd., phenols having 1 to 3 benzyl groups), and biphenol, etc.

[0334] In this disclosure, the term "hydroquinone, quinone, nitrobenzene, phenothiazine, phenotoxazine and catechol and their derivatives" includes both hydroquinone, quinone, nitrobenzene, phenothiazine, phenotoxazine and catechol, and compounds derived from them.

[0335] Examples of hydroquinone derivatives include methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,6-di-tert-butylhydroquinone.

[0336] Examples of quinone derivatives include tert-butylbenzoquinone, 2,6-di-tert-butyl-1,4-benzoquinone, and 2,5-di-tert-butyl-1,4-benzoquinone.

[0337] Examples of nitrobenzene derivatives include 4-nitrotoluene.

[0338] Examples of phenothiazine derivatives include 2,8-dioctylphenothiazine, 2-methoxyphenothiazine, 3-methoxyphenothiazine, 2-methylphenothiazine, 2-ethylphenothiazine, 2-trifluoromethylphenothiazine, 3,7-dibutylphenothiazine, 3,7-dioctylphenothiazine, 3,7-dicumylphenothiazine, 2-cyano-8-methoxyphenothiazine, 2-cyanophenothiazine, 2-bromophenothiazine, 2-chlorophenothiazine, bis(α-dimethylbenzyl)phenothiazine, and bis(α-methylbenzyl)phenothiazine.

[0339] Examples of phenoxazine derivatives include 1-methyl-phenoxazine, 2-methyl-phenoxazine, 3-methyl-phenoxazine, 4-methyl-phenoxazine, 10-methyl-phenoxazine, 2-hydroxy-phenoxazine, 3-hydroxy-phenoxazine, 4-hydroxy-phenoxazine, 10-bromo-phenoxazine, 3,7-dimethyl-phenoxazine, 2,8-dimethyl-phenoxazine, 1-amino-phenoxazine, 2-amino-phenoxazine, 3-amino-phenoxazine, 2-ethyl-phenoxazine, 3-ethyl-phenoxazine, 2-formonitrile-phenoxazine, 3-formonitrile-phenoxazine, 2-methoxy-phenoxazine, 3-methoxy-phenoxazine, and 12H-benzophenoxazine.

[0340] Examples of catechol derivatives include 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol.

[0341] By including phenothiazine or phenothiazine derivatives and phenolic polymerization inhibitors, the NH groups contained in the phenothiazine site form hydrogen bonds with the OH groups of the phenolic polymerization inhibitors, thereby preventing the phenolic polymerization inhibitors from volatilizing or diffusing from the photosensitive resin composition layer.

[0342] That is, a photosensitive resin composition and a method for forming resist patterns are provided that are not affected by manufacturing and storage conditions determined by film thickness and have excellent sensitivity and resolution.

[0343] Based on the above viewpoint, the photosensitive resin composition of this embodiment preferably contains phenothiazine or phenothiazine derivatives as (D) polymerization inhibitor.

[0344] At this time, based on the total solid content of the photosensitive resin composition of this embodiment, the content of phenothiazine or phenothiazine derivative in the photosensitive resin composition of this embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.4% by mass or less, and particularly preferably 0.3% by mass or less.

[0345] Furthermore, based on the total solid content of the photosensitive resin composition of this embodiment, the content of phenothiazine or phenothiazine derivative in the photosensitive resin composition of this embodiment is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, and even more preferably 0.002% by mass or more.

[0346] From the viewpoint of resolution, the photosensitive resin composition of this embodiment preferably contains catechol or a catechol derivative as a (D) polymerization inhibitor, wherein, particularly preferably, it contains 3-tert-butylcatechol or 4-tert-butylcatechol.

[0347] At this time, based on the total solid content of the photosensitive resin composition of this embodiment, the content of catechol or catechol derivative in the photosensitive resin composition of this embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.4% by mass or less, and particularly preferably 0.3% by mass or less.

[0348] Furthermore, based on the total solid content of the photosensitive resin composition of this embodiment, the content of catechol or catechol derivative in the photosensitive resin composition of this embodiment is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, and even more preferably 0.002% by mass or more.

[0349] Based on the total solid content of the photosensitive resin composition of this embodiment, the content of (D) polymerization inhibitor in the photosensitive resin composition of this embodiment is preferably 0.0001% to 10% by mass.

[0350] From the viewpoint of excellent adhesion and resolution, the content of the (D) polymerization inhibitor in this embodiment is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, even more preferably 0.005% by mass or more, and particularly preferably 0.01% by mass or more.

[0351] On the other hand, from the perspective of minimizing sensitivity reduction and improving resolution, the content of the polymerization inhibitor in (D) of this embodiment is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less, even more preferably 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1.5% by mass or less.

[0352] ·additive

[0353] The photosensitive resin composition of this embodiment may contain additives such as dyes, binding agents, and plasticizers.

[0354] ·dye

[0355] In this embodiment, the photosensitive resin composition may contain a dye. Alternatively, in another embodiment, the photosensitive resin composition may contain a color-developing dye that develops color upon light irradiation.

[0356] In the dry film resist provided as one type of photosensitive resin laminate in this embodiment, a dye is preferably added. By adding a dye, the resist pattern formed on the developed substrate appears to have good contrast, which also helps to improve the resolution.

[0357] As a dye, diamond green is preferred.

[0358] As colorimetric dyes, combinations of leuco dyes and halogen compounds are known.

[0359] Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane [pigment name: leuco crystal violet] and tris(4-dimethylamino-2-methylphenyl)methane [pigment name: leuco malachite green].

[0360] Examples of halogenated compounds include bromopentane, bromoisopentane, bromoisobutylene, bromoethylene, diphenylmethyl bromide, benzyl dibromo, dibromomethane, tribromomethyl sulfone, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and hexachloroethane.

[0361] • Sealing agent

[0362] In this embodiment, the photosensitive resin composition may contain a binding agent.

[0363] In the dry film resist provided as one type of photosensitive resin laminate in this embodiment, an adhesion promoter is preferably added. By adding an adhesion promoter, the adhesion of the resist pattern formed on the substrate after development to copper is improved.

[0364] As a sealing aid, triazoles and benzotriazoles are preferred, and carboxybenzotriazoles are more preferred.

[0365] Plasticizers

[0366] In this embodiment, the photosensitive resin composition may contain additives such as plasticizers, as needed.

[0367] As plasticizers and other additives, examples include phthalates such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ethers, and polypropylene glycol alkyl ethers.

[0368] <Photosensitive resin laminate>

[0369] The photosensitive resin laminate of this embodiment includes a support film and a resist layer containing a photosensitive resin composition (in one embodiment, a photosensitive resin composition layer), and the support film and resist layer are the same as described above.

[0370] As the photosensitive resin laminate of this embodiment, it can be formed by laminating at least one resist layer on a support film, or by laminating two or more resist layers on a support film.

[0371] From the viewpoint that the effects of this embodiment can be easily and significantly realized, the photosensitive resin laminate of this embodiment is preferably a dry film resist or a transfer film, and more preferably a dry film resist.

[0372] In addition to a supporting film and a resist layer, the photosensitive resin laminate of this embodiment may also have a protective film.

[0373] In this embodiment, when the photosensitive resin laminate includes a support film, a resist layer, and a protective film, the protective film is adhered to the side of the resist layer that is not laminated with the support film, and functions as a cover.

[0374] Compared to the adhesion between the photosensitive resin composition layer and the support film in this embodiment, the adhesion between the photosensitive resin composition layer and the protective film is sufficiently small, so the protective film can be easily peeled off from the photosensitive resin composition layer.

[0375] For example, polyethylene film, polypropylene film, stretched polypropylene film, polyester film, etc. can be preferred as protective films.

[0376] Among these, polypropylene film and polyester film are preferred, and polyethylene terephthalate film is even more preferred as polyester film.

[0377] Alternatively, a release layer can be applied to the surface of the protective film.

[0378] The thickness of the protective film is preferably 10~100μm, more preferably 10~50μm. Examples of protective films include ALPHAN (registered trademark) EM-501, E-200, E-201F, FG-201, and MA-411 (all manufactured by Oji F-Tex Co., Ltd).

[0379] TORAYFAN (registered trademark) KW37, series 2578, series 2548, series 2500, series YM17S; CERAPEEL (registered trademark) PJ271, series PJ111, HP2, series PJ101, series WZ, series MDA, series MFA, series TK07, series BKE, series BX8A, series SY (all manufactured by Toray Industries, Inc.)

[0380] GF-18, GF-818, GF-858 (all manufactured by Tamapoly), etc.

[0381] The photosensitive resin laminate of this embodiment may further include an intermediate layer between the support film and the resist layer, or between the support film and the protective film.

[0382] [Photosensitive resin laminate roll]

[0383] The photosensitive resin laminate described above can be a strip-shaped photosensitive resin laminate wound onto a core, thus being used in the form of a roll of photosensitive resin laminate.

[0384] [Methods for forming corrosion-resistant patterns]

[0385] The method for forming the resist pattern of the photosensitive resin laminate using this embodiment includes, for example, the following steps:

[0386] A lamination process in which a resist layer (in one embodiment, a photosensitive resin composition layer) constituting the photosensitive resin laminate of this embodiment is laminated on a substrate.

[0387] The exposure process that exposes the resist layer of a photosensitive resin laminate; and

[0388] The developing process involves developing and removing the unexposed portions of the resist layer.

[0389] It is preferable to perform the procedures in the order described above.

[0390] <Lamination Process>

[0391] In the lamination process, specifically, after the protective film is peeled off from the photosensitive resin laminate of this embodiment, the resist layer is heated and pressed onto the substrate surface using a laminator, and lamination is performed once or multiple times.

[0392] Materials used as substrates include, for example, copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc., with copper-clad laminates being preferred.

[0393] As desired, for example, the substrate can be cleaned and leveled using an aqueous solution of H2SO4 with a concentration of about 10% by mass.

[0394] The heating temperature during lamination is typically 40°C to 160°C. Heat lamination can be performed using a laminator equipped with rollers, or by repeatedly passing the substrate and the photosensitive resin composition layer through the rollers several times. Heat lamination can also be performed under reduced pressure if necessary.

[0395] <Exposure Process>

[0396] In the exposure process, exposure machines such as contact aligners, mirror projectors, and steppers are used to expose the resist layer through a patterned photomask or reticle, or directly using an ultraviolet light source.

[0397] The exposure process can be performed either after the support film is peeled off or through the support film, depending on the desired outcome.

[0398] When exposure is performed using a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and can also be measured using a photometer. Direct imaging exposure can also be performed during the exposure process. In direct imaging exposure, a photomask is not used; instead, exposure is performed on the substrate using a direct drawing device.

[0399] As a light source, a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350nm~410nm is used.

[0400] When the pattern is drawn using computer control, the exposure is determined by the illuminance of the exposure light source and the speed of the substrate movement.

[0401] The exposure method used in the exposure process is preferably selected from at least one of the following methods: projection exposure, proximity exposure, contact exposure, direct imaging exposure, and direct electron beam mapping, and more preferably, it is performed by projection exposure or direct imaging exposure.

[0402] <Heating Process>

[0403] A heating process can be set between the exposure process and the development process.

[0404] The heating temperature is preferably 30℃~200℃, more preferably 30℃~150℃, and even more preferably 35℃~120℃. Implementing this heating process improves resolution and sealing. Heating can be performed using hot air, infrared, or far-infrared heating furnaces, constant temperature baths, hot plates, hot air dryers, infrared dryers, hot rollers, etc.

[0405] The heating time is preferably 1 to 300 seconds, more preferably 5 to 120 seconds.

[0406] The elapsed time from the exposure step to the heating step, and more specifically from the moment the exposure stops to the moment the heating starts, is preferably 10 to 600 seconds, more preferably 20 to 300 seconds. The elapsed time from the moment the heating starts to the moment the heating stops is preferably 1 to 120 seconds, more preferably 5 to 60 seconds.

[0407] <Developing Process>

[0408] In the developing process, a developing device is used to remove the unexposed portion of the exposed resist layer using a developing solution to form a resist pattern.

[0409] After exposure, if a support film is present on the resist layer, the support film is removed. Next, a developer containing an alkaline aqueous solution is used to develop and remove the unexposed areas, resulting in the resist pattern.

[0410] As a development method for developing the exposed (irradiated) resist layer, any method can be selected from existing known photoresist development methods, such as spin spraying, paddle spraying, and immersion with ultrasonic treatment.

[0411] For the alkaline aqueous solution used as the developer, aqueous solutions of Na₂CO₃, K₂CO₃, and tetramethylammonium hydroxide are preferred. The alkaline aqueous solution is selected according to the characteristics of the resist layer, and a Na₂CO₃ aqueous solution with a concentration of 0.2% to 2% by mass is usually used. Surfactants, defoamers, and small amounts of organic solvents for promoting development can be added to the alkaline aqueous solution. The temperature of the developer in the developing process is preferably kept constant within the range of 20°C to 40°C.

[0412] The developing process preferably includes a water washing step to remove the developer contained in the resist pattern after developing. The washing water can be selected according to the characteristics of the resist layer, in addition to pure water or industrial water. However, to improve resolution and the shape of the resist pattern, a polyvalent metal salt such as MgSO4 at a concentration of 0.001% to 1% by mass can be added. The temperature of the washing water in the water washing step is preferably kept constant within the range of 20°C to 40°C.

[0413] The anti-corrosion pattern obtained through the above process can be further heat-treated at 60℃~300℃ for 1~120 minutes, if necessary. This heat treatment improves the chemical resistance of the anti-corrosion pattern. The heat treatment can be performed using a furnace employing hot air, infrared radiation, or far-infrared radiation.

[0414] To obtain a conductor pattern, a conductor pattern forming process can be performed after the developing or heating process, wherein the conductor pattern forming process etches or plates the substrate on which the resist pattern is formed.

[0415] <Conductor Pattern Forming Process>

[0416] The conductor patterning process is a process of forming conductor patterns on the surface of a substrate (e.g., a copper surface) that has been formed with resist patterns by development, using known etching or plating methods.

[0417] As an example, the method for forming conductor patterns based on plating is described below.

[0418] After the development process, the substrate is immersed in an acidic degreasing bath such as a 1-50% by mass sulfuric acid aqueous solution at 20-60°C for 1-60 minutes. After rinsing the immersed substrate with water, it is immersed in a 1-50% by mass sulfuric acid aqueous solution at room temperature for 1-60 minutes.

[0419] Prepare aqueous solutions containing 1-15% by mass copper sulfate, 0.1-30% by mass sulfuric acid, and 1-1000 ppm hydrochloric acid.

[0420] Next, a brightener (made by ATOTECH Corporation: Cupracid HL and Cupracid GS) was added at concentrations of 0.01~40 ml / l and 1~200 ml / l, respectively, to prepare a copper sulfate plating solution.

[0421] Using the prepared copper sulfate plating solution, a Haring Cell uniform plating apparatus (manufactured by Yamamoto Gold Plating Tester Co., Ltd.) is used to apply a current of 0.01 to 10 A for 1 to 300 minutes to form a conductor pattern.

[0422] While the thickness of the copper plating film also depends on the thickness of the resist pattern, it is preferably 1 μm or more and (the thickness of the resist pattern (μm) - 2 μm) or less. In this disclosure, the thickness of the resist pattern refers to the thickness of the cured resist layer.

[0423] For example, flash etching is a method for forming conductor patterns based on etching.

[0424] In flash etching, the copper seed layer can be removed using a specified etching solution. Examples of etching solutions include, for instance, a mixture of sulfuric acid and hydrogen peroxide water (manufactured by Ebara Densha Co., Ltd.), but it is not limited to this.

[0425] [Methods for manufacturing conductor patterns]

[0426] The conductor pattern is manufactured by, for example, using a metal plate or a metal-coated insulating plate as a substrate and forming a resist pattern using the above-described resist pattern forming method, followed by a conductor pattern forming process.

[0427] <Stripping Process>

[0428] Furthermore, after manufacturing the conductor pattern using the aforementioned method, a stripping process can be performed to peel the resist pattern off the substrate using an aqueous solution with a stronger alkalinity than the developer. By performing the stripping process, a wiring board (in one embodiment, a printed wiring board) with the desired wiring pattern can be obtained.

[0429] There are no particular restrictions on the alkaline aqueous solution (hereinafter also referred to as "stripping solution") used for stripping. Usually, an aqueous solution of NaOH or KOH with a concentration of 2% to 20% by mass or an organic amine-based stripping solution is used.

[0430] A small amount of water-soluble solvent may be added to the stripping solution. Examples of water-soluble solvents include alcohols. The temperature of the stripping solution in the stripping process is preferably in the range of 40°C to 70°C, and the immersion time in the stripping solution is preferably 1 to 60 minutes.

[0431] [Manufacturing method of wiring board]

[0432] A method for manufacturing a wiring board using the photosensitive resin laminate of this embodiment includes, in one aspect, the following steps:

[0433] The process of laminating a resist layer on a substrate;

[0434] An exposure process that exposes an anti-corrosion layer;

[0435] The developing process that removes the unexposed portions of the resist layer to form the resist pattern;

[0436] A conductor pattern forming process that etches or plates a substrate with a resist pattern to form a conductor pattern; and

[0437] The stripping process that removes the resist pattern from the substrate.

[0438] The wiring board manufacturing method in this embodiment includes the same processes as described above, namely, the lamination process, the exposure process, the development process, the conductor pattern formation process, and the stripping process.

[0439] The photosensitive resin laminate in this embodiment can be used for: manufacturing printed wiring boards; manufacturing lead frames for IC chip mounting; precision machining of metal foils such as metal mask manufacturing; manufacturing of packages such as ball grid arrays (BGA) and chip-scale packages (CSP); manufacturing of tape substrates such as chip-on-film (COF) and tape-and-reel automatic bonding (TAB); manufacturing of semiconductor bumps; and manufacturing of partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shielding.

[0440] It should be noted that, unless otherwise specified, the values ​​of the above parameters shall be determined according to the measurement methods described in the embodiments below.

[0441] [Method for manufacturing photosensitive resin laminates]

[0442] The photosensitive resin laminate of this embodiment can be manufactured by the method shown below.

[0443] That is, in one embodiment, the method for manufacturing the photosensitive resin laminate is a method for manufacturing a photosensitive resin laminate comprising a support film and a resist layer containing a photosensitive resin composition, which includes the following steps:

[0444] The preparation process of a photosensitive resin composition solution comprising a compound having an olefinic unsaturated bond as component (A), an alkali-soluble resin as component (B), and a solvent.

[0445] A coating process for coating a photosensitive resin composition solution onto a support film;

[0446] A resist layer forming process involves heating a support film coated with a photosensitive resin composition solution to form a resist layer.

[0447] In one embodiment, component (A) comprises a polyglycerol-based (meth)acrylate (A1) and a compound (A2) that does not have a carboxyl group but has an olefinic unsaturated bond.

[0448] The method for manufacturing photosensitive resin laminates according to this embodiment enables the production of photosensitive resin laminates that are not affected by manufacturing or storage conditions determined by the thickness of the resist layer, and that exhibit excellent sensitivity and resolution.

[0449] <Preparation Process>

[0450] This process involves preparing a photosensitive resin composition solution by adding a solvent to the above-mentioned (A) compound having olefinic unsaturated bonds and (B) alkali-soluble resin.

[0451] Suitable solvents include ketones, such as methyl ethyl ketone (MEK), as well as alcohols such as methanol, ethanol, and isopropanol.

[0452] One solvent can be used, or two or more solvents can be mixed.

[0453] The solvent content relative to the photosensitive resin composition solution is preferably 30-60% by mass, more preferably 33-55% by mass, and even more preferably 35-57% by mass.

[0454] The solvent is preferably added to the photosensitive resin composition such that the viscosity of the photosensitive resin composition solution is 500~4000 mPa·sec at 25°C.

[0455] Viscosity was measured at 25°C using a Brookfield viscometer (manufactured by Ingol, model DVNext).

[0456] <Coating Process>

[0457] This process involves coating a photosensitive resin composition solution onto a support film.

[0458] The photosensitive resin composition solution can be coated onto the support film using conventional methods, such as coating with a roller coater, spin coater, bar coater, scraper coater, curtain coater, or screen printer; or spray coating with a spray coater.

[0459] <Resistant Layer Formation Process>

[0460] This process involves heating a support film coated with a photosensitive resin composition solution to remove the solvent from the photosensitive resin composition solution by heating and distillation, thereby forming a resist layer containing the photosensitive resin composition.

[0461] Furthermore, the heating temperature of the support film coated with the photosensitive resin composition solution is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher. By heating to 90°C or higher, the evaporation of the solvent contained in the photosensitive resin composition solution is accelerated, thereby improving the production efficiency of the photosensitive resin laminate.

[0462] The heating temperature of the support film coated with the photosensitive resin composition solution is preferably below 140°C, more preferably below 130°C, and even more preferably below 120°C. By maintaining the temperature below 140°C, thermal polymerization of the photosensitive resin composition can be prevented.

[0463] The heating time for the support film coated with the photosensitive resin composition solution is preferably 1 to 10 minutes.

[0464] Depending on the needs, after the resist layer formation process, a protective layer, such as a protective film, can be laminated on the resist layer. The protective layer is adhered to the side of the resist layer where the supporting film is not laminated, serving as a cover.

[0465] The protective film used in the protection process is the same as described above.

[0466] Example

[0467] Next, examples and comparative examples will be given to describe this embodiment in more detail. However, this embodiment is not limited to the following examples as long as it does not depart from its spirit. The physical properties in the examples were measured by the following methods.

[0468] (B) The weight-average molecular weight of the alkali-soluble resin was determined by gel permeation chromatography (GPC) and then derived by conversion using a standard curve of standard polystyrene. The GPC conditions are as follows.

[0469] (GPC conditions)

[0470] Pump: PU-980 manufactured by Japan Shoko Corporation

[0471] Columns: A total of 2 columns below

[0472] Shodex KF-80Y / KF-806M

[0473] Eluent: Tetrahydrofuran

[0474] Measurement temperature: 40℃

[0475] Flow rate: 2.05 mL / min

[0476] Detector: RI-1530 manufactured by Japan Spectrophotometer Co., Ltd.

[0477] Standard monodisperse polystyrene: Manufactured by Tosoh Corporation; product name: TSKgel standard polystyrene

[0478] The photosensitive resin laminate is prepared as described below.

[0479] <Preparation of Photosensitive Resin Laminates>

[0480] The photosensitive resin compositions (Examples 1-21 and Comparative Examples 1-5) were prepared by mixing the components (A) to (E) shown in Table 1 below (where the numbers of each component indicate the content (parts by mass) based on the solid content).

[0481] The photosensitive resin compositions of Examples 1-21 and Comparative Examples 1-5, and ethanol measured in such a way that the solid component concentration of these photosensitive resin compositions is 60% by mass, were thoroughly stirred and mixed to obtain a formulation containing the photosensitive resin compositions of Examples 1-21 and Comparative Examples 1-5.

[0482] Using a 16μm thick polyethylene terephthalate film (manufactured by Toray Industries, QS71) as a support film, these mixed liquids were evenly coated on its surface using a bar coater (trade name: Type A automatic coater, manufactured by Toyo Seiki Co., Ltd.), and heated / dried in a dryer at 95°C for 2 minutes and 30 seconds to form a 25μm thick resist layer.

[0483] Next, a 19 μm thick polyethylene film (manufactured by TAMAPOLY, GF-858) was laminated onto the surface of the unlaminated polyethylene terephthalate film of the resist layer as a protective layer to obtain a photosensitive resin laminate containing the photosensitive resin compositions of Examples 1-21 and Comparative Examples 1-5.

[0484] Fabrication of substrates for performance evaluation

[0485] The substrate for performance evaluation is fabricated as described below.

[0486] <Substrate Leveling>

[0487] Prepare a 0.4 mm thick copper-clad laminate with rolled copper foil of 18 μm thickness. Clean the surface of the substrate with a 10% by mass H2SO4 aqueous solution.

[0488] Lamination

[0489] While peeling off the polyethylene film of the photosensitive resin laminate prepared above, the photosensitive resin laminate prepared above is laminated onto a copper-clad laminate that has been preheated to 50°C using the above-described method and flattened using a hot roll laminator (manufactured by Asahi Kasei Corporation, AL-700) at a roll temperature of 105°C to obtain a substrate for performance evaluation. The air pressure is set to 0.35 MPa and the lamination speed is set to 1.5 m / min.

[0490] <Exposure Process>

[0491] Two hours after lamination, the performance evaluation substrate is exposed at a wavelength of 365nm using a projection exposure machine (USHIO Electric Co., Ltd., UX-44101 SM) through a glass mask. Similarly, the performance evaluation substrate is exposed at a wavelength of 402nm using a direct drawing exposure machine (ORC Manufacturing Co., Ltd., FDi-3) with a specified direct imaging (DI) exposure pattern.

[0492] <Heating Process>

[0493] After exposure for 1 minute, the substrate used for performance evaluation was heated for 30 seconds using a constant temperature thermostat (manufactured by YAMATO Scientific Co., Ltd., DKM600) with a forced air supply set to 60°C.

[0494] <Developing Process>

[0495] After peeling off the polyethylene terephthalate film (support film), an alkaline developer (Fujiki Kogyo Co., Ltd., dry film developer) is used to spray a 1% by mass Na2CO3 aqueous solution at 30°C for a specified time for development.

[0496] The developing spray time is set to twice the minimum developing time, and the post-developing cleaning spray time is set to twice the minimum developing time.

[0497] <Plating Process>

[0498] For substrates that have undergone the same leveling and lamination as described above, a pattern is drawn using a linewidth (L) / line spacing (S) (hereinafter referred to as "L / S") of x / x (x = 1~20 (varying in 1μm intervals)) (unit: μm). After exposure at energy level 17 of a Hitachi 41-level staged exposure meter, the same heating and developing processes as described above are performed to form the resist pattern. The developed substrate is then immersed in an acidic degreasing FRX bath (10% by mass sulfuric acid aqueous solution, manufactured by ATOTECH JAPAN) at 40°C for 4 minutes. After rinsing with water, it is immersed in a 10% by mass sulfuric acid aqueous solution at room temperature for 2 minutes.

[0499] Prepare a 121 g / L copper sulfate aqueous solution, dilute it with 19% (w / w) sulfuric acid to a volume ratio of 3.6, and then add concentrated hydrochloric acid at a concentration of 200 ppm. Next, as brighteners, add Cupracid HL and Cupracid GS at concentrations of 0.4 ml / L and 20 ml / L respectively to prepare the copper sulfate plating solution.

[0500] For the pre-plating treatment substrate (6cm × 12.5cm) used for plating resistance evaluation, the prepared copper sulfate plating solution was used, and a Haring Cell uniform plating apparatus (manufactured by Yamamoto Gold Plating Tester Co., Ltd.) was used to apply a current of 0.4A for 65 minutes. The thickness of the copper plating film at this time was 20μm.

[0501] <Stripping Process>

[0502] A stripping solution with a concentration of 20% by mass was prepared by mixing products under the trade names "Clean Etch (registered trademark) R-100S" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and "Clean Etch (registered trademark) R-101" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) at a volume ratio of 2:1 and diluting with pure water. The substrate used for performance evaluation after plating treatment was immersed in the stripping solution heated to 50°C for 4 minutes without stirring to remove the resist pattern.

[0503] [evaluate]

[0504] <Reproducibility>

[0505] The substrate for performance evaluation is exposed and developed according to the above method, and the shortest development time is the shortest time required for the unexposed part of the resist layer to completely dissolve.

[0506] The shorter the minimum development time, the higher the developability. The minimum development time is evaluated according to the following criteria.

[0507] If the rating is 0 or △, it can be suitably used as a photosensitive resin laminate for use in resist patterning.

[0508] ○: Shortest development time less than 18 seconds is considered "Good".

[0509] △: The minimum development time is 18 seconds or more but less than 20 seconds.

[0510] ×: Minimum developing time of 20 seconds or more is "not allowed".

[0511] <Flexibility>

[0512] Following the above method, the flexible substrate that has undergone substrate leveling and lamination was exposed to an energy level of 17 residual levels using a 41-level staged exposure table manufactured by Stouffer. The substrate was then cut into 1-inch widths to produce samples.

[0513] Using this sample, a mandrel test was performed according to JIS K5600-5-1. Flexibility was evaluated by the smallest mandrel diameter that did not produce cracks in the exposed portion. A smaller value indicated higher flexibility, evaluated according to the following criteria.

[0514] If the rating is 0 or △, it can be suitably used as a photosensitive resin laminate for use in resist patterning.

[0515] ○: Diameter less than 6mm "Good"

[0516] △: Diameter 6mm or more but less than 10mm "acceptable"

[0517] ×: Diameters larger than 10mm are "not allowed".

[0518] <Seamlessness>

[0519] For the substrate used for performance evaluation, a pattern is drawn using a line width (L) / line spacing (S) (hereinafter referred to as "L / S") of x / 3x (x = 1~20 (in 1μm intervals)) (unit: μm). After exposure with an energy of 17 residual levels of a 41-level staged exposure table manufactured by Hitachi, the above-mentioned heating and development processes are performed to form a resist pattern.

[0520] The resist pattern was observed using an optical microscope, and the adhesion was evaluated based on the minimum linewidth of the exposed portion without producing meandering or incomplete lines. The smaller the value, the higher the adhesion, and the evaluation was conducted according to the following criteria.

[0521] If the rating is 0 or △, it can be suitably used as a photosensitive resin laminate for use in resist patterning.

[0522] ○: Minimum linewidth less than 6μm "Good"

[0523] △: Minimum linewidth of 6μm or more but less than 8μm is "acceptable".

[0524] ×: Minimum linewidth of 8μm or more is "not allowed".

[0525] <resolution>

[0526] For the substrate used for performance evaluation, a pattern is drawn using a line width (L) / line spacing (S) (hereinafter referred to as "L / S") of x / x (x=1~20 (varies in 1μm intervals)) (unit: μm). After exposure with an energy of 17 residual levels of a 41-level staged exposure table manufactured by Hitachi, the above-mentioned heating and development processes are performed to form a resist pattern.

[0527] The resist pattern was observed using an optical microscope, and the resolution was evaluated based on the minimum linewidth at which no meandering or gaps were produced in the exposed areas and no residue was removed in the unexposed areas. The smaller this value, the higher the resolution, and the evaluation was carried out according to the following criteria.

[0528] If the rating is 0 or △, it can be suitably used as a photosensitive resin laminate for use in resist patterning.

[0529] ○: Minimum linewidth less than 6μm "Good"

[0530] △: Minimum linewidth of 6μm or more but less than 8μm is "acceptable".

[0531] ×: Minimum linewidth of 8μm or more is "not allowed".

[0532] <Stripping Evaluation>

[0533] After performing the above-described plating process on the substrate used for performance evaluation, the above-described peeling process is performed. The minimum mask width at which the cured resist lines between the plating patterns are completely peeled off is taken as the peelability value after plating. The smaller this value, the higher the peelability, and the evaluation is carried out according to the following criteria.

[0534] If the rating is ◎, 〇 or △, it can be appropriately used as a printed circuit board for plating after the resist pattern is formed.

[0535] ◎: Minimum mask width less than 6μm "Excellent"

[0536] ○: Minimum mask width is 6μm or more but less than 7μm. "Good"

[0537] △: Minimum mask width of 7μm or more but less than 9μm is "acceptable".

[0538] ×: Minimum mask width of 9μm or more is "not allowed".

[0539] The evaluation results of the substrate used for performance evaluation of the embodiments are shown in Table 1. Furthermore, details of the components shown in Table 1 are shown in Table 2.

[0540] In addition, Table 3 shows the total value of k, each li and m (number of repeating units) in the formula (I) of the polyglycerol (meth) acrylate, as well as the total value of the number of repeating units (k, each li and m) / (n+2) and the value of n.

[0541] It should be noted that Table 3 shows the total values ​​of k, li, and m for (A1-1) to (A1-5) from top to bottom, as well as the value of n.

[0542] [Table 1-1]

[0543]

[0544] [Table 1-2]

[0545]

[0546] [Table 1-3]

[0547]

[0548] [Table 2]

[0549]

[0550] [Table 3]

[0551]

[0552] As shown in Table 1, in the embodiments that meet the requirements of this embodiment, the developability, flexibility, resolution, adhesion and peelability are all good.

[0553] On the other hand, when (A) contains (A1) polyglycerol (meth)acrylate and (A2) a compound that does not have a carboxyl group but has an olefinic unsaturated bond, the developability, softness, resolution, adhesion and peelability are not all good.

[0554] In addition, when component (A) contains a compound (A3) having a carboxyl group and an olefinic unsaturated bond, the developability and resolution are poor compared to the examples.

[0555] The embodiments of the present invention have been described above, but the present invention is not limited thereto and can be appropriately modified without departing from the spirit of the invention.

[0556] Industrial availability

[0557] By using the photosensitive resin laminate of the present invention, the coating / drying conditions and storage conditions of the photosensitive resin laminate are not affected, resulting in excellent developability, flexibility, resolution, adhesion, and peelability. In other words, it can be widely used as a photosensitive resin laminate for forming resist patterns, and is particularly suitable for forming resist patterns on printed circuit boards where plating is required after the resist pattern is formed.

Claims

1. A photosensitive resin laminate comprising a supporting film and a resist layer containing a photosensitive resin composition, The photosensitive resin composition comprises the following components: (A) Compounds containing olefinic unsaturated bonds; and (B) Alkali-soluble resin, The (A) component comprises: (A1) Polyglycerol-based (meth)acrylates represented by the following general formula (I); and (A2) Compounds that do not have a carboxyl group but have olefinic unsaturated bonds. In equation (I), n ranges from 2 to 20. Each i is a natural number from 1 to n. k, each li, and m are independently 0~30. R1, R 2i R and R3 each independently represent a hydrogen atom or a methyl group. R4, R 5i R6 and R6 are each independently selected from one of the following groups consisting of an alkylene group having 1 to 10 carbon atoms, a group represented by formula (II) below, and a group represented by formula (III) below. In formula (II), R7 and R8 are each independently an alkylene group having 1 to 10 carbon atoms. In formula (III), R9 is an alkylene group having 1 to 10 carbon atoms.

2. The photosensitive resin laminate according to claim 1, wherein, Based on the total solid content of the photosensitive resin composition, the total content of component (A) and component (B) in the photosensitive resin composition is 80% by mass or more and 98% by mass or less.

3. The photosensitive resin laminate according to claim 1 or 2, wherein, Based on the total content of component (A) and component (B), the content of component (B) is less than 70% by mass.

4. The photosensitive resin laminate according to claim 1 or 2, wherein, Component (B) comprises structural units derived from styrene and benzyl (meth)acrylate.

5. The photosensitive resin laminate according to claim 1 or 2, wherein, The (B) component contains structural units derived from styrene, and the styrene content in the (B) component is more than 35% by mass and less than 80% by mass.

6. The photosensitive resin laminate according to claim 1 or 2, wherein, The photosensitive resin composition further comprises a photopolymerization initiator as component (C).

7. The photosensitive resin laminate according to claim 6, wherein, Based on the content of component (A), the content of component (C) in the photosensitive resin composition is 25% by mass or less.

8. The photosensitive resin laminate according to claim 6, wherein, The component (C) contains a hexaaryl biimidazole compound.

9. The photosensitive resin laminate according to claim 1 or 2, wherein, The photosensitive resin composition further comprises (D) a polymerization inhibitor.

10. The photosensitive resin laminate according to claim 1 or 2, wherein, The (A2) component is a compound having 2 to 6 olefinic unsaturated bonds.

11. The photosensitive resin laminate according to claim 1 or 2, wherein, The (A2) component comprises a compound having two olefinic unsaturated bonds.

12. The photosensitive resin laminate according to claim 1 or 2, wherein, The (A2) component comprises a compound having one olefinic unsaturated bond.

13. The photosensitive resin laminate according to claim 1 or 2, wherein, The (A2) component contains a di(meth)acrylate compound having a bisphenol A structure.

14. The photosensitive resin laminate according to claim 1 or 2, wherein, In the general formula (I), R1 and R 2i R3 is a methyl group.

15. The photosensitive resin laminate according to claim 1 or 2, wherein, R4O and R in the general formula (I) 5i O and R6O in formula R j When represented in the form of O, the number of (meth)acryloyl groups is relative to the R. j The ratio of the total number of O to less than 20, the formula R j In O, j = 4, 5i, 6, and i = 1, 2, ..., n.

16. The photosensitive resin laminate according to claim 1 or 2, wherein, In the general formula (I), n is an integer from 2 to 15.

17. The photosensitive resin laminate according to claim 1 or 2, wherein, In the general formula (I), n is 2 to 15, which is the mean of the numbers.

18. The photosensitive resin laminate according to claim 1 or 2, wherein, The R4, R 5i R6 is an alkylene group.

19. The photosensitive resin laminate according to claim 1 or 2, wherein, The R4, R 5i R6 contains ethylene and / or propylene.

20. The photosensitive resin laminate according to claim 1 or 2, wherein, The R4, R 5i R6 is ethylene and / or propylene.

21. The photosensitive resin laminate according to claim 1 or 2, wherein, The R4, R 5i R6 is ethylene.

22. The photosensitive resin laminate according to claim 1 or 2, further comprising a protective film.

23. A photosensitive resin laminate comprising a supporting film and a resist layer comprising a photosensitive resin composition, The photosensitive resin composition comprises the following components: (A) Compounds containing olefinic unsaturated bonds; and (B) Alkali-soluble resin, The (A) component comprises: (A3) Compounds that do not have a quaternary carbon and / or an aromatic ring, and have more than four olefinic unsaturated bonds in one molecule; and (A4) A compound having a quaternary carbon and / or an aromatic ring, but not a carboxyl group, and having an olefinic unsaturated bond.

24. The photosensitive resin laminate according to claim 23, wherein, The (A4) compound comprises a compound having one or two olefinic unsaturated bonds.

25. The photosensitive resin laminate according to claim 23 or 24, wherein, The amount of olefinic unsaturated bonds in each 100g of the (A4) compound is less than 0.25mol.

26. The photosensitive resin laminate according to claim 23 or 24, wherein, Based on the total solid content of the photosensitive resin composition, the content of component (A) is 20% by mass or more.

27. The photosensitive resin laminate according to claim 23 or 24, wherein, Component (B) contains a copolymer comprising structural units derived from (meth)acrylic acid as a monomer component. The content of the structural unit derived from (meth)acrylic acid in component (B) is less than 27% by mass.

28. The photosensitive resin laminate according to claim 23 or 24, wherein, Component (B) contains a copolymer comprising structural units derived from (meth)acrylic acid as a monomer component. The content of the structural unit derived from (meth)acrylic acid in component (B) is less than 25% by mass.

29. A method for forming a resist pattern, comprising the steps of forming a resist pattern using the photosensitive resin laminate of claim 1 or 2: The process of laminating a resist layer on a substrate; The exposure process for exposing the anti-etching layer; and The developing process involves developing and removing the unexposed portions of the resist layer.

30. A method for manufacturing a wiring board, comprising the following steps: (The method describes a method for manufacturing a wiring board using the photosensitive resin laminate as described in claim 1 or 2.) The process of laminating a resist layer on a substrate; An exposure process that exposes an anti-corrosion layer; The developing process that removes the unexposed portions of the resist layer to form the resist pattern; A conductor pattern forming process involves etching or plating a substrate with the resist pattern to form a conductor pattern; and The stripping process that peels the resist pattern off the substrate.

Images