TW202448973A - Photosensitive resin laminate and method for forming photoresist pattern - Google Patents

Abstract

Provided is a photosensitive resin laminate comprising a support film and a resist layer that contains a photosensitive resin composition, wherein the photosensitive resin composition contains (A) a compound having an ethylenically unsaturated bond, and (B) an alkali-soluble resin, the (A) compound including (A1) a polyglycerin-based (meth)acrylate represented by 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; R1, R2i, and R3 each independently represent a hydrogen atom or a methyl group; and R4, R5i, and R6 are each independently selected from the group consisting of C1-C10 alkylene groups, groups represented by formula (II) [in the formula, R7 and R8 are each independently a C1-C10 alkylene group], and groups represented by formula (III) [in the formula, R9 is a C1-C10 alkylene group]], and (A2) a compound that does not have a carboxyl group and has an ethylenically unsaturated bond.

Description

Photosensitive resin laminate and method for forming photoresist pattern

The present invention relates to a photosensitive resin laminate and a method for forming a photoresist pattern.

Printed wiring boards are generally manufactured using a photolithography process. Photolithography refers to a method of forming a desired wiring pattern on a substrate by the following steps. That is, first, a layer containing a photosensitive resin composition is formed on the substrate, and the coating is pattern-exposed and developed to form a photoresist pattern. Then, a conductor pattern is formed by etching or plating. After that, the photoresist pattern on the substrate is removed, thereby forming the desired wiring pattern on the substrate.

Generally speaking, the formation of a photoresist pattern in a photolithography process is performed by, for example, applying a solution of a photosensitive resin composition on a substrate and drying it, or by laminating a photoresist layer of a dry film photoresist (a photosensitive resin laminate including a photoresist layer and a support film) on a substrate.

Photosensitive resin laminates are often used in the manufacture of printed wiring boards. In the production and use of photosensitive resin laminates, the important factors are the developability, flexibility, resolution, adhesion, and release properties, which are determined by the type and combination of compounds with ethylenic unsaturated bonds and the content setting, as well as the productivity.

For example, Patent Document 1 discloses that developing properties and peeling properties are improved by using glyceryl triacrylate. Patent Document 2 discloses that resolution and adhesion are improved by using a (meth)acrylate compound having a skeleton derived from pentaerythritol. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 10-198031 [Patent Document 2] Japanese Patent Publication No. 2013-92693

[The technical problem that the invention is intended to solve]

However, although the photosensitive resin composition described in Patent Document 1 has the specified developing properties and peeling properties, there is still room for further improvement from the perspective of resolution and adhesion. In addition, although the curable resin composition described in Patent Document 2 has the specified resolution and adhesion, there is still room for further improvement from the perspective of developing properties and flexibility.

The purpose of the present invention is to provide a photosensitive resin laminate with excellent developability, flexibility, resolution, and adhesion, and a method for forming a photoresist pattern. [Technical means]

The present invention is as follows.

[1] A photosensitive resin laminate having a supporting film and a photoresist layer containing a photosensitive resin composition; wherein the photosensitive resin composition contains the following components: (A) a compound having an ethylenically unsaturated bond, and (B) an alkali-soluble resin; wherein the component (A) contains (A1) a polyglycerol (meth)acrylate represented by the following general formula (I): [Chemical 1] [In the formula, n is 2 to 20; each i is a natural number from 1 to n; k, each li, and m are each independently 0 to 30; R ₁ , R _2i , and R ₃ are each independently a hydrogen atom or a methyl group; R ₄ , R _5i , and R ₆ are each independently a group selected from an alkylene group having 1 to 10 carbon atoms and represented by the following formula (II): [Chemical 2] [In the formula, _R7 and _R8 are each independently an alkylene group having 1 to 10 carbon atoms.], and a group represented by the following formula (III): [Chemical 3] [wherein, R ₉ is an alkylene group having 1 to 10 carbon atoms. ]; and (A2) a compound having no carboxyl group and having an ethylenically unsaturated bond. [2] The photosensitive resin laminate as described in [1], wherein the total content of the aforementioned component (A) and the aforementioned component (B) in the aforementioned photosensitive resin composition is 80 mass % or more and 98 mass % or less, based on the total solid content of the aforementioned photosensitive resin composition. [3] The photosensitive resin laminate as described in [1] or [2], wherein the content of the aforementioned component (B) is 70 mass % or less, based on the total content of the aforementioned component (A) and the aforementioned component (B). [4] The photosensitive resin laminate as described in any one of [1] to [3], wherein the component (B) contains constituent units derived from styrene and benzyl (meth)acrylate. [5] The photosensitive resin laminate as described in any one of [1] to [4], wherein the component (B) contains constituent units derived from styrene, and the content of styrene in the component (B) is 35 mass % or more and 80 mass % or less. [6] The photosensitive resin laminate as described in any one of [1] to [5], wherein the photosensitive resin composition further contains a photopolymerization initiator as component (C). [7] The photosensitive resin laminate as described in [6], wherein 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] The photosensitive resin laminate as described in [6] or [7], wherein the aforementioned component (C) contains a hexaarylbiimidazole compound. [9] The photosensitive resin laminate as described in any one of [1] to [8], wherein the aforementioned photosensitive resin composition further contains (D) a polymerization inhibitor. [10] The photosensitive resin laminate as described in any one of [1] to [9], wherein the aforementioned component (A2) is a compound having 2 to 6 ethylenically unsaturated bonds. [11] The photosensitive resin laminate as described in any one of [1] to [9], wherein the component (A2) contains a compound having two ethylenically unsaturated bonds. [12] The photosensitive resin laminate as described in any one of [1] to [9], wherein the component (A2) contains a compound having one ethylenically unsaturated bond. [13] The photosensitive resin laminate as described in any one of [1] to [12], wherein the component (A2) contains a di(meth)acrylate compound having a bisphenol A structure. [14] The photosensitive resin laminate as described in any one of [1] to [13], wherein R ₁ , R _2i , and R ₃ in the general formula (I) are methyl groups. [15] The photosensitive resin laminate as described in any one of [1] to [14], wherein R ₄ O, R _5i O and R ₆ O in the general formula (I) are represented by the formula R _j O {wherein j = 4, 5i, 6 (wherein i = 1, 2, …, n)}, the ratio of the total number of the aforementioned R _j O to the number of (meth)acryloyl groups is 20 or less. [16] The photosensitive resin laminate as described in any one of [1] to [15], wherein n in the general formula (I) is an integer of 2 to 15. [17] The photosensitive resin laminate as described in any one of [1] to [15], wherein n in the general formula (I) is an integer of 2 to 15 as a numerical average. [18] The photosensitive resin laminate as described in any one of [1] to [17], wherein R ₄ , R _5i , and R ₆ are alkylene groups. [19] The photosensitive resin laminate as described in any one of [1] to [18], wherein R ₄ , R _5i , and R ₆ are ethylene groups and/or propylene groups. [20] The photosensitive resin laminate as described in any one of [1] to [18], wherein R ₄ , R _5i , and R ₆ are ethylene groups and/or propylene groups. [21] The photosensitive resin laminate as described in any one of [1] to [18], wherein R ₄ , R _5i , and R ₆ are ethylene groups. [22] A photosensitive resin laminate as described in any one of [1] to [21], further comprising a protective film. [23] A photosensitive resin laminate comprising a support film and a photoresist layer containing a photosensitive resin composition; wherein the photosensitive resin composition comprises the following components: (A) a compound having an ethylenically unsaturated bond, and (B) an alkali-soluble resin; wherein the component (A) comprises (A3) a compound having no quaternary carbon and/or aromatic ring and having 4 or more ethylenically unsaturated bonds in one molecule; and (A4) a compound having a quaternary carbon and/or aromatic ring, having no carboxyl group, and having an ethylenically unsaturated bond. [24] The photosensitive resin laminate as described in [23], wherein the compound (A4) is a compound having one or two ethylenically unsaturated bonds. [25] The photosensitive resin laminate as described in [23] or [24], wherein the amount of ethylenically unsaturated bonds in 100 g of the compound (A4) is 0.25 mol or less. [26] The photosensitive resin laminate as described in any one of [23] to [25], wherein the content of the component (A) is 20% by mass or more based on the mass of all solid components of the photosensitive resin composition. [27] The photosensitive resin laminate as described in any one of [23] to [26], wherein the component (B) is a copolymer containing a constituent unit derived from (meth) acrylic acid as a monomer component; and the content of the constituent unit derived from (meth) acrylic acid in the component (B) is 27% by mass or less. [28] The photosensitive resin laminate as described in any one of [23] to [26], wherein the component (B) is a copolymer containing a constituent unit derived from (meth) acrylic acid as a monomer component; and the content of the constituent unit derived from (meth) acrylic acid in the component (B) is 25% by mass or less. [29] A method for forming a photoresist pattern, which uses a photosensitive resin laminate as described in any one of [1] to [28] and includes the following steps: a lamination step of laminating a photoresist layer on a substrate; an exposure step of exposing the photoresist layer; and a development step of developing and removing unexposed portions of the photoresist layer. [30] A method for manufacturing a wiring board, which uses the photosensitive resin laminate as described in any one of [1] to [28], and comprises the following steps: a lamination step of laminating a photoresist layer on a substrate; an exposure step of exposing the photoresist layer; a development step of developing and removing the unexposed portion of the photoresist layer to form a photoresist pattern; a conductor pattern forming step of etching or plating the substrate on which the photoresist pattern is formed to form a conductor pattern; and a stripping step of stripping the photoresist pattern from the substrate. [Effects of the Invention]

According to the present invention, a photosensitive resin laminate having a photoresist layer containing a photosensitive resin composition having excellent developability, flexibility, resolution, adhesion and peeling properties, and a method for forming a photoresist pattern can be provided.

The following is a detailed description of the exemplary embodiment of the present invention (hereinafter referred to as "this embodiment"). The present invention is not limited to this embodiment, and can be implemented in various modifications within the scope of its gist. In this specification, the upper limit and lower limit of each numerical range can be arbitrarily combined. Furthermore, in this embodiment, the upper limit or lower limit recorded in a numerical range can also be replaced by the value shown in the embodiment. In addition, in this specification, the numerical range represented by "～" includes the numerical values of the upper limit and the lower limit. Regarding the term "step" in the following description, it not only includes independent steps, but also includes steps that cannot be clearly distinguished from other steps as long as the function of the "step" can be achieved.

In addition, in this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid; "(meth)acryl" means acrylyl or methacryl; and "(meth)acrylate" means "acrylate" or "methacrylate".

<Photosensitive resin laminate> The photosensitive resin laminate of the present embodiment, in one aspect, has a support film and a photoresist layer containing a photosensitive resin composition. In particular, the photosensitive resin composition constituting the photosensitive resin laminate provided in one aspect of the present embodiment contains: (A) a compound having an ethylenically unsaturated bond, and (B) an alkali-soluble resin. In particular, in the photosensitive resin laminate of the present embodiment, the photosensitive resin composition of the present embodiment contains (A1) polyglycerol (meth)acrylate and (A2) a compound having no carboxyl group and having an ethylenic unsaturated bond as (A) a compound having an ethylenic unsaturated bond.

The inventors of the present invention have found that the photosensitive resin composition of the present embodiment has good developing properties, flexibility, resolution, adhesion and release properties by combining polyglycerol (meth)acrylate (A1) and a compound (A2) having no carboxyl group and having an ethylenic unsaturated bond as components of the photosensitive resin composition of the present embodiment. That is, according to the present embodiment, a photosensitive resin composition having excellent developing properties, flexibility, resolution, adhesion and release properties, and a method for forming a photoresist pattern can be provided.

In the photosensitive resin laminate of other embodiments, the photosensitive resin composition of the present embodiment contains, as (A) the compound having ethylenic unsaturated bonds, (A3) a compound having no quaternary carbon and/or aromatic ring and having 4 or more ethylenic unsaturated bonds in one molecule, and (A4) a compound having quaternary carbon and/or aromatic ring and having no carboxyl group and having ethylenic unsaturated bonds.

<Supporting film> The supporting film of this embodiment is a layer or film used to support the photoresist layer, and is ideally a transparent substrate film that can transmit active light.

As transparent substrate films, films made of synthetic resins such as polyethylene, polypropylene, polycarbonate, polyethylene terephthalate (PET), cellulose triacetate, and cycloolefin polymers can be cited. Among these, it is ideal to use high-quality films with less internal foreign matter. Specifically, as high-quality films, polyethylene terephthalate (PET) films, cellulose triacetate films, cycloolefin polymer films, etc. are ideal, and it is more ideal to use polyethylene terephthalate (PET) films with appropriate flexibility and strength. Among PET films, the following films are more preferably used: PET films synthesized using Ti-based catalysts, PET films with small diameters and low lubricant content, PET films containing lubricants only on one side of the film, thin film PET films, PET films with smoothing treatment applied on at least one side, PET films with roughening treatments such as plasma treatment applied on at least one side, etc. In this way, the exposure light can be irradiated to the photoresist layer without being blocked by internal foreign matter, which can improve the resolution of the photosensitive resin composition.

The thickness of the support film is preferably 5 μm to 25 μm, more preferably 6 μm to 20 μm. The thinner the support film, the fewer foreign matter there is inside, which can prevent the resolution from decreasing. However, if the film is too thin, during the coating and winding manufacturing steps, it will be stretched and deformed in the winding direction due to tension or ruptured due to tiny scratches, or the film strength will be insufficient, resulting in wrinkles during lamination.

At least one side of the support film may be subjected to a smoothing treatment using a calendering device, etc. This can reduce the surface roughness of one side of the support film, especially the side in contact with the photosensitive resin composition layer described later, making the effect of this embodiment more excellent.

The haze of the support film is preferably 0.01% to 1.5%, more preferably 0.01% to 1.2%, and further preferably 0.01% to 0.95%, from the viewpoint of improving the parallelism of the light irradiating the photoresist layer and obtaining a higher resolution after exposure and development of the photosensitive resin laminate.

<Photoresist layer> The photoresist layer of this embodiment contains a photosensitive resin composition. In addition, the photoresist layer of this embodiment is a photosensitive resin composition layer in one embodiment. The thickness of the photoresist layer of this embodiment is preferably 3 to 100 μm, and more preferably 3 to 50 μm. The closer the thickness of the photoresist layer is to 3 μm, the higher the resolution, and the closer it is to 100 μm, the higher the film strength, so it can be appropriately selected depending on the purpose. The thickness of the photoresist layer of this embodiment can also be more than 100 μm and less than 500 μm. By having the thickness of the photoresist layer in the above range, it can also be appropriately used for bump formation and copper column formation.

<Photosensitive resin composition> The photosensitive resin composition of this embodiment contains (A) a compound having an ethylenically unsaturated bond and (B) an alkali-soluble resin.

・(A) Compounds having ethylenically unsaturated bonds In the present embodiment, (A) compounds having ethylenically unsaturated bonds (hereinafter referred to as component (A)) contain (A1) polyglycerol (meth)acrylate and (A2) a compound having no carboxyl group and having ethylenically unsaturated bonds. In one embodiment, component (A) contains polyglycerol (meth)acrylate (A1) represented by general formula (I) described below and a compound having no carboxyl group and having ethylenically unsaturated bonds (A2). As the component (A) contained in the photosensitive resin composition of this embodiment, a polyglycerol-based (meth)acrylate (A1) and a compound (A2) having no carboxyl group and having an ethylenically unsaturated bond are combined, whereby the developing property, flexibility, resolution, adhesion and release properties are improved.

・(A1) Polyglycerol (meth)acrylate In this embodiment, (A1) polyglycerol (meth)acrylate refers to a compound having a polyglycerol skeleton 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)).

[Chemistry 4] [In the formula, n is 2 to 20; each i is a natural number from 1 to n; k, each li, and m are each independently 0 to 30; R ₁ , R _2i , and R ₃ are each independently a hydrogen atom or a methyl group; R ₄ , R _5i , and R ₆ are each independently a group selected from an alkylene group having 1 to 10 carbon atoms and represented by the following formula (II): [Chemical 5] [wherein, _R7 and _R8 are each independently an alkylene group having 1 to 10 carbon atoms.], and a group represented by the following formula (III): [Chemical 6] [In the formula, R ₉ is an alkylene group having 1 to 10 carbon atoms.]

The (A1) polyglycerol-based (meth)acrylate may be used alone or in combination of two or more.

The polyglycerol (meth)acrylate having repeating units represented by R ₄ O, R _5i O and R ₆ O can be synthesized, for example, by the following method, but the synthesis method of the polyglycerol (meth)acrylate (A1) of the present embodiment is not limited thereto. After reacting the hydroxyl group of polyglycerol with an alkylene oxide, the terminal hydroxyl group is reacted with acrylic acid or methacrylic acid to obtain a polyglycerol (meth)acrylate in which R ₄ , R _5i and R ₆ are alkylene groups. In the reaction, a compound having a cleavage group and an epoxy group such as epichlorohydrin is used to replace the alkylene oxide, thereby obtaining the polyglycerol (meth)acrylate in which R ₄ , R _5i and R ₆ are represented by the chemical formula (II). By using a lactone compound to replace the alkylene oxide in the reaction, a polyglycerol-based (meth)acrylate in which R ₄ , R _5i and R ₆ are represented by the chemical formula (III) can be obtained. These reactions can be freely combined. In addition, acrylic acid or methacrylic acid can be reacted with the hydroxyl group of polyglycerol without introducing the repeating units represented by R ₄ O, R _5i O and R ₆ O. Specifically, as the polyglycerol-based (meth)acrylate, SA-TE6, SA-TE60, etc. manufactured by Sakamoto Chemical Industries, Ltd. can be used.

From the viewpoint of softness and adhesion, k, each li, and m in formula (I) are each independently preferably 2 to 20, more preferably 2 to 15, further preferably 2 to 12, further more preferably 2 to 10, particularly preferably 2 to 8, and most preferably 2 to 6. In addition, in the present specification, when the (A1) polyglycerol (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. In addition, when the (A1) polyglycerol (meth)acrylate represented by formula (I) is composed of a plurality of types of molecules, k, each li, and m can be represented by a numerical average value.

From the viewpoint of softness and release properties, n in the structural formula (I) is preferably an integer of 2 to 15, more preferably 2 to 10, further preferably 2 to 8, further preferably 2 to 6, and particularly preferably 2 to 4. In addition, when the (A1) polyglycerol (meth)acrylate represented by the general formula (I) is composed of a plurality of types of molecules, n can be represented by a numerical average. In one embodiment, n in the formula (I) is preferably 2 to 15, more preferably 2 to 10, further preferably 2 to 8, further preferably 2 to 6, and particularly preferably 2 to 4, in terms of numerical average.

In the present specification, the value of (k+ ₁₁ + ₁₂ +…+ _1n +m)/(n+2) of the structural formula (I), that is, the ratio of the total number of RjO to the number of (meth)acryloyl groups when _R4O , _R5iO and _R6O in the formula (I) are expressed as _RjO {wherein _j =4, 5i, 6 (wherein i=1, 2, …, n)}, is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and particularly preferably 6 or less from the viewpoint of resolution and adhesion. In one embodiment, the value of (k+1+m)/(n+2) of the structural formula (I) is preferably 2 or more. In the present specification, k, each li, and m in the polyglycerol (meth)acrylate represented by formula (I) are referred to as repeating units. From the viewpoint of adhesion and resolution, R ₁ , R _2i , and R ₃ in formula (I) are preferably methyl groups.

From the viewpoint of adhesion and resolution, R ₄ , R _5i , and R ₆ in structural formula (I) are preferably alkylene groups, more preferably alkylene groups having 1 to 10 carbon atoms, further preferably alkylene groups containing at least one selected from the group consisting of ethylene groups, propylene groups, and tetramethylene groups, further preferably containing ethylene groups and/or propylene groups, more particularly preferably ethylene groups and/or propylene groups, and most preferably ethylene groups.

The content of (A1) polyglycerol (meth)acrylate in the photosensitive resin composition of the present embodiment is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 7% by mass or more, particularly preferably 10% by mass or more, and most preferably 12% by mass or more, based on the total solid content of the photosensitive resin composition. In addition, the content of (A1) polyglycerol (meth)acrylate in the photosensitive resin composition of the present embodiment is preferably 50% by mass or less, more preferably 48% by mass or less, further preferably 45% by mass or less, further preferably 43% by mass or less, and particularly preferably 40% by mass or less, based on the total solid content of the photosensitive resin composition.

・(A2) Compounds having no carboxyl group and having ethylenic unsaturated bonds In this embodiment, the compound (A2) having no carboxyl group and having ethylenic unsaturated bonds (hereinafter referred to as (A2) compound or (A2) component) is not particularly limited as long as it is a compound other than (A1) and has no carboxyl group and has one or more ethylenic unsaturated bonds. The (A2) compound preferably contains a compound having two or more ethylenic unsaturated bonds. In addition, the (A2) compound may be used alone or in combination of two or more compounds. By containing the (A2) compound in the (A) component, the adhesion of the photosensitive resin composition of this embodiment to the substrate and the releasability of the photoresist pattern are improved.

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

(A2) Compounds preferably have two ethylenically unsaturated bonds. Examples of compounds having two ethylenically 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, tricyclodecanol di(meth)acrylate, ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, hydroxytetramethylene glycoxylated (hydrogenated) bisphenol A di(meth)acrylate, fluorene di(meth)acrylate, etc.

Among these, from the viewpoint of excellent adhesion to the substrate, the compound having an ethylenically unsaturated bond preferably contains a di(meth)acrylate compound having a bisphenol A structure, and preferably contains a compound represented by the following general formula (IV): [Chemical 7] (In the formula, R ₁₀ and R ₁₁ are each independently a hydrogen atom or a methyl group; R ₁₂ O, R ₁₃ O, R ₁₄ O and R ₁₅ O are each independently an oxyalkylene group; p, q, r and s are each independently an integer of 0 to 40; p+q is 1 to 40; and r+s is 0 to 20.).

_R12O , _R13O , _R14O and _R15O are each independently preferably oxyethyl and oxypropyl. As a compound having a bisphenol A structure, from the viewpoint of resolution and adhesion, 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 may be 2 or more. p, q, r and s are each independently preferably 0 to 10, more preferably 2 to 8.

Examples of commercially available compounds having two ethylenically unsaturated bonds include NK ESTER (registered trademark) A-HD-N, NK ESTER A-NOD-N, NK ESTER A-DOD-N, NK ESTER A-NPG, NK ESTER 701A, NK ESTER A-200, NK ESTER A-400, NK ESTER A-600, NK ESTER A-1000, NK ESTER APG-200, NK ESTER APG-400, NK ESTER APG-700, NK ESTER A-PTMG65, NK ESTER A-DCP, NK ESTER ABE-2, NK ESTER ABE-2.2, NK ESTER ABE-300, NK ESTER A-BPE-4, NK ESTER A-BPE-10, NK ESTER NK ESTER 9PG, NK ESTER DCP, NK ESTER BPE-80N, NK ESTER BPE-100, NK ESTER BPE-200, NK ESTER BPE-300, NK ESTER BPE-500, NK ESTER BPE-900, NK ESTER BPE-1300N, NK OLIGO (registered trademark) UA-4200, NK OLIGO UA-160TM, NK OLIGO UA-290TM, NK OLIGO UA-W2A, NK OLIGO UA-4400, NK OLIGO UA-122P, NK OLIGO U-200PA (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); LIGHT ACRYLATE (registered trademark) 3EG-A, LIGHT ACRYLATE 4EG-A, LIGHT ACRYLATE 9EG-A, LIGHT ACRYLATE 14EG-A, LIGHT ACRYLATE PTMGA-250, LIGHT ACRYLATE NP-A, LIGHT ACRYLATE MPD-A, LIGHT ACRYLATE 1.6HX-A, LIGHT ACRYLATE 1.9ND-A, LIGHT ACRYLATE DCP-A, LIGHT ACRYLATE BP-4EAL, LIGHT ACRYLATE BP-4PA, LIGHT ACRYLATE HPP-A, LIGHT ESTER G-201P (all manufactured by Kyoeisha Chemical Co., Ltd.); FANCRYL (registered trademark) FA-124AS, FANCRYL FA-023M, FANCRYL FA-121M, FANCRYL FA-124M, FANCRYL FA-125M, FANCRYL FA-129AS, FANCRYL FA-137M, FANCRYL FA-220M, FANCRYL FA-222A, FANCRYL FA-240A, FANCRYL FA-240M, FANCRYL FA-320M, FANCRYL FA-3218M, FANCRYL FA-321A, FANCRYL FA-321M, FANCRYL FA-324A, FANCRYL FA-731A, FANCRYL FA-P240A, FANCRYL FA-P270A, FANCRYL FA-PTG9A, FANCRYL FA-PTG9M, FANCRYL FA-PTG28A, FANCRYL FA-PTG49A (all manufactured by Showa Denko Materials Co., Ltd.); DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (all manufactured by Daicel-Allnex Co., Ltd.); 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 Co., Ltd.); KAYARAD (registered trademark) NPGDA, KAYARAD PEG400DA, KAYARAD FM-400, KAYARAD R-167, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-551, KAYARAD R-712, KAYARAD R-604, KAYARAD R-684 (the above manufactured by Nippon Kayaku Co., Ltd.), etc.

The (A2) compound may also contain a compound having 3 or more ethylenic unsaturated bonds. The (A2) compound may be, for example, a compound having 3 to 6 ethylenic unsaturated bonds. That is, the (A2) compound may also contain a compound having 3 to 6 ethylenic unsaturated bonds.

Examples of compounds having three or more ethylenic unsaturated bonds include trihydroxymethylpropane tri(meth)acrylate, glycerol tri(meth)acrylate, 4,4',4''-ethyltrisphenol tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, ditrihydroxymethylpropane (tetra/penta/hexa) (meth)acrylate, and dipentaerythritol (tetra/penta/hexa) (meth)acrylate.

In addition, compounds having more than three ethylene unsaturated bonds may also be listed, for example: trihydroxymethylpropane epoxide-modified tri(meth)acrylate, glycerol epoxide-modified tri(meth)acrylate, epoxide-modified 4,4',4''-ethylene phenol tri(meth)acrylate, epoxide-modified isocyanuric acid tri(meth)acrylate, epoxide-modified pentaerythritol (tri/tetra) (meth)acrylate, epoxide-modified ditrihydroxymethylpropane (tetra/penta/hexa) (meth)acrylate, epoxide-modified dipentaerythritol (tetra/penta/hexa) (meth)acrylate, etc. From the viewpoint of excellent developing properties and flexibility, the (A2) compound preferably contains glycerol tri(meth)acrylate or epoxide-modified glycerol tri(meth)acrylate.

Examples of commercially available compounds having three or more ethylenically unsaturated bonds include NK ESTER (registered trademark) A-TMPT, NK ESTER A-TMPT-9EO, NK ESTER AT-20E, NK ESTER A-GLY-3E, NK ESTER A-GLY-9E, NK ESTER A-GLY-20E, NK ESTER A-9300, NK ESTER A-9200YN, NK ESTER A-TMM-3, NK ESTER A-TMM-3L, NK ESTER A-TMM-3LM-N, NK ESTER A-TMMT, NK ESTER ATM-35E, NK ESTER AD-TMP, NK ESTER A-DPH, NK ESTER A-9550, NK ESTER A-DPH-12E, NK ESTER TPOA-50, NK OLIGO (registered trademark) UA-7100, NK OLIGO UA-1100H, NK OLIGO U-6LPA, NK OLIGO UA-33H, NK OLIGO U-10HA, NK OLIGO U-10PA, NK OLIGO U-15HA (produced by Shin-Nakamura Chemical Co., Ltd.); LIGHT ACRYLATE (registered trademark) TMP-A, CPE-3A, LIGHT ACRYLATE PE-4A, LIGHT ACRYLATE DPE-6A (produced by Kyoeisha Chemical Co., Ltd.); FA-731A (produced by Resonac Co., Ltd.); 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 Dacel-Zhanxin Co., Ltd.); SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (all manufactured by Arkema Co., Ltd.); KAYARAD (registered trademark) GPO-303, KAYARAD TMPTA, KAYARAD THE-330, KAYARAD TPA-330, KAYARAD PET-30, KAYARAD T-1420 (T), KAYARAD RP-1040, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD D-310, KAYARAD DPCA-20 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

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

From the viewpoint of improving the stripping property, the component (A2) may contain a compound having one ethylenically unsaturated bond.

For example, as compounds having one ethylenically unsaturated bond, there can be listed: alkylene oxide-modified phenol (meth)acrylate, alkylene oxide-modified nonylphenol (meth)acrylate, alkylene oxide-modified 2-ethylhexyl (meth)acrylate, N-acryloxyethyl 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, (meth)acrylate, ) isoamyl (meth)acrylate, hexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, tetradecyl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2-decyl-1-tetradecyl (meth)acrylate, isoborneol (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate and 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctyl (meth)acrylate, etc.

The upper limit of the ratio of the component (A1) to the component (A2) (i.e., the ratio of the content of the component (A1) to the content of the component (A2)) is preferably 4 or less, more preferably 3.5 or less, further preferably 3 or less, further 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 component (A1) to the component (A2) is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.12 or more, further preferably 0.15 or more, and particularly preferably 0.20 or more.

In particular, the upper limit of the ratio of the total amount of the compound having one or two ethylenically unsaturated bonds in the component (A1) to the component (A2) (i.e., the ratio of the content of the component (A1) to the total amount of the compound having one or two ethylenically unsaturated bonds in the component (A2)) is preferably 4 or less, more preferably 3.5 or less, further preferably 3 or less, further 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 the compound having one or two ethylenically unsaturated bonds in the component (A1) to the component (A2) is preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.12 or more, further preferably 0.15 or more, and particularly preferably 0.20 or more.

The content of the compound having ethylenic unsaturated bonds (A) in the photosensitive resin composition of this embodiment is preferably 30% by mass or more, preferably 35% by mass or more, based on the mass of all solid components of the photosensitive resin composition, from the perspective of sensitivity, viscosity and tracking. In addition, the content of the compound having ethylenic unsaturated bonds (A) in the photosensitive resin composition is preferably 50% by mass or less, preferably 45% by mass or less, and preferably 43% by mass or less, based on the mass of all solid components of the photosensitive resin composition, from the perspective of edge melting, viscosity and resolution. In one embodiment, the content of the compound (A) having an ethylenically unsaturated bond in the photosensitive resin composition of the present embodiment is preferably 20% by mass or more and 60% by mass or less based on the mass of all solid components of the photosensitive resin composition from the viewpoints of resolution, adhesion and release properties.

Furthermore, from the viewpoints of flexibility, resolution and adhesion, the ratio of the content of the compound having three or more ethylenically unsaturated groups to the content of the compound having (A) ethylenically unsaturated bonds contained in the photosensitive resin composition of the present embodiment (i.e., the ratio of the content of the compound having three or more ethylenically unsaturated groups/the content of the compound having (A) ethylenically unsaturated bonds) is preferably 0.95 or less, more preferably 0.90 or less.

In addition, from the viewpoint of edge melting property, viscosity and resolution, the upper limit of the ratio of the content of the compound having ethylenically unsaturated bonds (A) to the content of the alkali-soluble resin (B) contained in the photosensitive resin composition of the present embodiment (i.e., the ratio of the content of the compound having ethylenically unsaturated bonds (A) / the content of the alkali-soluble resin (B)) is preferably 1.4 or less, more preferably 1.3 or less, further preferably 1.2 or less, further preferably 1.1 or less, particularly preferably 1.0 or less, and most preferably 0.9 or less. The lower limit of the ratio of (A) the content of the compound having ethylenically unsaturated bonds / (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 preferably 0.75 or more, and particularly preferably 0.80 or more.

The photosensitive resin composition of this embodiment is preferably such that the value of ethylene unsaturated bonds per 100 g of the solid component of the photosensitive resin composition is set to 0.10 mol to 0.30 mol. By setting it to 0.10 mol or more, it is possible to prevent the components of the photosensitive resin composition from being eluted from the hardened photoresist pattern in the water washing step after development and contaminating the water washing step. By setting it to 0.30 mol or less, it is possible to prevent the hardened photoresist pattern from being damaged and falling off in the water washing step after development and contaminating the water washing step.

The amount of ethylenic unsaturated bonds per 100 g of the solid content of the photosensitive resin composition of this embodiment is preferably 0.10 mol or more, more preferably 0.11 mol or more, further preferably 0.12 mol or more, and further preferably 0.13 mol or more. In addition, the amount of ethylenic unsaturated bonds per 100 g of the solid content of the photosensitive resin composition of this embodiment is preferably 0.30 mol or less, more preferably 0.28 mol or less, further preferably 0.25 mol or less, further preferably 0.22 mol or less, particularly preferably 0.20 mol or less, more particularly preferably 0.18 mol or less, and very preferably 0.15 mol or less. The amount of ethylenic unsaturated bonds per 100 g of the solid component of 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, further more preferably 0.11 mol to 0.20 mol, and very preferably 0.11 mol to 0.15 mol.

(B) Alkali-soluble resin In the present embodiment, (B) alkali-soluble resin (hereinafter referred to as (B) component) is preferably obtained by polymerizing at least one of the first monomers described below, and more preferably obtained by copolymerizing at least one of the first monomers and at least one of the second monomers described below.

The first monomer is a monomer having a carboxyl group in the molecule. As the first monomer, for example, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester, etc. Among them, (meth)acrylic acid is preferred from the viewpoint of excellent adhesion and resolution, and methacrylic acid is more preferred.

The copolymerization ratio of the first monomer is preferably in the range of 10 to 50 mass % based on the total mass of all monomer components. From the perspective of excellent adhesion and resolution, it is ideal to make the copolymerization ratio 10 mass % or more, more preferably 15 mass % or more, further preferably 18 mass % or more, and further preferably 21 mass % or more. From the perspective of excellent adhesion and resolution, it is ideal to make the copolymerization ratio 50 mass % or less, more preferably 40 mass % or less, further preferably 35 mass % or less, further preferably 30 mass % or less, and particularly preferably 27 mass % or less. When two or more first monomers are used for polymerization, it is ideal that the total copolymerization ratio of each falls within the above range.

The second monomer is a monomer having at least one ethylenic unsaturated bond in the molecule and having no carboxyl group. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isoborneol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, pentamethylpiperidinyl (meth)acrylate, and tetramethylpiperidinyl (meth)acrylate. 、tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (meth)acrylate (2-methyl-2-ethyl-1,3-dioxacyclopentan-4-yl)methyl ester, cyclotrihydroxymethylpropane formal (meth)acrylate, (meth)acrylate 3,3,5-trimethylcyclohexyl ester and other (meth)acrylates; styrene derivatives such as styrene, methyl styrene, vinyl toluene, tertiary butoxy styrene, acetyloxy styrene, N-phenylmaleimide, styrene dimer, and styrene trimer; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile, etc.

(B) The weight average molecular weight Mw of the alkali-soluble resin is preferably 10,000 to 60,000. It is ideal to set the weight average molecular weight Mw to 60,000 or less from the perspective of achieving both the flexibility and resolution of the photoresist pattern. From the same perspective, it is more ideal to set it to 55,000 or less, and further ideal to set it to 50,000 or less. From the same perspective, it is ideal to set the weight average molecular weight Mw to 10,000 or more, more ideal to set it to 12,000 or more, and further ideal to set it to 14,000 or more.

(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, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

(B) Alkali-soluble resins may be used alone or in combination of two or more. When two or more (B) components are used in combination, the content of the monomers in the multiple (B) components is preferably selected so that the weighted average molecular weight and polydispersity of the weighted average molecular weight and polydispersity of each type of (B) component are within the following ranges. In addition, the weighted average value refers to the value obtained by multiplying the weight ratio of each type of alkali-soluble resin relative to the total weight of the mixed (B) components in this specification by the weight average molecular weight or polydispersity of each type of alkali-soluble resin. The weighted average value of the weight average molecular weight of the (B) component is preferably 10,000 or more, or 15,000 or more, or 20,000 or more, and is preferably 60,000 or less, or 55,000 or less, or 50,000 or less. The weighted average value of the polydispersity of the (B) component is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

(B) The synthesis of alkali-soluble resin is ideally carried out in the following manner: to a solution of a single or multiple monomers described above diluted with a solvent such as acetone, methyl ethyl ketone and isopropanol, an appropriate amount of free radical polymerization initiators such as benzoyl peroxide and azoisobutyronitrile are added, and the mixture is heated and stirred. There are also cases where a part of the mixture containing monomers and solvents is added dropwise to the reaction solution such as the free radical polymerization initiator while the synthesis is carried out. After the polymerization reaction is completed, a solvent can be further added to adjust the desired concentration. As a means of synthesizing component (B), in addition to solution polymerization, living free radical polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used.

The content of the alkali-soluble resin (B) in the photosensitive resin composition of the present 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, based on the mass of all solid components of the photosensitive resin composition. In addition, the content of the alkali-soluble resin (B) in the photosensitive resin composition of the present 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, based on the mass of all solid components of the photosensitive resin composition.

Based on the total solid content of the photosensitive resin composition of the present embodiment, it is ideal to set the content of (B) alkali-soluble resin to 90% by mass or less from the perspective of controlling the development time, and to set it to 10% by mass or more from the perspective of suppressing the overflow of the photoresist layer from the end surface of the film.

Among these, from the viewpoint of excellent adhesion to the substrate, it is ideal that component (B) contains either or both of styrene and benzyl (meth)acrylate. That is, it is ideal that component (B) contains constituent units derived from styrene and/or benzyl (meth)acrylate. When the alkali-soluble resin (B) contains a plurality of alkali-soluble resins, they may each contain an alkali-soluble resin containing styrene and an alkali-soluble resin containing benzyl (meth)acrylate.

In addition, from the perspective of flexibility, resolution and adhesion, the total content of the components (A) and (B) contained in the photosensitive resin composition of the present embodiment is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more, based on the mass of all solid components of the photosensitive resin composition. From the perspective of sensitivity, resolution and adhesion, the total content of the components (A) and (B) contained in the photosensitive resin composition of the present embodiment is preferably 98% by mass or less, more preferably 96% by mass or less, based on the mass of all solid components of the photosensitive resin composition.

When the component (B) contains a constituent unit derived from styrene, from the viewpoint of adhesion, the content of styrene in the component (B) is preferably 25% by mass or more, or 30% by mass or more, or 35% by mass or more. In addition, the content of styrene in the component (B) may be 80% by mass or less, or 75% by mass or less, or 70% by mass or less, or 65% by mass or less, or 60% by mass or less.

When the component (B) contains a constituent unit derived from styrene, the content of styrene in the component (B) may be 25 mass % to 80 mass %, or 30 mass % to 80 mass %, or 35 mass % to 80 mass %, from the viewpoint of adhesion.

In addition, from the viewpoint of developing property, resolution and adhesion, the content of component (B) contained 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, based on the total content of component (A) and component (B). In addition, the content of component (B) contained in the photosensitive resin composition is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more, relative to the total content of component (A) and component (B).

・Photosensitive resin laminate in other embodiments In one embodiment of the photosensitive resin laminate in other embodiments, a supporting film and a photoresist layer containing a photosensitive resin composition are provided. In addition, the photosensitive resin composition constituting the photosensitive resin laminate provided in one embodiment of the other embodiments contains (A) a compound having an ethylenically unsaturated bond, and (B) an alkali-soluble resin (hereinafter, component (B)). The supporting film provided in the photosensitive resin laminate in other embodiments is the same as described above.

In other embodiments of the photosensitive resin laminate, the photosensitive resin composition preferably contains (A3) a compound having no quaternary carbon and/or aromatic ring and having 4 or more ethylenic unsaturated bonds in one molecule (hereinafter, (A3) compound or (A3) component) as (A) a compound having ethylenic unsaturated bonds (in one embodiment, (A) component). In other embodiments of the photosensitive resin laminate, the photosensitive resin composition preferably contains (A4) a compound having quaternary carbon and/or aromatic ring and having no carboxyl group and having ethylenic unsaturated bonds (hereinafter, (A4) compound or (A4) component) as (A) a compound having ethylenic unsaturated bonds. In other embodiments of the photosensitive resin laminate, the photosensitive resin composition preferably comprises (A) component: (A3) a compound having no quaternary carbon and/or aromatic ring and having 4 or more ethylenic unsaturated bonds in one molecule; and (A4) a compound having quaternary carbon and/or aromatic ring and having no carboxyl group and having ethylenic unsaturated bonds.

(A3) Compounds without quaternary carbon and/or aromatic rings and having 4 or more ethylenically unsaturated bonds in one molecule (A3) Compounds are compounds without quaternary carbon and/or aromatic rings and having 4 or more ethylenically unsaturated bonds in one molecule. (A1) Compounds can be cited as an example of (A3) Compounds. The same as above is true for (A1) Compounds. In addition, as (A3) Compounds, di(meth)acrylate compounds having a bisphenol A structure are preferably compounds represented by the following general formula (IV). (A3) Compounds are presumed to have no quaternary carbon and/or aromatic rings, so that the photoresist pattern formed by using the photosensitive resin composition containing (A3) Compounds as (A) component has high flexibility. In addition, it is speculated that the (A3) compound has more than 4 ethylenic unsaturated bonds in one molecule, so that when hardened by exposure, the structure of the (A3) compound will be complexly bonded, thereby making the photoresist pattern strong. Therefore, it is speculated that the photoresist pattern formed using the photosensitive resin composition containing the (A3) compound has excellent toughness, and thus exhibits excellent flexibility, resolution and adhesion.

By setting the contents of the constituent units derived from (meth)acrylic acid, styrene and benzyl (meth)acrylate in the component (B) to be within the above-specified range, when a photosensitive resin composition containing the compound (A3) is used, the developability, flexibility and rigidity can be well balanced, and excellent flexibility, resolution and adhesion can be easily obtained.

(A4) Compounds having quaternary carbon and/or aromatic rings, no carboxyl group, and ethylenically unsaturated bonds Compound (A4) is a compound having quaternary carbon and/or aromatic rings, no carboxyl group, and ethylenically unsaturated bonds. In other embodiments of the photosensitive resin laminate, the photosensitive resin composition, as (A) a compound having ethylenically unsaturated bonds, preferably contains (A4) a compound having quaternary carbon and/or aromatic rings, no carboxyl group, and ethylenically unsaturated bonds.

The (A4) compound is presumed to have a quaternary carbon and/or an aromatic ring, so that the photoresist pattern formed by using the photosensitive resin composition containing the (A4) compound as the (A) component is rigid. Therefore, it is presumed that by using a photosensitive resin composition containing both the (A3) compound and the (A4) compound, flexibility and rigidity can be balanced to form a photoresist pattern with excellent toughness and strength. Therefore, the photoresist pattern obtained by using the photosensitive resin composition containing both the (A3) compound and the (A4) compound has particularly excellent resolution and adhesion.

As an example of the (A4) compound, the compound listed as the (A2) component can be cited. The (A2) compound is the same as above. As the (A4) compound, among the compounds listed as the (A2) component, for example, epoxide-modified phenol (meth) acrylate, epoxide-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, hydroxytetramethyleneoxylated (hydrogenated) bisphenol A di(meth) acrylate, naphthalene di(meth) acrylate, fluorene di(meth) acrylate, trihydroxymethylpropane tri(meth) acrylate, Isocyanuric acid tri(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, ditrihydroxymethylpropane (tetra/penta/hexa)(meth)acrylate, dipentaerythritol (tetra/penta/hexa)(meth)acrylate, epoxide-modified tri(meth)acrylate of trihydroxymethylpropane, epoxide-modified isocyanuric acid tri(meth)acrylate, epoxide-modified pentaerythritol (tri/tetra)(meth)acrylate, epoxide-modified ditrihydroxymethylpropane (tetra/penta/hexa)(meth)acrylate, epoxide-modified dipentaerythritol (tetra/penta/hexa)(meth)acrylate, etc. Among them, as the (A4) compound, bisphenol A di(meth)acrylate is preferred.

Commercially available products that can be used as (A4) compounds include, for example, A-1000, A-BPE-20, A-BPE-30, 23G, BPE-900, BPE-1300N (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); 25PDC-900B, 30PDC-950B-H, 40PDC-1700B (all manufactured by NOF Corporation); BP-1206A (manufactured by Toho Chemical Industry Co., Ltd.); FA-2100A, FA-2200A, FA-P2200M, FA-P2300M, FA-P2200A, FA-P2300A, FA-3218A, FA-027M (all manufactured by Liseno Corporation), etc.

The (A4) compound is preferably a compound having 1 or 2 ethylenic unsaturated bonds. In addition, the amount of ethylenic unsaturated bonds in 100 g of the (A4) compound is preferably 0.25 mol or less. Thereby, when a photosensitive resin composition containing both the (A3) compound and the (A4) compound is used to form a photoresist pattern, it becomes easy to balance flexibility and rigidity, and it is easy to form a photoresist pattern with excellent toughness and strength, so the flexibility and adhesion are excellent. From the above viewpoints, the amount of ethylenic unsaturated bonds in 100 g of the (A4) compound is more preferably 0.22 mol or less, and further preferably 0.20 mol or less. In addition, the amount of ethylenic unsaturated bonds in 100 g of the (A4) compound can be 0.10 mol or more.

The photosensitive resin composition contained in the photosensitive resin laminate of other embodiments contains component (B). Component (B) is the same as described above. Component (B) preferably contains a copolymer containing a constituent unit derived from (meth) acrylic acid as a monomer component. In one embodiment, the content of the constituent unit 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 further preferably 23% by mass or less. The content of the constituent unit derived from (meth) acrylic acid in the copolymer of component (B) may be 10% by mass or more, and may be 15% by mass or more.

(C) Photopolymerization initiator In the present embodiment, the photosensitive resin composition preferably contains (C) photopolymerization initiator (hereinafter referred to as (C) component). Examples of (C) photopolymerization initiator include hexaarylbiimidazole 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 ketal compounds, thioxanone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, and halogen compounds. In one embodiment, hexaarylbiimidazole compounds are preferably contained as (C) component.

As the hexaarylbiimidazole compound, for example, a porphyrin dimer, that is, a dimer of 2,4,5-triarylimidazole can be cited.

Examples of the porphyrin dimer, that is, the dimer of 2,4,5-triaryl imidazole include: 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer (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, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenyl Phenyl biimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenyl biimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'- Tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4 ,4’,5,5’-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,4,6-trifluorophenyl)-4,4’,5,5’-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3,4,5-tetrafluorophenyl)-4,4’,5,5’-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2’-bis-(2,3,4,6-tetrafluorophenyl)-4,4’,5,5’-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2’-bis-(2,3,4,5,6-pentafluorophenyl)-4,4’,5,5’-tetrakis-(3-methoxyphenyl)-biimidazole, etc.

From the viewpoint of high sensitivity, resolution and adhesion, the component (C) preferably contains a porphyrin dimer, and among them, a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, N-phenylglycine has a high sensitization effect and is therefore ideal.

Examples of the quinone compound 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-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone and 3-chloro-2-methylanthraquinone.

As the aromatic ketone compound, for example, a phenyl ketone compound can be cited. As the phenyl ketone compound, for example, phenyl ketone, Michelle's ketone [4,4'-bis(dimethylamino)phenyl ketone] and 4-methoxy-4'-dimethylaminophenyl ketone can be cited. As the aromatic ketone compound, from the viewpoint of the sensitization effect and adhesion, 4,4'-bis(diethylamino)phenyl ketone can also be cited.

In this specification, the term "anthracene derivatives" includes both anthracene and compounds derived therefrom. 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-anthracene boronic acid. From the viewpoint of sensitization effect and adhesion, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.

As acetophenone compounds, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-(N-morpholinyl)phenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-(N-morpholinyl)-propanone-1, etc. can be cited. As commercially available products of acetophenone compounds, for example, the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.) can be cited.

Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, and bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available acylphosphine oxide compounds include Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin. Examples of dialkyl ketal compounds include benzil dimethyl ketal and benzil diethyl ketal. Examples of thiothione compounds include 2,4-diethylthiothione, 2,4-diisopropylthiothione, and 2-chlorothiothione. Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

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. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

As the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred in terms of sensitivity, resolution, and availability.

As pyrazoline derivatives, from the viewpoint of adhesion and rectangularity of the resist pattern, the following are preferred: 1-phenyl-3-(4-tert-butyl-phenyl)-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-methoxyphenyl)-5-(4-methoxyphenyl)-pyrazoline.

Examples of the ester compounds of N-aryl amino acids include methyl N-phenylglycine, ethyl N-phenylglycine, n-propyl N-phenylglycine, isopropyl N-phenylglycine, 1-butyl N-phenylglycine, 2-butyl N-phenylglycine, tertiary butyl N-phenylglycine, pentyl N-phenylglycine, hexyl N-phenylglycine, pentyl N-phenylglycine, and octyl N-phenylglycine.

Examples of halogen compounds include bromopentane, isopentane bromopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylmethane, benzyl bromide, dibromomethane, tribromomethylphenylsulfonium, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, iodopentane, isobutylene iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diallyliodonium compounds. Among them, tribromomethylphenylsulfonium is ideal.

The content of the (C) photopolymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.01 to 20% by mass, and more preferably 0.5 to 10% by mass, based on the mass of all solid components of the photosensitive resin composition. By adjusting the content of the (C) photopolymerization initiator to the above range, it becomes easy to obtain sufficient sensitivity, so it becomes easy to make light fully transmit to the bottom of the photosensitive resin composition layer, and thus it becomes easy to achieve an improvement in resolution.

From the viewpoint of high sensitivity, resolution and adhesion, it is desirable to contain porphyrin dimer as (C) photopolymerization initiator. In this case, the content of porphyrin dimer in the photosensitive resin composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the mass of all solid components of the photosensitive resin composition.

As the (C) photopolymerization initiator, it is ideal to use an anthracene derivative and a hexaaryl biimidazole compound together. At this time, the content of the anthracene derivative contained in the (C) photopolymerization initiator in the photosensitive resin composition of this embodiment is ideally 0.5% by mass or less, and more ideally 0.01% by mass to 0.4% by mass, based on the total solid content of the photosensitive resin composition. In addition, the content of the hexaaryl biimidazole compound contained in the (C) photopolymerization initiator in the photosensitive resin composition of this embodiment is ideally 0.1% to 10% by mass, and more ideally 0.5% to 8% by mass, based on the total solid content of the photosensitive resin composition.

The content of the photopolymerization initiator (C) in the photosensitive resin composition of the present embodiment is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 18% by mass or less, based on the content of the compound (A) having an ethylenic unsaturated bond. In addition, the content of the photopolymerization initiator (C) in the photosensitive resin composition of the present embodiment is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 4% by mass or more, and particularly preferably 5% by mass or more, based on the content of the compound (A) having an ethylenic unsaturated bond.

(D) Polymerization inhibitor In this embodiment, the photosensitive resin composition may also contain (D) polymerization inhibitor. Examples of (D) polymerization inhibitors include free radical polymerization inhibitors, phenol polymerization inhibitors, hydroquinone, quinone, nitrobenzene, phenathiophene, phenanthrene, o-catechin, or derivatives thereof.

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 salts thereof; and hindered amine compounds such as 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine.

As phenolic polymerization inhibitors, there are: p-methoxyphenol, hydroquinone, ocellol, tertiary butyl ocellol, 2,6-bis-tertiary butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-ethyl-6-tertiary butylphenol), 2,6-bis-tertiary butyl-4-methylphenol, 2,5-bis-tertiary amylhydroquinone, 2,5-bis-tertiary butyl-p-cresol, Diphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis(2-hydroxy-3-tert-butyl-5-ethylphenyl)methane, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-bist-tert-butyl-4-hydroxyphenyl)propionate], tetrakis[3-(3,5-bist-tert-butyl-4-hydroxyphenyl)propionic acid ] neopentyl tetradecanoate, 2,2-thio-diethyl bis[3-(3,5-bis-tert-butyl-4-hydroxyphenyl) propionate], 3-(3,5-bis-tert-butyl-4-hydroxyphenyl) propionate octadecyl, N,N'-hexamethylenebis(3,5-bis-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-bis-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3, 5-bis(tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-bis(tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-butylenebis(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 Industries, Ltd.), tribenzylphenol (e.g., TBP manufactured by Kawaguchi Chemical Industries, Ltd., phenol having 1 to 3 benzyl groups), and biphenol, etc.

In this specification, the term "hydroquinone, quinone, nitrobenzene, thiophene, phenanthrene, o-catechol, and derivatives thereof" includes both hydroquinone, quinone, nitrobenzene, thiophene, phenanthrene, o-catechol, and compounds derived therefrom. Examples of hydroquinone derivatives include methyl hydroquinone, 2-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2,6-di-tert-butyl hydroquinone, etc. Examples of quinone derivatives include tert-butyl benzoquinone, 2,6-di-tert-butyl-1,4-benzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, etc.

As nitrobenzene derivatives, there can be cited, for example, 4-nitrotoluene, etc. As thiophene derivatives, there can be cited, for example, 2,8-dioctylthiophene, 2-methoxythiophene, 3-methoxythiophene, 2-methylthiophene, 2-ethylthiophene, 2-trifluoromethylthiophene, 3,7-dibutylthiophene, 3,7-dioctylthiophene, 3,7-diisopropylthiophene, 2-cyano-8-methoxythiophene, 2-cyanothiophene, 2-bromothiophene, 2-chlorothiophene, bis-(α-dimethylbenzyl)thiophene and bis-(α-methylbenzyl)thiophene. As the phenanthrene derivatives, there can be listed: 1-methyl-phenanthrene, 2-methyl-phenanthrene, 3-methyl-phenanthrene, 4-methyl-phenanthrene, 10-methyl-phenanthrene, 2-hydroxy-phenanthrene, 3-hydroxy-phenanthrene, 4-hydroxy-phenanthrene, 10-bromo-phenanthrene, 3,7-dimethyl-phenanthrene, 2,8-dimethyl-phenanthroline, 1-amino-phenanthroline, 2-amino-phenanthroline, 3-amino-phenanthroline, 2-ethyl-phenanthroline, 3-ethyl-phenanthroline, 2-carbonitrile-phenanthroline, 3-carbonitrile-phenanthroline, 2-methoxy-phenanthroline, 3-methoxy-phenanthroline and 12H-benzophenanthroline, etc.

Examples of the o-catechol derivatives include 2-methyl o-catechol, 3-methyl o-catechol, 4-methyl o-catechol, 2-ethyl o-catechol, 3-ethyl o-catechol, 4-ethyl o-catechol, 2-propyl o-catechol, 3-propyl o-catechol, 4-propyl o-catechol, 2-n-butyl o-catechol, 3-n-butyl o-catechol, 4-n-butyl o-catechol, 2-tert-butyl o-catechol, 3-tert-butyl o-catechol, 4-tert-butyl o-catechol, and 3,5-di-tert-butyl o-catechol.

By containing phenanthrene or a phenanthrene derivative and a phenolic polymerization inhibitor, the NH group contained in the phenanthrene site and the OH group of the phenolic polymerization inhibitor form a hydrogen bond, which can prevent the phenolic polymerization inhibitor from volatilizing or diffusing from the photosensitive resin composition layer. That is, a photosensitive resin composition that is not affected by the manufacturing conditions and storage conditions determined by the film thickness and has excellent sensitivity and resolution can be provided; and a method for forming a photoresist pattern.

From the above viewpoints, the photosensitive resin composition of the present embodiment preferably contains phenanthrenethioate or a phenanthrenethioate derivative as (D) a polymerization inhibitor. At this time, the content of phenanthrenethioate or a phenanthrenethioate derivative in the photosensitive resin composition of the present embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.4% by mass or less, and particularly preferably 0.3% by mass or less, based on the mass of all solid components of the photosensitive resin composition of the present embodiment. In addition, the content of phenanthrene or phenanthrene derivatives in the photosensitive resin composition of the present embodiment is preferably 0.0001 mass % or more, more preferably 0.0005 mass % or more, further preferably 0.001 mass % or more, and further preferably 0.002 mass % or more, based on the mass of all solid components of the photosensitive resin composition of the present embodiment.

From the viewpoint of resolution, the photosensitive resin composition of the present embodiment preferably contains catechol or a catechol derivative as (D) a polymerization inhibitor; particularly preferably, it contains 3-tert-butyl catechol or 4-tert-butyl catechol. At this time, the content of catechol or a catechol derivative in the photosensitive resin composition of the present embodiment is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.4% by mass or less, and particularly preferably 0.3% by mass or less, based on the mass of all solid components of the photosensitive resin composition of the present embodiment. In addition, the content of o-catechol or o-catechol derivatives in the photosensitive resin composition of the present embodiment is preferably 0.0001 mass % or more, more preferably 0.0005 mass % or more, further preferably 0.001 mass % or more, and further preferably 0.002 mass % or more, based on the mass of all solid components of the photosensitive resin composition of the present embodiment.

The content of the polymerization inhibitor (D) in the photosensitive resin composition of this embodiment is preferably 0.0001 mass% to 10 mass% based on the mass of all solid components of the photosensitive resin composition of this embodiment. The content of the polymerization inhibitor (D) in this embodiment is preferably 0.0001 mass% or more, more preferably 0.0005 mass% or more, further preferably 0.001 mass% or more, further more preferably 0.005 mass% or more, and particularly preferably 0.01 mass% or more from the viewpoint of excellent adhesion and resolution. On the other hand, the content of the polymerization inhibitor (D) in this embodiment is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1.5% by mass or less in terms of minimizing the decrease in sensitivity and improving resolution.

・Additives The photosensitive resin composition of this embodiment may also contain additives such as dyes, adhesion aids and plasticizers.

・Dye In this embodiment, a dye may be included in the photosensitive resin composition. In addition, in one embodiment, a color-developing dye that develops color by light irradiation may be included in the photosensitive resin composition. In the dry film photoresist provided as one embodiment of the photosensitive resin laminate of this embodiment, a dye is preferably added. By adding a dye, the photoresist pattern formed on the substrate after development can be observed more clearly by contrast, which also helps to improve the resolution.

As dyes, diamond green is ideal. As color-developing dyes, for example, combinations of chromogenic dyes and halogen compounds are known. As chromogenic dyes, for example, tris(4-dimethylamino-2-methylphenyl)methane [pigment name: chromogenic crystal violet] and bis(4-dimethylaminophenyl)phenylmethane [pigment name: chromogenic malachite green] can be cited. Examples of halogen compounds include: bromopentane, isopentane bromopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylmethane, α,α-dibromotoluene, dibromomethane, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, iodopentane, isoiodobutane, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane and hexachloroethane.

・Adhesion aid In this embodiment, the photosensitive resin composition may also contain an adhesion aid. In the dry film photoresist provided as one aspect of the photosensitive resin laminate of this embodiment, it is ideal to add an adhesion aid. By adding the adhesion aid, it helps to improve the adhesion of the photoresist pattern formed on the substrate after development to copper.

As the adhesion aid, triazoles and benzotriazoles are preferred, and carboxybenzotriazole is more preferred.

・Plasticizer In this embodiment, the photosensitive resin composition may contain additives such as plasticizers as needed. Examples of additives such as plasticizers include phthalates such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.

<Photosensitive resin laminate> The photosensitive resin laminate of this embodiment has a support film and a photoresist layer containing a photosensitive resin composition (in one embodiment, a photosensitive resin composition layer); the support film and the photoresist layer are the same as described above. The photosensitive resin laminate of this embodiment is, for example, formed by laminating at least one photoresist layer on a support film, or may be formed by laminating two or more photoresist layers on a support film. The photosensitive resin laminate of this embodiment is preferably a dry film photoresist or a transfer film, and more preferably a dry film photoresist, from the viewpoint of significantly facilitating the effect of this embodiment.

The photosensitive resin laminate of this embodiment may also have a protective film in addition to the supporting film and the photoresist layer. When the photosensitive resin laminate of this embodiment includes the supporting film, the photoresist layer and the protective film, the protective film is attached to the side of the photoresist layer where the supporting film is not laminated, and functions as a cover.

Compared with the adhesion between the photosensitive resin composition layer and the supporting film in the present 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. For example, polyethylene film, polypropylene film, stretched polypropylene film, polyester film, etc. can be used as an ideal protective film. Among them, polypropylene film and polyester film are more ideal; as a polyester film, polyethylene terephthalate film is further ideal. In addition, a release layer can also be provided on the surface of the protective film.

The ideal thickness of the protective film is 10 to 100 μm, more preferably 10 to 50 μm. As protective films, for example: ALPHAN (registered trademark) EM-501, ALPHAN E-200, ALPHAN E-201F, ALPHAN FG-201, ALPHAN MA-411 (all manufactured by Prince Airt Co., Ltd.); TORAYFAN (registered trademark) KW37, TORAYFAN 2578, TORAYFAN 2548, TORAYFAN 2500, TORAYFAN YM17S, CERAPEEL (registered trademark) PJ271, CERAPEEL PJ111, CERAPEEL HP2, CERAPEEL PJ101, CERAPEEL WZ, CERAPEEL MDA, CERAPEEL MFA, CERAPEEL TK07, CERAPEEL BKE, CERAPEEL BX8A, CERAPEEL SY (made by Toray Co., Ltd.); GF-18, GF-818, GF-858 (made by Tamapoli Co., Ltd.), etc.

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

[Photosensitive resin laminate roll] The photosensitive resin laminate described above can also be used in the form of a roll-shaped photosensitive resin laminate roll by winding a long strip of the photosensitive resin laminate around a winding core.

[Photoresist pattern formation method] The photoresist pattern formation method using the photosensitive resin laminate of the present embodiment, for example, includes the following steps: A lamination step is to laminate a photoresist layer (in one embodiment, a photosensitive resin component layer) constituting the photosensitive resin laminate of the present embodiment on a substrate; An exposure step is to expose the photoresist layer of the photosensitive resin laminate; and A development step is to develop and remove the unexposed portion of the photoresist layer. It is ideal to implement the steps in the above order.

<Lamination step> Specifically, in the lamination step, after the protective film is peeled off from the photosensitive resin laminate of the present embodiment, the photoresist layer is heated and pressed onto the surface of the substrate using a lamination machine, and the lamination is performed once or multiple times. The material of the substrate may be, for example, copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc., and a copper-clad laminate is ideal. As desired, the substrate may be cleaned with, for example, an aqueous solution of H ₂ SO ₄ having a concentration of about 10 mass %, and the entire surface of the substrate may be subjected to lamination. The heating temperature during lamination is generally 40°C to 160°C. The heat-pressing bonding can be performed by using a laminating machine equipped with rollers, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer through the rollers several times. The heat-pressing bonding can be performed in a reduced pressure environment as desired.

<Exposure step> In the exposure step, the photoresist layer is exposed through a patterned mask or a multiplication mask or directly through a UV light source, using an exposure machine such as a contact aligner, a mirror projection, or a stepper. The exposure step can be performed after the support film is peeled off or through the support film as desired. When exposing through a mask, the exposure amount is determined by the light source illumination and the exposure time, and can also be measured using a light meter. In the exposure step, direct imaging exposure can also be performed. In direct imaging exposure, exposure is performed on the substrate by a direct drawing device without using a mask. As a light source, a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350nm to 410nm is used. When drawing patterns using computer control, the exposure amount is determined by the illumination of the exposure light source and the movement speed of the substrate.

The exposure method used in the exposure step is preferably at least one method selected from the group consisting of projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, and is more preferably performed by projection exposure or direct imaging exposure.

<Heating step> A heating step may be provided between the exposure step and the development step. The heating temperature is preferably 30°C to 200°C, more preferably 30°C to 150°C, and further preferably 35°C to 120°C. By implementing this heating step, the resolution and adhesion can be improved. For heating, a heating furnace, a constant temperature bath, a heating plate, a hot air dryer, an infrared dryer, a heating roller, etc. using hot air, infrared, or far infrared methods may be used. The heating time is preferably 1 to 300 seconds, and more preferably 5 to 120 seconds.

The time from the exposure step to the heating step, more strictly speaking, is the time from the time point when the exposure stops to the time point when the heating starts, and is preferably 10 seconds to 600 seconds, more preferably 20 seconds to 300 seconds. The time from the time point when the heating starts to the time point when the heating stops is preferably 1 second to 120 seconds, more preferably 5 seconds to 60 seconds.

<Developing step> In the developing step, a developing device is used to remove the unexposed portion of the photoresist layer after exposure with a developer to form a photoresist pattern. After exposure, if there is a supporting film on the photoresist layer, the supporting film is removed. Then, a developer composed of an alkaline aqueous solution is used to develop and remove the unexposed portion to obtain a photoresist pattern. As a developing method for developing the photoresist layer after exposure (irradiation), any method can be selected from the conventionally known photoresist developing methods, such as the rotary spray method, the puddle method, and the immersion method accompanied by ultrasonic treatment.

The alkaline aqueous solution used as the developer is preferably an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ and tetramethylammonium hydroxide. The alkaline aqueous solution is selected according to the characteristics of the photoresist layer, but generally a Na ₂ CO ₃ aqueous solution with a concentration of 0.2 mass % to 2 mass % is used. Surfactants, defoaming agents and a small amount of organic solvents to promote development can also be added to the alkaline aqueous solution. The temperature of the developer in the development step is ideally kept constant in the range of 20°C to 40°C.

In the developing step, it is desirable to include a washing step for removing the developer contained in the photoresist pattern after development. As washing water, in addition to pure water, industrial water, etc., it can be selected in accordance with the characteristics of the photoresist layer. However, in order to improve the resolution and the shape of the photoresist pattern, a polyvalent metal salt such as MgSO ₄ can also be added at a concentration of 0.001 mass% to 1 mass%. In the washing step, the temperature of the washing water is ideally maintained at a constant range of 20°C to 40°C.

The photoresist pattern can be obtained through the above steps. However, it can be further heated at 60℃ to 300℃ for 1 to 120 minutes as desired. By implementing this heating treatment, the chemical resistance of the photoresist pattern can be improved. The heating treatment can be performed using a heating furnace using hot air, infrared, or far infrared.

In order to obtain a conductor pattern, a conductor pattern forming step of etching or plating the substrate having the photoresist pattern formed thereon may be performed after the developing step or the heating step.

<Conductor pattern forming step> The conductor pattern forming step is a step of forming a conductor pattern on a substrate surface (e.g., a copper surface) on which a photoresist pattern is formed by development using a known etching method or plating method.

As a conductor pattern forming method by plating, for example, the following is described. The substrate after the development step is immersed in an acidic degreasing bath such as a 1 to 50 mass % sulfuric acid aqueous solution at 20 to 60°C for 1 to 60 minutes. After the immersed substrate is washed with water, it is immersed in a 1 to 50 mass % sulfuric acid aqueous solution at room temperature for 1 to 60 minutes.

Prepare an aqueous solution containing 1-15 mass% copper sulfate, 0.1-30 mass% sulfuric acid and 1-1000 ppm hydrochloric acid in concentration, Then add a brightener (in one embodiment, Cupracid HL and Cupracid GS manufactured by Atotech Co., Ltd.) at a concentration of 0.01-40 ml/l and a concentration of 1-200 ml/l respectively to prepare a copper sulfate plating solution. The prepared copper sulfate plating solution is used to form a conductor pattern by plating for 1-300 minutes using a Haring cell uniform plating device (manufactured by Yamamoto Plating Tester Co., Ltd.) at an applied current of 0.01-10A. The thickness of the copper-plated film is also affected by the thickness of the photoresist pattern, but ideally it is above 1μm (the thickness of the photoresist pattern (μm) - 2μm). In this manual, the thickness of the photoresist pattern refers to the thickness of the photoresist layer after curing.

As a conductor pattern forming method by etching, for example, rapid etching can be cited. In rapid etching, the copper seed layer can be removed by using a specified etching solution. As an etching solution, for example, a mixed etching solution of sulfuric acid and hydrogen peroxide (manufactured by EBARA Electric Co., Ltd.) can be cited, but it is not limited to this.

[Method for manufacturing a conductor pattern] The method for manufacturing a conductor pattern is performed, for example, by using a metal plate or a metal film insulating plate as a substrate, forming a photoresist pattern by the above-mentioned photoresist pattern forming method, and then performing a conductor pattern forming step.

<Stripping step> Furthermore, after the conductor pattern is manufactured by the above-mentioned conductor pattern manufacturing method, a stripping step of stripping the photoresist pattern from the substrate using an aqueous solution having a stronger alkalinity than the developer can be performed. By performing the stripping step, a wiring board (in one embodiment, a printed wiring board) having a desired wiring pattern can be obtained.

Regarding the alkaline aqueous solution for stripping (hereinafter also referred to as "stripping solution"), although there is no particular limitation, generally a 2% to 20% by mass aqueous solution of NaOH or KOH or an organic amine-based stripping solution is used. A small amount of water-soluble solvent may also be added to the stripping solution. Examples of water-soluble solvents include alcohols. The temperature of the stripping solution in the stripping step is ideally in the range of 40°C to 70°C; the immersion time of the stripping solution is ideally 1 to 60 minutes.

[Manufacturing method of wiring board] The manufacturing method of wiring board using the photosensitive resin laminate of the present embodiment, in one embodiment, includes the following steps: Lamination step, which is to laminate a photoresist layer on a substrate; Exposure step, which is to expose the photoresist layer; Development step, which is to develop and remove the unexposed part of the photoresist layer to form a photoresist pattern; Conductor pattern forming step, which is to etch or plate the substrate formed with the photoresist pattern to form a conductor pattern; and Stripping step, which is to strip the photoresist pattern from the substrate. The steps included in the manufacturing method of the wiring board of this embodiment, namely, the lamination step, exposure step, development step, conductor pattern forming step and stripping step, are the same as those mentioned above.

The photosensitive resin laminate in this embodiment can be used in: the manufacture of printed wiring boards; the manufacture of lead frames for IC chip mounting; the manufacture of metal foil precision processing such as metal mask manufacturing; the manufacture of packages such as ball grid array (BGA) and chip size package (CSP); the manufacture of tape substrates such as chip on film (COF) and tape automated bonding (TAB); the manufacture of semiconductor bumps; and the manufacture of partitions of flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shielding covers. In addition, the values of the above parameters are measured according to the measurement methods in the embodiments described below unless otherwise stated.

[Manufacturing method of photosensitive resin laminate] The photosensitive resin laminate of this embodiment can be manufactured by the method shown below. That is, the method for manufacturing a photosensitive resin laminate of the present embodiment, in one aspect, is a method for manufacturing a photosensitive resin laminate having a support film and a photoresist layer containing a photosensitive resin composition, and comprises the following steps: A blending step is to blend a photosensitive resin composition solution containing a compound having an ethylenically unsaturated bond as component (A), an alkali-soluble resin as component (B), and a solvent; A coating step is to coat the photosensitive resin composition solution on the support film; A photoresist layer forming step is to heat the support film coated with the photosensitive resin composition solution to form the photoresist layer. In one embodiment, component (A) contains polyglycerol (meth)acrylate (A1) and a compound (A2) having no carboxyl group and having an ethylenically unsaturated bond.

By using the method for manufacturing a photosensitive resin laminate of the present embodiment, a photosensitive resin laminate having excellent sensitivity and resolution can be manufactured which is not affected by the manufacturing conditions and storage conditions determined by the film thickness of the photoresist layer.

<Blending step> This step is a step of adding a solvent to the above-mentioned (A) compound having ethylenically unsaturated bonds and (B) alkali-soluble resin to blend a photosensitive resin composition solution.

As ideal solvents, ketones represented by methyl ethyl ketone (MEK) and alcohols such as methanol, ethanol, and isopropyl alcohol can be listed. The solvent can be used alone or two or more solvents can be mixed and used. The content of the solvent is preferably 30-60% by mass, more preferably 33-55% by mass, and further preferably 35-57% by mass relative to the photosensitive resin composition solution. Ideally, the solvent is added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition solution is 500-4000 mPa·sec at 25°C. The viscosity is measured at 25°C using a Brookfield viscometer (manufactured by Eikon Co., Ltd., model DVNext).

<Coating step> This step is to coat the photosensitive resin composition solution on the support film. For coating the photosensitive resin composition solution on the support film, for example, a conventional method can be used, such as a coating method using a roll coater, a rotary coater, a rod coater, a blade coater, a curtain coater, and a screen printer; a spray coating method using a spray coater, etc.

<Photoresist layer forming step> This step is to heat the support film coated with the photosensitive resin composition solution to heat and dilute the solvent in the photosensitive resin composition solution, thereby forming a photoresist layer composed of the photosensitive resin composition. In addition, the heating temperature of the support film coated with the photosensitive resin composition solution is preferably above 70°C, more preferably above 80°C, and further preferably above 90°C. By heating to above 90°C, the evaporation of the solvent contained in the photosensitive resin composition solution will be accelerated, so the production efficiency of the photosensitive resin laminate will be improved. 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 further preferably below 120°C. By keeping the temperature below 140°C, the thermal polymerization of the photosensitive resin composition can be prevented. The heating time of the support film coated with the photosensitive resin composition solution is preferably 1 to 10 minutes.

If necessary, after the photoresist layer forming step, there may be a protective step of laminating a protective layer such as a protective film on the photoresist layer. The protective layer is attached to the side of the photoresist layer where the supporting film is not laminated, and functions as an outer cover. The protective film used in the protective step is the same as described above. [Example]

Next, the present embodiment is described in more detail with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it deviates from the gist thereof. The physical properties in the examples are measured by the following methods.

(B) The weight average molecular weight of the alkali-soluble resin is determined by gel permeation chromatography (GPC) and converted using the calibration curve of standard polystyrene. The GPC conditions are as follows.

(GPC conditions) Pump: PU-980 manufactured by JASCO Corporation Column: 2 in total KF-80Y/KF-806M manufactured by Shodex Corporation Solvent: Tetrahydrofuran Measurement temperature: 40°C Flow rate: 2.05 mL/min Detector: RI-1530 manufactured by JASCO Corporation Standard monodisperse polystyrene: manufactured by Tosoh Corporation, product name TSKgel standard polystyrene

The photosensitive resin laminate is prepared as follows. <Preparation of the photosensitive resin laminate> The components (A) to (E) shown in Table 1 described later (however, the numbers of each component represent the content (mass percentage) as a solid component) are mixed to prepare a photosensitive resin composition (Examples 1 to 21 and Comparative Examples 1 to 5). The photosensitive resin compositions of Examples 1 to 21 and Comparative Examples 1 to 5 and ethanol measured so that the solid content concentration of these photosensitive resin compositions becomes 60 mass % are fully stirred and mixed to obtain a prepared solution containing the photosensitive resin compositions of Examples 1 to 21 and Comparative Examples 1 to 5. A 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Ltd., QS71) was used as a support film, and the mixture was evenly applied on its surface using a rod coater (trade name: Type A automatic coater, manufactured by Toyo Seiki Seisakusho, Ltd.), and heated and dried in a dryer at 95°C for 2 minutes and 30 seconds to form a photoresist layer with a film thickness of 25 μm. Then, a 19 μm thick polyethylene film (manufactured by Tamapoli Co., Ltd., GF-858) was attached to the surface of the unlaminated polyethylene terephthalate film side of the photoresist layer as a protective layer, and a photosensitive resin laminate containing the photosensitive resin composition of Examples 1 to 21 and Comparative Examples 1 to 5 was obtained.

[Preparation of substrate for performance evaluation] The substrate for performance evaluation is prepared as follows.

<Entire substrate> A 0.4 mm thick copper-clad laminate with a 18 μm thick rolled copper foil was prepared. The surface of the substrate was cleaned with a 10 mass % H ₂ SO ₄ aqueous solution.

<Lamination> While peeling off the polyethylene film of the photosensitive resin laminate produced above, the copper-clad laminate that was preheated to 50°C after the substrate was fully coated by the above method was laminated with the photosensitive resin laminate produced above at a roll temperature of 105°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Co., Ltd.) to obtain a substrate for performance evaluation. The air pressure was set to 0.35MPa and the lamination speed was set to 1.5m/min.

<Exposure step> After 2 hours of lamination, the performance evaluation substrate was exposed at a wavelength of 365nm through a glass mask using a projection exposure machine (UX-44101SM, manufactured by UXWON Electric Co., Ltd.). In addition, the performance evaluation substrate was also exposed at a wavelength of 402nm using a direct drawing exposure machine (FDi-3, manufactured by ORC MANUFACTURING CO., LTD.) using a designated drawing pattern for direct imaging (DI) exposure.

<Heating step> The performance evaluation substrate, which had been exposed for 1 minute, was heated for 30 seconds using a constant temperature thermostat (DKM600, manufactured by Yamato Scientific Co., Ltd.) set at 60°C.

<Developing step> After the polyethylene terephthalate film (supporting film) was peeled off, an alkaline developer (manufactured by Fuji Kiko Co., Ltd., developer for dry films) was used to spray a 1 mass% Na ₂ CO ₃ aqueous solution at 30°C for a specified time to develop. The developing spraying time was set to twice the shortest developing time, and the water washing spraying time after developing was set to twice the shortest developing time.

<Plating step> For the substrate that has been subjected to the same full-surface and layering as above, a pattern with a line width (L)/space width (S) (hereinafter referred to as "L/S") of x/x (x = 1 to 20 (varied at intervals of 1 μm)) (unit: μm) is used, and after exposure at an energy when the residual stage number of the Hitachi 41-stage step exposure meter is 17 stages, the same heating and development steps as above are performed to form a photoresist pattern. The developed substrate is immersed in an acid degreasing FRX (10 mass% sulfuric acid aqueous solution, manufactured by Atotech Co., Ltd., Japan) bath at 40°C for 4 minutes. After washing with water, it is immersed in a 10 mass% sulfuric acid aqueous solution at room temperature for 2 minutes.

Prepare a copper sulfate aqueous solution with a concentration of 121g/l, dilute it with sulfuric acid with a concentration of 19 mass% to 3.6 times the volume, and then add concentrated hydrochloric acid with a concentration of 200ppm. Then add Cupracid HL and Cupracid GS as brighteners at a concentration of 0.4ml/l and 20ml/l respectively to prepare a copper sulfate plating solution. The plating resistance evaluation substrate (6cm × 12.5cm) after pre-plating treatment was plated with the prepared copper sulfate plating solution through a Haring trough uniform plating device (manufactured by Yamamoto Plating Tester Co., Ltd.) at an applied current of 0.4A for 65 minutes. At this time, the thickness of the copper plating film is 20μm thick.

<Stripping step> Mix the trade name "Clean Etch (registered trademark) R-100S" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the trade name "Clean Etch (registered trademark) R-101" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in a volume ratio of 2/1, and dilute with pure water to prepare a stripping solution with a concentration of 20 mass%. Immerse the plated performance evaluation substrate in the stripping solution heated to 50°C for 4 minutes without stirring to strip the photoresist pattern.

[Evaluation] ＜Developability＞ The prepared performance evaluation substrate was exposed and developed according to the above method, and the shortest time required for the unexposed part of the photoresist layer to completely dissolve was set as the shortest development time. The shorter the shortest development time, the higher the developability. The shortest development time was evaluated according to the following criteria. As long as the evaluation is 0 or △, it can be appropriately used as a photosensitive resin laminate for photoresist pattern formation. 0: The shortest development time is less than 18 seconds "Good" △: The shortest development time is more than 18 seconds and less than 20 seconds "Acceptable" ×: The shortest development time is more than 20 seconds "Unacceptable"

<Flexibility> Following the above method, the flexible substrate that has been laminated and laminated is exposed to the energy when the residual stage number is 17 of the 41-stage exposure meter made by Stouffer, and then the substrate is cut into 1 inch wide samples. This sample is used to perform the mandrel test in accordance with JIS K5600-5-1, and the flexibility is evaluated by the minimum mandrel diameter without cracks in the exposed part. The smaller this value means the higher the flexibility, and the evaluation is performed using the following criteria. As long as the evaluation is 0 or △, it can be appropriately used as a photosensitive resin laminate for photoresist pattern formation. ０: Diameter less than 6mm　                         "Good" △: Diameter 6mm or more and less than 10mm　"Acceptable" ×: Diameter 10mm or more　                       "Unacceptable"

<Adhesion> For the prepared performance evaluation substrate, a pattern with a line width (L)/space width (S) (hereinafter referred to as "L/S") of x/3x (x = 1 to 20 (varied in intervals of 1 μm)) (unit: μm) was used, and after exposure with an energy of 17 residual stages of a 41-stage step exposure meter manufactured by Hitachi, the above-mentioned heating and development steps were performed to form a photoresist pattern. This photoresist pattern was observed under an optical microscope, and the adhesion was evaluated by the minimum line width at which the formed line portion (exposed portion) did not have snaking and defects. The smaller this value is, the higher the adhesion is, and the evaluation is performed using the following criteria. As long as the evaluation is 0 or △, it can be appropriately used for photosensitive resin laminates for photoresist pattern formation. 0: Minimum line width is less than 6μm　                     "Good" △: Minimum line width is more than 6μm and less than 8μm　"Acceptable" ×: Minimum line width is more than 8μm　                      "Unacceptable"

<Resolution> For the prepared performance evaluation substrate, a pattern with a line width (L)/space width (S) of x/x (x = 1 to 20 (varied in 1μm intervals)) (unit: μm) was used, and after exposure with an energy of 17 residual stages of a 41-stage step exposure meter manufactured by Hitachi, the above-mentioned heating and development steps were performed to form a photoresist pattern. The photoresist pattern was observed under an optical microscope, and the resolution was evaluated by the minimum line width at which no meandering or defects occurred in the line part (exposed part) and no residue was confirmed when the space part (unexposed part) was removed. The smaller this value is, the higher the resolution is, and the evaluation is performed using the following criteria. As long as the evaluation is 0 or △, it can be appropriately used as a photosensitive resin laminate for photoresist pattern formation. 0: Minimum line width is less than 6μm "Good" △: Minimum line width is more than 6μm and less than 8μm "Acceptable" ×: Minimum line width is more than 8μm "Unacceptable"

<Evaluation of peelability> The above-mentioned stripping step is performed after the above-mentioned plating step on the prepared performance evaluation substrate. The minimum mask width of the hardened photoresist line between the completely stripped plating patterns is set as the value of the stripping property after plating. The smaller this value means the higher the stripping property, and the evaluation is performed using the following criteria. As long as the evaluation is ◎, 0 or △, it can be appropriately used as a printed wiring board that is plated after the photoresist pattern is formed. ◎: Minimum mask width is less than 6μm                     "Excellent" ○: Minimum mask width is 6μm or more and less than 7μm "Good" △: Minimum mask width is 7μm or more and less than 9μm "Acceptable" ×: Minimum mask width is 9μm or more                      "Unacceptable"

The evaluation results of the performance evaluation substrate of the embodiment are shown in Table 1. In addition, the components shown in Table 1 are shown in detail in Table 2. In addition, the total value of k, each li, and m (the number of repeating units) in the formula of (A1) polyglycerol (meth)acrylate represented by formula (I), the total value of the number of repeating units (k, each li, and m)/(n+2), and the value of n are shown in Table 3. In addition, Table 3 shows the total value of k, each li, and m, and the value of n of (A1-1) to (A1-5) in order from top to bottom.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 2]

[Table 3]

As is apparent from Table 1, in the examples satisfying the requirements of this embodiment, the developing property, flexibility, resolution, adhesion and release properties are all good. On the other hand, when the (A) component does not simultaneously contain (A1) polyglycerol (meth)acrylate and (A2) a compound having no carboxyl group and having an ethylenically unsaturated bond, the developing property, flexibility, resolution, adhesion and release properties are all not good. In addition, when the (A) component contains (A3) a compound having a carboxyl group and having an ethylenically unsaturated bond, the developing property and resolution are inferior to those of the examples.

The above is an explanation of the implementation form of the present invention, but the present invention is not limited thereto and can be appropriately modified within the scope of the invention. [Industrial Applicability]

By using the photosensitive resin laminate of the present invention, it is possible to achieve excellent developability, flexibility, resolution, adhesion and peelability without being affected by the coating and drying conditions and storage conditions of the photosensitive resin laminate. That is, the photosensitive resin laminate can be widely used for photoresist pattern formation, and is particularly suitable for photoresist pattern formation of printed wiring boards that require plating after the photoresist pattern is formed.

Claims (30)

A photosensitive resin laminate having a supporting film and a photoresist layer containing a photosensitive resin composition; wherein the photosensitive resin composition contains the following components: (A) a compound having an ethylenically unsaturated bond, and (B) an alkali-soluble resin; wherein the component (A) contains (A1) a polyglycerol (meth)acrylate represented by the following general formula (I): [Chemical 1] [In the formula, n is 2 to 20; each i is a natural number from 1 to n; k, each li, and m are each independently 0 to 30; R ₁ , R _2i , and R ₃ are each independently a hydrogen atom or a methyl group; R ₄ , R _5i , and R ₆ are each independently a group selected from an alkylene group having 1 to 10 carbon atoms and represented by the following formula (II): [Chemical 2] [wherein, _R7 and _R8 are each independently an alkylene group having 1 to 10 carbon atoms], and a group represented by the following formula (III): [Chemical 3] [wherein R ₉ is one of the group consisting of an alkylene group having 1 to 10 carbon atoms]; and (A2) a compound having no carboxyl group and having an ethylenically unsaturated bond. The photosensitive resin laminate as claimed in claim 1, wherein the total content of the component (A) and the component (B) in the photosensitive resin composition is 80 mass % or more and 98 mass % or less based on the mass of all solid components of the photosensitive resin composition. The photosensitive resin laminate as claimed in claim 1 or 2, wherein the content of the component (B) is 70% by mass or less based on the total content of the component (A) and the component (B). The photosensitive resin laminate as claimed in claim 1 or 2, wherein the component (B) contains constituent units derived from styrene and benzyl (meth)acrylate. The photosensitive resin laminate as claimed in claim 1 or 2, wherein the component (B) contains a constituent unit derived from styrene, and the content of styrene in the component (B) is 35 mass % or more and 80 mass % or less. The photosensitive resin laminate as described in claim 1 or 2, wherein the photosensitive resin composition further contains a photopolymerization initiator as component (C). The photosensitive resin laminate as claimed in claim 6, wherein the content of the component (C) in the photosensitive resin composition is 25% by mass or less based on the content of the component (A). The photosensitive resin laminate as claimed in claim 6, wherein the component (C) contains a hexaarylbiimidazole compound. The photosensitive resin laminate as claimed in claim 1 or 2, wherein the photosensitive resin composition further contains (D) a polymerization inhibitor. The photosensitive resin laminate as claimed in claim 1 or 2, wherein the component (A2) is a compound having 2 to 6 ethylenically unsaturated bonds. The photosensitive resin laminate as claimed in claim 1 or 2, wherein the component (A2) contains a compound having two ethylenically unsaturated bonds. The photosensitive resin laminate as claimed in claim 1 or 2, wherein the component (A2) contains a compound having one ethylenically unsaturated bond. The photosensitive resin laminate as claimed in claim 1 or 2, wherein the component (A2) contains a di(meth)acrylate compound having a bisphenol A structure. The photosensitive resin laminate as claimed in claim 1 or 2, wherein R ₁ , R _2i , and R ₃ in the general formula (I) are methyl groups. A photosensitive resin laminate as described in claim 1 or 2, wherein when R ₄ O, R _5i O and R ₆ O in the general formula (I) are represented by the formula R _j O {wherein j = 4, 5i, 6 (wherein i = 1, 2, …, n)}, the ratio of the total number of R _j O to the number of (meth)acryloyl groups is less than 20. The photosensitive resin laminate as claimed in claim 1 or 2, wherein n in the general formula (I) is an integer of 2 to 15. The photosensitive resin laminate as claimed in claim 1 or 2, wherein n in the general formula (I) is 2 to 15 in terms of numerical average value. The photosensitive resin laminate as claimed in claim 1 or 2, wherein R ₄ , R _5i , and R ₆ are alkylene groups. The photosensitive resin laminate as claimed in claim 1 or 2, wherein R ₄ , R _5i , and R ₆ contain ethylene and/or propylene. The photosensitive resin laminate as claimed in claim 1 or 2, wherein R ₄ , R _5i , and R ₆ are ethylene and/or propylene. The photosensitive resin laminate as claimed in claim 1 or 2, wherein R ₄ , R _5i , and R ₆ are ethylene groups. The photosensitive resin laminate as described in claim 1 or 2, further comprising a protective film. A photosensitive resin laminate having a supporting film and a photoresist layer containing a photosensitive resin composition; and the photosensitive resin composition contains the following components: (A) a compound having an ethylenic unsaturated bond, and (B) an alkali-soluble resin; the (A) component contains (A3) a compound having no quaternary carbon and/or aromatic ring and having 4 or more ethylenic unsaturated bonds in one molecule; and (A4) a compound having a quaternary carbon and/or aromatic ring and having no carboxyl group and having an ethylenic unsaturated bond. The photosensitive resin laminate as described in claim 23, wherein the (A4) compound contains a compound having 1 or 2 ethylenically unsaturated bonds. The photosensitive resin laminate as claimed in claim 23 or 24, wherein the amount of ethylenically unsaturated bonds in 100 g of the compound (A4) is 0.25 mol or less. The photosensitive resin laminate as claimed in claim 23 or 24, wherein the content of the component (A) is 20% by mass or more based on the mass of all solid components of the photosensitive resin composition. A photosensitive resin laminate as described in claim 23 or 24, wherein: the component (B) is a copolymer containing a constituent unit derived from (meth) acrylic acid as a monomer component; the content of the constituent unit derived from (meth) acrylic acid in the component (B) is 27% by mass or less. A photosensitive resin laminate as described in claim 23 or 24, wherein: the component (B) is a copolymer containing a constituent unit derived from (meth) acrylic acid as a monomer component; the content of the constituent unit derived from (meth) acrylic acid in the component (B) is 25% by mass or less. A method for forming a photoresist pattern, which uses a photosensitive resin laminate as described in claim 1 or 2, and comprises the following steps: A lamination step, which is to laminate a photoresist layer on a substrate; An exposure step, which is to expose the photoresist layer; and A development step, which is to develop and remove the unexposed portion of the photoresist layer. A method for manufacturing a wiring board, which uses a photosensitive resin laminate as described in claim 1 or 2, and comprises the following steps: A lamination step, which is to laminate a photoresist layer on a substrate; An exposure step, which is to expose the photoresist layer; A development step, which is to develop and remove the unexposed portion of the photoresist layer to form a photoresist pattern; A conductor pattern forming step, which is to etch or plate the substrate formed with the photoresist pattern to form a conductor pattern; and A stripping step, which is to strip the photoresist pattern from the substrate.