JP2019035932A - Photosensitive resin composition, photosensitive resin laminate, substrate having resist pattern formed thereon, and method of manufacturing circuit board - Google Patents

Abstract

To provide a photosensitive resin composition capable of forming a resist pattern which suppresses foamability, has good sensitivity, resolution and adhesion, can shorten peeling time, and is excellent in flexibility.SOLUTION: The photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a sensitizer. As the compound (B) having an ethylenically unsaturated double bond, a compound represented by general formula (1) is contained. The sensitizer (D) contains at least one selected from a pyrazoline compound, an anthracene compound, a triarylamine compound, and an oxazole compound.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, a substrate on which a resist pattern is formed, and a method for manufacturing a circuit board.

  A printed wiring board is generally manufactured by photolithography. Photolithography is a method for forming a desired wiring pattern on a substrate by the following steps. That is, first, a layer made of a photosensitive resin composition is formed on a substrate, and a resist pattern is formed by pattern exposure and development on the coating film. Next, a conductor pattern is formed by etching or plating. Thereafter, a desired wiring pattern is formed on the substrate by removing the resist pattern on the substrate.

  In the production of a printed wiring board, a photosensitive element (photosensitive resin laminate) is often used. Many known examples exist as a method for forming a wiring pattern using this photosensitive element and a photosensitive resin composition suitable for this method (Patent Documents 1 to 3).

International Publication No.2012-101908 International Publication No. 2015-174467 International Publication No. 2015-174468

  However, all of the materials described in Patent Documents 1 to 3 described above have room for further improvement from the viewpoints of sensitivity, resolution, adhesion, peeling time, flexibility, and developer foamability. .

  The present invention has been made in view of the above situation. That is, an object of the present invention is a photosensitive resin composition that can suppress foaming, has good sensitivity, resolution, adhesion, can shorten the peeling time, and can form a resist pattern with excellent flexibility, It is providing the manufacturing method of the photosensitive resin laminated body, the board | substrate with which the resist pattern was formed, and a circuit board.

｛式中、Ａは、Ｃ_２Ｈ_４又はＣ_３Ｈ_６であり、−（Ａ−Ｏ）_ｎ１−及び−（Ａ−Ｏ）_ｎ３−において、−Ｃ_２Ｈ_４−Ｏ−及び−Ｃ_３Ｈ_６−Ｏ−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、該配列がブロックである場合には、−Ｃ_２Ｈ_４−Ｏ−及び−Ｃ_３Ｈ_６−Ｏ−のいずれかが−Ｂ−Ｏ−基側であってもよい。Ｂは、炭素数４〜８の２価のアルキル鎖である。ｎ１は、０〜１０の整数であり、ｎ３は、０〜１０の整数であり、ｎ１＋ｎ３は、０〜２０の整数であり、そして、ｎ２は１２〜４２の整数である。｝で表される化合物を含み、
前記（Ｄ）増感剤が、ピラゾリン化合物、アントラセン化合物、トリアリールアミン化合物およびオキサゾール化合物からなる群より選ばれる少なくとも１つを含むこと、を特徴とする感光性樹脂組成物。
［２］
前記感光性樹脂組成物中の固形分１００ｇ当たりのエチレン性不飽和二重結合のモル数が０．１〜０．３である、［１］に記載の感光性樹脂組成物。
［３］
前記感光性樹脂組成物中の固形分１００ｇ当たりのエチレン性不飽和二重結合のモル数が０．１１〜０．１５である、［２］に記載の感光性樹脂組成物。
［４］
前記一般式（１）において、ＡがＣ_３Ｈ_６である、［１］から［３］のいずれかに記載の感光性樹脂組成物。
［５］
前記一般式（１）において、ｎ１＋ｎ３が１〜２０である、［１］から［４］のいずれかに記載の感光性樹脂組成物。
［６］
前記一般式（１）において、ｎ１＋ｎ３が１〜１０である、［１］から［５］のいずれかに記載の感光性樹脂組成物。
［７］
前記（Ｄ）増感剤が、ピラゾリン化合物を含む、［１］から［６］のいずれかに記載の感光性樹脂組成物。
［８］
前記（Ｄ）増感剤が、アントラセン化合物を含む、［１］から［７］のいずれかに記載の感光性樹脂組成物。
［９］
前記（Ｄ）増感剤が、トリアリールアミン化合物を含む、［１］から［８］のいずれかに記載の感光性樹脂組成物。
［１０］
前記感光性樹脂組成物は、
前記一般式（１）で表される化合物を、前記感光性樹脂組成物の全固形分に対して３〜３０質量％含み、
前記（Ｄ）増感剤を、前記感光性樹脂組成物の全固形分に対して０．０５〜２質量％含む、［１］から［９］のいずれかに記載の感光性樹脂組成物。
［１１］
少なくともスチレンおよびメタクリル酸ベンジルを共重合したアルカリ可溶性高分子を、前記（Ａ）アルカリ可溶性高分子全体の５０質量％以上含む、［１］から［１０］のいずれかに記載の感光性樹脂組成物。
［１２］
ビスフェノールＡ骨格を有する化合物を、前記（Ｂ）エチレン性不飽和二重結合を有する化合物全体の４０質量％以上含む、［１］から［１１］のいずれかに記載の感光性樹脂組成物。
［１３］
前記感光性樹脂組成物は、
前記一般式（１）で表される化合物を、前記感光性樹脂組成物の全固形分に対して３〜１７質量％含む、［１］から［１２］のいずれかに記載の感光性樹脂組成物。
［１４］
前記感光性樹脂組成物は、
前記一般式（１）で表される化合物を、前記感光性樹脂組成物の全固形分に対して３〜１５質量％含む、［１３］に記載の感光性樹脂組成物。
［１５］
前記感光性樹脂組成物中の
前記（Ａ）アルカリ可溶性高分子の固形分量に対する（Ｂ）エチレン性不飽和二重結合を有する化合物固形分量の値は０．７以上１．４以下である、［１］から［１４］のいずれかに記載の感光性樹脂組成物。
［１６］
前記感光性樹脂組成物中の
前記（Ａ）アルカリ可溶性高分子の固形分量に対する（Ｂ）エチレン性不飽和二重結合を有する化合物固形分量の値は０．８以上１．３以下である、［１５］に記載の感光性樹脂組成物。
［１７］
支持体上に、［１］〜［１６］のいずれかに記載の感光性樹脂組成物を含む感光性樹脂層が積層されている、感光性樹脂積層体。
［１８］
以下の工程：
基板上に、［１７］に記載の感光性樹脂積層体をラミネートするラミネート工程、
該感光性樹脂積層体を露光する露光工程、及び
未露光部を除去する現像工程、
を含む、レジストパターンが形成された基板の製造方法。
［１９］
［１８］に記載の方法により製造された基板に対してエッチング又はめっきを施すことにより回路基板を形成する、回路基板の製造方法。 The present inventors have found that the above object can be achieved by the following technical means, and have completed the present invention. The present invention is as follows.
[1]
The following ingredients:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated double bond,
(C) a photopolymerization initiator, and (D) a photosensitive resin composition containing a sensitizer,
As the compound (B) having an ethylenically unsaturated double bond, the following general formula (1):

{In the formula, A represents C ₂ H ₄ or C ₃ H ₆ , and — (A—O) _n1 — and — (A—O) _n3 — represent —C ₂ H ₄ —O— and —C _3. The sequence of the repeating unit of H ₆ —O— may be random or block, and when the sequence is a block, —C ₂ H ₄ —O— and —C ₃ H ₆ —O Any of-may be on the -B-O-group side. B is a divalent alkyl chain having 4 to 8 carbon atoms. n1 is an integer of 0 to 10, n3 is an integer of 0 to 10, n1 + n3 is an integer of 0 to 20, and n2 is an integer of 12 to 42. }, And a compound represented by
The photosensitive resin composition characterized in that the (D) sensitizer contains at least one selected from the group consisting of a pyrazoline compound, an anthracene compound, a triarylamine compound, and an oxazole compound.
[2]
The photosensitive resin composition according to [1], wherein the number of moles of ethylenically unsaturated double bonds per 100 g of solid content in the photosensitive resin composition is 0.1 to 0.3.
[3]
The photosensitive resin composition according to [2], wherein the number of moles of ethylenically unsaturated double bonds per 100 g of solid content in the photosensitive resin composition is 0.11 to 0.15.
[4]
In the general formula (1), A is _C 3 _{H 6,} the photosensitive resin composition according to any one of [1] to [3].
[5]
The photosensitive resin composition in any one of [1] to [4] whose n1 + n3 is 1-20 in the said General formula (1).
[6]
The photosensitive resin composition in any one of [1] to [5] whose n1 + n3 is 1-10 in the said General formula (1).
[7]
The photosensitive resin composition according to any one of [1] to [6], wherein the (D) sensitizer includes a pyrazoline compound.
[8]
The photosensitive resin composition according to any one of [1] to [7], wherein the (D) sensitizer includes an anthracene compound.
[9]
The photosensitive resin composition according to any one of [1] to [8], wherein the (D) sensitizer includes a triarylamine compound.
[10]
The photosensitive resin composition is
Containing 3 to 30% by mass of the compound represented by the general formula (1) with respect to the total solid content of the photosensitive resin composition;
The photosensitive resin composition in any one of [1] to [9] which contains 0.05-2 mass% of said (D) sensitizers with respect to the total solid of the said photosensitive resin composition.
[11]
The photosensitive resin composition according to any one of [1] to [10], which contains at least 50% by mass of the alkali-soluble polymer obtained by copolymerizing at least styrene and benzyl methacrylate (A). .
[12]
The photosensitive resin composition according to any one of [1] to [11], comprising a compound having a bisphenol A skeleton in an amount of 40% by mass or more based on the total amount of the compound (B) having an ethylenically unsaturated double bond.
[13]
The photosensitive resin composition is
The photosensitive resin composition according to any one of [1] to [12], comprising 3 to 17% by mass of the compound represented by the general formula (1) with respect to the total solid content of the photosensitive resin composition. object.
[14]
The photosensitive resin composition is
The photosensitive resin composition as described in [13] which contains 3-15 mass% of compounds represented by the said General formula (1) with respect to the total solid of the said photosensitive resin composition.
[15]
The value of (B) the solid content of the compound having an ethylenically unsaturated double bond relative to the solid content of the (A) alkali-soluble polymer in the photosensitive resin composition is 0.7 or more and 1.4 or less. The photosensitive resin composition according to any one of [1] to [14].
[16]
The value of the solid content of the compound (B) having an ethylenically unsaturated double bond relative to the solid content of the (A) alkali-soluble polymer in the photosensitive resin composition is 0.8 or more and 1.3 or less, 15]. The photosensitive resin composition as described in 15].
[17]
The photosensitive resin laminated body by which the photosensitive resin layer containing the photosensitive resin composition in any one of [1]-[16] is laminated | stacked on the support body.
[18]
The following steps:
A laminating step of laminating the photosensitive resin laminate according to [17] on a substrate;
An exposure step of exposing the photosensitive resin laminate, and a development step of removing unexposed portions,
A method for manufacturing a substrate on which a resist pattern is formed.
[19]
A method for manufacturing a circuit board, comprising forming a circuit board by etching or plating the board manufactured by the method according to [18].

  According to the present invention, there is provided a photosensitive resin composition that is capable of forming a resist pattern that has low foaming properties, has good sensitivity, resolution, adhesion, can shorten the peeling time, and has excellent flexibility. be able to.

｛式中、Ａは、Ｃ_２Ｈ_４又はＣ_３Ｈ_６であり、−（Ａ−Ｏ）_ｎ１−及び−（Ａ−Ｏ）_ｎ３−において、−Ｃ_２Ｈ_４−Ｏ−及び−Ｃ_３Ｈ_６−Ｏ−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、該配列がブロックである場合には、−Ｃ_２Ｈ_４−Ｏ−及び−Ｃ_３Ｈ_６−Ｏ−のいずれかが−Ｂ−Ｏ−基側であってもよい。Ｂは、炭素数４〜８の２価のアルキル鎖である。ｎ１は、０〜１０の整数であり、ｎ３は、０〜１０の整数であり、ｎ１＋ｎ３は、０〜２０の整数であり、そして、ｎ２は１２〜４２の整数である。｝で表される化合物を含み、
（Ｄ）増感剤が、ピラゾリン化合物、アントラセン化合物、トリアリールアミン化合物およびオキサゾール化合物からなる群より選ばれる少なくとも１つを含むこと、を特徴とする。 Embodiments of the present invention will be described below.
The photosensitive resin composition of this embodiment contains (A) an alkali-soluble polymer, (B) a compound having an ethylenic double bond, (C) a photopolymerization initiator, and (D) a sensitizer.
And the photosensitive resin composition of this embodiment is the following general formula (1) as a compound which has (B) ethylenically unsaturated double bond:

{In the formula, A represents C ₂ H ₄ or C ₃ H ₆ , and — (A—O) _n1 — and — (A—O) _n3 — represent —C ₂ H ₄ —O— and —C _3. The sequence of the repeating unit of H ₆ —O— may be random or block, and when the sequence is a block, —C ₂ H ₄ —O— and —C ₃ H ₆ —O Any of-may be on the -B-O-group side. B is a divalent alkyl chain having 4 to 8 carbon atoms. n1 is an integer of 0 to 10, n3 is an integer of 0 to 10, n1 + n3 is an integer of 0 to 20, and n2 is an integer of 12 to 42. }, And a compound represented by
(D) The sensitizer includes at least one selected from the group consisting of a pyrazoline compound, an anthracene compound, a triarylamine compound, and an oxazole compound.

<(A) Alkali-soluble polymer>
(A) The alkali-soluble polymer is preferably obtained by polymerizing at least one of the first monomers described below. Further, (A) the alkali-soluble polymer is obtained by copolymerizing at least one of the first monomers and at least one of the second monomers described later. preferable.

  The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. Among these, (meth) acrylic acid is particularly preferable. In this specification, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means “acrylate” and “methacrylate”.

  (A) The copolymerization ratio of the first monomer in the alkali-soluble polymer is preferably 10% by mass to 35% by mass, and 15% by mass to 30% by mass with respect to the total mass of all monomers. More preferably, it is more preferably 16% by mass to 28% by mass.

  The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Acrylic acid esters; esters of vinyl alcohol such as vinyl acetate; and (meth) acrylonitrile, styrene, and polymerizable styrene derivatives (eg, methylstyrene, vinyltoluene, tert-butoxystyrene, Tokishisuchiren, 4-vinylbenzoic acid, styrene dimer, styrene trimer), and the like. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferable. Benzyl (meth) acrylate is particularly preferable from the viewpoint of the shortness of the bottom of the resist pattern.

  (A) The copolymerization ratio of the second monomer in the alkali-soluble polymer is 70% by mass to 90% by mass with respect to the total mass of all monomers constituting the copolymer to be the (A) alkali-soluble polymer. %, More preferably 70% by mass to 85% by mass, and even more preferably 72% by mass to 84% by mass.

  In this embodiment, from the viewpoint of improving the resolution of the resist pattern, the (A) alkali-soluble polymer preferably has an aromatic group in the side chain of the structure.

  (A) Alkali-soluble polymer having an aromatic group in the side chain is a compound having an aromatic group as at least one of the first monomer and the second monomer. Can be used. Examples of the monomer having an aromatic group include (meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, styrene, cinnamic acid, polymerizable styrene derivatives ( Examples thereof include methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, and the like. It is preferable that both (meth) acrylic acid aralkyl ester and styrene are included from the viewpoint of resolution, adhesion, and balance of the skirt of the resist pattern. In particular, from the viewpoint of further shortening the bottom of the resist pattern, the (meth) acrylic acid aralkyl ester is preferably benzyl (meth) acrylate.

  The copolymerization ratio of the compound having an aromatic group is 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, and 70% by mass with respect to the total mass of all monomers. % Or more, or 80% by mass or more is preferable. From the viewpoint of maintaining alkali solubility, the copolymerization ratio of the compound having an aromatic group is preferably 95% by mass or less, more preferably 90% by mass or less. In particular, when styrene is used as the compound having an aromatic group, the copolymerization ratio of styrene is preferably 40% by mass or more and less than 80% by mass.

  (A) The alkali-soluble polymer preferably includes at least an alkali-soluble polymer copolymerized with styrene and benzyl methacrylate, and the alkali-soluble polymer is 50 masses of the total amount of the (A) alkali-soluble polymer. It is more preferable that it contains more than%. Thereby, the resolution of the resist pattern can be improved and the bottom of the resist pattern can be shortened.

  In this embodiment, (A) the alkali-soluble polymer is a known polymerization method, preferably an addition of one or more monomers selected from the first monomer and the second monomer. It can be prepared by polymerization, more preferably by radical polymerization.

  (A) The acid equivalent of the alkali-soluble polymer (the acid equivalent of the entire mixture when a plurality of types of copolymers are included) is the development resistance of the photosensitive resin layer, and the resolution and adhesion of the resist pattern. In view of the above, it is preferably 100 or more, and from the viewpoint of developability and peelability of the photosensitive resin layer, it is preferably 600 or less. (A) The acid equivalent of the alkali-soluble polymer is more preferably 200 to 500, and further preferably 250 to 450.

  (A) The weight average molecular weight of the alkali-soluble polymer (hereinafter sometimes abbreviated as “Mw”) (in the case where a plurality of types of alkali-soluble polymers are used in combination) means the total Mw) It is preferably 5,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 65,000.

Dispersity (Mw / Mn), which is the ratio of the weight average molecular weight to the number average molecular weight (hereinafter sometimes abbreviated as “Mn”) (when a plurality of types of alkali-soluble polymers are used in combination, the total dispersion The degree) is preferably 1.0 or more from the viewpoint of peelability, and preferably 6.0 or less from the viewpoint of resolution. It is preferably 1.0 to 6.0, more preferably 1.5 to 5.0, still more preferably 2.0 to 5.0, and 2.5 to 4.5. Is more preferable, and 3.0 to 4.2 is particularly preferable.
(A) It is preferable that the weight average molecular weight and dispersity of the alkali-soluble polymer are in the above ranges from the viewpoint of obtaining appropriate developability, high coating strength, and resist thickness uniformity.

(A) When using a plurality of alkali-soluble polymers in combination as alkali-soluble polymers,
(A-1) an alkali-soluble polymer whose Mw is less than 50,000, and (A-2) an alkali-soluble polymer whose Mw is 50,000 or more,
It is particularly preferable from the viewpoint of flexibility, resolution, and product life.

The Mw of the alkali-soluble polymer (A-1) is more preferably 5,000 or more and less than 50,000, further preferably 10,000 to 45,000, or 10,000 to 35,000. It is particularly preferred that It is preferable that Mw of the alkali-soluble polymer (A-1) is in this range from the viewpoint of achieving both flexibility and resolution.
On the other hand, the Mw of the alkali-soluble polymer (A-2) is more preferably 50,000 to 100,000, still more preferably 50,000 to 75,000, and 50,000 to 65,000. 000 is particularly preferred. The Mw of the alkali-soluble polymer (A-2) being in this range makes the product life longer when the photosensitive resin composition of the present embodiment is applied to a photosensitive element (dry film resist). From the viewpoints and flexibility, it is preferable.

The content ratio of the alkali-soluble polymer (A-1) component to the total solid content of the photosensitive resin composition is preferably 3% by mass to 30% by mass, more preferably 5% by mass to 25% by mass. It is below, More preferably, it is 10 to 25 mass%. Setting the use ratio of the component (A-1) within the above range is preferable from the viewpoint of achieving both flexibility, resolution, and product life.
The content ratio of the alkali-soluble polymer (A-2) component to the total solid content of the photosensitive resin composition is preferably 5% by mass to 50% by mass, more preferably 15% by mass to 48% by mass. It is below, More preferably, they are 18 mass% or more and 45 mass% or less. It is preferable to set the use ratio of the component (A-2) within the above range from the viewpoint of resolution, flexibility, and product life of the photosensitive element.

  The proportion of the (A) alkali-soluble polymer used in the photosensitive resin composition of the present embodiment is preferably 25% by mass or more, and 30% by mass or more with respect to the total amount of solid content of the photosensitive resin composition. It is preferable that it is 35 mass% or more, it is preferable that it is 40 mass% or more, and it is preferable that it is 45 mass% or more. The upper limit is not particularly limited, but may be 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, or 65% by mass or less.

  The use ratio of the (A) alkali-soluble polymer in the photosensitive resin composition of the present embodiment is preferably 25% by mass to 85% by mass, and preferably 35% by mass to the total amount of the solid content of the photosensitive resin composition. 75 mass% is more preferable, and 40 mass%-65 mass% is more preferable. (A) Setting the use ratio of the alkali-soluble polymer within the above range is preferable from the viewpoints of resolution, adhesion, flexibility, resist pattern peelability, and product life of the photosensitive element.

｛式中、Ａは、Ｃ_２Ｈ_４又はＣ_３Ｈ_６であり、−（Ａ−Ｏ）_ｎ１−及び−（Ａ−Ｏ）_ｎ３−において、−Ｃ_２Ｈ_４−Ｏ−及び−Ｃ_３Ｈ_６−Ｏ−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、該配列がブロックである場合には、−Ｃ_２Ｈ_４−Ｏ−及び−Ｃ_３Ｈ_６−Ｏ−のいずれかが−Ｂ−Ｏ−基側であってもよい。Ｂは、炭素数４〜８の２価のアルキル鎖であり、ｎ１は、０〜１０の整数である。ｎ３は、０〜１０の整数であり、ｎ１＋ｎ３は、０〜２０の整数である。そして、ｎ２は１２〜４２の整数である。｝で表される化合物を含む。 <(B) Compound having ethylenic double bond>
(B) A compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated group in its structure.
The photosensitive resin composition of this embodiment is represented by the following general formula (1) as a compound having (B) an ethylenically unsaturated double bond:

{In the formula, A represents C ₂ H ₄ or C ₃ H ₆ , and — (A—O) _n1 — and — (A—O) _n3 — represent —C ₂ H ₄ —O— and —C _3. The sequence of the repeating unit of H ₆ —O— may be random or block, and when the sequence is a block, —C ₂ H ₄ —O— and —C ₃ H ₆ —O Any of-may be on the -B-O-group side. B is a C4-C8 bivalent alkyl chain, and n1 is an integer of 0-10. n3 is an integer of 0 to 10, and n1 + n3 is an integer of 0 to 20. And n2 is an integer of 12-42. } Is included.

The —C ₄ H ₈ —O— chain is more hydrophobic than the —C ₂ H ₄ —O— chain and more flexible than the —C ₃ H ₆ —O— chain, and has both properties. . By using this monomer, it is possible to achieve both high resolution, adhesion and flexibility. Further, the foaming property of the developer can be suppressed.
In the formula (1), A is preferably —C ₃ H ₆ — in terms of resolution and adhesion.
In the formula (1), n1 + n3 is preferably 1 or more from the viewpoint of peelability and foaming suppression, and from the viewpoint of flexibility, it is preferably 20 or less, more preferably 15 or less, and more preferably 10 or less. More preferably.
Accordingly, it is possible to provide a photosensitive resin composition that has good sensitivity, resolution, and adhesion, can shorten the peeling time, and can form a resist pattern with excellent flexibility.

  The ratio of the compound (B) having an ethylenically unsaturated double bond to the total solid mass of the photosensitive resin composition is preferably 30% by mass or more, and 35% by mass or more from the viewpoints of sensitivity, tackiness and followability. preferable. Moreover, 50 mass% or less is preferable from a viewpoint of edge fusion property, tack property, and resolution, 45 mass% or less is preferable, and 42 mass% or less is preferable.

  In addition, from the viewpoint of edge fusion, tackiness, and resolution, (B) a solid compound having an ethylenically unsaturated double bond with respect to the solid content of (A) the alkali-soluble polymer contained in the photosensitive resin composition The value of the amount (that is, (B) the solid content of the compound having an ethylenically unsaturated double bond / (A) the solid content of the alkali-soluble polymer) is preferably 1.4 or less, and preferably 1.3 or less. 1.2 or less is preferable, and 1.1 or less is preferable. The lower limit is preferably 0.7 or more, preferably 0.8 or more, preferably 0.9 or more, and preferably 1.0 or more.

(B) As a compound which has an ethylenically unsaturated double bond, the ratio with respect to the total solid content mass of the photosensitive resin composition of the compound represented by the said General formula (1), Preferably it is 3 mass%-30 mass%. It is. Setting this ratio to 2% by mass or more, particularly 3% by mass or more is preferable from the viewpoint of resolution, adhesion, and flexibility, and it is more preferable to set this ratio to 5% by mass or more.
On the other hand, it is preferable to set this ratio to 30% by mass or less from the viewpoint of resolution and adhesion, and it is more preferable to set this ratio to 25% by mass or less.

  (B) As a compound which has an ethylenically unsaturated double bond, the ratio with respect to the total solid mass of the photosensitive resin composition of the compound represented by the said General formula (1) is from a viewpoint of resolution and adhesiveness. 17% by mass or less, particularly preferably 15% by mass or less, particularly preferably 13% by mass or less, and particularly preferably 10% by mass or less.

  The photosensitive resin composition of the present embodiment preferably contains a compound obtained by modifying bisphenol A (having a bisphenol A skeleton). In the photosensitive resin composition of the present embodiment, the proportion of the compound obtained by modifying bisphenol A is preferably 12% by mass to 45% by mass, and 17% by mass with respect to the total mass of the solid content of the photosensitive resin composition. -40 mass% is more preferable, and 20 mass%-40 mass% is still more preferable. Setting the use ratio within this range is suitable from the viewpoint of obtaining a photosensitive resin composition having an excellent balance between resolution and developability. Moreover, the balance of resolution and adhesiveness is more excellent by making the compound which modified | denatured bisphenol A into 40 mass% or more of the whole compound which has (B) ethylenically unsaturated double bond.

  In the photosensitive resin composition of the present invention, the number of moles of ethylenically unsaturated double bonds per 100 g of the solid content of the photosensitive resin composition is preferably 0.1 to 0.3. By setting it to 0.1 or more, it is possible to prevent the photosensitive resin component from being eluted from the cured photosensitive resin composition (also referred to as a resist pattern) and contaminating the water washing step in the water washing step after development. By setting it to 0.3 or less, it is possible to prevent the cured photosensitive resin composition (also referred to as a resist pattern) from being lost in the washing step after the development and contaminating the washing step.

The number of moles of ethylenically unsaturated double bonds per 100 g of solid content of the photosensitive resin composition is preferably 0.1 or more, more preferably 0.11 or more, more preferably 0.12 or more. Yes, more preferably 0.13 or more. Further, it is preferably 0.3 or less, preferably 0.28 or less, preferably 0.25 or less, preferably 0.22 or less, preferably 0.20 or less, preferably 0. .18 or less, preferably 0.15 or less.
More preferably, it is 0.1-0.25, More preferably, it is 0.1-0.2, More preferably, it is 0.11-0.2, Most preferably, it is 0.11. From above to 0.15.

<(C) Photopolymerization initiator>
(C) As the photopolymerization initiator, for example, hexaarylbiimidazole compound, quinone compound, aromatic ketone compound, acetophenone compound, acylphosphine oxide compound, benzoin compound, benzoin ether compound, dialkyl ketal compound, thioxanthone compound, oxime An ester compound, an acridine compound, etc. are mentioned.

Examples of the hexaarylbiimidazole compound include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl). ) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o- Chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4', 5 5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl)- Biimidazole, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2 , 6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4-trifluorophenyl) -4, 4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4', 5,5'-tetrakis -(3-methoxyphenyl) -biimidazole, 2, '-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-methoxy Phenyl) -biimidazole and 2,2′-bis- (2,3,4,5,6) Pentafluorophenyl) -4,4 ', 5,5'-tetrakis - (3-methoxyphenyl) - biimidazole. Among these, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable from the viewpoints of high sensitivity, resolution, and adhesion.

  Examples of the quinone compound include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloro. Anthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone and the like.

Examples of the aromatic ketone compound include benzophenone.
Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and 1- (4 -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-benzyl- And 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals. From the viewpoint of adhesion, 4,4′-bis (diethylamino) benzophenone is preferable.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phosphine oxide, and bis (2,6-dimethoxybenzoyl) -2. 4,4-trimethyl-pentylphosphine oxide and the like. As a commercial item of an acylphosphine oxide compound, for example, Lucilin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Specialty Chemicals are listed.

Examples of the benzoin compound and benzoin ether compound include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.
Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal.
Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

  Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, and the like. . Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals.

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

  The proportion of the photopolymerization initiator (C) used in the photosensitive resin composition of the present embodiment is preferably 0.01% by mass to 20% by mass with respect to the total mass of the solid content of the photosensitive resin composition. 0.5 mass%-10 mass% are more preferable. (C) By setting the use ratio of the photopolymerization initiator within this range, sufficient sensitivity can be obtained, light can be sufficiently transmitted to the bottom of the resist, high resolution can be obtained, and adhesion can be obtained. Can be obtained.

  (C) It is preferable to use a hexaarylbisimidazole compound as a photopolymerization initiator. In this case, the usage ratio of the hexaarylbisimidazole compound is preferably 0.1% by mass to 10% by mass, and preferably 0.5% by mass to 5% by mass with respect to the total mass of the solid content of the photosensitive resin composition. Is more preferable.

  The use ratio of the hexaarylbisimidazole compound is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass with respect to the total mass of the solid content of the photosensitive resin composition. .

<(D) Sensitizer>
In the photosensitive resin composition of the present embodiment, (D) the sensitizer includes at least one selected from a pyrazoline compound, an anthracene compound, a triarylamine compound, and an oxazole compound. These compounds have a large absorption of light around 405 nm called h-line. By using these compounds as sensitizers, sensitivity and image forming properties are improved. Among these, it is more preferable that the (D) sensitizer contains at least one selected from a pyrazoline compound and an anthracene compound.

  The (D) sensitizer is preferably 0.005 to 2% by mass with respect to the total mass of the solid content of the photosensitive resin composition. By using the sensitizer (D) within this range, good sensitivity, resolution and adhesion can be obtained.

(D) The sensitizer in this invention should just be a thing which a sensitivity improves by combining with (C) initiator. (D) The function of the sensitizer is to absorb light at the exposure wavelength and give energy or electrons to the initiator, (C) to promote the cleavage of the initiator, (C) onset generated from the initiator The radicals or the radicals once added to the monomer and polymerized can move to (D) the sensitizer and regenerate the radicals through new cleavage and decomposition.
(D) Sensitizers other than pyrazoline compounds, anthracene compounds, triarylamine compounds and oxazole compounds include N-aryl-α-amino acid compounds, aromatic ketone compounds substituted with alkylamino groups, and dialkylaminobenzoic acid esters. Examples thereof include compounds, pyrazoline derivatives, anthracene derivatives, triphenylamine derivatives, N-aryl amino acid ester compounds, halogen compounds, and the like.

Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. In particular, N-phenylglycine is preferable because of its high sensitizing effect.
Examples of the aromatic ketone compound substituted with an alkylamino group include Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone. Etc.
Examples of the dialkylaminobenzoic acid ester compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4- (dimethylamino) benzoate, and the like.

Examples of the pyrazoline derivative include 5- (4-tert-butylphenyl) -3- (4-tert-butylstyryl) -1-phenyl-2-pyrazolin, 5- ( 4-tert-butylphenyl) -1-phenyl-3- (4-phenylphenyl) -4,5-dihydro-1H-pyrazole, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropyl Phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4 -Methoxyphenyl) -pyrazolin, 1-phenyl-3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoli 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,6-dimethoxystyryl) -5- (2,6 -Dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,3-dimethoxystyryl)- 5- (2,3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3,5-bis (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3,5-bis (4-methoxy-phenyl) -pyrazoline, 1-phenyl-3- (4-methoxy Phenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-phenyl) -5- (4-methoxy-phenyl) -pyrazoline, 1-phenyl-3 -(4-Isopropyl-phenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-phenyl) -5- (4-isopropyl-phenyl) -pyrazoline 1-phenyl-3- (4-methoxy-phenyl) -5- (4-isopropyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropyl-phenyl) -5- (4-methoxy-phenyl) -Pyrazolin, 1,5-diphenyl-3- (4-tert-butyl-phenyl) -pyrazoline, 1,3-diphenyl-5- (4-tert- Butyl-phenyl) -pyrazoline, 1,5-diphenyl-3- (4-isopropyl-phenyl) -pyrazoline, 1,3-diphenyl-5- (4-isopropyl-phenyl) -pyrazoline, 1,5-diphenyl-3 -(4-methoxy-phenyl) -pyrazoline, 1,3-diphenyl-5- (4-methoxy-phenyl) -pyrazoline, 1-phenyl-3,5-bis (4-tert-butyl-phenyl) -pyrazoline, 1,5-diphenyl-3- (4-tert-butyl-phenyl) -pyrazoline is preferred.
1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl)- Pyrazoline is preferred.

上記一般式（２）中、Ｒ_１、Ｒ_２及びＲ_３はそれぞれ独立に、炭素数１〜１０の直鎖状若しくは分岐鎖状のアルキル基又は炭素数１〜４の直鎖状若しくは分岐鎖状のアルコキシ基を示す。ｎ４、ｎ５及びｎ６は、ｎ４＋ｎ５＋ｎ６の値が１以上となるように選ばれる０〜５の整数を示す。なお、ｎ４が２以上の場合、複数存在するＲ_１は同一でも異なっていてもよく、ｎ５が２以上の場合、複数存在するＲ_２は同一でも異なっていてもよく、ｎ６が２以上の場合、複数存在するＲ_３は同一でも異なっていてもよい。 As the anthracene compound, anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene are preferable. Among these, 9,10-dibutoxyanthracene is more preferable from the viewpoint of sensitivity. Examples of the triarylamine compound include compounds having a triphenylamine skeleton in the molecule. As the anthracene compound, a compound represented by the following formula (2) is preferable.

In the general formula (2), R ₁ , R ₂ and R ₃ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched chain having 1 to 4 carbon atoms. In the form of an alkoxy group. n4, n5, and n6 represent an integer of 0 to 5 that is selected so that the value of n4 + n5 + n6 is 1 or more. When n4 is 2 or more, a plurality of R ₁ may be the same or different, and when n5 is 2 or more, a plurality of R ₂ may be the same or different, and n6 is 2 or more. A plurality of R ₃ may be the same or different.

In the compound represented by the general formula (2), R ₂ is a linear or branched alkyl group having 1 to 10 carbon atoms and n4 and n6 are 0 from the viewpoint of resolution and adhesion. N5 is preferably 1, R ₂ is a linear or branched alkyl group having 1 to 4 carbon atoms, n4 and n6 are 0, and n5 is more preferably 1. .

  Examples of the oxazole compound include compounds having an oxazole skeleton in the molecule. From the viewpoint of sensitivity, 5-tert-butyl-2- [5- (5-tert-butyl-1,3-benzoxazol-2-yl) thiophen-2-yl] -1,3-benzoxazole, 2- [4- (1,3-Benzoxazol-2-yl) naphthalen-1-yl] -1,3-benzoxazole is preferred.

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

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds, diallyl iodonium compounds, and the like. In particular, tribromomethylphenylsulfone is preferred.

<Other ingredients>
The photosensitive resin composition of the present embodiment may contain only the components (A) to (D) described above, or may contain other components together with these. Examples of other components that can be used here include leuco dyes, base dyes, antioxidants, and stabilizers.

<Leuco dye>
The leuco dye can be blended in the photosensitive resin composition of the present embodiment in order to impart suitable color developability and excellent peeling characteristics to the resist cured film.
Specific examples of the leuco dye include leuco crystal violet (tris [4- (dimethylamino) phenyl] methane), 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, and the like. be able to. Of these, leuco crystal violet is preferred.

  The proportion of the leuco dye used in the photosensitive resin composition of the present embodiment is preferably 0.01% by mass to 2% by mass with respect to the total mass of the solid content of the photosensitive resin composition. It is more preferable that it is 1 mass%-1.5 mass%. By setting the use ratio of the leuco dye within this range, it is possible to realize good color developability and sensitivity.

<Base dye>
Examples of the base dye include basic green 1 [CAS number (hereinafter the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), malachite green oxalate [ 2437-29-8] (for example, Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Co., Ltd.), brilliant green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4] , Methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94-0], Victoria blue B [2580-56-5], basic blue 7 [2390-60 -5] (for example, Aizen Victoria Pur e Blue BOH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2] and the like. Among these, one or more selected from Basic Green 1, Malachite Green Oxalate, and Basic Blue 7 are preferable, and Basic Green 1 is particularly preferable from the viewpoint of hue stability and exposure contrast.

  As for the usage-amount of the base dye in the photosensitive resin composition of this embodiment, 0.001 mass%-3 mass% are preferable with respect to the total mass of solid content of this photosensitive resin composition, More preferably, it is 0.00. It is the range of 01 mass%-2 mass%, More preferably, it is the range of 0.01 mass%-1.2 mass%. By setting the use ratio within this range, good colorability can be obtained.

<Stabilizer>
From the viewpoint of improving the thermal stability or storage stability of the photosensitive resin composition, or both, it is preferable to use a stabilizer. Examples of the stabilizer include at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazole compounds, carboxybenzotriazole compounds, and alkylene oxide compounds having a glycidyl group. These compounds can be used singly or in combination of two or more.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4) -Hydroxyphenyl) propionate], nitrosophenylhydroxyamine aluminum salt (for example, aluminum salt added with 3 mol of nitrosophenylhydroxylamine), diphenylnitrosamine and the like. Among these, an aluminum salt added with 3 moles of triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] or nitrosophenylhydroxylamine is preferable. Moreover, these compounds can be used individually by 1 type or in combination of 2 or more types.

  Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole, 1- (2-di-n- And a 1: 1 mixture of butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole. Among these, a 1: 1 mixture of 1- (2-di-n-butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole is preferable. . Moreover, these compounds can be used individually by 1 type or in combination of 2 or more types.

  Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. These compounds can be used singly or in combination of two or more.

  Examples of the alkylene oxide compound having a glycidyl group include neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), Bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc. . These compounds can be used singly or in combination of two or more.

  In the present embodiment, the total content of the radical polymerization inhibitor, the benzotriazole compound, the carboxybenzotriazole compound, and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably 0.001% by mass to 3%. It is the range of mass%, More preferably, it is the range of 0.05-1.5 mass%. This total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition. On the other hand, it is preferable that it is 3 mass% or less from a viewpoint of maintaining the sensitivity of the photosensitive resin layer.

<Photosensitive resin composition preparation solution>
In this embodiment, the photosensitive resin composition preparation liquid can be prepared by adding a solvent to the above photosensitive resin composition. Suitable solvents used here include ketones such as methyl ethyl ketone (MEK); alcohols such as methanol, ethanol and isopropyl alcohol. It is preferable to prepare a preparation liquid by adding a solvent to the photosensitive resin composition so that the viscosity of the preparation liquid of the photosensitive resin composition is 500 mPa · sec to 4,000 mPa · sec at 25 ° C.

<Photosensitive element>
Another aspect of the present invention is a photosensitive element (photosensitive resin laminate) having a support and a photosensitive resin composition layer formed on the support from the photosensitive resin composition of the present embodiment described above. )I will provide a. The photosensitive element of this embodiment may have a protective layer on the surface of the photosensitive resin composition layer opposite to the support, if necessary.

<Support>
As the support, a transparent substrate that transmits light emitted from the exposure light source is preferable. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used.

  The haze of the support is preferably 0.01% to 5.0%, more preferably 0.01% to 3.5%, still more preferably 0.01% to 2.5%, and 0.01% to 1.0% is still more preferable.

  A thinner support is advantageous in terms of image formation and economy, but it is necessary to maintain strength. Considering both of these, a 10 to 30 μm support can be preferably used.

<Photosensitive resin composition layer>
The photosensitive resin composition layer in the photosensitive element of the present embodiment is a layer made of the photosensitive resin composition of the present embodiment described above. When the photosensitive resin composition used for forming the photosensitive resin composition layer contains a solvent, the solvent is preferably removed in the photosensitive resin composition layer, but the solvent remains. It doesn't matter.
The thickness of the photosensitive resin composition layer in the photosensitive element of this embodiment is preferably 5 to 100 μm, more preferably 5 to 50 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. Therefore, the thickness of the composition layer can be appropriately selected within the above range depending on the application.

<Protective film>
An important characteristic of the protective layer in the photosensitive element of the present embodiment is that the adhesive strength between the photosensitive resin composition layer is sufficiently smaller than the adhesive strength between the support and the photosensitive resin composition layer, and it is easily peeled off. It can be done. As the protective layer, for example, a polyethylene film, a polypropylene film and the like can be preferably used, and for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used.

  10-100 micrometers is preferable and, as for the thickness of a protective layer, 10-50 micrometers is more preferable.

<Method for producing photosensitive element>
The photosensitive element (photosensitive resin laminate) of the present embodiment can be produced by sequentially laminating a support, a photosensitive resin composition layer, and, if necessary, a protective layer. As a method for laminating the support, the photosensitive resin composition layer, and the protective layer, a known method can be employed.

  For example, the photosensitive resin composition of the present embodiment is prepared as the above-described photosensitive resin composition preparation solution, and first coated on a support using a bar coater or a roll coater and dried, and then on the support. A photosensitive resin composition layer made of the photosensitive resin composition is formed. Next, if necessary, a photosensitive element can be produced by laminating a protective layer on the formed photosensitive resin composition layer.

<Manufacturing method of substrate on which resist pattern is formed>
A resist pattern can be formed on a substrate using the photosensitive element as described above. A resist pattern forming method (a method for producing a substrate on which a resist pattern is formed) includes a laminating step of forming a photosensitive resin composition layer on a substrate using the photosensitive element of the present embodiment, the photosensitive resin composition The exposure process which exposes a physical layer, and the image development process which forms a resist pattern by removing the unexposed part of this photosensitive resin composition layer with a developing solution are included in order as described above.

  In the method for forming a resist pattern of the present embodiment, first, in a laminating step, a photosensitive resin composition layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, after the protective layer is peeled off, the photosensitive resin composition layer is heat-pressed and laminated on the substrate surface using a laminator. Examples of the material of the substrate used include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and a flexible base material on which a conductive thin film is laminated. Examples of the conductive thin film include ITO, copper, copper-nickel alloy, and silver; examples of the material constituting the flexible base include polyethylene terephthalate (PET). Said board | substrate may have a through hole for respond | corresponding to a multilayer board | substrate.

  The photosensitive element of this embodiment is suitable for manufacturing a multilayer printed wiring board by a build-up method. In order to form the wiring (conductor pattern) in the build-up method, a kind of plating method called an etching method or a semi-additive (SAP) method is generally applied. Since the SAP method can form a conductor pattern with better rectangularity, the SAP method is preferably used when the conductor pitch becomes fine. In the SAP method, the resist pattern adhesion, sword lift, sword shortness, and the resist pattern peelability after plating are important performances. In addition, since the build-up method is a manufacturing method of a multilayer printed wiring plate in which multiple layers of substrates are laminated, the base material is slightly deformed for each lamination, and it becomes difficult to align the wiring pattern of each layer and the exposure mask. From this point of view, exposure is often performed using direct imaging (also referred to as DI, maskless) exposure that is excellent in alignment accuracy. Direct imaging is an exposure method that uses a solid-state laser, semiconductor laser, or LED to emit light of a single wavelength or several types of wavelengths and scans only the desired pattern area by scanning, unlike batch exposure using a mask. is there. Some models are exposed by scanning using a mercury lamp light source. Because of such an exposure system, a higher sensitivity is required for the photosensitive element in the normal DI exposure than in the batch exposure. The photosensitive resin composition of the present invention is excellent in sensitivity, resolution, and adhesion, and can be particularly suitably used when DI exposure is used in a build-up method.

  The photosensitive element of this embodiment is also suitable for manufacturing a build-up substrate by an etching method. Since the photosensitive resin composition of the present invention is excellent in flexibility, the tent film strength is high. When a multilayer printed wiring board is manufactured by an etching method, a conduction hole called a through hole penetrating all layers is formed in the outermost layer. This hole is protected from the etching solution by a tenting method which is a kind of etching method. The strength of the tent film is an important performance from the viewpoint of protecting through holes. As described above, DI exposure is preferably used in the build-up method because the alignment accuracy is the same even in the tenting and etching methods. Also from this viewpoint, the photosensitive resin composition of the present invention is important.

  The photosensitive element of this embodiment is applicable to the manufacture of a touch panel sensor by an etching method. An etching method is generally used to form the wiring (conductor pattern) in the touch panel sensor. As described above, the touch panel sensor requires finer wiring formation than a normal printed wiring board. Here, when the etching method using the photosensitive element in the prior art is employed, the amount of side etching of the formed conductor pattern is large, so that there is a limit to the product yield of the touch panel sensor manufacturing. However, since the photosensitive element of this embodiment is excellent in reducing the amount of side etching, the touch panel sensor can be manufactured with a high yield.

  Here, the photosensitive resin composition layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces of the substrate as necessary. The heating temperature at this time is preferably 40 ° C to 160 ° C. By performing thermocompression bonding twice or more, the adhesion of the resulting resist pattern to the substrate is further improved. When two or more press bondings are performed, a two-stage laminator equipped with two rolls may be used, or a laminate of the substrate and the photosensitive resin composition layer is repeated several times to form a roll. It may be crimped through.

Next, in the exposure step, the photosensitive resin composition layer is exposed using an exposure machine. This exposure may be performed through the support without peeling off the support, or may be performed after peeling off the support, if necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after a development process described later. The pattern exposure may be performed by either a method of exposing through a photomask or a maskless exposure method.

In the case of exposure through a photomask, the exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter.
In maskless exposure, a photomask is not used and exposure is performed directly on the substrate by a drawing apparatus. As the light source, a solid laser having a wavelength of 350 nm to 410 nm, a semiconductor laser, an ultrahigh pressure mercury lamp, or the like is used. In maskless exposure, the drawing pattern is controlled by a computer, and the exposure amount is determined with the illuminance of the exposure light source and the moving speed of the substrate as major factors.

  Further, the substrate after exposure may be heat-treated. In general, this step is called post exposure bake (PEB) and has an effect of improving adhesion. An example of the heat treatment method is to put the substrate after exposure in an oven. Further, the exposed substrate can be heat-treated in a short time by passing the substrate through a laminator.

Next, in the development step, the unexposed part of the photosensitive resin composition layer is removed with a developer. After exposure, when there is a support on the photosensitive resin composition layer, it is preferably subjected to a development step after removing the support.
In the development step, the unexposed area is developed and removed using a developer comprising an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferably used. The alkaline aqueous solution is selected in accordance with the characteristics of the photosensitive resin composition layer, but it is preferable to use a Na ₂ CO ₃ aqueous solution having a concentration of 0.2% by mass to 2% by mass. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.
The temperature of the developer in the development step is preferably maintained at a constant temperature in the range of 18 ° C to 40 ° C.

  A resist pattern is obtained by the above-described steps. Depending on the case, you may perform the heating process of 100 to 300 degreeC further. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace of an appropriate system such as hot air, infrared rays, far infrared rays or the like can be used.

<Circuit board formation method>
The present invention further discloses a method of forming a circuit board (wiring board). A circuit board is formed by etching or plating the photosensitive element of this embodiment.
That is, a circuit board forming method includes a laminating step of forming a photosensitive resin composition layer on a substrate using the photosensitive element of the present embodiment, an exposure step of exposing the photosensitive resin composition layer, and the photosensitive step. A developing process for forming a resist pattern by removing an unexposed portion of the conductive resin composition layer with a developer, a conductor pattern forming process for etching or plating a substrate on which the resist pattern is formed, and peeling the resist pattern The peeling step is included in the order described above. By the above method, a circuit board (wiring board) in which a desired conductor pattern is formed on the substrate can be obtained.

The laminating step, the exposing step, and the developing step are the same as in the above <resist pattern forming method>. After the resist pattern is formed by the above-described resist pattern forming method, the wiring board having the conductor pattern formed on the substrate can be obtained through the following conductor pattern forming step and peeling step.
In the conductor pattern forming step, a conductor pattern can be formed on the substrate surface (for example, a copper surface) exposed by the developing step on the substrate on which the resist pattern is formed, using a known etching method or plating method.

  The photosensitive resin composition, photosensitive element (photosensitive resin laminate), and conductor pattern forming method in the present embodiment are, for example, a printed wiring board (circuit board), a lead frame, a substrate having a concavo-convex pattern, a semiconductor, and the like. The present invention can be very suitably applied to the manufacture of packages, touch panel sensors, and the like.

  About the evaluation value of various parameters mentioned above, unless otherwise indicated, it is a measured value measured according to the measuring method in the example mentioned below.

Hereinafter, the photosensitive resin composition of the present embodiment will be specifically described by way of examples.
The sample preparation methods and the sample evaluation methods in Examples and Comparative Examples are as follows.

(1) Measurement or calculation of physical properties <Measurement of weight average molecular weight or number average molecular weight of polymer>
The weight average molecular weight or number average molecular weight of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK). KF-807, KF-806M, KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve with Shodex STANDARD SM-105 manufactured by Showa Denko KK) It calculated | required as polystyrene conversion.
Furthermore, the degree of dispersion of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

<Acid equivalent>
In this specification, an acid equivalent means the mass (gram) of the polymer which has a 1 equivalent carboxyl group in a molecule | numerator. Hiranuma Sangyo Co., Ltd. Hiranuma automatic titrator (COM-555) was used, and acid equivalent was measured by potentiometric titration using 0.1 mol / L sodium hydroxide aqueous solution.

(2) Preparation method of evaluation sample The evaluation sample was prepared as follows.
<Preparation of photosensitive resin laminate>
The components shown in Table 1-1 to Table 1-3 described later (however, the numbers of the components indicate the blending amount (parts by mass) as a solid content) and the solvent are sufficiently stirred and mixed to be photosensitive. A resin composition preparation was obtained. In addition, the names of the components represented by abbreviations in Table 1-1 to Table 1-3 are shown in Table 2 below.

Using a 16 μm-thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB-40) as a support, using a bar coater on the surface, uniformly apply this prepared solution and in a dryer at 95 ° C., 2 Dry for 5 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 25 μm.
Next, a 19 μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) is bonded as a protective layer on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film is not laminated. A laminate was obtained.

<Board surface preparation>
Using scrub random R (registered trademark # 220, manufactured by Nippon Carlit Co., Ltd.), a 0.4 mm thick copper clad laminate with 35 μm rolled copper foil is jet scrubbed at a spray pressure of 0.2 MPa. Thus, an evaluation substrate was produced.

<Laminate>
While peeling off the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was applied to a copper-clad laminate that had been leveled and preheated to 60 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). A test piece was obtained by laminating at a roll temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
Mask pattern for stove 41 step tablet or predetermined direct imaging (DI) exposure by direct writing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ± 5 nm) Were exposed under the conditions of an illuminance of 85 mW / cm ² . The exposure was performed with an exposure amount at which the maximum number of remaining film steps when the exposure and development were performed using the stove 41 step tablet as a mask was 14 steps.

<Development>
After peeling the polyethylene terephthalate film of the exposed evaluation substrate, a 1% by weight aqueous solution of Na ₂ CO _{3 at} 30 ° C. is sprayed for a predetermined time using an alkali developing machine (produced by Fuji Kiko Co., Ltd., a dry film developing machine). The unexposed part of the resin layer was dissolved and removed. At this time, development was carried out over twice the minimum development time to produce a cured resist pattern. The minimum development time refers to the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve.
After development, the substrate was washed with water using a flat type nozzle at a water spray pressure of 0.15 MPa for the same time as the development step.

(3) Sample evaluation method <Sensitivity evaluation>
The substrate for sensitivity evaluation, which had passed 15 minutes after lamination, was exposed through a mask of a 41-step stove tablet. Development was carried out in a time twice as long as the minimum development time, and was ranked according to the following criteria according to the exposure amount at which the maximum number of remaining film stages was 14.
○ (good): exposure amount 70 mJ / cm ² or less △ (acceptable): exposure exceeds ^{70mJ / cm 2, 80mJ / cm} 2 or less × (bad): exposure amount exceeds 80 mJ / cm ^2.

<Resolution>
A resolution evaluation substrate that has passed 15 minutes after lamination has a correction of +2.6 μm in the exposed area and -2.6 μm in the unexposed area with respect to the ratio of the width of the exposed area to the unexposed area of 1: 1. The exposure was performed using drawing data having a negative line pattern. Development was performed with a development time twice the minimum development time to form a cured resist line. The line width value when a line having the minimum line width in which the cured resist line was normally formed was drawn was ranked according to the following criteria as a resolution value.
For example, when the resolution value is 10.4 μm, a pattern having a line / space of 13 μm (10.4 + 2.6 μm) /7.8 μm (10.4-2.6 μm) is actually drawn. Become.
○ (Good): Resolution value of 11 μm or less.
Δ (allowable): The resolution value exceeds 11 μm and is 13 μm or less.
X (defect): The resolution value exceeds 13 μm.

<Adhesion>
The adhesion evaluation substrate 15 minutes after lamination was exposed using drawing data having a line pattern in which the width of the exposed area and the unexposed area was 1: 400. Development was performed with a development time twice as long as the minimum development time, and the minimum line width in which a cured resist line was normally formed was ranked as an adhesion value according to the following criteria.
○ (Good): Adhesion value is 11 μm or less.
Δ (allowable): Adhesiveness value exceeds 11 μm and is 13 μm or less.
X (defect): Adhesion value exceeds 13 μm.

<Peelability evaluation>
The peelable evaluation substrate 15 minutes after lamination was exposed with a solid pattern of 5 cm in length and 3 cm in width. Development was performed with a development time twice as long as the minimum development time to obtain an evaluation sample. Separately, a stripping solution was prepared. As the stripping solution, an aqueous solution of R-100S (12 vol%, R-101 (4 vol%)) manufactured by Ryoko Chemical Co., Ltd. was used at 50 ° C.
The evaluation sample was immersed in a stripping solution, and the time until the cured film was peeled from the substrate was recorded and used as the peelability value.
○ (Good): The peelability is 45 seconds or less.
Δ (Acceptable): The peelability value exceeds 45 seconds and is 50 seconds or less.
X (defect): The peelability value exceeds 50 seconds.

<Flexibility evaluation>
Nikka Industry NIKAFLEX F-30VC1 25RC11 (H) was used as a base material and no pretreatment was performed, and lamination was performed according to the method described in “(2) Method for producing sample for evaluation”. The substrate for flexibility evaluation 15 minutes after the lamination was exposed with a solid pattern having a width of 42 mm. Development was performed with a development time twice as long as the minimum time. After the development, the sample was prepared by leaving it to stand for 1 day in an environment of a room temperature of 23 ° C. and a relative humidity of 50%.
The flexibility was evaluated by a mandrel tester according to the cylindrical mandrel method JIS K5600-5-1. After the test, the thickness within 10 mm from the end of the evaluation sample was ignored, and cracking or peeling of the cured film was confirmed visually or with a microscope. The diameter of the mandrel was changed to a smaller one until the cured film cracked or peeled off, and the minimum diameter was measured. Tested four times, the smallest minimum diameter value was ranked as a flexibility value according to the following criteria.
○ (Good): The value of flexibility is 3 mmΦ or less.
Δ (allowable): The value of flexibility exceeds 3 mm and is 4 mm or less.
X (defect): The value of flexibility exceeds 4 mm.

<Evaluation of developer foamability>
A photosensitive resin layer having a thickness of 25 μm per liter and an amount of 0.8 m ² was dissolved in 1% by mass sodium carbonate aqueous solution to 30 ° C. to prepare a developer. 400 mL of this developer was placed in a cylinder container such that the height to the liquid level was 104 mm from the bottom of the container. From the upper part of the cylinder container, the developer was sprayed onto the developer surface at 0.13 MPa for 15 minutes.
Immediately after spraying for 15 minutes, the height from the container bottom to the liquid level was measured, and the height from the container bottom to the liquid level before spraying was subtracted to obtain a foaming value.
○ (good): foaming value of 30 mm or less.
Δ (Acceptable): The foaming value exceeds 30 mm and is 35 mm or less.
X (defect): The foaming value exceeds 35 mm.

<Washing resistance evaluation>
The substrate for water resistance evaluation for 15 minutes after lamination was exposed using drawing data having a pattern of line / space = 100/100 μm over a range of 10 cm in length and 10 cm in width. Development was performed with a development time twice as long as the minimum development time to obtain a water wash resistance evaluation sample.
One water washing resistance evaluation sample was held for 1 minute in 1 L of ion-exchanged water stirred with a mechanical stirrer and taken out. Subsequently, the newly prepared water wash resistance evaluation sample was similarly put into 1 L of ion-exchanged water, held for 1 minute, and taken out. In this way, a total of 100 washing resistance evaluation samples were repeatedly put into 1 L of ion-exchanged water, held for 1 minute, and taken out to obtain a washing resistance evaluation solution A.
The water washing resistance evaluation solution A was filtered and dried with a filter paper, and the weight increment of the filter paper was weighed to determine the value of the water washing resistance.
○ (Good): Washing resistance value is 10 mg or less.
Δ (Acceptable): Washing resistance value exceeds 10 mg and 100 mg or less.
X (defect): The value of water-washing tolerance exceeds 100 mg.

(4) Evaluation Results Table 1-1 (Examples 1-9) and Table 1 show the components used in preparing the photosensitive resin compositions of Examples 1 to 20 and Comparative Examples 1 to 5, respectively. -2 (Examples 10 to 20, Comparative Examples 1 to 5), the evaluation results of these samples are also shown in Table 1-1 and Table 1-2.
Moreover, about Example 1 and Examples 21-23, the component used when preparing the photosensitive resin composition is set to Table 1-3, The evaluation result of those samples is ethylene per 100 g of photosensitive resin compositions. The results are shown in Table 1-3 together with the number of moles of the ionic double bond and the evaluation results on the washing resistance.
In addition, the names of components represented by abbreviations in Table 1-1, Table 1-2, and Table 1-3 are shown in Table 2-1 (components A and B) and Table 2-2 (components C to F).

  As is clear from Tables 1-1 and 1-2, in Comparative Example 3 that does not contain the compound represented by the general formula (1) as the component (B), the peelability and flexibility are poor, and foaming is also observed. It was. Moreover, the flexibility was poor in Comparative Example 1 using the compound (B-3) having a small number of repeating units (n2) of (BO) in the general formula (1) as the component (B). In addition, as Comparative Example 2 using the compound (B-8) having a large number of repeating units (n2) of (BO) in the general formula (1) as the component (B), the adhesion was poor. In addition, in Comparative Example 5 using the compound (B-11) having a large number of repeating units (n1 and n3) of (AO) as the component (B), the resolution and flexibility were poor. And in the comparative example 4 which does not contain a specific compound as (D) component, a sensitivity, resolution, adhesiveness, and a softness | flexibility were bad.

On the other hand, favorable results were obtained in Examples 1 to 20 using the compound represented by the general formula (1) as the component (B) and the specific compound as the component (D). Among them, particularly good results are obtained in Examples 8 and 9 using the compounds (B-9, B-10) in which A is C ₃ H ₆ in the general formula (1).

  Moreover, when copper plating was performed after image development, in the comparative example, the plating defect was seen. Shorts due to lack of resist pattern adhesion and shorts due to lack of resist pattern due to lack of resist pattern flexibility were observed. In the examples, plating defects were not observed, and it was estimated that defects could be reduced.

  Moreover, as shown in Table 1-3, in Examples 22 and 23 in which the number of moles of ethylenic double bonds per 100 g of the photosensitive resin composition was less than 0.1, the water washing resistance was slightly low. In Examples 1 and 21, which were set to 0.1 to 0.3, the washing resistance was good.

  From the above results, by using the photosensitive resin composition of the examples, it has good sensitivity, resolution, adhesion, can shorten the peeling time, and can form a resist pattern with excellent flexibility. Was confirmed.

  Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be appropriately changed without departing from the spirit of the invention.

  By using the photosensitive resin composition according to the present invention, foamability is suppressed, it has good sensitivity, resolution, adhesion, can shorten the peeling time, and can form a resist pattern with excellent flexibility. It can be widely used for forming a wiring pattern by photolithography.

Claims (19)

The following ingredients:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated double bond,
(C) a photopolymerization initiator, and (D) a photosensitive resin composition containing a sensitizer,
As the compound (B) having an ethylenically unsaturated double bond, the following general formula (1):

{In the formula, A represents C ₂ H ₄ or C ₃ H ₆ , and — (A—O) _n1 — and — (A—O) _n3 — represent —C ₂ H ₄ —O— and —C _3. The sequence of the repeating unit of H ₆ —O— may be random or block, and when the sequence is a block, —C ₂ H ₄ —O— and —C ₃ H ₆ —O Any of-may be on the -B-O-group side. B is a divalent alkyl chain having 4 to 8 carbon atoms. n1 is an integer of 0 to 10, n3 is an integer of 0 to 10, n1 + n3 is an integer of 0 to 20, and n2 is an integer of 12 to 42. }, And a compound represented by
The photosensitive resin composition characterized in that the (D) sensitizer contains at least one selected from the group consisting of a pyrazoline compound, an anthracene compound, a triarylamine compound, and an oxazole compound.   The photosensitive resin composition of Claim 1 whose mole number of the ethylenically unsaturated double bond per 100g of solid content in the said photosensitive resin composition is 0.1-0.3.   The photosensitive resin composition of Claim 2 whose mole number of the ethylenically unsaturated double bond per 100g of solid content in the said photosensitive resin composition is 0.11-0.15. The general formula (1), A is a C ₃ H _6, the photosensitive resin composition according to any one of claims 1 to 3.   The photosensitive resin composition as described in any one of Claim 1 to 4 whose n1 + n3 is 1-20 in the said General formula (1).   The photosensitive resin composition as described in any one of Claim 1 to 5 whose n1 + n3 is 1-10 in the said General formula (1).   The photosensitive resin composition as described in any one of Claim 1 to 6 in which the said (D) sensitizer contains a pyrazoline compound.   The photosensitive resin composition as described in any one of Claim 1 to 7 in which the said (D) sensitizer contains an anthracene compound.   The photosensitive resin composition as described in any one of Claim 1 to 8 in which the said (D) sensitizer contains a triarylamine compound. The photosensitive resin composition is
Containing 3 to 30% by mass of the compound represented by the general formula (1) with respect to the total solid content of the photosensitive resin composition;
The photosensitive resin composition as described in any one of Claims 1-9 which contains 0.05-2 mass% of said (D) sensitizers with respect to the total solid of the said photosensitive resin composition.   The photosensitive resin composition according to any one of claims 1 to 10, comprising at least 50% by mass of the alkali-soluble polymer obtained by copolymerizing at least styrene and benzyl methacrylate (A). .   The photosensitive resin composition as described in any one of Claims 1-11 containing 40 mass% or more of the compound which has a bisphenol A frame | skeleton with said (B) ethylenically unsaturated double bond. The photosensitive resin composition is
The photosensitive resin composition as described in any one of Claims 1-12 which contains 3-17 mass% of compounds represented by the said General formula (1) with respect to the total solid of the said photosensitive resin composition. object. The photosensitive resin composition is
The photosensitive resin composition of Claim 13 which contains 3-15 mass% of compounds represented by the said General formula (1) with respect to the total solid of the said photosensitive resin composition. The value of (B) the solid content of the compound having an ethylenically unsaturated double bond relative to the solid content of the (A) alkali-soluble polymer in the photosensitive resin composition is 0.7 or more and 1.4 or less, Item 15. The photosensitive resin composition according to any one of Items 1 to 14. The value of the solid content of the compound (B) having an ethylenically unsaturated double bond relative to the solid content of the (A) alkali-soluble polymer in the photosensitive resin composition is 0.8 or more and 1.3 or less, Item 16. A photosensitive resin composition according to Item 15.   The photosensitive resin laminated body by which the photosensitive resin layer containing the photosensitive resin composition as described in any one of Claims 1-16 is laminated | stacked on the support body. The following steps:
A laminating step of laminating the photosensitive resin laminate according to claim 17 on a substrate,
An exposure step of exposing the photosensitive resin laminate, and a development step of removing unexposed portions,
A method for manufacturing a substrate on which a resist pattern is formed.   A method for manufacturing a circuit board, comprising forming a circuit board by etching or plating the board manufactured by the method according to claim 18.