JP6567952B2 - Photosensitive resin composition, photosensitive resin laminate, and resist pattern forming method - Google Patents

Description

  The present invention relates to a photosensitive resin composition and the like.

  Conventionally, printed wiring boards are generally manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed, and an exposed portion of the photosensitive resin composition is polymerized and cured (in the case of a negative type) or solubilized in a developer (positive type). ) And remove the unexposed part (in the case of negative type) or exposed part (in the case of positive type) with a developer to form a resist pattern on the substrate, and then perform etching or plating to form a conductor pattern After that, the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate.

  In the photolithography method, usually, when the photosensitive resin composition is applied onto a substrate such as a copper clad laminate, a solution of the photosensitive resin composition is applied to the substrate and dried, or the support, the photosensitive A photosensitive resin laminate (hereinafter also referred to as “dry film resist”) in which a layer composed of a photosensitive resin composition (hereinafter also referred to as “photosensitive resin layer”) and, if necessary, a protective layer, are sequentially laminated. Any method of laminating is used. In the production of a printed wiring board, the latter dry film resist is frequently used.

  The dry film resist is an important element for responding to the increase in the density of printed wiring boards and the expansion of demand, and is required to improve various characteristics as compared with the conventional dry film. In order to improve the characteristics of the resist, various photosensitive resin compositions have been proposed (Patent Documents 1 to 3).

International Publication No. 2008/015754 Japanese Patent Laying-Open No. 2015-152854 JP 2012-203165 A

  In patent document 1, it has a thermoplastic polymer and an ethylenically unsaturated bond from a viewpoint of the adhesiveness of a resist pattern and the copper surface of a board | substrate, and the discoloration prevention property of the copper surface after forming a resist pattern on a board | substrate. In addition to photopolymerization initiators such as photopolymerizable monomers, amines, and 2,4,5-triazole dimers, complex compounds such as carboxylic acid compounds (excluding carboxybenzotriazole) and carboxybenzotriazoles A photosensitive resin composition containing a cyclic compound has been studied as an example.

  In recent years, with the simplification of the cooling process after laminating the photosensitive resin layer on the substrate, the substrate is maintained at a high temperature for a long time, and a thermal load is applied to the photosensitive resin composition, which is unexpected. The curing reaction has progressed, and etching residues or plating defects may occur. In this regard, in Patent Document 2, development of the photosensitive resin composition is performed in order to suppress the progress of the curing reaction even after the thermal storage of the photosensitive resin composition and to suppress etching residue or plating failure. The heating time required for the residue to be produced has been studied. Patent Document 2 discloses that the photosensitive resin composition extends the time required for developing residue in addition to an alkali-soluble polymer, an addition polymerizable monomer having an ethylenically unsaturated bond, and a photopolymerization initiator. It is described that a specific benzotriazole compound may be included from the viewpoint of achieving and a specific epoxy compound may be included from the viewpoint of resolution.

  In Patent Document 3, from the viewpoint of hue stability of a dry film resist, an alkali-soluble polymer, an addition polymerizable monomer having an ethylenically unsaturated bond, a photopolymerization initiator such as a triazole dimer, and two glycidyls A photosensitive resin composition containing an alkylene oxide compound having a group has been proposed.

  When the dry film resist is used for plating, the resist pattern is peeled off after the plating step. During the plating process or before the resist pattern peeling process after the plating process, a phenomenon in which copper in the plating solution enters the resist pattern (also referred to as “copper peeling”) may occur. Therefore, the resist pattern is required to have improved plating resistance.

  However, none of Patent Documents 1 to 3 discusses the plating resistance of the resist pattern. Furthermore, the photosensitive resin compositions described in Patent Documents 1 and 3 still have room for improvement from the viewpoint of achieving both high levels of plating resistance and hue stability.

  Therefore, the problem to be solved by the present invention is to provide a photosensitive resin composition having good plating resistance.

｛式中、Ｒ_１〜Ｒ_４は、それぞれ独立に、水素又はアルキル基であり、そしてＲ_５は、下記一般式（ＩＩ）：

（式中、Ｒ_６及びＲ_７は、それぞれ独立に、水素、置換基を有していてもよい直鎖若しくは分岐のアルキル基、又は置換基を有していてもよい直鎖若しくは分岐のヒドロキシルアルキル基から選択されるが、Ｒ_６とＲ_７の一方又は双方が水素ではなく、そしてｎは、１〜４の整数である）で表される基である｝
で表される化合物；及び
（ｅ）エポキシ化合物；
を含む感光性樹脂組成物。
［２］
前記エポキシ化合物は、下記一般式（ＩＩＩ）：

｛式中、Ｘは、酸素原子、又は式−Ｏ−Ｘ_１−Ｏ−（式中、Ｘ_１は、炭素数１〜１００の直鎖若しくは分岐のアルキレン基、炭素数３〜１０の脂環式アルキレン基、及び炭素数５〜２０のアリーレン基から成る群から選ばれる少なくとも１つの炭化水素基を含有する２価の基であり、かつ該炭化水素基は、ハロゲン原子、酸素原子及び窒素原子から成る群から選ばれる少なくとも１つの原子で置換されていてもよい）で表される基であり；Ｒ_８及びＲ_９は、それぞれ独立に、炭素数１〜１００の直鎖若しくは分岐のアルキレン基、炭素数３〜１０の脂環式アルキレン基、及び炭素数５〜２０のアリーレン基から成る群から選ばれる少なくとも１つの炭化水素基を含有する２価の基であり、かつ該炭化水素基は、ハロゲン原子、酸素原子及び窒素原子から成る群から選ばれる少なくとも１つの原子で置換されていてもよく、かつＲ_８及びＲ_９がともに存在する場合には、Ｒ_８及びＲ_９は、同一でも異なっていてもよく、Ｒ_８及びＲ_９が異なる場合には、−（Ｒ_８−Ｏ）−及び−（Ｒ_９−Ｏ）−の繰り返し単位の配列は、ブロックでもランダムでもよく；そしてｌ及びｍは、それぞれ独立に、０〜５０の整数であり、かつｌ＋ｍは１〜５０の整数である｝
で表される化合物を含む、［１］に記載の感光性樹脂組成物。
［３］
前記エポキシ化合物の含有量は、前記感光性樹脂組成物の固形分総量に対して、０．００１質量％以上０．１質量％未満である、［１］又は［２］に記載の感光性樹脂組成物。
［４］
前記２，４，５−トリアリールイミダゾール二量体は、下記一般式（ＩＶ）：

｛式中、Ｙ^１、Ｙ^２及びＹ^３は、それぞれ独立に、水素、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、及びハロゲンから成る群から選ばれる一種の基を表し、かつｐ、ｑ及びｒは、それぞれ独立に、１〜５の整数である｝
で表される化合物を含む、［１］〜［３］のいずれか１項に記載の感光性樹脂組成物。
［５］
前記感光性樹脂組成物は、Ｎ−アリールアミノ酸をさらに含む、［１］〜［４］のいずれか１項に記載の感光性樹脂組成物。
［６］
前記感光性樹脂組成物は、下記一般式（Ｖ）：

｛式中、Ｚは、水素又は炭素数１〜４のアルキル基である｝
で表される化合物をさらに含む、［１］〜［５］のいずれか１項に記載の感光性樹脂組成物。
［７］
［１］〜［６］のいずれか１項に記載の感光性樹脂組成物から成る感光性樹脂層、及び該感光性樹脂層を支持する支持体を含む感光性樹脂積層体。
［８］
［７］に記載の感光性樹脂積層体を基板上に積層する積層工程；
該感光性樹脂積層体に含まれる感光性樹脂層を露光する露光工程；及び
該露光後の感光性樹脂層における未露光部を現像液で除去してレジストパターンを形成する現像工程；
を含むレジストパターンの形成方法。
［９］
前記露光工程が、描画パターンの直接描画により露光を行う工程である、［８］に記載のレジストパターン形成方法。
［１０］
［７］に記載の感光性樹脂積層体を金属板又は金属皮膜絶縁板上に積層する積層工程；
該感光性樹脂積層体に含まれる感光性樹脂層を露光する露光工程；
該露光後の感光性樹脂層における未露光部を現像液で除去してレジストパターンを形成する現像工程；及び
該金属板又は金属皮膜絶縁板表面の該レジストパターンに被覆されていない部分をエッチング又はめっきする導体パターン形成工程；
を含む導体パターンの形成方法。
［１１］
［７］に記載の感光性樹脂積層体を銅張積層板又はフレキシブル基板上に積層する積層工程；
該感光性樹脂積層体に含まれる感光性樹脂層を露光する露光工程；
該露光後の感光性樹脂層における未露光部を現像液で除去してレジストパターンを形成する現像工程；
該銅張積層板又はフレキシブル基板表面の該レジストパターンに被覆されていない部分をエッチング又はめっきする導体パターン形成工程；及び
該レジストパターンを該銅張積層板又はフレキシブル基板から剥離する剥離工程；
を含むプリント配線板の製造方法。
［１２］
［７］に記載の感光性樹脂積層体を金属板上に積層する積層工程；
該感光性樹脂積層体に含まれる感光性樹脂層を露光する露光工程；
該露光後の感光性樹脂層における未露光部を現像液で除去してレジストパターンを形成する現像工程；
該金属板表面の該レジストパターンに被覆されていない部分をエッチングするエッチング工程；及び
該レジストパターンを該金属板から剥離する剥離工程；
を含むリードフレームの製造方法。
［１３］
［７］に記載の感光性樹脂積層体を、大規模集積化回路（ＬＳＩ）が形成されているウェハ上に積層する積層工程；
該感光性樹脂積層体に含まれる感光性樹脂層を露光する露光工程；
該露光後の感光性樹脂層における未露光部を現像液で除去してレジストパターンを形成する現像工程；
該ウェハ表面の該レジストパターンに被覆されていない部分をめっきするめっき工程；及び
該レジストパターンを該ウェハから剥離する剥離工程；
を含む半導体パッケージの製造方法。 As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by the following technical means.
That is, the present invention is as follows:
[1]
(A) an alkali-soluble polymer;
(B) an addition polymerizable monomer having an ethylenically unsaturated bond;
(C) 2,4,5-triarylimidazole dimer;
(D) The following general formula (I):

{Wherein R _{1 to} R ₄ each independently represents hydrogen or an alkyl group, and R ₅ represents the following general formula (II):

(Wherein R ₆ and R ₇ are each independently hydrogen, a linear or branched alkyl group which may have a substituent, or a linear or branched hydroxyl group which may have a substituent) Selected from alkyl groups, but one or both of R ₆ and R ₇ are not hydrogen, and n is an integer of 1 to 4}
And (e) an epoxy compound;
A photosensitive resin composition comprising:
[2]
The epoxy compound has the following general formula (III):

{In the formula, X is an oxygen atom, or a formula -O-X ₁ -O- (wherein X ₁ is a linear or branched alkylene group having 1 to 100 carbon atoms, or an alicyclic group having 3 to 10 carbon atoms. A divalent group containing at least one hydrocarbon group selected from the group consisting of an alkylene group and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group includes a halogen atom, an oxygen atom and a nitrogen atom R ₈ and R ₉ are each independently a linear or branched alkylene group having 1 to 100 carbon atoms, which may be substituted with at least one atom selected from the group consisting of A divalent group containing at least one hydrocarbon group selected from the group consisting of an alicyclic alkylene group having 3 to 10 carbon atoms and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is , Halogen atoms, oxygen atoms and May be substituted with at least one atom selected from the group consisting of nitrogen atom, and when R ₈ and R ₉ are present together, R ₈ and R _9, which may be the same or different, R _{When 8} and R ₉ are different, the sequence of repeating units of — (R ₈ —O) — and — (R ₉ —O) — may be block or random; and l and m are each independently It is an integer of 0-50, and l + m is an integer of 1-50}
The photosensitive resin composition as described in [1] containing the compound represented by these.
[3]
The photosensitive resin according to [1] or [2], wherein the content of the epoxy compound is 0.001% by mass or more and less than 0.1% by mass with respect to the total solid content of the photosensitive resin composition. Composition.
[4]
The 2,4,5-triarylimidazole dimer has the following general formula (IV):

{Wherein Y ¹ , Y ² and Y ³ are each independently a group selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and halogen. And p, q and r are each independently an integer of 1 to 5}
The photosensitive resin composition of any one of [1]-[3] containing the compound represented by these.
[5]
The photosensitive resin composition according to any one of [1] to [4], further including an N-aryl amino acid.
[6]
The photosensitive resin composition has the following general formula (V):

{Wherein Z is hydrogen or an alkyl group having 1 to 4 carbon atoms}
The photosensitive resin composition of any one of [1]-[5] which further contains the compound represented by these.
[7]
The photosensitive resin laminated body containing the photosensitive resin layer which consists of the photosensitive resin composition of any one of [1]-[6], and the support body which supports this photosensitive resin layer.
[8]
A laminating step of laminating the photosensitive resin laminate according to [7] on a substrate;
An exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate; and a development step of forming a resist pattern by removing an unexposed portion of the photosensitive resin layer after the exposure with a developer;
A resist pattern forming method including:
[9]
The resist pattern forming method according to [8], wherein the exposure step is a step of performing exposure by direct drawing of a drawing pattern.
[10]
A laminating step of laminating the photosensitive resin laminate according to [7] on a metal plate or a metal film insulating plate;
An exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate;
A developing step of removing a non-exposed portion of the photosensitive resin layer after the exposure with a developer to form a resist pattern; and etching or etching a portion of the surface of the metal plate or metal film insulating plate that is not covered with the resist pattern Conductor pattern forming step for plating;
A method for forming a conductor pattern including:
[11]
A laminating step of laminating the photosensitive resin laminate according to [7] on a copper-clad laminate or a flexible substrate;
An exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate;
A developing step of forming a resist pattern by removing unexposed portions of the exposed photosensitive resin layer with a developer;
A conductor pattern forming step of etching or plating a portion of the copper-clad laminate or flexible substrate surface not covered with the resist pattern; and a peeling step of peeling the resist pattern from the copper-clad laminate or flexible substrate;
A method of manufacturing a printed wiring board including:
[12]
A laminating step of laminating the photosensitive resin laminate according to [7] on a metal plate;
An exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate;
A developing step of forming a resist pattern by removing unexposed portions of the exposed photosensitive resin layer with a developer;
An etching step of etching a portion of the surface of the metal plate not covered with the resist pattern; and a peeling step of peeling the resist pattern from the metal plate;
A method for manufacturing a lead frame.
[13]
A laminating step of laminating the photosensitive resin laminate according to [7] on a wafer on which a large-scale integrated circuit (LSI) is formed;
An exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate;
A developing step of forming a resist pattern by removing unexposed portions of the exposed photosensitive resin layer with a developer;
A plating step of plating a portion of the wafer surface not covered with the resist pattern; and a peeling step of peeling the resist pattern from the wafer;
A method for manufacturing a semiconductor package comprising:

  According to the present invention, a photosensitive resin composition having good plating resistance is provided.

  Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

｛式中、Ｒ_１〜Ｒ_４は、それぞれ独立に、水素又はアルキル基であり、そしてＲ_５は、下記一般式（ＩＩ）：

（式中、Ｒ_６及びＲ_７は、それぞれ独立に、水素、置換基を有していてもよい直鎖若しくは分岐のアルキル基、又は置換基を有していてもよい直鎖若しくは分岐のヒドロキシルアルキル基から選択されるが、Ｒ_６とＲ_７の一方又は両方が水素ではなく、そしてｎは、１〜４の整数である）で表される基である｝
で表される化合物；及び
（ｅ）エポキシ化合物；
を含む。 <Photosensitive resin composition>
In the embodiment, the photosensitive resin composition has the following components (a) to (e):
(A) an alkali-soluble polymer;
(B) an addition polymerizable monomer having an ethylenically unsaturated bond;
(C) 2,4,5-triarylimidazole dimer;
(D) The following general formula (I):

{Wherein R _{1 to} R ₄ each independently represents hydrogen or an alkyl group, and R ₅ represents the following general formula (II):

(Wherein R ₆ and R ₇ are each independently hydrogen, a linear or branched alkyl group which may have a substituent, or a linear or branched hydroxyl group which may have a substituent) An alkyl group, but one or both of R ₆ and R ₇ are not hydrogen, and n is an integer of 1 to 4.
And (e) an epoxy compound;
including.

  If desired, the photosensitive resin composition may contain a photopolymerization initiator (except for the component (c)), a coloring substance, an additive, and the like. Each component contained in the photosensitive resin composition will be described below.

[(A) Alkali-soluble polymer]
The alkali-soluble polymer is typically a thermoplastic copolymer having a weight average molecular weight of 5,000 to 500,000 containing a carboxyl group-containing monomer as a copolymerization component.

  The weight average molecular weight of the thermoplastic copolymer is preferably 5,000 to 500,000. The weight average molecular weight of the thermoplastic copolymer is preferably 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, while being 500 from the viewpoint of maintaining developability. 1,000 or less is preferable. The lower limit of the weight average molecular weight of the more preferable thermoplastic copolymer is 20,000, and the upper limit is 300,000. The preferred molecular weight distribution is 1.5-7, the more preferred lower limit is 2, and the upper limit is 5.

  The thermoplastic copolymer is preferably obtained by copolymerizing a copolymer component composed of one or more first monomers described later and one or more second monomers described later.

  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, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. Here, (meth) acryl indicates acryl or methacryl. The same applies hereinafter.

  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, vinyl acetate, etc. And (meth) acrylonitrile, styrenic monomers (styrene and polymerizable styrene derivatives), and the like. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable.

  The alkali-soluble polymer is prepared by mixing the above monomers and diluting with a solvent such as acetone, methyl ethyl ketone, methanol, ethanol, normal propyl alcohol, or isopropanol, to a radical polymerization initiator such as benzoyl peroxide, The synthesis is preferably carried out by adding an appropriate amount of azoisobutyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

  As for the alkali-soluble polymer, the copolymerization ratio of the first monomer and the second monomer is preferably 10% by mass to 60% by mass of the first monomer, It is 40 mass%-90 mass%, More preferably, a 1st monomer is 15 mass%-35 mass%, and a 2nd monomer is 65 mass%-85 mass%.

  Specific examples of the alkali-soluble polymer include a polymer containing methyl methacrylate, methacrylic acid and styrene as a copolymer component, a polymer containing methyl methacrylate, methacrylic acid and n-butyl acrylate as a copolymer component, and methacryl Examples thereof include polymers containing benzyl acid, methyl methacrylate and 2-ethylhexyl acrylate as copolymerization components.

  In the embodiment, the content of the alkali-soluble polymer in the photosensitive resin composition (however, based on the total solid content of the photosensitive resin composition. Hereinafter, unless otherwise specified) Is the same in the components.) Is in the range of 20% by mass to 90% by mass, the preferred lower limit is 25% by mass, the preferred upper limit is 75% by mass, the more preferred lower limit is 40% by mass, and the more preferred upper limit is 65% by mass. It is. This content is preferably 20% by mass or more from the viewpoint of maintaining alkali developability, and on the other hand, 90% by mass from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist. The following is preferable.

[(B) Addition polymerizable monomer having an ethylenically unsaturated bond]
The addition polymerizable monomer having an ethylenically unsaturated bond is a compound having addition polymerizability by having at least one ethylenically unsaturated group in the molecule. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.

｛式中、ｍ_１は、２〜４０を満たす数である。｝
で表される付加重合性単量体；
（ｂ_２）下記一般式（ＶＩＩ）：

｛式中、Ｒ_１１及びＲ_１２は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ_２Ｈ_４であり、ＢはＣ_３Ｈ_６であり、ｎ_１、ｎ_２、ｎ_３及びｎ_４は、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＝２〜４０の関係を満たす整数であり、−（Ａ−Ｏ）−及び−（Ｂ−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、ブロックの場合、−（Ａ−Ｏ）−と−（Ｂ−Ｏ）−とのいずれがビスフェニル基側でもよい。｝
で表される付加重合性単量体；及び
（ｂ_３）上記（ｂ_１）及び（ｂ_２）成分以外の付加重合性単量体；
から成る群から選択される少なくとも１つを含む。 The photosensitive resin composition has the following (b ₁ ) to (b ₃ ) as component (b):
(B ₁ ) The following general formula (VI):

{Wherein m ₁ is a number satisfying 2-40. }
An addition polymerizable monomer represented by:
(B ₂ ) The following general formula (VII):

{In the formula, R ₁₁ and R ₁₂ each independently represents a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ is an integer satisfying the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 40, and the arrangement of repeating units of — (A—O) — and — (B—O) — is random. May be a block, and in the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenyl group side. }
(B ₃ ) addition polymerizable monomers other than the components (b ₁ ) and (b ₂ );
At least one selected from the group consisting of:

The photosensitive resin composition contains at least one addition-polymerizable monomer represented by the general formula (VI) as the component (b ₁ ) from the viewpoint of adjusting the size of the peeled piece of the resist pattern. Is preferred.

In the general formula (VI), m ₁ is preferably 2 or more from the viewpoint of the peeling piece size, and preferably 40 or less from the viewpoint of resolution and plating resistance.

Specific examples of the addition polymerizable monomer represented by the general formula (VI) include tetraethylene glycol diacrylate having m ₁ = 4, nonaethylene glycol diacrylate having m ₁ = 9, and polyethylene having m ₁ = 14. Glycol diacrylate is preferred.

It is preferable that the photosensitive resin composition contains at least one kind of addition polymerizable monomer represented by the general formula (VII) as the component (b ₂ ) from the viewpoint of resolution and plating resistance.

In General Formula (VII), B may be —CH ₂ CH ₂ CH ₂ — or —CH (CH ₃ ) CH ₂ —, and n ₁ , n ₂ , n ₃ and n ₄ representing the number of repetitions are independent of each other. In addition, it may be an integer of 0 or more and 20 or less, and preferably satisfies the relationship of n ₁ + n ₂ + n ₃ + n ₄ ≧ 2 from the viewpoint of tenting properties, and satisfies the relationship of n ₁ + n ₂ + n ₃ + n ₄ ≧ 4. It is more preferable to satisfy this, and it is preferable to satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ ≦ 40 from the viewpoint of resolution, and it is more preferable to satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ ≦ 35 or less. .

  Preferable specific examples of the addition polymerizable monomer represented by the general formula (VII) include di (meth) acrylate of polyethylene glycol obtained by adding an average of 1 unit of ethylene oxide to both ends of bisphenol A, and both ends of bisphenol A. Polyethylene glycol di (meth) acrylate with an average of 2 units of ethylene oxide added to both ends of bisphenol A and polyethylene glycol di (meth) acrylate with an average of 5 units of ethylene oxide added to both ends of bisphenol A, respectively. Polyalkylene with an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide added to both ends of polyethylene glycol di (meth) acrylate and bisphenol A with an average of 7 units of ethylene oxide added Glycol di (meth) acrylate, di (meth) acrylate of polyalkylene glycol obtained by adding propylene oxide average 2 units and ethylene oxide The average 15 units at both ends of bisphenol A and the like.

Examples of the component (b ₃ ) that is a monomer other than the components (b ₁ ) and (b ₂ ) include known compounds having at least one terminal ethylenically unsaturated group.

Specific examples of the component (b ₃ ) include, for example, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, phthalic anhydride and 2-hydroxypropyl acrylate Reaction product of half ester compound and propylene oxide, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyoxyethylene polyoxy Polyoxyalkylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, penta Rithritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxy Phenyl) propane, glycerol triacrylate, triacrylate obtained by acrylated trimethylolpropane, triacrylate obtained by adding an average of 3 units of ethylene oxide to trimethylolpropane, and glycol obtained by adding an average of 4 units of ethylene oxide to pentaerythritol. Tetraacrylate, polyfunctional group (meth) acrylate containing urethane group (eg hexamethylene diisocyanate and pentapropylene glycol mono Examples thereof include urethane compounds with methacrylate, more specifically, urethane compounds of hexamethylene diisocyanate and pentapropylene glycol monomethacrylate, polyfunctional (meth) acrylates of isocyanuric acid ester compounds, and the like. These may be used alone or in combination of two or more.

  The content of the addition polymerizable monomer (b) having an ethylenically unsaturated bond in the photosensitive resin composition is preferably in the range of 5% by mass to 75% by mass. This content is preferably 5% by mass or more from the viewpoint of suppressing curing failure and development time delay, while being 75% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist. It is preferable. The lower limit of the more preferable content is 15% by mass, and the upper limit is 60% by mass. Furthermore, the minimum with preferable content is 30 mass%, and an upper limit is 50 mass%.

[(C) 2,4,5-triarylimidazole dimer]
The photosensitive resin composition preferably contains a 2,4,5-triarylimidazole dimer as a photopolymerization initiator from the viewpoint of achieving both plating resistance and hue stability. The photopolymerization initiator is a compound that polymerizes a monomer by light.

｛式中、Ｙ^１、Ｙ^２及びＹ^３は、それぞれ独立に、水素、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、及びハロゲンから成る群から選ばれる一種の基を表し、かつｐ、ｑ及びｒは、それぞれ独立に、１〜５の整数である｝
で表される化合物であることが好ましい。 The 2,4,5-triarylimidazole dimer has the following general formula (IV):

{Wherein Y ¹ , Y ² and Y ³ are each independently a group selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and halogen. And p, q and r are each independently an integer of 1 to 5}
It is preferable that it is a compound represented by these.

  In the compound represented by the general formula (IV), the covalent bond connecting two lophine groups is 1,1'-, 1,2'-, 1,4'-, 2,2'-, 2 , 4′- or 4,4′-position, but compounds with 1,2′-position are preferred. Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis- ( m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc., and in particular, 2- (o-chlorophenyl) -4,5-diphenylimidazole. Dimers are preferred.

  The content of 2,4,5-triarylimidazole dimer in the photosensitive resin composition is preferably 0.1% by mass to 20% by mass. This content is 0.1% by mass or more from the viewpoint of resolution, adhesion, and plating resistance, and is 20% by mass or less from the viewpoint of hue stability and development aggregation. A more preferable range of this content is 0.5% by mass to 15% by mass, and a further preferable range is 1% by mass to 10% by mass.

[Photopolymerization initiator (excluding 2,4,5-triarylimidazole dimer)]
The photosensitive resin composition preferably contains a photopolymerization initiator other than 2,4,5-triarylimidazole dimer in order to improve the sensitivity during the exposure process.

  As photopolymerization initiators (excluding 2,4,5-triarylimidazole dimers), acridine compounds, pyrazoline compounds, N-aryl amino acids, quinones, aromatic ketones, benzoin ethers, etc. should be used. Can do.

  Examples of the acridine compound include acridine, 9-phenylacridine, 9- (4-tolyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-hydroxyphenyl) acridine, 9-ethylacridine, 9- Chloroethyl acridine, 9-methoxyacridine, 9-ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4 -N-butylphenyl) acridine, 9- (4-tert-butylphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine 9- (4-chlorophenyl) acridine, 9- (4-butyl) Mophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- ( 3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) ) Acridine and the like.

  Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline and the like.

  Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like.

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

  Examples of aromatic ketones include benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, and the like. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of improving the sensitivity of the photosensitive resin composition when used in combination with 2,4,5-triarylimidazole dimer.

  Examples of benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.

  Examples of oxime esters include 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, and the like. .

  Examples of combinations of thioxanthones and alkylaminobenzoic acid include, for example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and isopropylthioxanthone and ethyl dimethylaminobenzoate. The combination of is mentioned.

  Among the photopolymerization initiators listed above, N-aryl amino acids are preferred from the viewpoint of improving the sensitivity of the photosensitive resin composition when used in combination with 2,4,5-triarylimidazole dimer. N-phenylglycine is more preferable.

  The content of the photopolymerization initiator (excluding 2,4,5-triarylimidazole dimer) in the photosensitive resin composition is preferably 0.01% by mass to 20% by mass. This content is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity at the time of photopolymerization by exposure, and sufficient light is transmitted to the bottom surface of the photosensitive resin composition (that is, a portion far from the light source) at the time of photopolymerization. From the viewpoint of transmitting and obtaining good resolution and adhesion, it is 20% by mass or less. About this content, a more preferable minimum is 0.05 mass%, Furthermore, a preferable minimum is 0.1 mass%, A more preferable upper limit is 15 mass%, Furthermore, a preferable upper limit is 10 mass%.

｛式中、Ｒ_１〜Ｒ_４は、それぞれ独立に、水素又はアルキル基であり、そしてＲ_５は、下記一般式（ＩＩ）：

（式中、Ｒ_６及びＲ_７は、それぞれ独立に、水素、置換基を有していてもよい直鎖若しくは分岐のアルキル基、又は置換基を有していてもよい直鎖若しくは分岐のヒドロキシルアルキル基から選択されるが、Ｒ_６とＲ_７の一方又は両方が水素ではなく、そしてｎは、１〜４の整数である）で表される基である｝
で表される化合物を含むことが好ましい。 [(D) Compound represented by general formula (I)]
The photosensitive resin composition has the following general formula (I) from the viewpoint of achieving both plating resistance and hue stability:

{Wherein R _{1 to} R ₄ each independently represents hydrogen or an alkyl group, and R ₅ represents the following general formula (II):

(Wherein R ₆ and R ₇ are each independently hydrogen, a linear or branched alkyl group which may have a substituent, or a linear or branched hydroxyl group which may have a substituent) An alkyl group, but one or both of R ₆ and R ₇ are not hydrogen, and n is an integer of 1 to 4.
It is preferable that the compound represented by these is included.

  Here, although details are unknown about the mechanism in which the photosensitive resin composition containing said (c) component, (d) component, and (e) component expresses favorable plating resistance, it is considered as follows. Regarding the decrease in plating resistance, when the copper ion contained in the plating solution is coordinated to the carboxyl group contained in the component (a) and pseudo-crosslinking occurs, the cured resist pattern shrinks as a whole. The cause is considered to be easy to peel off from the substrate. Here, due to the coexistence with the component (d), the dispersibility in the composition is improved and the component (c) is efficiently advanced in the polymerization reaction of the component (b), so that the crosslinked structure becomes dense, Migration of copper ions to the cured resist pattern can be reduced. Further, in the coexistence environment of the component (d) and the component (e), the unpaired electron on the nitrogen atom in the component (d) or the unpaired electron on the oxygen atom in the component (e) interacts with the copper ion. It is presumed that the action suppresses the deterioration of the plating resistance.

The compound represented by the general formula (I) includes a group having a tertiary or secondary amino group as the group R ₅ although the hydrogen on the aromatic ring is not substituted with a polar group. The groups R ₆ and R ₇ in the general formula (II) are each independently more preferably a linear or branched alkyl group having 1 to 30 carbon atoms which may have a substituent. More preferably, it is a branched alkyl group having 1 to 30 carbon atoms which may have a substituent, and the substituent may be, for example, an aromatic group or an alicyclic group, but does not have a carboxyl group. Is preferred. Specifically, the groups R ₆ and R ₇ are each independently propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl. Group, isopentyl group, hexyl group, heptyl group, 1-ethylpentyl group, octyl group, 2-ethylhexyl group, tert-octyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tridecyl group , An isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an octadecyl group, an isooctadecyl group, a 2-heptylundecyl group, an icosyl group, a henicosyl group, and the like.

Examples of the group R ₅ in the general formula (I) include N, N-bis (2-ethylhexyl) aminomethyl group, 1-N-dibutylaminomethyl group and the like. Of these, N, N-bis (2-ethylhexyl) aminomethyl group is preferable.

  Examples of the compound represented by the general formula (I) include 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl]. Examples thereof include methylbenzotriazole, N (N, N-di-2-hydroxyethyl) aminomethylenebenzotriazole, 1-N-dipropylaminomethylbenzotriazole, 1-N-dibutylaminomethylbenzotriazole and the like. Among these, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole is preferable from the viewpoint of achieving both plating resistance and hue stability.

  Content of the compound represented with general formula (I) in the photosensitive resin composition is the range of 0.05 mass%-10 mass%, and is the range of 0.10 mass%-8 mass%. Is preferable, and it is more preferable that it is in the range of 0.15 mass% to 7 mass%. This content is 0.05% by mass or more from the viewpoint of lamination and hold time stability after exposure, and is 10% by mass or less from the viewpoint of resolution.

[(E) Epoxy compound]
It is preferable that the photosensitive resin composition contains an epoxy compound from the viewpoint of achieving both plating resistance and hue stability. The epoxy compound is a compound having an epoxy group. In the present embodiment, the acid scavenging action of the epoxy compound effectively prevents coloration during storage of the dry film resist and provides good storage stability of the hue and good resolution. .

  As an epoxy compound, an alkylene oxide compound etc. are mentioned, for example. The alkylene oxide compound preferably contains at least two glycidyl groups in the molecule.

｛式中、Ｘは、酸素原子、又は式−Ｏ−Ｘ_１−Ｏ−（式中、Ｘ_１は、炭素数１〜１００の直鎖若しくは分岐のアルキレン基、炭素数３〜１０の脂環式アルキレン基、及び炭素数５〜２０のアリーレン基から成る群から選ばれる少なくとも１つの炭化水素基を含有する２価の基であり、かつ該炭化水素基は、ハロゲン原子、酸素原子及び窒素原子から成る群から選ばれる少なくとも１つの原子で置換されていてもよい）で表される基であり；Ｒ_８及びＲ_９は、それぞれ独立に、炭素数１〜１００の直鎖若しくは分岐のアルキレン基、炭素数３〜１０の脂環式アルキレン基、及び炭素数５〜２０のアリーレン基から成る群から選ばれる少なくとも１つの炭化水素基を含有する２価の基であり、かつ該炭化水素基は、ハロゲン原子、酸素原子及び窒素原子から成る群から選ばれる少なくとも１つの原子で置換されていてもよく、かつＲ_８及びＲ_９がともに存在する場合には、Ｒ_８及びＲ_９は、同一でも異なっていてもよく、Ｒ_８及びＲ_９が異なる場合には、−（Ｒ_８−Ｏ）−及び−（Ｒ_９−Ｏ）−の繰り返し単位の配列は、ブロックでもランダムでもよく；そしてｌ及びｍは、それぞれ独立に、０〜５０の整数であり、かつｌ＋ｍは１〜５０の整数である｝
で表される化合物が挙げられる。 Examples of the alkylene oxide compound include the following general formula (III):

{In the formula, X is an oxygen atom, or a formula -O-X ₁ -O- (wherein X ₁ is a linear or branched alkylene group having 1 to 100 carbon atoms, or an alicyclic group having 3 to 10 carbon atoms. A divalent group containing at least one hydrocarbon group selected from the group consisting of an alkylene group and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group includes a halogen atom, an oxygen atom and a nitrogen atom R ₈ and R ₉ are each independently a linear or branched alkylene group having 1 to 100 carbon atoms, which may be substituted with at least one atom selected from the group consisting of A divalent group containing at least one hydrocarbon group selected from the group consisting of an alicyclic alkylene group having 3 to 10 carbon atoms and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is , Halogen atoms, oxygen atoms and May be substituted with at least one atom selected from the group consisting of nitrogen atom, and when R ₈ and R ₉ are present together, R ₈ and R _9, which may be the same or different, R _{When 8} and R ₉ are different, the sequence of repeating units of — (R ₈ —O) — and — (R ₉ —O) — may be block or random; and l and m are each independently It is an integer of 0-50, and l + m is an integer of 1-50}
The compound represented by these is mentioned.

  X in the general formula (III) is an oxygen atom, a divalent group obtained by removing hydrogen from the hydroxyl group of bisphenol A (hereinafter also referred to as bisphenol A type group), and the hydroxyl group of hydrogenated bisphenol A from the viewpoint of resolution. A divalent group obtained by removing hydrogen from hydrogen (hereinafter also referred to as hydrogenated bisphenol A type group) is preferred, and a bisphenol A type group and hydrogenated bisphenol A type group are more preferred.

  As preferable examples of the alkylene oxide compound, when X in the general formula (III) is an oxygen atom, ethylene glycol diglycidyl ether (for example, Epolite 40E manufactured by Kyoeisha Chemical Co., Ltd.), diethylene glycol diglycidyl ether (for example, Kyoeisha Chemical ( Epolite 100E), triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether (for example, Epolite 200E manufactured by Kyoeisha Chemical Co., Ltd.), pentaethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, heptaethylene glycol di Glycidyl ether, octaethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether (for example, Epolite 400 manufactured by Kyoeisha Chemical Co., Ltd.) ), Decaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (for example, Epolite 70P manufactured by Kyoeisha Chemical Co., Ltd.), dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether (for example, Epolite 200P manufactured by Kyoeisha Chemical Co., Ltd.) , Tetrapropylene glycol diglycidyl ether, pentapropylene glycol diglycidyl ether, hexapropylene glycol diglycidyl ether, heptapropylene glycol diglycidyl ether (for example, Epolite 400P manufactured by Kyoeisha Chemical Co., Ltd.), octapropylene glycol diglycidyl ether, nonapropylene glycol Diglycidyl ether, decapropylene glycol diglycidyl ether, tetramethylene glycol Cole diglycidyl ether, ditetramethylene glycol diglycidyl ether, tritetramethylene glycol diglycidyl ether, tetratetramethylene glycol diglycidyl ether, pentatetramethylene glycol diglycidyl ether, hexatetramethylene glycol diglycidyl ether, heptatetramethylene glycol di Glycidyl ether, octatetramethylene glycol diglycidyl ether, nonatetramethylene glycol diglycidyl ether, diglycidyl ether containing 1 mol and 2 mol of ethylene glycol and propylene glycol, respectively, 1 mol of ethylene glycol and propylene glycol, respectively Diglycidyl ether, ethylene glycol and propylene containing 3 moles each Diglycidyl ether containing 1 mol and 4 mol of lenglycol, diglycidyl ether containing 1 mol and 5 mol of ethylene glycol and propylene glycol, respectively, 1 mol and 9 mol of ethylene glycol and propylene glycol, respectively Diglycidyl ether containing 2 mol and 1 mol each of ethylene glycol and propylene glycol, diglycidyl ether containing 2 mol and 2 mol of ethylene glycol and propylene glycol respectively, and ethylene glycol Diglycidyl ether containing 2 mol and 3 mol of propylene glycol, and 2 mol and 4 mol of ethylene glycol and propylene glycol, respectively. Glycidyl ether, diglycidyl ether containing 2 mol and 5 mol of ethylene glycol and propylene glycol, diglycidyl ether containing 2 mol and 8 mol of ethylene glycol and propylene glycol, respectively, ethylene glycol and propylene glycol Diglycidyl ether containing 3 mol and 1 mol respectively, Diglycidyl ether containing 3 mol and 2 mol of ethylene glycol and propylene glycol, respectively, Diglycidyl ether containing 3 mol and 3 mol of ethylene glycol and propylene glycol respectively. Diglycidyl ether, ethylene glycol and propylene glycol each containing 3 mol and 4 mol of glycidyl ether, ethylene glycol and propylene glycol, respectively Diglycidyl ether containing 3 moles and 5 moles, respectively, Diglycidyl ether containing 3 moles and 7 moles each of ethylene glycol and propylene glycol, 5 moles and 1 mole respectively of ethylene glycol and propylene glycol Diglycidyl ether containing, diglycidyl ether containing 5 mol and 2 mol of ethylene glycol and propylene glycol, respectively, diglycidyl ether containing 5 mol and 3 mol of ethylene glycol and propylene glycol, respectively, ethylene glycol and propylene Diglycidyl ether containing 5 mol and 4 mol of glycol, respectively, Diglycidyl containing 5 mol and 5 mol of ethylene glycol and propylene glycol, respectively Diglycidyl ether containing 6 mol and 1 mol of ethylene glycol and propylene glycol, respectively, diglycidyl ether containing 6 mol and 2 mol of ethylene glycol and propylene glycol, respectively, ethylene glycol and propylene glycol Diglycidyl ether containing 6 mol and 3 mol respectively, Diglycidyl ether containing 6 mol and 4 mol of ethylene glycol and propylene glycol respectively, Diglycidyl ether containing 7 mol and 1 mol of ethylene glycol and propylene glycol respectively. Diglycidyl ether, ethylene glycol and propylene glycol containing 7 mol and 2 mol of glycidyl ether, ethylene glycol and propylene glycol, respectively Diglycidyl ether containing 7 mol and 3 mol of each, diglycidyl ether containing 8 mol and 1 mol of ethylene glycol and propylene glycol, respectively, and 8 mol and 2 mol of ethylene glycol and propylene glycol, respectively. Diglycidyl ether, diglycidyl ether containing 9 mol and 1 mol of ethylene glycol and propylene glycol, neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl Examples thereof include ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.), and the like. Of these, hydrogenated bisphenol A diglycidyl ether is preferred.

  When X in the general formula (III) is a bisphenol A type group, preferred examples of the alkylene oxide compound include diglycidyl ether of bisphenol A-propylene oxide 2 mol adduct (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.). ), Bisphenol A-propylene oxide 4 mol adduct diglycidyl ether, bisphenol A-propylene oxide 6 mol adduct diglycidyl ether, bisphenol A-propylene oxide 8 mol adduct diglycidyl ether, bisphenol A-propylene oxide 10 mol adduct Diglycidyl ether, bisphenol A-ethylene oxide 2 mol adduct diglycidyl ether, bisphenol A-ethylene oxide 4 mol adduct diglycidyl ether, bisphenol A Examples include tylene oxide 6 mol adduct diglycidyl ether, bisphenol A-ethylene oxide 8 mol adduct diglycidyl ether, and bisphenol A-ethylene oxide 10 mol adduct diglycidyl ether. Among these, bisphenol A-propylene oxide 2-mol adduct diglycidyl ether is preferable.

  When X in the general formula (III) is a hydrogenated bisphenol A type group, preferred examples of the alkylene oxide compound include hydrogenated bisphenol A-ethylene oxide 2 mol adduct diglycidyl ether, hydrogenated bisphenol A-ethylene oxide. 4 mol adduct diglycidyl ether, hydrogenated bisphenol A-ethylene oxide 6 mol adduct diglycidyl ether, hydrogenated bisphenol A-ethylene oxide 8 mol adduct diglycidyl ether, hydrogenated bisphenol A-ethylene oxide 10 mol adduct diglycidyl ether, Hydrogenated bisphenol A-propylene oxide 2 mol adduct diglycidyl ether, hydrogenated bisphenol A-propylene oxide 4 mol adduct diglycidyl ether, hydrogenated bisphenol A-propylene oxide 6 mol Adduct diglycidyl ether, hydrogenated bisphenol A-propylene oxide 8 mol adduct diglycidyl ether, hydrogenated bisphenol A-propylene oxide 10 mol adduct diglycidyl ether, and the like.

  The epoxy compound demonstrated above can be used individually or in combination of multiple types.

  The content of the epoxy compound in the photosensitive resin composition is preferably 0.001% by mass or more and 0.2% by mass or less from the viewpoint of maintaining an optimal balance between plating resistance and hue stability. The content is more preferably 0.001% by mass or more and 0.15% by mass or less, and particularly preferably 0.001% by mass or more and less than 0.1% by mass.

[Coloring substances]
From the viewpoint of sensitivity, the photosensitive resin composition preferably contains a coloring substance such as a dye or a pigment. As the dye, a basic dye is preferable.

｛式中、Ｚは、水素又は炭素数１〜４のアルキル基である｝
で表される化合物をさらに含むことが好ましい。 From the viewpoint of sensitivity, the photosensitive resin composition is represented by the following general formula (V) as a basic dye:

{Wherein Z is hydrogen or an alkyl group having 1 to 4 carbon atoms}
It is preferable that the compound further represented by these is included.

  Specific examples of the compound represented by the general formula (V) include Basic Blue 7 [CAS number: 2390-60-5] in which Z is an ethyl group.

  Examples of the coloring substance used in addition to the compound represented by the general formula (V) include, for example, Basic Green 1 [CAS number (hereinafter the same): 633-03-4], Malachite Green Oxalate [2437- 29-8], 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], rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [ 2465-27-2] and the like.

  It is preferable that content of the coloring substance in the photosensitive resin composition is 0.001 mass%-1 mass%. When the addition amount of the coloring substance is 0.001% by mass or more, there is an effect of improving the handleability, and when it is 1% by mass or less, there is an effect of maintaining the storage stability.

  Moreover, you may contain the color former in the photosensitive resin composition so that a visible image can be given by exposure. Examples of such a coloring dye include a leuco dye or a combination of a fluorane dye and a halogen compound.

  For example, as leuco dyes, tris (4-dimethylamino-2-methylphenyl) methane [leucocrystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and fluorane dye Is mentioned. Among these, when leuco crystal violet is used, the contrast is good and preferable.

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal 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, hexachloroethane, chlorinated triazine compounds and the like. .

  When the photosensitive resin composition contains these dyes, the content of the dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass, respectively.

[Additive]
The photosensitive resin composition contains various additives in addition to the components (a) to (e), the photopolymerization initiator (excluding 2,4,5-triarylimidazole dimer), and the coloring substance. be able to.

  In order to improve the thermal stability and storage stability of the photosensitive resin composition, it is preferable to contain a radical polymerization inhibitor or benzotriazoles (excluding component (d)) in the photosensitive resin composition.

  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), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.

  Examples of benzotriazoles (excluding component (d)) include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, 4-carboxy-1,2,3-benzotriazole 5-carboxy-1,2,3-benzotriazole, (N, N-dibutylamino) carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like.

  The total addition amount of the radical polymerization inhibitor and the benzotriazole (excluding the component (d)) is preferably 0.001% by mass to 3% by mass based on the total solid content of the photosensitive resin composition, and more A preferable lower limit is 0.05% by mass, and a more preferable upper limit is 1% by mass. The total addition amount is preferably 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

  You may make the photosensitive resin composition contain another plasticizer as needed. Examples of the plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monomethyl ether, Glycol esters such as oxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate, phthalic acid esters such as diethyl phthalate, o -Toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate Ethylene acetyl citrate, tri-n-propyl citrate citrate, tri-n-butyl acetyl citrate, propylene glycol with propylene oxide added to both sides of bisphenol A, ethylene with ethylene oxide added to both sides of bisphenol A Examples thereof include glycol, polyoxyethylene glyceryl ether and polyoxypropylene glyceryl ether. Among these, from the viewpoint of suppressing a delay in peeling time, p-toluenesulfonic acid amide and bisphenol A are preferably made of polypropylene glycol having an average of 3 units of propylene oxide added to both ends thereof, and polyoxypropylene glyceryl ether having a weight average molecular weight of 3000. .

  The content of the plasticizer in the photosensitive resin composition is preferably 0.1% by mass to 50% by mass, a more preferable lower limit is 1% by mass, and a more preferable upper limit is 30% by mass. This content is preferably 0.1% by mass or more from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, while being 50% from the viewpoint of suppressing insufficient curing and cold flow. % Or less is preferable.

  You may make the photosensitive resin composition contain other antioxidant as needed. Examples of antioxidants include triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, and bis (monononylphenyl) -dinonylphenyl phosphite. For example, fights.

  The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.8% by mass, and the more preferable lower limit is 0.01% by mass, and the preferable upper limit is 0.3%. % By mass. When this content is 0.01 mass% or more, the effect which is excellent in the hue stability of the photosensitive resin composition expresses favorably, and the sensitivity at the time of exposure of the photosensitive resin composition becomes favorable. On the other hand, when the content is 0.8% by mass or less, since color developability is suppressed, hue stability is improved and adhesion is also improved.

<Photosensitive resin composition preparation solution>
You may use the photosensitive resin composition mentioned above as the photosensitive resin composition formulation liquid formed by adding a solvent to this. Suitable solvents include ketones represented by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
In embodiment, the photosensitive resin laminated body contains the photosensitive resin layer which consists of the photosensitive resin composition mentioned above, and the support body which supports this photosensitive resin layer. If necessary, a protective layer may be provided on the surface of the photosensitive resin layer opposite to the support-forming side.

  The support is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film. , Polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. As these films, those stretched as necessary can be used.

  The haze of the support is preferably from 0.01% to 5.0%, more preferably from 0.01% to 2.5%, still more preferably from 0.01% to 1.0%. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 μm is preferably used in order to maintain the strength.

  Further, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and can be easily peeled with respect to the adhesion with the photosensitive resin layer. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Further, for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

  The thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. As the photosensitive resin layer is thinner, the resolution is improved, and as the photosensitive resin layer is thicker, the film strength is improved. Therefore, the thickness can be appropriately selected according to the application.

  As a method for producing a photosensitive resin laminate by laminating a support, a photosensitive resin layer, and if necessary, a protective layer, a conventionally known method can be employed.

  For example, the photosensitive resin composition used for forming the photosensitive resin layer is made into the above-mentioned photosensitive resin composition preparation solution, and is first coated on a support using a bar coater or a roll coater and dried. Then, a photosensitive resin layer made of the photosensitive resin composition is laminated on the support. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
In the embodiment, the resist pattern forming method includes, for example, a lamination step of forming a photosensitive resin layer on a substrate using the above-described photosensitive resin laminate, an exposure step of exposing the photosensitive resin layer, and the A development step for forming a resist pattern by removing unexposed portions of the exposed photosensitive resin layer with a developer is sequentially included.

  More specifically, for example, in the lamination step, a photosensitive resin layer is first formed on the substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. In this case, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature at the time of lamination is generally 40 ° C to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the resist pattern obtained by performing this thermocompression bonding twice or more improves. At this time, a two-stage laminator provided with two rolls may be used for pressure bonding, or a laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the roll and pressure bonded.

  Next, in the exposure step, the photosensitive resin composition is exposed to active light using an exposure machine. If necessary, the exposure can be performed after peeling off the support. In the case of exposure through a photomask, the exposure amount is determined by the light source illuminance and the exposure time, and may be measured using a light meter.

  In the exposure step, a maskless exposure method may be used. In maskless exposure, exposure is performed directly on the substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the development step, unexposed portions in the exposed photosensitive resin layer are removed with a developer using a developing device. After exposure, if a support is present on the photosensitive resin layer, this is excluded. Subsequently, the unexposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is preferable. These are selected in accordance with the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution having a concentration of 0.2% by mass to 2% by mass is common. 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. In addition, it is preferable to maintain the temperature of the developing solution in a development process at a constant temperature in the range of 20 ° C to 40 ° C.

  Although a resist pattern is obtained by the above-mentioned process, depending on the case, the heating process of 100 to 300 degreeC can also be performed further. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace such as hot air, infrared rays, or far infrared rays can be used.

  By applying such a resist pattern forming method, a conductor pattern, a printed wiring board, a lead frame, a substrate having an uneven pattern, a semiconductor package, and the like can be manufactured.

<Method for forming conductor pattern>
As a method for forming a conductor pattern, for example, a lamination step of forming a photosensitive resin layer on a substrate that is a metal plate or a metal film insulating plate using the above-described photosensitive resin laminate, An exposure step for exposing, a developing step for forming a resist pattern by removing a non-exposed portion of the exposed photosensitive resin layer with a developer, and an etching or plating for etching or plating a substrate on which the resist pattern is formed A method comprising steps in order is preferred.

<Method for manufacturing printed wiring board>
As a method for producing a printed wiring board, for example, after producing the above-described conductor pattern, a printed wiring board having a desired wiring pattern is obtained by peeling the resist pattern from the substrate with an aqueous solution having alkalinity stronger than the developer. Can be obtained. In the production of a printed wiring board, it is preferable to use a copper-clad laminate or a flexible substrate as the substrate. The alkali aqueous solution for peeling (hereinafter also referred to as “peeling liquid”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass is generally used. A small amount of a water-soluble solvent can be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably in the range of 40 ° C to 70 ° C.

<Lead frame manufacturing method>
As a lead frame manufacturing method, for example, using a metal plate such as copper, copper alloy, or iron-based alloy as a substrate, a resist pattern is formed by the above-described resist pattern forming method, and the exposed substrate is further etched by development. A method including an etching step is preferable. It is preferable that after the etching step, a desired lead frame is obtained by performing a peeling step in which the resist pattern is peeled by the same method as the above-described printed wiring board manufacturing method.

<Manufacturing method of substrate having concave / convex pattern>
The resist pattern formed by the resist pattern forming method can be used as a protective mask member when processing a substrate by a sandblasting method. In this case, examples of the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal material.

As a method for producing a base material having a concavo-convex pattern, for example, a resist pattern is formed on these substrates by the same method as the above-described resist pattern forming method. Thereafter, a blasting material is sprayed from the formed resist pattern, a sand blasting process for cutting to a desired depth, and a peeling process for removing the resist pattern portion remaining on the substrate from the substrate with an alkaline stripping solution, The method of manufacturing the base material which has a fine uneven | corrugated pattern on a board | substrate is mentioned. A known material can be used as the blasting material used in the above-described sandblasting process, and for example, fine particles such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, and stainless steel are used. The particle diameter of the fine particles is preferably about 2 μm to about 100 μm.

<Semiconductor package manufacturing method>
As a method for manufacturing a semiconductor package, for example, a wafer on which a large-scale integrated circuit (LSI) is formed is used as a substrate, and a resist pattern is formed on the wafer by the above-described resist pattern forming method. Through the process, a semiconductor package can be manufactured. First, a plating process for forming a conductor pattern by performing columnar plating of copper, solder, or the like on the opening exposed by development is performed. Thereafter, a peeling process for peeling the resist pattern by the same method as the above-described method for manufacturing a printed wiring board is performed, and further, a thin metal layer other than the columnar plating is removed by etching. A semiconductor package can be obtained.

  Further, the above-described photosensitive resin composition can be used for the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the manufacture of metal foils such as the manufacture of metal masks, ball grid arrays (BGA), or chip size packages. Manufacturing of packages such as (CSP), manufacturing of tape substrates such as chip-on-film (COF) or tape automated bonding (TAB), manufacturing of semiconductor bumps, flat panel displays such as ITO electrodes or address electrodes, electromagnetic shielding It can be used for the manufacture of partition walls.

  The various parameters described above are measured according to the measurement methods in the examples described later unless otherwise specified.

  Below, it shows about the production method of the sample for evaluation of Examples 1-6 and Comparative Examples 1-6, and the evaluation method and evaluation result about the obtained sample.

1. Production of Evaluation Samples The photosensitive resin laminates in Examples 1 to 6 and Comparative Examples 1 to 6 were produced as follows.

<Preparation of photosensitive resin laminate>
The compounds shown in Table 1 below were blended in the composition ratios (units are parts by mass) shown in Table 2 or 3 below, and sufficiently stirred and mixed to prepare a photosensitive resin composition solution. The obtained photosensitive resin composition solution was uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film (Teijin DuPont Films, manufactured by GR-16) as a support using a bar coater, and dried at 95 ° C. The photosensitive resin layer was formed by drying in the machine for 3 minutes. The thickness of the photosensitive resin layer was 38 μm.

  In the compositions shown in Tables 2 and 3 below, the mass parts of B-1 and B-2 are solid amounts.

  Next, on the surface of the photosensitive resin layer on which the polyethylene terephthalate film is not laminated, a 19 μm-thick polyethylene film (Tamapoly Co., Ltd., GF-18) is bonded as a protective layer to evaluate the hue stability. A photosensitive resin laminate sample was obtained.

<Board surface preparation>
As a substrate for evaluating overhang peelability, plating resistance, peel piece size, resolution, and sensitivity, a 1.6 mm thick copper clad laminate with 35 μm rolled copper foil is used, and the surface is wet buffol Polishing (manufactured by 3M, Scotch Bright (registered trademark) HD # 600, twice) was performed.

<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, it was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-70) on a copper clad laminate that had been leveled and preheated to 60 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
A mask film necessary for evaluation is placed on a photosensitive resin layer on a polyethylene terephthalate film as a support, and exposure is performed in 8 steps with a 21-step tablet made by Stofer using an ultra-high pressure mercury lamp (OMW, HMW-201KB). Exposed in quantity.

<Development>
After the polyethylene terephthalate film is peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution 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), and an unexposed portion of the photosensitive resin layer Was removed by dissolution in a time twice as long as the minimum development time. Here, “minimum development time” refers to the shortest time required for the photosensitive resin layer in the unexposed portion to be completely dissolved.

<Resist stripping>
After copper sulfate plating described later, using a small peeling device (manufactured by Yamagata Kikai Co., Ltd.), a 4 mass% sodium hydroxide aqueous solution at 50 ° C. was sprayed for 72 seconds, and the cured resist was peeled off.

2. Evaluation method (1) Weight average molecular weight, molecular weight distribution Using a calibration curve of standard polystyrene (Showex STANDARD SM-105 manufactured by Showa Denko KK) using a gel permeation chromatography (GPC) system manufactured by JASCO Corporation. did. Details of the measurement conditions are as follows.
Differential refractometer: RI-1530,
Pump: PU-1580,
Degasser: DG-980-50,
Column oven: CO-1560,
Column: KF-8025, KF-806M × 2, KF-807, in order
Eluent: THF

(2) Evaluation of Plating Resistance Using a substrate that had passed 15 minutes after the treatment described in the above <laminate>, the exposed portion and the unexposed portion were exposed and developed with a line pattern having a ratio of 1: 1. In addition, about the exposure, it exposed with the exposure amount used as 6 steps | paragraphs with the 21 step step tablet made from a stoufer with the ultra high pressure mercury lamp (the product made by Oak Manufacturing, HMW-201KB).

Furthermore, copper sulfate plating was performed according to the following plating conditions.
<Plating conditions>
Pretreatment: Immerse in an acidic degreaser bath (LP-200: 10%, Rohm and Haas LP / 200%, sulfuric acid: 10% aqueous solution) at 40 ° C. for 10 minutes. Thereafter, it was washed with water, immersed in an APS aqueous solution (ammonium persulfate aqueous solution, concentration 200 g / L) for 1 minute at room temperature, washed with water, and then immersed in a 10% sulfuric acid aqueous solution for 2 minutes.
Copper sulfate plating: Plating was performed for 50 minutes at a current density of 2.0 A / dm ² with the above plating solution composition. At this time, the plating height measured using a micron depth height (thickness) measuring device (manufactured by Nissho Precision Optical Co., Ltd., KY-90 type) was 20 μm.

The copper sulfate plating line of L / S = 125/125 μm after the cured resist was peeled was observed with an optical microscope and ranked as follows. The cured resist was peeled off by immersing the evaluation substrate after development in a 4 mass% sodium hydroxide aqueous solution heated to 50 ° C.
A (remarkably good): No peeling of secondary copper plating is observed.
○ (Good): Scouring of secondary copper plating is observed, but the drilling width is less than 2 μm on one side of the line.
Δ (permissible): Although secondary copper plating is seen, the bore width is 2 μm or more and 5 μm or less on one side of the line.
X (defect): Bored width of the secondary copper plating exceeds 5 μm on one side of the line.

(3) Hue stability evaluation (difference in transmittance at 600 nm)
The polyethylene film was peeled off from the photosensitive resin laminate, and the transmittance of light having a wavelength of 600 nm was measured using a UV-vis spectrometer (manufactured by Shimadzu Corporation, UV-240). At this time, the same polyethylene terephthalate film as that used for the photosensitive resin laminate was put on the reference side of the spectrometer to cancel the transmittance derived from the polyethylene terephthalate film.

Sample for evaluating hue stability of a photosensitive resin laminate prepared using a photosensitive resin composition solution after storage at a temperature of 40 ° C. for 3 days and a photosensitive resin prepared using a photosensitive resin composition solution before storage The transmittances of the conductive resin laminates were compared, and the ranks were classified as follows based on the difference.
○ (Good): The absolute value of the difference in transmittance at 600 nm is less than 1%.
Δ (allowable): The absolute value of the difference in transmittance at 600 nm is 1% or more and less than 5%.
X (defect): The absolute value of the difference in transmittance at 600 nm is 5% or more.

(4) Evaluation of Sensitivity using a substrate that has elapsed 15 minutes after the processes described in the <laminating> was exposed with an exposure amount of 45 mJ / cm ² through a Stouffer made 21-step tablet and developed. The highest number of remaining film steps of the obtained cured resist was regarded as sensitivity, and ranked as follows.
(Remarkably good): The sensitivity value is 8 or more.
○ (Good): The sensitivity value is 7 steps or more and less than 8 steps.

  The evaluation results of Examples 1 to 6 are shown in Table 2 below, and the evaluation results of Comparative Examples 1 to 6 are shown in Table 3 below.

Claims (13)

(A) an alkali-soluble polymer;
(B) an addition polymerizable monomer having an ethylenically unsaturated bond;
(C) 2,4,5-triarylimidazole dimer;
(D) The following general formula (I):

{Wherein R _{1 to} R ₄ each independently represents hydrogen or an alkyl group, and R ₅ represents the following general formula (II):

(Wherein R ₆ and R ₇ are each independently hydrogen, a linear or branched alkyl group which may have a substituent, or a linear or branched hydroxyl group which may have a substituent) Selected from alkyl groups, but one or both of R ₆ and R ₇ are not hydrogen, and n is an integer of 1 to 4}
And (e) an epoxy compound;
A photosensitive resin composition comprising: The epoxy compound has the following general formula (III):

{In the formula, X is an oxygen atom, or a formula -O-X ₁ -O- (wherein X ₁ is a linear or branched alkylene group having 1 to 100 carbon atoms, or an alicyclic group having 3 to 10 carbon atoms. A divalent group containing at least one hydrocarbon group selected from the group consisting of an alkylene group and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group includes a halogen atom, an oxygen atom and a nitrogen atom R ₈ and R ₉ are each independently a linear or branched alkylene group having 1 to 100 carbon atoms, which may be substituted with at least one atom selected from the group consisting of A divalent group containing at least one hydrocarbon group selected from the group consisting of an alicyclic alkylene group having 3 to 10 carbon atoms and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is , Halogen atoms, oxygen atoms and May be substituted with at least one atom selected from the group consisting of nitrogen atom, and when R ₈ and R ₉ are present together, R ₈ and R _9, which may be the same or different, R _{When 8} and R ₉ are different, the sequence of repeating units of — (R ₈ —O) — and — (R ₉ —O) — may be block or random; and l and m are each independently It is an integer of 0-50, and l + m is an integer of 1-50}
The photosensitive resin composition of Claim 1 containing the compound represented by these.   The photosensitive resin composition according to claim 1 or 2, wherein the content of the epoxy compound is 0.001% by mass or more and less than 0.1% by mass with respect to the total solid content of the photosensitive resin composition. . The 2,4,5-triarylimidazole dimer has the following general formula (IV):

{Wherein Y ¹ , Y ² and Y ³ are each independently a group selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and halogen. And p, q and r are each independently an integer of 1 to 5}
The photosensitive resin composition of any one of Claims 1-3 containing the compound represented by these.   The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises an N-aryl amino acid. The photosensitive resin composition has the following general formula (V):

{Wherein Z is hydrogen or an alkyl group having 1 to 4 carbon atoms}
The photosensitive resin composition of any one of Claims 1-5 which further contains the compound represented by these.   The photosensitive resin laminated body containing the photosensitive resin layer which consists of the photosensitive resin composition of any one of Claims 1-6, and the support body which supports this photosensitive resin layer. A laminating step of laminating the photosensitive resin laminate according to claim 7 on a substrate;
An exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate; and a development step of forming a resist pattern by removing an unexposed portion of the photosensitive resin layer after the exposure with a developer;
A resist pattern forming method including:   The resist pattern forming method according to claim 8, wherein the exposure step is a step of performing exposure by direct drawing of a drawing pattern. A laminating step of laminating the photosensitive resin laminate according to claim 7 on a metal plate or a metal film insulating plate;
An exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate;
A developing step of removing a non-exposed portion of the photosensitive resin layer after the exposure with a developer to form a resist pattern; and etching or etching a portion of the surface of the metal plate or metal film insulating plate that is not covered with the resist pattern Conductor pattern forming step for plating;
A method for forming a conductor pattern including: A laminating step of laminating the photosensitive resin laminate according to claim 7 on a copper clad laminate or a flexible substrate;
An exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate;
A developing step of forming a resist pattern by removing unexposed portions of the exposed photosensitive resin layer with a developer;
A conductor pattern forming step of etching or plating a portion of the copper-clad laminate or flexible substrate surface not covered with the resist pattern; and a peeling step of peeling the resist pattern from the copper-clad laminate or flexible substrate;
A method of manufacturing a printed wiring board including: A laminating step of laminating the photosensitive resin laminate according to claim 7 on a metal plate;
An exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate;
A developing step of forming a resist pattern by removing unexposed portions of the exposed photosensitive resin layer with a developer;
An etching step of etching a portion of the surface of the metal plate not covered with the resist pattern; and a peeling step of peeling the resist pattern from the metal plate;
A method for manufacturing a lead frame. A lamination step of laminating the photosensitive resin laminate according to claim 7 on a wafer on which a large-scale integrated circuit (LSI) is formed;
An exposure step of exposing the photosensitive resin layer contained in the photosensitive resin laminate;
A developing step of forming a resist pattern by removing unexposed portions of the exposed photosensitive resin layer with a developer;
A plating step of plating a portion of the wafer surface not covered with the resist pattern; and a peeling step of peeling the resist pattern from the wafer;
A method for manufacturing a semiconductor package comprising: