JP5948539B2 - Photosensitive resin composition - Google Patents

Description

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

  Conventionally, a printed wiring board is 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). Mold) and unexposed areas (in the case of negative molds) or exposed areas (in the case of positive molds) are removed with a developer to form a resist pattern on the substrate, and etching or plating is performed to form a conductor pattern. After forming, the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate.

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

  Here, with the recent miniaturization of the wiring interval in the printed wiring board, various characteristics are being required for the dry film resist. Patent Document 1 discloses a photosensitive element including a support film and a photosensitive layer made of a photosensitive resin composition formed on the support film. The photosensitive layer includes a binder polymer, an ethylenically unsaturated bond. As a photopolymerizable compound containing a photopolymerizable compound having a photopolymerization initiator and a photopolymerization initiator and having an ethylenically unsaturated bond, pentaerythritol (poly) alkoxytetraacrylate and 2,2-bis (4- ( Photosensitive elements have been described including (meth) acryloxypolyethoxy) phenyl) propane and the like.

International Publication No. 2010/013623 Pamphlet

However, the photosensitive element described in Patent Document 1 still has room for improvement in terms of the resist pattern sword shape, resolution, and remaining film ratio.
Accordingly, it is an object of the present invention to provide a photosensitive resin composition excellent in resist pattern sedge shape, resolution and remaining film ratio, a resist pattern forming method using the same, and a wiring board manufacturing method.

  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.

｛式中、Ｒ_１〜Ｒ_４は、それぞれ独立に、炭素数１〜４のアルキル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、ｍ_１、ｍ_２、ｍ_３及びｍ_４は、それぞれ独立に、０〜４０の整数であり、ｍ_１＋ｍ_２＋ｍ_３＋ｍ_４は、１〜４０であり、そしてｍ_１＋ｍ_２＋ｍ_３＋ｍ_４が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい。｝で表される化合物を含む感光性樹脂組成物。 [1] Based on the total solid content of the photosensitive resin composition, the following components:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass,
(B) Compound having ethylenically unsaturated bond: 5% by mass to 70% by mass, and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass,
And (B) the compound having an ethylenically unsaturated bond, the following general formula (I):

{Wherein R _{1 to} R ₄ each independently represents an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, m ₁ , m ₂ , m ₃ and m ₄ is each independently an integer of 0 to 40, m ₁ + m ₂ + m ₃ + m ₄ is 1 to 40, and when m ₁ + m ₂ + m ₃ + m ₄ is 2 or more, a plurality of X's may be the same as or different from each other. } The photosensitive resin composition containing the compound represented by this.

  [2] The (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, and has an aromatic group in its side chain. Photosensitive resin composition.

｛式中、Ｒ_５及びＲ_６は、それぞれ独立に、水素原子又はメチル基を表し、Ｙは、それぞれ独立に、炭素数２〜６のアルキレン基を表し、ｎ_１及びｎ_２は、それぞれ独立に、０又は正の整数であり、そしてｎ_１＋ｎ_２は、２〜４０である。｝で表される化合物をさらに含む、［１］又は［２］に記載の感光性樹脂組成物。 [3] As the compound (B) having an ethylenically unsaturated bond, the following general formula (II):

{In the formula, R ₅ and R ₆ each independently represent a hydrogen atom or a methyl group; Y independently represents an alkylene group having 2 to 6 carbon atoms; and n ₁ and n ₂ represent each independently And 0 or a positive integer, and n ₁ + n ₂ is 2 to 40. } The photosensitive resin composition as described in [1] or [2] which further contains the compound represented by these.

[4] The photosensitive resin composition according to [3], wherein in the general formula (II), n ₁ + n ₂ is 2 to 10.

  [5] The photosensitive resin composition according to any one of [1] to [4], which contains a hexaarylbisimidazole compound as the (C) photopolymerization initiator.

[6] The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [5] on a support;
An exposure step of exposing the photosensitive resin layer; and a development step of developing the exposed photosensitive resin layer;
A resist pattern forming method including:

[7] The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [5] on a substrate;
An exposure step of exposing the photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
A method of manufacturing a wiring board, comprising: a conductor pattern forming step of etching or plating a substrate on which the resist pattern is formed; and a peeling step of peeling the resist pattern.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in the skirt shape of a resist pattern, the resolution, and a residual film rate, and the resist pattern and wiring board using the same can be provided.

  Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be specifically described.

<Photosensitive resin composition>
In this embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. Moreover, in this embodiment, the photosensitive resin composition can form the photosensitive resin layer by applying to arbitrary supports. Hereinafter, each component contained in the photosensitive resin composition will be described.

(A) Alkali-soluble polymer (A) An alkali-soluble polymer is a polymer that can be dissolved in an alkaline substance. In this embodiment, (A) the alkali-soluble polymer preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and contains a carboxyl group-containing monomer as a copolymerization component. More preferably, it is a copolymer. Further, (A) the alkali-soluble polymer may be thermoplastic.

  (A) The acid equivalent of the alkali-soluble polymer is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin layer and the resolution and adhesion of the resist pattern, while the development of the photosensitive resin layer. Is preferably 600 or less from the viewpoints of releasability and releasability. The acid equivalent of (A) 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 is preferably 5,000 to 500,000. (A) The weight average molecular weight of the alkali-soluble polymer 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. From the viewpoint of maintaining developability, it is preferably 500,000 or less. The weight average molecular weight of the (A) alkali-soluble polymer is more preferably 10,000 to 200,000, and further preferably 40,000 to 130,000. Further, (A) the dispersity of the alkali-soluble polymer is preferably 1.0 to 6.0.

  (A) The alkali-soluble polymer is preferably obtained by polymerizing at least one of the first monomers described below. The (A) alkali-soluble polymer is more preferably obtained by copolymerizing at least one of the first monomers and at least one of the second monomers described below.

  The first monomer is a monomer 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. In the present specification, “(meth) acryl” means acryl or methacryl, and “(meth) acrylate” means “acrylate” and “methacrylate”.

  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, and benzyl (meth) acrylate; vinyl acetate Esters of vinyl alcohol such as; and (meth) acrylonitrile, styrene, and polymerizable styrene derivatives such as methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl Ikikosan, dimer, styrene trimer), and the like. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene and benzyl (meth) acrylate are preferable.

  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. The (A) alkali-soluble polymer having an aromatic group in the side chain is prepared by using a compound having an aromatic group as the first monomer and / or the second monomer. be able to. Examples of the monomer having an aromatic group include benzyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, styrene, cinnamic acid, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxy). Styrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.).

  In this embodiment, (A) the alkali-soluble polymer polymerizes the first monomer and / or the second monomer by a known polymerization method, preferably addition polymerization, more preferably radical polymerization. Can be prepared.

  In the present embodiment, the content of the (A) alkali-soluble polymer in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition. Hereinafter, the same applies to each component unless otherwise specified. Is preferably in the range of 10% to 90% by weight, more preferably in the range of 20% to 80% by weight, and still more preferably in the range of 50% to 70% by weight. (A) The content of the alkali-soluble polymer is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, while the resist pattern formed by exposure is used as a resist material. It is preferable that it is 90 mass% or less from a viewpoint of fully exhibiting the performance of this.

｛式中、Ｒ_１〜Ｒ_４は、それぞれ独立に、炭素数１〜４のアルキル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、ｍ_１、ｍ_２、ｍ_３及びｍ_４は、それぞれ独立に、０〜４０の整数であり、ｍ_１＋ｍ_２＋ｍ_３＋ｍ_４は、１〜４０であり、そしてｍ_１＋ｍ_２＋ｍ_３＋ｍ_４が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい。｝で表される化合物を含むことが好ましい。
また、作用機序に拘束されることを望むものではないが、上記一般式（Ｉ）で表される化合物は、基Ｒ_１〜Ｒ_４を有することにより、例えばＨ_２Ｃ＝ＣＨ−ＣＯ−Ｏ−部分を有するテトラアクリレートに比べて、アルカリ溶液中での加水分解性が抑制されていると推定される。それ故に、上記一般式（Ｉ）で表される化合物を含む感光性樹脂組成物を使用することにより、レジストパターンの解像度、詳細にはライン形状、より詳細にはラインのスソ形状、並びにレジストの残膜率を向上することができるため好ましい。 (B) Compound having an ethylenically unsaturated bond (B) A compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated group in its structure. In the present embodiment, the photosensitive resin composition has the following general formula (I) as a compound having (B) an ethylenically unsaturated bond:

{Wherein R _{1 to} R ₄ each independently represents an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, m ₁ , m ₂ , m ₃ and m ₄ is each independently an integer of 0 to 40, m ₁ + m ₂ + m ₃ + m ₄ is 1 to 40, and when m ₁ + m ₂ + m ₃ + m ₄ is 2 or more, a plurality of X's may be the same as or different from each other. } Is preferably included.
Moreover, although not wishing to be restrained by an action mechanism, the compound represented by the general formula (I) has, for example, H ₂ C═CH—CO— by having groups R _{1 to} R _4. It is presumed that hydrolyzability in an alkaline solution is suppressed as compared with tetraacrylate having an O- moiety. Therefore, by using the photosensitive resin composition containing the compound represented by the above general formula (I), the resolution of the resist pattern, specifically the line shape, more specifically the line shape, and the resist This is preferable because the remaining film ratio can be improved.

In the present embodiment, from the viewpoint of obtaining a desired resolution, sword shape and remaining film ratio for the resist pattern, in the general formula (I), R _{1 to} R ₄ are each independently an alkyl having 1 to 4 carbon atoms. It is preferably a group, at least one of R _{1 to} R ₄ is preferably a methyl group, and more preferably all of the groups R _{1 to} R ₄ are methyl groups.

In the present embodiment, from the viewpoint of obtaining a desired resolution, sword shape and remaining film ratio for the resist pattern, in the general formula (I), X is preferably an alkylene group having 2 to 6 carbon atoms, More preferably, it is CH ₂ —CH ₂ —.

Further, from the viewpoint of obtaining a desired resolution, sword shape and remaining film ratio for the resist pattern, in the general formula (I), m ₁ , m ₂ , m ₃ and m ₄ are each independently 0 to 40 It is preferably an integer, more preferably an integer of 1 to 10, and still more preferably an integer of 1 to 5. Furthermore, in the said general formula (I), it is preferable that m < ₁ > + m < ₂ > + m < ₃ > + m < ₄ > is 1-40, It is more preferable that it is 1-36, It is further more preferable that it is 4-12.

In the present embodiment, in the above general formula (I), when m ₁ + m ₂ + m ₃ + m ₄ is 2 or more, a plurality of Xs may be the same or different from each other.

Examples of the compound represented by the general formula (I) include pentaerythritol (poly) alkoxytetramethacrylate. In addition, in this specification, “pentaerythritol (poly) alkoxytetramethacrylate” includes “pentaerythritol alkoxytetramethacrylate” in which m ₁ + m ₂ + m ₃ + m ₄ = 1 in the general formula (I) and m ₁ It should be understood that both “pentaerythritol polyalkoxytetramethacrylates” where + m ₂ + m ₃ + m ₄ = 2-40 are included.

  Examples of pentaerythritol (poly) alkoxytetramethacrylate include pentaerythritol (poly) ethoxytetramethacrylate, pentaerythritol (poly) propoxytetramethacrylate, pentaerythritol (poly) butoxytetramethacrylate, pentaerythritol (poly) ethoxy (poly) propoxy. Examples include tetramethacrylate. These can be used alone or in combination of two or more.

  Examples of the pentaerythritol (poly) ethoxytetramethacrylate include pentaerythritol ethoxytetramethacrylate, pentaerythritol diethoxytetramethacrylate, pentaerythritol triethoxytetramethacrylate, pentaerythritol tetraethoxytetramethacrylate, pentaerythritol pentaethoxytetramethacrylate, and pentaerythritol. Hexaethoxytetramethacrylate, pentaerythritol heptaethoxytetramethacrylate, pentaerythritol octaethoxytetramethacrylate, pentaerythritol nonaethoxytetramethacrylate, pentaerythritol decaethoxytetramethacrylate, pentaerythritol totaling 9 moles Tetramethacrylate obtained by adding ethylene oxide, and the like. These can be used alone or in combination of two or more. Among these, pentaerythritol tetraethoxytetramethacrylate and tetramethacrylate having a total of 9 moles of ethylene oxide added to the four terminals of pentaerythritol are preferable.

  Examples of pentaerythritol (poly) propoxytetramethacrylate include pentaerythritol propoxytetramethacrylate, pentaerythritol dipropoxytetramethacrylate, pentaerythritol tripropoxytetramethacrylate, pentaerythritol tetrapropoxytetramethacrylate, pentaerythritol pentapropoxytetramethacrylate, and pentaerythritol hexamethacrylate. Examples thereof include propoxytetramethacrylate, pentaerythritol heptapropoxytetramethacrylate, pentaerythritol octapropoxytetramethacrylate, pentaerythritol nonapropoxytetramethacrylate, and pentaerythritol decapropoxytetramethacrylate. These can be used alone or in combination of two or more.

  Examples of pentaerythritol (poly) butoxytetramethacrylate include pentaerythritol butoxytetramethacrylate, pentaerythritol dibutoxytetramethacrylate, pentaerythritol tributoxytetramethacrylate, pentaerythritol tetrabutoxytetramethacrylate, pentaerythritol pentabutoxytetramethacrylate, pentaerythritol hexamethacrylate. Examples thereof include butoxytetramethacrylate, pentaerythritol heptavoxytetramethacrylate, pentaerythritol octabutoxytetramethacrylate, pentaerythritol nonabutoxytetramethacrylate, pentaerythritol decabutoxytetramethacrylate and the like. These can be used alone or in combination of two or more.

  Examples of pentaerythritol (poly) ethoxy (poly) propoxytetramethacrylate include, for example, pentaerythritol ethoxypropoxytetramethacrylate, pentaerythritol diethoxypropoxytetramethacrylate, pentaerythritol triethoxydipropoxytetramethacrylate, pentaerythritol diethoxytetrapropoxytetramethacrylate, Examples include pentaerythritol tetraethoxytetrapropoxytetramethacrylate. These can be used alone or in combination of two or more.

｛式中、Ｒ_５及びＲ_６は、それぞれ独立に、水素原子又はメチル基を表し、Ｙは、それぞれ独立に、炭素数２〜６のアルキレン基を表し、ｎ_１及びｎ_２は、それぞれ独立に、０又は正の整数であり、そしてｎ_１＋ｎ_２は、２〜４０である。｝で表される化合物をさらに含むことが好ましい。また、感光性樹脂組成物が上記一般式（ＩＩ）で表される化合物を含むことによって、レジストパターンの解像性及び密着性が向上するため好ましい。 In the present embodiment, the photosensitive resin composition is represented by the following general formula (II) as a compound having (B) an ethylenically unsaturated bond:

{In the formula, R ₅ and R ₆ each independently represent a hydrogen atom or a methyl group; Y independently represents an alkylene group having 2 to 6 carbon atoms; and n ₁ and n ₂ represent each independently And 0 or a positive integer, and n ₁ + n ₂ is 2 to 40. } It is preferable that the compound further represented by this is further included. Further, it is preferable that the photosensitive resin composition contains the compound represented by the general formula (II) because the resolution and adhesion of the resist pattern are improved.

  Moreover, the aromatic ring in the general formula (II) may have a hetero atom and / or a substituent. Examples of the hetero atom include a halogen atom, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group. , Amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, allyl group, hydroxyl group , A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in an alkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, an alkoxy group having 1 to 20 carbon atoms, C1-C20 alkoxycarbonyl group, C2-C10 alkylcarbonyl group, C2-C10 alkenyl group, C2-C10 - alkylcarbamoyl group or a group containing a heterocyclic ring, or the like an aryl group substituted with these substituents include. Moreover, these substituents may form a condensed ring, or a hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom. Furthermore, when the aromatic ring in the general formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.

  Examples of the compound represented by the general formula (II) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic). Loxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) Examples thereof include bisphenol A-based (meth) acrylate compounds such as propane.

Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexa) Decaethoxy) phenyl) propane and bisphenol A polyethylene glycol having an average of 1 mole of ethylene oxide added to each end. Each of dimethacrylate and bisphenol A was added with an average of 2 moles of ethylene oxide at each end, and polyethylene glycol dimethacrylate and bisphenol A were added with an average of 5 moles of ethylene oxide at each end. Examples include polyethylene glycol dimethacrylate. Among them, polyethylene glycol dimethacrylate having an average of 1 mol of ethylene oxide added to both ends of bisphenol A, and an average of 2 mol of ethylene oxide to each end of bisphenol A were added. Polyethylene glycol dimethacrylate and polyethylene glycol dimethacrylate having an average of 5 moles of ethylene oxide added to both ends of bisphenol A are preferred. In particular, polyethylene glycol dimethacrylate having an average of 1 mole of ethylene oxide added to both ends of bisphenol A is preferred from the viewpoint of resolution.
More specifically, as 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) is commercially available. . These can be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Xinonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meth)) And acryloxyhexadecapropoxy) phenyl) propane. These can be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydibutoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytributoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrabutoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaboxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexabutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptavoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctabutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonabutoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecabutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecabutoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydecabutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecabutoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecabutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexa) And decabutoxy) phenyl) propane. These can be used alone or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Both sides of 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane, bisphenol A And polyalkylene glycol dimethacrylates each having an average of 2 mol of propylene oxide and an average of 15 mol of ethylene oxide. Among these, polyalkylene glycol dimethacrylates in which an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide are added to both sides of bisphenol A are preferable. These can be used alone or in combination of two or more.

In the present embodiment, in the general formula (II), R ₅ and R ₆ each independently represent a hydrogen atom or a methyl group, and Y each independently represents an alkylene group having 2 to 6 carbon atoms ( Preferably, it represents —CH ₂ —CH ₂ — or —CH ₂ —CH ₂ —CH ₂ —, and n ₁ and n ₂ are each independently 0 or a positive integer (preferably an integer of 1 to 20). And n ₁ + n ₂ is 2 to 40 (preferably 2 to 35, more preferably 2 to 10). Furthermore, the compound whose n < ₁ > + n < ₂ > in the said general formula (II) is 2-10 is preferable in order to improve the resolution of a resist pattern. Specifically, examples of the compound in which n ₁ + n ₂ in the general formula (II) is ₂ to 10 include polyethylene glycol having an average of 1 mol of ethylene oxide added to both ends of bisphenol A, respectively. Dimethyl acrylate, polyethylene glycol dimethacrylate having an average of 2 moles of ethylene oxide added to both ends of bisphenol A, and an average of 5 moles of ethylene oxide to both ends of bisphenol A, respectively. Examples thereof include diglycolates of added polyethylene glycol.

  In the present embodiment, the photosensitive resin composition includes (B) the compound having an ethylenically unsaturated bond, not only the compounds represented by the general formulas (I) and (II), but also other compounds. May include. Examples of other compounds include polyalkylene glycol di (meth) acrylate, a photopolymerizable compound having one ethylenically unsaturated bond, a (meth) acrylate compound having a urethane bond, and α, β-unsaturated polyhydric alcohol. Examples include compounds obtained by reacting saturated carboxylic acids, compounds obtained by reacting glycidyl group-containing compounds with α, β-unsaturated carboxylic acids, and phthalic acid compounds. These can be used alone or in combination of two or more.

  As polyalkylene glycol di (meth) acrylate, for example, nonaethylene glycol diacrylate, polyalkylene glycol having an average of 12 moles of propylene oxide added and an ethylene oxide added to both ends at an average of 3 moles at both ends, respectively. For example, dimethacrylate. In addition, polyalkylene glycol dimethacrylate in which ethylene oxide is added to polypropylene glycol added with nonaethylene glycol diacrylate and an average of 12 moles of propylene oxide on both ends is added to the resist pattern. It is preferable from the viewpoint of controlling the shape and the remaining film ratio. These can be used alone or in combination.

｛式中、Ｒ_７は、水素原子又はメチル基であり、水素原子であることが好ましく、Ｚは、上記一般式（Ｉ）及び（ＩＩ）中のＸ及びＹと同様に定義されるものであり、−ＣＨ_２−ＣＨ_２−であることが好ましく、ｋは、４〜２０の整数を示し、レジストパターンの現像性の観点から、５〜１８の整数であることが好ましく、６〜１２の整数であることがより好ましく、６〜１０の整数であることがさらに好ましい。｝ A photopolymerizable compound having one ethylenically unsaturated bond is preferable in order to improve developability such as adhesion and resolution of a resist pattern and releasability. Examples of the photopolymerizable compound having one ethylenically unsaturated bond include the following general formula (III):

{Wherein R ₇ is a hydrogen atom or a methyl group, preferably a hydrogen atom, and Z is defined in the same manner as X and Y in the above general formulas (I) and (II). Yes, preferably —CH ₂ —CH ₂ —, k represents an integer of 4 to 20, and is preferably an integer of 5 to 18, from the viewpoint of developability of the resist pattern, An integer is more preferable, and an integer of 6 to 10 is more preferable. }

  Moreover, the aromatic ring in the general formula (III) may have a hetero atom and / or a substituent. Examples of the heteroatom and the substituent include those exemplified for the general formula (II).

  Specific examples of the compound represented by the general formula (III) include nonylphenoxypolyethyleneoxy (meth) acrylate, nonylphenoxypolypropyleneoxy (meth) acrylate, butylphenoxypolyethyleneoxy (meth) acrylate, and butylphenoxypolypropylene. Examples include oxy (meth) acrylate. These can be used alone or in combination of two or more.

  Nonylphenoxypolyethyleneoxy (meth) acrylates include, for example, nonylphenoxytetraethyleneoxy (meth) acrylate, nonylphenoxypentaethyleneoxy (meth) acrylate, nonylphenoxyhexaethyleneoxy (meth) acrylate, nonylphenoxyheptaethyleneoxy (meth) ) Acrylate, nonylphenoxyoctaethyleneoxy (meth) acrylate, nonylphenoxynonaethyleneoxy (meth) acrylate, nonylphenoxydecaethyleneoxy (meth) acrylate, nonylphenoxyundecaethyleneoxy (meth) acrylate, nonylphenoxide dodecaethyleneoxy ( And (meth) acrylate. These can be used alone or in combination of two or more.

  Nonylphenoxypolypropyleneoxy (meth) acrylate includes nonylphenoxypropyleneoxy (meth) acrylate, nonylphenoxydipropyleneoxy (meth) acrylate, nonylphenoxytripropyleneoxy (meth) acrylate, nonylphenoxytetrapropyleneoxy (meth) acrylate, Nonylphenoxypentapropyleneoxy (meth) acrylate, Nonylphenoxyhexapropyleneoxy (meth) acrylate, Nonylphenoxyheptapropyleneoxy (meth) acrylate, Nonylphenoxyoctapropyleneoxy (meth) acrylate, Nonylphenoxynonapropyleneoxy (meth) acrylate, Nonylphenoxydecapropyleneoxy (meth) acrylate etc. are mentioned. These can be used alone or in combination of two or more.

  Examples of butylphenoxypolyethyleneoxy (meth) acrylate include butylphenoxytetraethyleneoxy (meth) acrylate, butylphenoxypentaethyleneoxy (meth) acrylate, butylphenoxyhexaethyleneoxy (meth) acrylate, butylphenoxyheptaethyleneoxy (meth) ) Acrylate, butylphenoxyoctaethyleneoxy (meth) acrylate, butylphenoxynonaethyleneoxy (meth) acrylate, butylphenoxydecaethyleneoxy (meth) acrylate, butylphenoxyundecaethyleneoxy (meth) acrylate, and the like. These can be used alone or in combination of two or more.

  Examples of butylphenoxypolypropyleneoxy (meth) acrylate include butylphenoxytetrapropyleneoxy (meth) acrylate, butylphenoxypentapropyleneoxy (meth) acrylate, butylphenoxyhexapropylene oxy (meth) acrylate, butylphenoxyheptapropyleneoxy (meth) ) Acrylate, butylphenoxyoctapropyleneoxy (meth) acrylate, butylphenoxynonapropyleneoxy (meth) acrylate, butylphenoxydecapropyleneoxy (meth) acrylate, butylphenoxyundecapropyleneoxy (meth) acrylate, and the like. These can be used alone or in combination of two or more.

  A (meth) acrylate compound having a urethane bond is preferable in order to improve the tenting property of the resist pattern. Examples of the (meth) acrylate compound having a urethane bond include a (meth) acryl monomer having a hydroxyl group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene. Examples include addition reaction products with diisocyanate compounds such as diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. Further, in the present specification, “EO” represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. In the present specification, “PO” represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups. These can be used alone or in combination of two or more.

  Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meta). ) Acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO and PO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These can be used alone or in combination of two or more.

  Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) acryloxy- 2-hydroxy-propyloxy) phenyl and the like are fisted.

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o—. A phthalate etc. are mentioned. These can be used alone or in combination of two or more.

  In this embodiment, content of the compound which has (B) ethylenically unsaturated bond in the photosensitive resin composition becomes like this. Preferably it is the range of 5 mass%-70 mass%, More preferably, it is 20 mass%-60 It is the range of mass%, More preferably, it is the range of 30 mass%-50 mass%. (B) The content of the compound having an ethylenically unsaturated bond is preferably 5% by mass or more from the viewpoint of suppressing the curing failure of the photosensitive resin layer and the delay of the development time. It is preferable that it is 70 mass% or less from a viewpoint of suppressing the peeling delay of a flow and hardened resist.

(C) Photopolymerization initiator (C) The photopolymerization initiator is a compound that polymerizes a monomer by light. In the present embodiment, from the viewpoint of improving the resolution of the resist pattern and the strength of the cured resist, the photosensitive resin composition preferably includes a hexaarylbisimidazole compound as a (C) photopolymerization initiator.

  Examples of hexaarylbisimidazole compounds include hexaarylbisimidazole derivatives (hereinafter also referred to as “triarylimidazolyl dimer” or “triarylimidazolyl dimer”).

  Examples of the hexaarylbisimidazole derivative include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter, “2,2′-bis (2-chlorophenyl) -4,4 ′, 5, 5'-tetraphenyl-1,1'-bisimidazole "or" 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer "), 2,2 ', 5-tris- (o- Chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenyl Imidazolyl dimer, 2,4,5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4 Dimethoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2-fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2 '-Bis- (2,3-difluoromethylphenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4- Difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5 , 5′-Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxy Phenyl) -imidazolyl 2,2′-bis- (2,3,4-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2 ′ -Bis- (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3 , 6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4', 5 , 5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′- Bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and 2,2′-bis- (2 , 3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer. These can be used alone or in combination of two or more.

  In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable for improving the resolution of the resist pattern and the strength of the cured resist.

  In the present embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is 0.05% by mass to 7% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer. It is preferable that it is 0.1 mass%-6 mass%.

  In the present embodiment, the photosensitive resin layer may contain not only the hexaarylbisimidazole compound but also other photopolymerization initiators as the (C) photopolymerization initiator. Examples of other photopolymerization initiators include acridine compounds, N-aryl amino acids, organic halogen compounds, and photosensitizers. These can be used alone or in combination of two or more.

  Acridine compounds are preferred because they give good release properties to the resin. Examples of the acridine compound include acridine, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, etc. It is done. Among these, 9-phenylacridine is preferable from the viewpoint of improving the h-ray sensitivity of the photosensitive resin layer. Moreover, these can be used individually by 1 type or in combination of 2 or more types. Furthermore, in this embodiment, it is preferable that content of the acridine compound in the photosensitive resin composition is the range of 0.1 mass%-2 mass% from a viewpoint of obtaining favorable peeling characteristics.

  Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like. Among these, N-phenylglycine is preferable. These can be used alone or in combination of two or more. In the present embodiment, the content of the N-aryl amino acid in the photosensitive resin composition is 0.05% by mass to 5% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer. It is preferable that it is 0.1-2 mass%.

  Examples of the organic 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 and the like. Among these, tribromomethylphenyl sulfone is preferable. Moreover, these can be used individually by 1 type or in combination of 2 or more types. Furthermore, in this embodiment, the content of the organic halogen compound in the photosensitive resin composition is 0.05% by mass to 5% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer. It is preferable that the content is 0.1% by mass to 3% by mass.

  Examples of the photosensitizer 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, quinones such as 3-chloro-2-methylanthraquinone, benzophenone, Michler's ketone [4 , 4′-bis (dimethylamino) benzophenone], and aromatic ketones such as 4,4′-bis (diethylamino) benzophenone, and benzene such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin. Inethers, benzyl dimethyl ketal, benzyl diethyl ketal, and 1-phenyl-1,2-propanedione-2-O-benzoinoxime, and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) ) Oxime esters such as oximes. These can be used alone or in combination of two or more.

  In this embodiment, it is also preferable that the photosensitive resin composition contains a pyrazoline compound as a photosensitizer. 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. Among these, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is preferable. These can be used alone or in combination of two or more.

  In this embodiment, content of the photosensitizer in the photosensitive resin composition is 0.05 mass%-5 mass% from a viewpoint of improving the peeling characteristic and / or sensitivity of the photosensitive resin layer. It is preferably 0.1% by mass to 3% by mass, and more preferably 0.1% by mass to 1% by mass.

  In this embodiment, it is preferable that content of (C) photoinitiator in the photosensitive resin composition is 0.01 mass%-20 mass%. (C) The content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of the sensitivity of the photosensitive resin layer, and on the other hand, 20% by mass or less from the viewpoint of the resolution of the resist pattern. Is preferred. The content of the (C) photopolymerization initiator is more preferably 0.1% by mass to 10% by mass, and further preferably 0.1% by mass to 6% by mass. Furthermore, as the (C) photopolymerization initiator, one of the above-listed compounds may be used alone, or two or more may be used in combination.

(D) Other component In this embodiment, it is preferable that the photosensitive resin composition contains additives, such as a dye, a plasticizer, antioxidant, a stabilizer, if desired.

  Examples of the dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], fuchsin, phthalocyanine green, auramine base, paramadienta, crystal violet, Methyl orange, Nile blue 2B, Victoria blue, Malachite green (Hodogaya Chemical Co., Ltd., Eisen (registered trademark) MALACHITE GREEN), Basic Blue 20, Diamond Green (Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH) Etc. Among these, diamond green and leuco crystal violet are preferable from the viewpoint of improving colorability, hue stability and exposure contrast. These can be used alone or in combination of two or more.

  In the present embodiment, the content of the dye in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.01% by mass to 2% by mass. More preferably, it is the range of 0.04 mass%-1 mass%. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, while being 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. preferable.

  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 and polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, citric acid Triethyl acid, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate Propylene glycol respectively by adding propylene oxide to both sides of the bisphenol A, and ethylene glycol, respectively adding ethylene oxide to both sides of the bisphenol A and the like. These can be used alone or in combination of two or more.

  In this embodiment, content of the plasticizer in the photosensitive resin composition becomes like this. Preferably it is 0.1 mass%-50 mass%, More preferably, it is 1 mass%-20 mass%. The content of the plasticizer is preferably 0.1% by mass or more from the viewpoint of suppressing the delay in the development time of the photosensitive resin layer and imparting flexibility to the cured film, while the cured film is insufficiently cured. And it is preferable that it is 50 mass% or less from a viewpoint of suppressing a cold flow.

  Examples of the antioxidant include triphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris (2,4-di-tert-butylphenyl) phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd.). , Product name 2112), tris (monononylphenyl) phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., product name: 1178), bis (monononylphenyl) -dinonylphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., product) Name: 329K). These can be used alone or in combination of two or more.

  In this embodiment, content of antioxidant in the photosensitive resin composition becomes like this. Preferably it is the range of 0.01 mass%-0.8 mass%, More preferably, it is 0.01 mass%-0.00. The range is 3% by mass. The content of the antioxidant is preferably 0.01% by mass or more from the viewpoint of favorably developing the hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer. From the viewpoints of exhibiting good hue stability and improving adhesion while suppressing the color developability, it is preferably 0.8% by mass or less.

  The stabilizer is preferably used from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. Examples of the stabilizer include at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having a glycidyl group. These can be used alone 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), nitrosophenylhydroxyamine aluminum salt (for example, aluminum salt with 3 mol of nitrosophenylhydroxylamine added) And diphenylnitrosamine. Among these, an aluminum salt added with 3 mol of nitrosophenylhydroxylamine is preferable. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of benzotriazoles 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 can be used individually by 1 type or in combination of 2 or more types.

  Examples of carboxybenzotriazoles 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 can be used alone 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 can be used alone or in combination of two or more.

  In this embodiment, the total content of the radical polymerization inhibitor, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds 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 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, while, on the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. It is preferable that it is 3 mass% or less.

<Photosensitive resin composition preparation solution>
In this embodiment, the photosensitive resin composition preparation liquid can be formed by adding a solvent to the photosensitive resin composition. Suitable solvents include, for example, ketones typified 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 mPa · sec to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
In this embodiment, the photosensitive resin laminated body which has a support body and the photosensitive resin layer which consists of the said photosensitive resin composition laminated | stacked on this support body can be provided. If desired, the photosensitive resin laminate may have a protective layer on the side opposite to the support side of the photosensitive resin layer.

  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. , 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 is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and still more preferably 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 because the strength needs to be maintained.

  In addition, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is smaller than the support in terms of adhesion to the photosensitive resin layer and can be easily peeled off. As a protective layer, a polyethylene film, a polypropylene film, etc. are preferable, for example. 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, and more preferably 10 μm to 50 μm.

  In this embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, and more preferably 7 μm to 60 μm. The smaller the thickness of the photosensitive resin layer is, the more the resolution of the resist pattern is improved. On the other hand, the larger the thickness is, the more the strength of the cured film is improved.

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

  For example, the photosensitive resin composition preparation liquid is prepared, then coated on a support using a bar coater or roll coater and dried, and the photosensitive resin composition containing the photosensitive resin composition preparation liquid is formed on the support. A resin layer is laminated. Furthermore, if desired, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
The present invention includes a lamination step of laminating the photosensitive resin layer on a support, an exposure step of exposing the photosensitive resin layer, and a development step of developing the exposed photosensitive resin layer (preferably in order). A resist pattern forming method is also provided. An example of a specific method for forming a resist pattern in the present embodiment is shown below.

  First, in a laminating process, a photosensitive resin layer is formed on a 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 the present embodiment, 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 during lamination is generally 40 ° C to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the resist pattern obtained can be improved by performing the thermocompression bonding at the time of lamination twice or more. At the time of thermocompression bonding, a two-stage laminator provided with two rolls may be used, or the lamination of the substrate and the photosensitive resin layer may be repeated several times and passed through the roll.

  Next, in the exposure step, the photosensitive resin assembly layer is exposed to active light using an exposure machine. The exposure can be performed after peeling the support, if desired. In the case of exposing 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 process, 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, the unexposed or exposed portion of the exposed photosensitive resin layer is 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 or the exposed 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 , K ₂ CO ₃ or the like is preferable. The alkaline aqueous solution is 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 generally used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting 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 steps, in some cases, a heating step of 100 ° C. to 300 ° C. can be further performed. By performing this heating step, the chemical resistance of the resist pattern can be improved. A heating furnace of a hot air, infrared ray, far infrared ray, or the like can be used for the heating step.

<Conductor pattern manufacturing method>
The present invention includes a laminating step of laminating the photosensitive resin layer on a substrate such as a metal plate or a metal film insulating plate, an exposure step of exposing the photosensitive resin layer, an unexposed portion of the exposed photosensitive resin layer, or Conductor pattern including (preferably in sequence) a development step of obtaining a substrate on which a resist pattern is formed by removing the exposed portion with a developer, and a conductor pattern formation step of etching or plating the substrate on which the resist pattern is formed A manufacturing method is also provided. In this embodiment, the conductor pattern manufacturing method is performed by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-described resist pattern forming method, and then performing a conductor pattern forming step. In the conductor pattern forming step, a conductor pattern is formed on a substrate surface (for example, a copper surface) exposed by development using a known etching method or plating method.

  Furthermore, the present invention is suitably applied in the following applications, for example.

<Manufacturing method of wiring board>
After producing a conductor pattern according to the present invention, a wiring board having a desired wiring pattern (for example, a printed wiring board) is obtained by further performing a peeling step of peeling the resist pattern from the substrate with an aqueous solution having alkalinity stronger than the developer. ) Can be obtained. In the production of the wiring board, a copper-clad laminate or a flexible board is preferably used as the board. The alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”) 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. Examples of the water-soluble solvent include alcohol. The temperature of the stripping solution in the stripping step is preferably in the range of 40 ° C to 70 ° C.

<Manufacture of lead frames>
A lead frame can be manufactured by forming a resist pattern by the above-mentioned resist pattern forming method using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate and then performing the following steps. First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Then, a desired lead frame can be obtained by performing a peeling process in which the resist pattern is peeled by the same method as the method for manufacturing the wiring board.

<Manufacture of a substrate having an uneven 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. Examples of the substrate at this time include glass, a silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and a metal material. A resist pattern is formed on these substrates by the same method as the above resist pattern forming method. Thereafter, the substrate is subjected to a sandblasting process in which a blast material is sprayed from the formed resist pattern and cut to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkali stripping solution or the like. The base material which has a fine uneven | corrugated pattern on it can be manufactured. As a blasting material used in the above-mentioned sandblasting process, known materials can be used. For example, fine particles having a particle size of about 2 μm to 100 μm, such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel, etc. Is commonly used.

<Manufacture of semiconductor packages>
A semiconductor package can be manufactured by using a wafer on which a large-scale integrated circuit (LSI) has been formed as a substrate and forming a resist pattern on the wafer by the resist pattern forming method, followed by the following steps. First, a step of forming a conductor pattern by performing columnar plating such as copper or solder on the opening exposed by development is performed. Then, a desired semiconductor package is obtained by performing a peeling process for peeling the resist pattern by the same method as the method for manufacturing the wiring board, and further removing a thin metal layer by etching other than the columnar plating. Can be obtained.

  In this embodiment, the photosensitive resin composition is 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 sizes, Manufacture of packages such as packages (CSP), manufacture of tape substrates such as chip-on-film (COF) or tape automated bonding (TAB), manufacture of semiconductor bumps, flat panels such as ITO electrodes or address electrodes, electromagnetic wave shields, etc. It can be used for manufacturing a partition of a display.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

<Measurement of weight average molecular weight>
In this specification, the weight average molecular weight means a weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko KK). The weight average molecular weight can be measured under the following conditions using gel permeation chromatography manufactured by JASCO Corporation.
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

<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.

<Resolution evaluation>
Jet scrub polishing of a 0.4mm thick copper clad laminate laminated with 35μm rolled copper foil using a grinding material (Nippon Carlit Co., Ltd., Sacradund R (registered trademark # 220)) with a spray pressure of 0.2MPa did. Next, while peeling the polyethylene film of the photosensitive resin laminate, roll the photosensitive resin laminate on a copper clad laminate preheated to 60 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). A test piece was obtained by laminating at a temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min. With a direct drawing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ± 5 nm), a line pattern with a ratio of 1: 1 between the exposed area and the unexposed area is formed. The exposure was performed at 85 mW with an exposure amount of 70 mJ / cm ² . For Example 3, a line pattern having a ratio of the width of the exposed area to the unexposed area of 1: 1 using a parallel light exposure machine (HMW-801, manufactured by Oak Manufacturing Co., Ltd.) during exposure is used. Using the chromium glass mask which has, the test piece was exposed with the exposure amount of 100 mJ / cm < ² >. Thereafter, development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which a cured resist line was normally formed was defined as a resolution value, and the resolution was ranked as follows. In this specification, the minimum development time is defined as the minimum time required for the photosensitive resin layer in the unexposed portion to be completely dissolved. In addition, the minimum mask width formed normally without the collapse of the cured resist pattern or the adhesion between the cured resists was evaluated:
A: Resolution value is 10 μm or less;
○: The resolution value exceeds 10 μm and is 12 μm or less;
(Triangle | delta): The value of resolution exceeds 12 micrometers and is 14 micrometers or less;
×: Resolution value exceeds 14 μm

<Susole shape evaluation>
Jet scrub polishing of a 0.4mm thick copper clad laminate laminated with 35μm rolled copper foil using a grinding material (Nippon Carlit Co., Ltd., Sacradund R (registered trademark # 220)) with a spray pressure of 0.2MPa did. Next, while peeling the polyethylene film of the photosensitive resin laminate, roll the photosensitive resin laminate on a copper clad laminate preheated to 60 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). A test piece was obtained by laminating at a temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min. With a direct drawing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ± 5 nm), a line pattern with a ratio of 1: 1 between the exposed area and the unexposed area is formed. The exposure was performed at 85 mW with an exposure amount of 70 mJ / cm ² . For Example 3, a line pattern having a ratio of the width of the exposed area to the unexposed area of 1: 1 using a parallel light exposure machine (HMW-801, manufactured by Oak Manufacturing Co., Ltd.) during exposure is used. Using the chromium glass mask which has, the test piece was exposed with the exposure amount of 100 mJ / cm < ² >. Thereafter, development was performed with a development time twice as long as the minimum development time to obtain a resist pattern. Subsequently, the obtained resist pattern was observed with a scanning electron microscope (manufactured by Hitachi High-Tech Fielding, S-3400N), and the sword shape of the resist pattern was ranked as follows.
○: There is almost no rattling in the formed sword.
X: The formed sword has rattling.

<Residual film rate evaluation>
70 mJ / cm ² exposure at 85 W with a direct drawing type exposure apparatus (manufactured by Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode, main wavelength 405 ± 5 nm) from the support film side of the photosensitive resin laminate Exposed in quantity. In addition, for Example 3, exposure was performed at an exposure amount of 100 mJ / cm ² using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd., HMW-801) during exposure. Thereafter, 0.5 g of the cured resist was immersed in 100 mL of 3% NaOH solution and stirred for 3 hours. After the stirring, the cured resist was recovered by suction filtration of the solution and washed with pure water. The resulting cured resist was vacuum dried, the rate of change in weight before and after the test was measured, and ranked according to the following criteria to evaluate the residual film rate of the resist pattern:
○: Remaining film ratio is 80% or more;
Δ: Remaining film ratio is less than 80%, 50% or more;
X: Remaining film ratio is less than 50%

<Examples 1-11 and Comparative Examples 1 and 2 (Example 7 is merely a reference example) >
The components shown in Tables 1 and 2 were stirred and mixed in the blending amounts shown in Tables 1 and 2 to prepare a photosensitive resin composition. The photosensitive resin composition is uniformly applied using a blade coater on the surface of a 16 μm-thick polyethylene terephthalate film (Toray Industries, Inc., FB40) as a support film, and then 2.5 minutes in a 95 ° C. drier. It dried and formed the uniform photosensitive resin layer on the support film. The thickness of the photosensitive resin layer was 25 μm. Next, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) was bonded as a protective film on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate. Each evaluation demonstrated above was performed about the photosensitive resin laminated body. The evaluation results are shown in Table 1.

From the results shown in Table 1, it can be seen that the example is superior in the resolution, the sword shape, and the remaining film ratio of the resist pattern as compared with the comparative example. Moreover, it turns out from the comparison with Examples 1-6 and Example 7 that the resolution of a resist pattern improves by using (A) alkali-soluble polymer which has an aromatic group in a side chain. Further, from comparison between Examples 1 to 6 and Examples 8 and 9, by using the compound represented by the general formula (II) as a compound having (B) an ethylenically unsaturated bond, It can be seen that the resolution is improved. Moreover, from the comparison with Examples 1-6 and Example 10, the resolution of a resist pattern improves by using the compound whose n < ₁ > + n < ₂ > is 2-10 in the said general formula (II). I understand.

  The photosensitive resin composition described above is used for the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the precision processing of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA or CSP, and the tapes such as COF or TAB. It can be used for the production of substrates, the production of semiconductor bumps, the production of partition walls for flat panel displays such as ITO electrodes or address electrodes, and electromagnetic wave shields.

Claims (7)

Based on the total solid content of the photosensitive resin composition, the following components:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass,
(B) Compound having ethylenically unsaturated bond: 5% by mass to 70% by mass, and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass,
The (A) alkali-soluble polymer has a weight average molecular weight of 5,000 to 55,000, and (B) the compound having an ethylenically unsaturated bond, The following general formula (I):

{Wherein R _{1 to} R ₄ each independently represents an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, m ₁ , m ₂ , m ₃ and m ₄ is each independently an integer of 0 to 40, m ₁ + m ₂ + m ₃ + m ₄ is 1 to 40, and when m ₁ + m ₂ + m ₃ + m ₄ is 2 or more, a plurality of X's may be the same as or different from each other. } The photosensitive resin composition containing the compound represented by this. The photosensitivity according to claim 1, wherein the (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 55,000 , and has an aromatic group in its side chain. Resin composition. As the compound (B) having an ethylenically unsaturated bond, the following general formula (II):

{In the formula, R ₅ and R ₆ each independently represent a hydrogen atom or a methyl group; Y independently represents an alkylene group having 2 to 6 carbon atoms; and n ₁ and n ₂ represent each independently And 0 or a positive integer, and n ₁ + n ₂ is 2 to 40. } The photosensitive resin composition of Claim 1 or 2 which further contains the compound represented by these. The photosensitive resin composition according to claim 3, wherein n ₁ + n ₂ is 2 to 10 in the general formula (II).   The photosensitive resin composition of any one of Claims 1-4 containing a hexaarylbisimidazole compound as said (C) photoinitiator. The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 5 on a support;
An exposure step of exposing the photosensitive resin layer; and a development step of developing the exposed photosensitive resin layer;
A resist pattern forming method including: The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 5 on a substrate;
An exposure step of exposing the photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
A method of manufacturing a wiring board, comprising: a conductor pattern forming step of etching or plating a substrate on which the resist pattern is formed; and a peeling step of peeling the resist pattern.