JP2010197831A - Photosensitive resin composition and photosensitive element using the composition, method for forming resist pattern and method for manufacturing printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in sensitivity, resolution, adhesiveness, resist features, and peeling characteristics and sludge removing property after cured; and to provide a photosensitive element, a method for forming a resist pattern and a method for manufacturing a printed wiring board using the composition. <P>SOLUTION: The photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator containing a hexarylbiimidazole compound, and (D) a sensitizing dye containing a compound expressed by general formula (4). In general formula (4), R<SP>31</SP>to R<SP>33</SP>each independently represents a 1C-3C alkyl group or a 1C-10C alkoxy group, and when a plurality of R<SP>31</SP>to R<SP>33</SP>are present in one molecule, they may be identical or different from each other; and the sum of a, b and c is 1 to 6. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for forming a resist pattern, and a method for producing a printed wiring board.

  In the field of manufacturing printed wiring boards, photosensitive resin compositions and photosensitive elements (laminates) are widely used as resist materials used for etching and plating.

  A printed wiring board is manufactured as follows, for example. First, the photosensitive resin composition layer of the photosensitive element is laminated (laminated) on the circuit forming substrate. Next, a predetermined part of the photosensitive resin composition layer is irradiated with actinic rays to cure the exposed part. Then, after peeling off and removing the support film, a resist pattern made of a cured product of the photosensitive resin composition is formed on the substrate by removing (developing) the unexposed portion from the substrate. An etching process or a plating process is performed on the obtained resist pattern to form a circuit on the substrate, and finally the resist is peeled and removed to produce a printed wiring board.

  Here, the etching treatment is a method of removing the resist after etching away the conductor layer of the circuit forming substrate not covered with the resist pattern. On the other hand, the plating process is performed by plating copper or solder on the conductor layer of the circuit forming substrate that is not covered with the resist pattern, and then removing the resist and soft etching the metal surface covered with the resist. Is the method.

  As the exposure method, conventionally, a method of exposing through a photomask using a mercury lamp as a light source has been used. In recent years, there has been proposed a direct drawing exposure method called DLP (Digital Light Processing) or LDI (Laser Direct Imaging) for directly drawing pattern digital data on a photosensitive resin composition layer (for example, non-patent literature). 1). This direct drawing exposure method has better alignment accuracy than an exposure method through a photomask, and a high-definition pattern can be obtained, so that it is being introduced for the production of a high-density package substrate.

  In the exposure process, it is necessary to shorten the exposure time as much as possible in order to improve production efficiency. However, in the direct drawing exposure method described above, a monochromatic light such as a laser is used as a light source, and a light beam is irradiated while scanning the substrate. Therefore, a long exposure time is required compared to an exposure method using a conventional photomask. There is. Therefore, it is necessary to further improve the sensitivity of the photosensitive resin composition as compared with the conventional case.

  On the other hand, with the recent increase in the density of printed wiring boards, there is an increasing demand for high resolution and high adhesion for photosensitive resin compositions. In particular, in the production of a package substrate, a photosensitive resin composition capable of forming a resist pattern having an L / S (line width / space width) of 10/10 (unit: μm) or less is required.

  In a high-density package substrate, since the width between circuits is narrow, it is also important that the resist shape is excellent. If the cross-sectional shape of the resist is trapezoidal or inverted trapezoidal, or if there is a tailing of the resist, the circuit formed by the subsequent etching process or plating process may cause a short circuit or disconnection. It is desirable to have a rectangular shape and no tailing.

  Furthermore, the photosensitive resin composition is required to improve workability, production efficiency, and production yield when manufacturing a printed wiring board. Specifically, it is required that the photosensitive resin composition is excellent in peeling characteristics after curing, deposit (sludge) removability in the development process, and the like. In other words, shortening the resist stripping time improves the production efficiency of the stripping process, and reducing the resist stripping piece size prevents reattachment of the stripping piece on the circuit board, resulting in a production yield. Will improve. In addition, the excellent deposit (sludge) removal performance prevents sludge from adhering to the developer tank, improving workability, and suppressing problems such as short circuits and disconnections due to sludge adhering to the circuit forming substrate. And the production yield is improved.

  Here, Patent Document 1 discloses a photosensitive resin composition using a specific binder polymer, a sensitizing dye, or the like as a photosensitive resin composition having good sensitivity that can be applied to a direct drawing exposure method. Yes.

  Patent Document 2 discloses a photosensitive resin composition in which a polyfunctional acrylate compound is introduced to increase the number of crosslinking points in order to improve adhesion to a substrate (developer resistance).

  Patent Document 3 discloses a photosensitive resin composition using a polymerization inhibitor such as catechol or hydroquinone in order to improve the contrast (imaging property) between an exposed portion and an unexposed portion.

JP 2005-122123 A JP 2003-215799 A JP 2000-162767 A

“Electronic Packaging Technology”, June 2002, p. 74-79

  However, although the photosensitive resin composition of Patent Document 1 is good in terms of sensitivity and peeling properties, it is not necessarily sufficient in terms of resolution and adhesion.

  The photosensitive resin composition of Patent Document 2 has good adhesion, but is not sufficient in terms of peeling characteristics, and the cured product tends to be difficult to peel off from the substrate.

  The photosensitive resin composition of Patent Document 3 is good in terms of resolution, adhesion, and imaging properties, but is not sufficient in terms of sensitivity, and requires a lot of exposure time when using a direct drawing exposure method.

  As described above, none of the conventional photosensitive resin compositions sufficiently satisfy the required characteristics.

  Accordingly, the present invention provides a photosensitive resin composition having good sensitivity, resolution, adhesion, resist shape, release property after curing, and sludge removal, and a photosensitive element and a resist pattern using the same. It is an object to provide a method and a printed wiring board manufacturing method.

  The present invention includes [1] (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator containing a compound represented by the following general formula (1), and (D) the following general formula (4). The photosensitive resin composition containing the sensitizing dye containing the compound represented by this is provided. Since the present invention has the above-described configuration, the sensitivity, resolution, adhesion, resist shape, release property after curing, and sludge removability are all good.

［一般式（１）中、Ｚ^１及びＺ^２は、それぞれ独立に下記一般式（２）又は（３）で表される１価の基を示す。］

[In the general formula (1), ^{Z 1} and ^{Z 2} is a monovalent group represented by the following general formula (2) or (3) independently. ]

［一般式（２）及び一般式（３）中、Ｒ^１〜Ｒ^３０は、それぞれ独立に水素原子、ハロゲン原子又は炭素数１〜５のアルコキシ基を示し、同一分子中にＲ^１〜Ｒ^３０が複数存在するときそれらは同一でも異なっていてもよく、Ｒ^１〜Ｒ^３０の少なくとも１つは炭素数１〜５のアルコキシ基を示す。］

[In General Formula (2) and General Formula (3), R ^{1 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, or an alkoxy group having 1 to 5 carbon atoms, and R ^{1 to} R ^{30 in the} same molecule. When two or more are present, they may be the same or different, and at least one of R ^{1 to} R ³⁰ represents an alkoxy group having 1 to 5 carbon atoms. ]

［一般式（４）中、Ｒ^３１〜Ｒ^３３は、それぞれ独立に炭素数１〜３のアルキル基又は炭素数１〜１０のアルコキシ基を示し、同一分子中にＲ^３１〜Ｒ^３３が複数存在するときそれらは同一でも異なっていてもよく、ａ、ｂ及びｃの総和は、１〜６である。］
また、本発明は、［２］前記一般式（１）で表される化合物を含む光重合開始剤のＲ^１〜Ｒ^３０は、それぞれ独立に水素原子、塩素原子又はメトキシ基を示し、Ｒ^１〜Ｒ^３０の少なくとも１つはメトキシ基である上記［１］に記載の感光性樹脂組成物を提供する。これにより、感光性樹脂組成物の現像液に対する分散性又は溶解性が増し、スラッジ除去性を向上することができる。

[In General Formula (4), R ^{31 to} R ³³ each independently represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and a plurality of R ^{31 to} R ³³ are present in the same molecule. They may be the same or different and the sum of a, b and c is 1-6. ]
Further, the present invention is [2] the general formula ⁽¹⁾ R 1 ~R ³⁰ of the photopolymerization initiator comprising a compound represented by each independently represent a hydrogen atom, a chlorine atom or a methoxy group, R ¹ at least one of to R ³⁰ is to provide a photosensitive resin composition according to [1] a methoxy group. Thereby, the dispersibility or solubility with respect to the developing solution of the photosensitive resin composition increases, and sludge removability can be improved.

The present invention also provides [3] The above [1] or [2] wherein R ^{31 to} R ^{33 of the} sensitizing dye containing the compound represented by the general formula (4) each independently represent an isopropyl group or a methoxy group. ] The photosensitive resin composition as described in this invention is provided. The present invention also provides [4] any one of [1] to [3] above, wherein the sum of a, b and c of the sensitizing dye containing the compound represented by the general formula (4) is 1 to 2. The photosensitive resin composition as described above is provided. Thereby, the effect of this invention can be acquired more reliably.

  Moreover, this invention is [5] the photosensitive in any one of said [1]-[4] in which the (A) binder polymer contains the structural unit based on (meth) acrylic acid and styrene or a styrene derivative. A functional resin composition is provided. Thereby, alkali developability, resolution, and adhesiveness are improved in a balanced manner.

  [6] The photosensitive resin composition according to any one of [1] to [5], wherein the photopolymerizable compound (B) includes a bisphenol A-based (meth) acrylate compound. To do. Thereby, the alkali developability, the resolution, or the peeling property after curing is improved.

  The present invention also provides [7] The above (B), wherein the photopolymerizable compound includes a trimethylolpropane tri (meth) acrylate compound having a (poly) oxyethylene chain or a (poly) oxypropylene chain in the molecule. The photosensitive resin composition as described in any one of 1] to [6] is provided. Thereby, the alkali developability, the resolution, the adhesion, or the release characteristics after curing is improved.

  The present invention also provides [8] (B) the photopolymerizable compound further comprising a polyalkylene glycol di (meth) acrylate having both a (poly) oxyethylene chain and a (poly) oxypropylene chain in the molecule. The photosensitive resin composition as described in any one of [1] to [7] above is provided. Thereby, the flexibility of the cured product (cured film) of the photosensitive resin composition is improved.

  Moreover, this invention provides the photosensitive resin composition in any one of said [1]-[8] whose acid value of [9] said (A) binder polymer is 80-250 mgKOH / g. Moreover, this invention provides the photosensitive resin composition in any one of said [1]-[9] whose weight average molecular weights of [10] said (A) binder polymer are 5000-200000. Thereby, alkali developability, development time and developer resistance are improved in a balanced manner.

  Moreover, this invention provides the photosensitive resin composition in any one of said [1]-[10] which further contains [11] (E) amine type compound. Thereby, the sensitivity of the photosensitive resin composition is further improved.

  Further, the present invention provides [12] a support film, and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of the above [1] to [11] formed on the support film, A photosensitive element is provided. By using such a photosensitive element, it is possible to efficiently and efficiently form a resist pattern having good resolution, adhesion, resist shape, and release characteristics after curing.

  The present invention also provides [13] a lamination step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to [11] on a substrate, and a photosensitive resin composition. An exposure step of irradiating a predetermined portion of the physical layer with actinic rays to expose and cure the predetermined portion, and removing a portion other than the predetermined portion of the photosensitive resin composition layer from the substrate, And a development step of forming a resist pattern made of a cured product of the photosensitive resin composition on a substrate. According to the above method, it is possible to efficiently and efficiently form a resist pattern having good resolution, adhesion, resist shape, and release characteristics after curing.

  The present invention also provides [14] the method for forming a resist pattern according to the above [13], wherein the wavelength of the actinic ray is in the range of 390 to 420 nm. In the resist pattern forming method, the wavelength of the active light to be irradiated is preferably in the range of 390 to 420 nm. As a result, a resist pattern with better resolution, adhesion, and resist shape can be efficiently formed with higher sensitivity.

  The present invention also provides [15] a method for manufacturing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern according to [13] or [14]. To do. According to this manufacturing method, a printed wiring board having high-density wiring such as a high-density package substrate can be efficiently manufactured with high accuracy.

  According to the present invention, a photosensitive resin composition having good sensitivity, resolution, adhesion, resist shape, and release property after curing, a photosensitive element using the same, a method for forming a resist pattern, and printed wiring A method for manufacturing a plate can be provided.

It is a top view which shows typically the drawing pattern for evaluating resolution and adhesiveness (L / S = x / x). It is a top view which shows typically the drawing pattern for evaluating resolution (L / S = 3x / x). It is a top view which shows typically the drawing pattern for evaluating adhesiveness (L / S = x / 3x).

Hereinafter, the best mode for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or methacrylate, and (meth) acryloyl group means acryloyl group or methacryloyl. Means group. The (poly) oxyethylene chain means an oxyethylene group or a polyoxyethylene chain, and the (poly) oxypropylene chain means an oxypropylene group or a polyoxypropylene chain. Further, “EO-modified” means a compound having a (poly) oxyethylene chain, and “PO-modified” means a compound having a (poly) oxypropylene chain. “PO-modified” means a compound having both a (poly) oxyethylene chain and a (poly) oxypropylene chain.
(Photosensitive resin composition)
The photosensitive resin composition of the present embodiment includes (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator containing a compound represented by the above general formula (1), and (D) the above A sensitizing dye containing the compound represented by the general formula (4) is contained.

  The binder polymer as component (A) will be described.

  Examples of the binder polymer as component (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, and the like, from the viewpoint of alkali developability. Therefore, an acrylic resin is preferable.

  (A) The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer (monomer). Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyl toluene, α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, vinyl-n-. Esters of vinyl alcohol such as butyl ether, (meth) acrylic acid alkyl esters, (meth) acrylic acid cycloalkyl esters, (meth) acrylic acid benzyl esters, (meth) acrylic acid furfuryl esters, (meth) acrylic acid tetrahydrofurates Furyl ester, (meth) acrylic acid isobornyl ester, (meth) acrylic acid adamantyl ester, (meth) acrylic acid dicyclopentanyl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylamino No ethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α- Bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, Examples include maleic acid monoesters such as monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These may be used alone or in any combination of two or more.

  (A) It is preferable that a binder polymer consists of 1 type, or 2 or more types of the polymer which has a carboxyl group from the viewpoint of alkali developability. Such a (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer. The polymerizable monomer having a carboxyl group is preferably (meth) acrylic acid, more preferably methacrylic acid, from the viewpoint of improving alkali developability.

  In addition, (A) the binder polymer may be produced by radical polymerization of styrene or a derivative thereof and other polymerizable monomers from the viewpoint of improving the balance between adhesion and release properties. preferable.

  (A) When a binder polymer has a structural unit based on styrene or its derivative in a molecule | numerator, it is preferable that the content is 5-65 mass% on the basis of a molecule | numerator total mass, and is 10-65 mass%. More preferably, it is more preferably 20 to 65% by mass, particularly preferably 30 to 60% by mass, and particularly preferably 35 to 55% by mass. If this content is less than 5% by mass, sufficient adhesion tends to be difficult to obtain, and if this content exceeds 65% by mass, the peel piece tends to be large and the peel time tends to be long. .

  (A) The binder polymer preferably contains a structural unit based on (meth) acrylic acid alkyl ester from the viewpoint of improving alkali developability and peeling properties, and from the viewpoint of improving resolution, (meth) It is preferable to include a structural unit based on benzyl acrylate.

  (A) When a binder polymer contains the structural unit based on the (meth) acrylic-acid alkylester, it is preferable that the content is 25-70 mass% on the basis of the molecular total mass, and is 30-65 mass%. More preferably, it is more preferably 40 to 65% by mass. If this content is less than 25% by mass, sufficient adhesion tends to be difficult to obtain, and if this content exceeds 70% by mass, the peel piece tends to be large and the peel time tends to be long.

Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (5), compounds obtained by substituting alkyl groups of these compounds with hydroxyl groups, epoxy groups, halogen groups, and the like. In the following general formula (5), R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ represents an alkyl group having 1 to 12 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ³⁵ in the general formula (5), a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl Group, decyl group, undecyl group, dodecyl group and structural isomers thereof. From the viewpoint of further improving sensitivity and peeling properties, the alkyl group is preferably one having 4 or less carbon atoms.

  Examples of the compound (monomer) represented by the general formula (5) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, ( (Meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, ( Examples include meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, and the like. These may be used alone or in any combination of two or more.

  (A) The acid value of the binder polymer is preferably 80 to 250 mgKOH / g, more preferably 100 to 220 mgKOH / g, still more preferably 110 to 200 mgKOH / g, and 120 to 180 mgKOH / g. It is particularly preferred that When the acid value is less than 80 mgKOH / g, the development time tends to be long, and when it exceeds 250 mgKOH / g, the developer resistance of the cured product of the photosensitive resin composition tends to be insufficient. . In addition, when performing solvent image development, it is preferable to prepare the polymerizable monomer (monomer) which has a carboxyl group in a small quantity.

  (A) The weight average molecular weight (Mw) of the binder polymer is preferably 5,000 to 200,000 when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene), and preferably 10,000 to 100,000. It is more preferable that it is 20000-80000, and it is especially preferable that it is 30000-70000. When Mw is less than 5000, the developing solution resistance of the cured product of the photosensitive resin composition tends to be insufficiently obtained, and when it exceeds 200,000, the development time tends to be long.

  (A) The dispersity (Mw / Mn) of the binder polymer is preferably 1.0 to 3.0, and more preferably 1.0 to 2.0. If the degree of dispersion exceeds 3.0, the adhesion and resolution tend not to be obtained sufficiently.

  Moreover, (A) binder polymer may have a characteristic group having photosensitivity to light having a wavelength within the range of 350 to 440 nm in the molecule, if necessary.

  (A) As the binder polymer, one kind of binder polymer may be used alone, or two or more kinds of binder polymers may be used in any combination. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymer components (including different monomer units as copolymer components), two or more types of different weight average molecular weights Examples of the binder polymer include two or more types of binder polymers having different degrees of dispersion. In addition, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.

  The content of the component (A) is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is especially preferable to set it as -60 mass parts. If this content is less than 30 parts by mass, it tends to be difficult to form a film, and if it exceeds 70 parts by mass, the sensitivity and resolution tend to be difficult to obtain sufficiently.

  Next, the photopolymerizable compound as the component (B) will be described.

  (B) The photopolymerizable compound is not particularly limited as long as it has at least one ethylenically unsaturated bond in the molecule. For example, bisphenol A (meth) acrylate compound, polyhydric alcohol with α, β -Compounds obtained by reacting unsaturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond in the molecule, nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, (meth) acrylic acid alkyl esters, glycidyl Examples include compounds obtained by reacting a group-containing compound with an α, β-unsaturated carboxylic acid. These are used alone or in combination of two or more.

  (B) It is preferable that a photopolymerizable compound contains a bisphenol A type (meth) acrylate compound from a viewpoint of improving resolution and peeling characteristics. These are more preferably contained in an amount of 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total amount of the component (B).

  Examples of bisphenol A-based (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl. ) Propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane and the like. Of these, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is preferred from the viewpoint of further improving the resolution and peeling properties.

  As 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 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) acryloxy) Pentaethoxy) 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) acryloxynononaethoxy) fe ) 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) acryloxyhexadeca) And ethoxy) phenyl) propane.

  As 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 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) acryloxy) Pentapropoxy) 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) acryloxy) Propoxy) 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) acryloxy) Hexadecapropoxy) phenyl) propane and the like.

  Among these, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) or FA-321M (manufactured by Hitachi Chemical Co., Ltd., 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Is available. The number of ethylene oxide groups in one molecule of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is preferably 4 to 20, and more preferably 8 to 15. These may be used alone or in any combination of two or more.

  As 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, 2, Examples include 2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane.

  As a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, and 2 to 14 propylene groups Polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Ruhexa (meth) acrylate and the like. These are used alone or in combination of two or more.

  Among these, A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, tetramethylol methane triacrylate), TMPT21E, TMPT30E (manufactured by Hitachi Chemical Co., Ltd., sample name, EO) are available. Modified trimethylolpropane trimethacrylate) and the like.

  (B) The photopolymerizable compound is a trimethylolpropane having a (poly) oxyethylene chain or a (poly) oxypropylene chain in the molecule from the viewpoint of improving alkali developability, resolution, adhesion, or release properties after curing. It is preferable to include a tri (meth) acrylate compound, and it is more preferable to include a trimethylolpropane tri (meth) acrylate compound having a (poly) oxyethylene chain in the molecule. These are more preferably contained in an amount of 5 to 50% by mass, more preferably 10 to 40% by mass, based on the total amount of the component (B).

  In addition, (B) the photopolymerizable compound has (poly) oxyethylene chains and (poly) oxypropylene chains in the molecule from the viewpoint of improving the flexibility of the cured product (cured film) of the photosensitive resin composition. It is preferable to include polyalkylene glycol di (meth) acrylate having both. These are more preferably contained in an amount of 5 to 50% by mass, more preferably 10 to 40% by mass, based on the total amount of the component (B).

  As said polyalkylene glycol di (meth) acrylate, (poly) oxyethylene chain and (poly) oxypropylene chain ((poly) oxy-n-propylene) chain or (poly) The one having both) oxyisopropylene chain) is preferred. In addition, polyalkylene glycol di (meth) acrylate further includes (poly) oxy-n-butylene chain, (poly) oxyisobutylene chain, (poly) oxy-n-pentylene chain, (poly) oxyhexylene chain, It may have a (poly) oxyalkylene chain having about 4 to 6 carbon atoms, such as these structural isomers.

  In the molecule of polyalkylene glycol di (meth) acrylate, the (poly) oxyethylene chain and the (poly) oxypropylene chain may be continuously present in blocks or randomly. In the (poly) oxyisopropylene chain, the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.

  As the polyalkylene glycol di (meth) acrylate, a compound represented by the following general formula (6), (7) or (8) is particularly preferable. These may be used alone or in combination of two or more.

In the general formulas (6), (7) and (8), R independently represents a hydrogen atom or a methyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group. m ₁ , m ₂ , m ₃ and m ₄ represent the number of repeating structural units composed of oxyethylene groups, and n ₁ , n ₂ , n ₃ and n ₄ represent the number of repeating structural units composed of oxypropylene groups. And the total number of repeating oxyethylene groups m ₁ + m ₂ , m ₃ and m ₄ (average value) each independently represents an integer of 1 to 30, and the total number of repeating oxypropylene groups n ₁ , n ₂ + n ₃ and n ₄ (average value) independently represents an integer of 1 to 30.

In the compound represented by the general formula (6), (7) or (8), the total number of repeating oxyethylene groups m ₁ + m ₂ , m ₃ and m ₄ is an integer of 1 to 30, preferably 1. It is an integer of -10, More preferably, it is an integer of 4-9, Most preferably, it is an integer of 5-8. If the total number of repetitions exceeds 30, sufficient resolution, adhesion, and resist shape tend to be difficult to obtain.

The total number of repeating oxypropylene groups n ₁ , n ₂ + n ₃ and n ₄ is an integer of 1 to 30, preferably an integer of 5 to 20, more preferably an integer of 8 to 16, Preferably it is an integer of 10-14. When the total number of repetitions exceeds 30, it is difficult to obtain a sufficient resolution and sludge tends to be generated.

As the compound represented by the general formula (6), R = methyl group, m ₁ + m ₂ = 6 (average value), n ₁ = 12 (average value) vinyl compound (manufactured by Hitachi Chemical Co., Ltd., Trade name FA-023M). As the compound represented by the general formula (7), R = methyl group, m ₃ = 6 (average value), n ₂ + n ₃ = 12 (average value) vinyl compound (manufactured by Hitachi Chemical Co., Ltd., Trade name FA-024M). As the compound represented by the general formula (8), R = hydrogen atom, m ₄ = 1 (average value), n ₄ = 9 (average value) vinyl compound (manufactured by Shin-Nakamura Chemical Co., Ltd., sample) Name NK ester HEMA-9P) and the like. These can be used alone or in combination of two or more.

  As the (meth) acrylate compound having a urethane bond in the molecule, a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1 , 6-hexamethylene diisocyanate, etc.), tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, etc. Can be mentioned. Examples of the EO-modified urethane di (meth) acrylate include UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Examples of EO and PO-modified urethane di (meth) acrylate include UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). These are used alone or in combination of two or more.

  Examples of the nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethylene Examples include oxyacrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate. These may be used alone or in any combination of two or more.

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxyalkyl-o-phthalate, and the like. Is mentioned. These are used alone or in combination of two or more.

  Moreover, (B) a photopolymerizable compound contains the photopolymerizable compound which has one ethylenically unsaturated bond in a molecule | numerator from a viewpoint of improving the peelability of the hardened | cured material (cured film) of the photosensitive resin composition. The content is more preferably 3 to 30% by mass, and further preferably 5 to 20% by mass, based on the total amount of the component (B).

  The content of the component (B) is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is especially preferable to set it as -60 mass parts. If the content is less than 30 parts by mass, sufficient sensitivity and resolution tend to be difficult to obtain, and if it exceeds 70 parts by mass, a film tends to be difficult to form, and a good resist shape is obtained. There is a tendency to become difficult to be.

  Next, the photoinitiator which is (C) component is demonstrated.

  (C) The photoinitiator which is a component contains the compound represented by (C) following General formula (1).

上記一般式（１）中、Ｚ^１及びＺ^２は、それぞれ独立に下記一般式（２）又は（３）で表される１価の基を示す。

In the general formula (1), Z ¹ and Z ² each independently represent a monovalent group represented by the following general formula (2) or (3).

上記一般式（２）及び一般式（３）中、Ｒ^１〜Ｒ^３０は、それぞれ独立に水素原子、ハロゲン原子又は炭素数１〜５のアルコキシ基を示す。このＲ^１〜Ｒ^３０のうち少なくとも１つは、炭素数１〜５のアルコキシ基であり、２つ以上が炭素数１〜５のアルコキシ基であることが好ましく、４つ以上が炭素数１〜５のアルコキシ基であることがより好ましい。Ｒ^１〜Ｒ^３０のうち炭素数１〜５のアルコキシ基を示すものが１つもない場合、解像度、密着性、スラッジ除去性が不十分となる傾向がある。

In General Formula (2) and General Formula (3), R ^{1 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, or an alkoxy group having 1 to 5 carbon atoms. At least one of R ^{1 to} R ³⁰ is an alkoxy group having 1 to 5 carbon atoms, preferably 2 or more are alkoxy groups having 1 to 5 carbon atoms, and 4 or more are carbon atoms having 1 to 5 carbon atoms. More preferred is an alkoxy group of 5. When none of R ^{1 to} R ³⁰ shows an alkoxy group having 1 to 5 carbon atoms, resolution, adhesion, and sludge removability tend to be insufficient.

  Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group and structural isomers thereof. Of these, a methoxy group is preferable.

  As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Especially, it is preferable that it is a chlorine atom.

From the viewpoint of further improving the resolution and adhesion, it is preferable that at least one of R ^{1 to} R ³⁰ represents an alkoxy group having 1 to 5 carbon atoms, and at least one of the remaining represents a halogen atom. Moreover, when there are a plurality of R ^{1 to} R ³⁰ in the same molecule, they may be the same or different.

In the present specification, groups represented as “R ^{1 to} R ³⁰ ” are R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^10. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ shows a group of ^{R 28, R 29} or ^{R 30.}

  Examples of the compound represented by the general formula (1) include 2- (o-chlorophenyl) -4,5-bis (m-methoxyphenyl) imidazole dimer, 2- (o-methoxyphenyl) -4. , 5-diphenylimidazole dimer, 2,4-bis (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) imidazole dimer, and the like. These can be used alone or in combination of two or more.

In the general formula (1), Z ¹ and Z ² may be the same or different, and the hexaarylbisimidazole compound represented by the general formula (1) is symmetric or asymmetric. A hexaarylbisimidazole compound having one or more alkoxy groups having 1 to 5 carbon atoms may be used from the viewpoint of enhancing the solubility of the compound represented by the general formula (1) in the photosensitive resin composition. It is preferable that the asymmetric compound obtained by the used cross-coupling reaction is included. As asymmetric compounds, for example, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole and 2,2 ′, 4,4′-tetra (o-chlorophenyl)- Compound obtained by coupling reaction of 5,5′-bis (3,4-dimethoxyphenyl) -bisimidazole, 2,2 ′, 4-tris (o-chlorophenyl) -4 ′, 5′-diphenyl-5 (3,4 dimethoxyphenyl) -bisimidazole and the like.

  Moreover, to the photosensitive resin composition of this invention, photoinitiators other than the compound represented by the said General formula (1) can be mix | blended to such an extent that the effect of this invention is not impaired.

  Examples of the photopolymerization initiator other than the compound represented by the general formula (1) include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- Aromatic ketones such as [4- (methylthio) phenyl] -2-morpholino-propanone-1, quinones such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyldimethyl ketal Such as benzyl derivatives such as 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, etc. 4,5-triarylimidazole dimer, 9-pheny Acridine, 1,7 (9,9'-acridinyl) include acridine derivatives such as heptane. These can be used alone or in combination of two or more.

  The content ratio of the compound represented by the general formula (1) in the photopolymerization initiator which is the component (C) is preferably 10 to 100% by mass in the total amount of the component (C). More preferably, it is 100 mass%, and it is especially preferable that it is 50-100 mass%. If the blending amount is less than 10% by mass, high sensitivity and high resolution tend not to be obtained.

  Moreover, it is preferable that content of (C) component is 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and it is 1-7 mass parts. More preferably, it is 2-6 mass parts, More preferably, it is 3-5 mass parts. If the blending amount is less than 0.1 parts by mass, good sensitivity, resolution or adhesion tends not to be obtained, and if it exceeds 10 parts by mass, a good resist shape tends not to be obtained.

  Next, the sensitizing dye as component (D) will be described.

  The sensitizing dye as component (D) contains a compound represented by the following general formula (4).

上記一般式（４）中、Ｒ^３１〜Ｒ^３３は、少なくとも１つが炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基を示し、ａ、ｂ及びｃの総和は、１〜６である。ａ、ｂ及びｃの総和は、２〜６のとき、同一分子中にＲ^３１〜Ｒ^３３が複数存在するときそれらは同一でも異なっていてもよい。

In the general formula ^{(4), R} 31 ~R ³³ is at least one represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms having 1 to 10 carbon atoms, a, sum of b and c is 1 to 6 It is. When the sum of a, b and c is 2 to 6, and when there are a plurality of R ^{31 to} R ³³ in the same molecule, they may be the same or different.

  The alkyl group having 1 to 10 carbon atoms or the alkoxy group having 1 to 10 carbon atoms may be linear or branched. Examples of the alkyl group having 1 to 10 carbon atoms include, but are not limited to, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isopentyl group, and a tert-octyl group. Moreover, the sum total of a, b, and c in General formula (4) is 1-6, it is preferable that it is 1-4, and it is more preferable that it is 1-3.

In the general formula (4), R ^{31 to} R ³³ preferably represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 10 carbon atoms from the viewpoint of further improving sensitivity and solubility in a solvent. . From the viewpoint of improving the ease of synthesis and sensitivity, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline is particularly preferable. From the viewpoint of improving the solubility, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline is particularly preferable.

In the present specification, a group represented as “R ^{31 to} R ³³ ” represents a group of R ³¹ , R ³² or R ³³ .

  Examples of the compound represented by the general formula (4) include 1- (4-methoxyphenyl) -3-styryl-5-phenyl-pyrazolin, 1-phenyl-3- (4-methoxystyryl) -5 (4-methoxyphenyl) -pyrazoline, 1,5-bis- (4-methoxyphenyl) -3- (4-methoxystyryl) -pyrazoline, 1- (4-isopropylphenyl) -3-styryl-5-phenyl- Pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1,5-bis- (4-isopropylphenyl) -3- (4-isopropylstyryl) -pyrazoline, 1- (4-methoxyphenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, -(4-tert-butyl-phenyl) -3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (4-tert-butyl- Styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-isopropyl-styryl) -5- (4-isopropyl-phenyl) -pyrazoline 1- (4-methoxyphenyl) -3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1- (4-isopropylphenyl) -3- (4-methoxystyryl) -5 -(4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pi Zoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,6-dimethoxystyryl) -5- (2, 6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (3,4-dimethoxystyryl) -5 3,4-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) ) -3- (2,5-Dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (2,3-dimethoxystyryl) -5- (2 , 3-Dimethoxyphenyl) -pyrazoline, 1- (4-methoxyphenyl) -3- (2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl) -Phenyl) -3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3,4-dimethyl) Xystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl)- Pyrazoline, 1- (4-tert-butyl-phenyl) -3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl-phenyl)- 3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (2,4-dimethoxystyryl) -5- ( 2,4-dimethoxyphenyl) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, -(4-Isopropyl-phenyl) -3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxyphenyl) -pyrazoline, 1- (4-Isopropyl-phenyl) -3- (2,6- Dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline 1- (4-isopropyl-phenyl) -3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1- (4-isopropyl-phenyl) -3- (2, 4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, -Phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-butyl-phenyl) -3- (4- tert-butyl-styryl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-octyl-styryl) -5- ( 4-tert-octyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-octyl-phenyl) -3- (4-tert-octyl-styryl) -pyrazoline, 1- (4-dodecyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline 1- (4-dodecyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3- (4-tert -Butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert -Octyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert -Butyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-ter t-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl- Phenyl) -pyrazoline, 1- (2,4-dibutyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1-phenyl-3- (3,5- Di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,6-di-tert-butyl-styryl) -5- ( 2,6-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,5-di-tert-butyl-styryl) -5- (2,5-di-tert-butyl-phenyl) -Pi Zolin, 1-phenyl-3- (2,6-di-n-butyl-styryl) -5- (2,6-di-n-butyl-phenyl) -pyrazoline, 1- (3,4-di-tert -Butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (3,5-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (3,5-di -Tert-butyl-phenyl) -3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline and the like. These are used alone or in combination of two or more.

  Moreover, to the photosensitive resin composition of this invention, a sensitizing dye other than the compound represented by the said General formula (4) can be mix | blended to such an extent that the effect of this invention is not impaired.

  Examples of the sensitizing dye other than the compound represented by the general formula (4) include, for example, dialkylaminobenzophenones, anthracenes, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, and triazoles. , Stilbenes, triazines, thiophenes, naphthalimides, triarylamines and the like. These are used alone or in combination of two or more.

  The content ratio of the compound represented by the general formula (4) in the sensitizing dye as the component (D) is preferably 10 to 100% by mass in the total amount of the component (D), and 30 to 100. It is more preferable that it is mass%, and it is especially preferable that it is 50-100 mass%. If the blending amount is less than 10% by mass, high sensitivity and high resolution tend not to be obtained.

  The content of the component (D) is preferably 0.01 to 10 parts by mass, and 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferably, it is 0.75-2 mass parts, More preferably, it is 0.1-1 mass part. If this content is less than 0.01 parts by mass, the sensitivity and resolution tend to be difficult to obtain, and if it exceeds 10 parts by mass, a sufficiently good resist shape tends to be difficult to obtain.

  It is preferable that the photosensitive resin composition of this embodiment further contains (E) an amine compound.

  Examples of (E) amine compounds include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leucocrystal violet. These can be used alone or in combination of two or more.

  When the photosensitive resin composition contains the component (E), the content is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is more preferable to set it as 0.05-5 mass parts, and it is especially preferable to set it as 0.1-2 mass parts. If the content is less than 0.01 parts by mass, sufficient sensitivity tends to be difficult to obtain, and if it exceeds 10 parts by mass, excessive (E) component tends to precipitate as foreign matter after film formation. .

  If necessary, the photosensitive resin composition of the present embodiment includes a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, malachite green, and the like. Dye, photochromic agent such as tribromophenylsulfone, leucocrystal violet, thermochromic inhibitor, plasticizer such as p-toluenesulfonamide, pigment, filler, antifoaming agent, flame retardant, stabilizer, adhesion promoter , Leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, and the like. These are used alone or in combination of two or more. These contents are preferably about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) (binder polymer) and component (B) (photopolymerizable compound).

(Photosensitive resin composition solution)
The photosensitive resin composition of this embodiment can be dissolved in an organic solvent and used as a solution (coating solution) having a solid content of about 30 to 60% by mass. Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof.

  The said coating liquid is apply | coated on surfaces, such as a metal plate, and the photosensitive resin composition layer which consists of the photosensitive resin composition of this embodiment can be formed by making it dry. Examples of the metal plate include iron alloys such as copper, copper alloys, nickel, chromium, iron, and stainless steel, preferably copper, copper alloys, and iron alloys.

  The thickness of the photosensitive resin composition layer varies depending on its use, but is preferably about 1 to 100 μm after drying. You may coat | cover the surface on the opposite side to the metal plate of the photosensitive resin composition layer with a protective film. Examples of the protective film include polymer films such as polyethylene and polypropylene.

(Photosensitive element)
The photosensitive resin composition layer comprising the photosensitive resin composition can be formed on the support film by applying the solution of the photosensitive resin composition onto the support film and drying the solution. Thus, the photosensitive element of this embodiment provided with a support film and the said photosensitive resin composition layer formed on this support film is obtained.

  As the support film, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. The thickness of the support film (polymer film) is preferably 1 to 100 μm, more preferably 5 to 50 μm, and still more preferably 5 to 30 μm. When this thickness is less than 1 μm, the support film tends to be easily broken when the support film is peeled off, and when it exceeds 100 μm, the resolution tends to be difficult to obtain sufficiently.

  The photosensitive element may include a protective film that covers the surface of the photosensitive resin composition layer opposite to the support film, if necessary.

  As a protective film, the adhesive force with respect to the photosensitive resin composition layer is smaller than the adhesive force with respect to the photosensitive resin composition layer of a support film, and a film with a low fish eye is preferable. Here, “fish eye” means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.

  Specifically, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used as the protective film. Examples of commercially available products include polypropylene films such as Alfan MA-410 and E-200C manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and polyethylene terephthalate films such as PS series such as PS-25 manufactured by Teijin Limited. It is done. The protective film may be the same as the support film.

  The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. When the thickness is less than 1 μm, the protective film tends to be broken when the photosensitive resin composition layer and the protective film are laminated (laminated) on the substrate, and when the thickness exceeds 100 μm, the cost is sufficient. There is a tendency to disappear.

  Application of the photosensitive resin composition solution onto the support film can be performed by a known method such as a roll coater, comma coater, gravure coater, air knife coater, die coater, or bar coater.

  The solution is preferably dried at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  Although the thickness of the photosensitive resin composition layer in a photosensitive element changes with uses, it is preferable that it is 1-100 micrometers by the thickness after drying, it is more preferable that it is 1-50 micrometers, and it is 5-40 micrometers. Further preferred. When this thickness is less than 1 μm, it tends to be difficult to apply industrially, and when it exceeds 100 μm, adhesion and resolution tend to be difficult to obtain sufficiently.

  The transmittance of the photosensitive resin composition layer with respect to ultraviolet rays is preferably 5 to 75%, more preferably 10 to 65%, and more preferably 15 to 55% with respect to ultraviolet rays having a wavelength of 405 nm. Particularly preferred. If this transmittance is less than 5%, sufficient adhesion tends to be difficult to obtain, and if it exceeds 75%, sufficient resolution tends to be difficult to obtain. The transmittance can be measured with a UV spectrometer. Examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

  The photosensitive element may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.

  The obtained photosensitive element can be stored in the form of a sheet or a roll wound around a core. When it winds up in roll shape, it is preferable to wind up so that a support film may become an outer side. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). From the viewpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance. As a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.

(Method for forming resist pattern)
A resist pattern can be formed using the photosensitive resin composition. The resist pattern forming method according to the present embodiment includes (i) a lamination step of laminating a photosensitive resin composition layer composed of the photosensitive resin composition on a substrate, and (ii) a predetermined photosensitive resin composition layer. An exposure step of irradiating a portion with an actinic ray to expose and cure the predetermined portion; and (iii) removing a portion other than the predetermined portion of the photosensitive resin composition layer on the substrate, And a development step of forming a resist pattern made of a cured product of the photosensitive resin composition.

(I) Lamination process The photosensitive resin composition layer which consists of a photosensitive resin composition is laminated | stacked on a board | substrate. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.

  Lamination of the photosensitive resin composition layer on the substrate is performed, for example, by removing the protective film of the photosensitive element and then pressing the photosensitive resin composition layer of the photosensitive element on the substrate while heating. Is called. Thereby, the laminated body which consists of a board | substrate, the photosensitive resin composition layer, and the support film, and these were laminated | stacked in order is obtained.

This lamination operation is preferably performed under reduced pressure from the viewpoint of adhesion and followability. The photosensitive resin composition layer and / or the substrate is preferably heated at a temperature of 70 to 130 ° C. at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). Although pressure bonding is preferable, these conditions are not particularly limited. In addition, if the photosensitive resin composition layer is heated to 70 to 130 ° C., it is not necessary to pre-heat the substrate in advance, but the substrate can be pre-heated in order to further improve the stackability.

(Ii) Exposure Step Next, the predetermined portion of the photosensitive resin composition layer on the substrate is irradiated with actinic rays to expose and cure the predetermined portion. In this case, when the support film present on the photosensitive resin composition layer is transmissive to actinic rays, it can be irradiated with actinic rays through the support film, but the support film is light-shielding. In this case, after removing the support film, the photosensitive resin composition layer is irradiated with actinic rays.

  Examples of the exposure method include a method (mask exposure method) of irradiating an image with active light through a negative or positive mask pattern called an artwork. Alternatively, a method of irradiating actinic rays in the form of an image by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.

  As the actinic ray light source, a known light source can be used. For example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, a gas laser such as an argon laser, a solid laser such as a YAG laser, a semiconductor laser, etc. Those that effectively emit ultraviolet light, visible light, and the like are used.

  The wavelength of the actinic ray (exposure wavelength) is preferably in the range of 350 to 420 nm, more preferably in the range of 390 to 420 nm, from the viewpoint of more reliably obtaining the effects of the present invention.

(Iii) Development Step Furthermore, a resist pattern made of a cured product of the photosensitive resin composition is formed on the substrate by removing portions other than the predetermined portion of the photosensitive resin composition layer from the substrate. When the support film is present on the photosensitive resin composition layer, the support film is removed, and then the portion (unexposed portion) other than the predetermined portion (exposed portion) is removed (developed). Development methods include wet development and dry development, but wet development is widely used.

  In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a method using a dip method, a battle method, a spray method, brushing, slapping, scraping, rocking immersion, and the like. From the viewpoint of improving the resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.

  Examples of the developer include an alkaline aqueous solution, an aqueous developer, an organic solvent developer, and the like.

  The alkaline aqueous solution is safe and stable when used as a developer, and has good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate, and the like. Alkali metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

  As alkaline aqueous solution, 0.1-5 mass% dilute solution of sodium carbonate, 0.1-5 mass% dilute solution of potassium carbonate, 0.1-5 mass% dilute solution of sodium hydroxide, 0.1-5 A dilute solution of mass% sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the alkali developability of the photosensitive resin composition layer. 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.

  The aqueous developer is, for example, a developer composed of water or an alkaline aqueous solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, in addition to the substances described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1 , 3-propanediol, 1,3-diaminopropanol-2, morpholine and the like. The pH of the aqueous developer is preferably as low as possible within a range where development is sufficiently performed, preferably pH 8 to 12, and more preferably pH 9 to 10.

  Examples of the organic solvent used in the aqueous developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. Etc. These are used alone or in combination of two or more. In general, the concentration of the organic solvent in the aqueous developer is preferably 2 to 90% by mass, and the temperature can be adjusted according to alkali developability. A small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.

  Examples of organic solvent developers include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. Water is preferably added to these organic solvents in the range of 1 to 20% by mass in order to prevent ignition.

After removing the unexposed portion, the resist pattern may be further cured by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary.

(Printed wiring board manufacturing method)
A printed wiring board can be manufactured by etching or plating a substrate on which a resist pattern is formed by the above method. Etching or plating of the substrate is performed on the conductor layer of the substrate using the formed resist pattern as a mask.

  Etching solutions used for etching include cupric chloride solution, ferric chloride solution, alkaline etching solution, and hydrogen peroxide etching solution. It is preferable to use an iron solution.

  The plating methods for plating include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, Examples thereof include gold plating such as hard gold plating and soft gold plating.

  After the etching or plating is completed, the resist pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As this strongly alkaline aqueous solution, for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used. Especially, it is preferable to use 1-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and it is more preferable to use 1-5 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

  Examples of the resist pattern peeling method include an immersion method and a spray method, which may be used alone or in combination. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

(Examples 1-18 and Comparative Examples 1-9)
(Preparation of solution of photosensitive resin composition)
By mixing the components shown in Tables 1 to 3 in the blending amounts shown in the same table, solutions of the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 9 were prepared. In addition, the compounding quantity of (A) component shown in Table 1 and Table 2 is the mass (solid content) of a non volatile matter. Details of each component shown in the following Table 1 and Table 2 are as follows.

<(A) Binder polymer>
[Synthesis of Binder Polymer (A-1)]
A solution obtained by mixing 75 g of methacrylic acid which is a polymerizable monomer (monomer), 105 g of methyl methacrylate and 120 g of styrene (mass ratio 25/35/40) and 1.5 g of azobisisobutyronitrile. This was designated as “Solution a”.

  A solution obtained by dissolving 1.0 g of azobisisobutyronitrile in 100 g of a mixed solution (mass ratio 3: 2) of 60 g of propylene glycol monomethyl ether and 40 g of toluene was designated as “Solution b”.

  A flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube was charged with 300 g of a mixture of 180 g of propylene glycol monomethyl ether and 120 g of toluene (mass ratio 3: 2), and nitrogen was added to the flask. The mixture was stirred while blowing gas and heated to 80 ° C.

  The solution a was added dropwise to the mixed solution in the flask over 4 hours, and then kept at 80 ° C. for 2 hours with stirring. Next, the solution b was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was kept at 80 ° C. for 3 hours while stirring. Furthermore, the solution in the flask was heated to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a solution of the binder polymer (A-1).

The binder polymer (A-1) had a non-volatile content (solid content) of 48.6% by mass, a weight average molecular weight of 50,000, and an acid value of 163 mgKOH / g. The weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
GPC conditions Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: 3 in total
Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Synthesis of Binder Polymer (A-2)]
The solution of the binder polymer (A-2) is the same as that for obtaining the solution of the binder polymer (A-1) except that benzyl methacrylate is used instead of methyl methacrylate as the polymerizable monomer (monomer). Got. The binder polymer (A-2) had a non-volatile content (solid content) of 43.8% by mass, a weight average molecular weight of 50,000, and an acid value of 163 mgKOH / g.

<(B) Photopolymerizable compound>
-FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.):
2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane · FA-023M (trade name, manufactured by Hitachi Chemical Co., Ltd.):
In the above general formula (6), R = methyl group, m ₁ + m ₂ = 6 (average value), n ₁ = 12 (average value) compound-TMPT21 (manufactured by Hitachi Chemical Co., Ltd., trade name):
EO-modified trimethylolpropane triacrylate (the total number of repeating oxyethylene groups is 21)
・ M-114 (trade name, manufactured by Toagosei Co., Ltd.):
4-normal nonylphenoxyoctaethylene glycol acrylate BPE-100 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.):
EO-modified bisphenol A dimethacrylate (the total number of repeating oxyethylene groups is 2.6)

<(C) Photopolymerization initiator>
-B-CIM (product name, manufactured by Hampford):
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole (C-1):
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole (B-CIM) and 2,2 ′, 4,4′-tetra (o-chlorophenyl) -5 , 5′-bis (3,4-dimethoxyphenyl) -bisimidazole (TCTM-HABI) coupling reaction. Mixing ratio is coupling body 2,2 ′, 5′-tris (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenyl-bisimidazole (TCDM-HABI) 46 mass Part, B-CIM 16 parts by mass, TCTM-HABI 38 parts by mass.

<(D) Sensitizing dye>
(D-1):
1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline (D-2):
1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) pyrazoline (D-3):
1-phenyl-3- (4-tert-butylstyryl) -5- (4-tert-butylphenyl) pyrazoline / EAB (trade name, manufactured by Hodogaya Chemical Co., Ltd.):
4,4′-bis (diethylamino) benzophenone / N-methyl-9-acridone (manufactured by Tokyo Chemical Industry Co., Ltd.)

<(E) Amine compound>
LCV (trade name, manufactured by Yamada Chemical Co., Ltd.): Leuco Crystal Violet

<Dye>
・ MKG (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.): Malachite Green

(Photosensitive element)
The solutions of the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 9 were uniformly applied on a polyethylene terephthalate film (product name “HTF-01” manufactured by Teijin Limited) having a thickness of 16 μm. The photosensitive resin composition layer having a dried film thickness of 15 μm was formed by drying with a hot air convection dryer at 70 ° C. and 110 ° C. On this photosensitive resin composition layer, a protective film (manufactured by Tamapoly Co., Ltd., product name “NF-15”) is laminated by roll pressurization, whereby a polyethylene terephthalate film (supporting film) and the photosensitive resin composition The photosensitive element which concerns on Examples 1-18 and Comparative Examples 1-9 with which the layer and the protective film were laminated | stacked in order was obtained.

(Laminated substrate)
The copper surface of a copper-clad laminate (made by Hitachi Chemical Co., Ltd., product name MCL-E-67) composed of a glass epoxy material and copper foil (thickness 35 μm) formed on both surfaces thereof is equivalent to # 600. Polishing was performed using a polishing machine having a brush (manufactured by Sankei Co., Ltd.), washed with water, and then dried with an air stream. After heating this copper clad laminated board (henceforth "a board | substrate") and heating up at 80 degreeC, the photosensitive element of Examples 1-18 and Comparative Examples 1-9 is laminated on the copper surface of a board | substrate. (Laminated). Lamination was performed under conditions of a temperature of 110 ° C. and a lamination pressure of 4 kgf / cm ² so that the photosensitive resin composition layer of each photosensitive element was in close contact with the copper surface of the substrate while removing the protective film. Thus, the laminated substrate by which the photosensitive resin composition layer and the polyethylene terephthalate film were laminated | stacked on the copper surface of the board | substrate was obtained.

(Evaluation of sensitivity)
The obtained laminated substrate was allowed to cool and when the temperature reached 23 ° C., on the polyethylene terephthalate film of the laminated substrate, a concentration region of 0.00 to 2.00, a concentration step of 0.05, and a tablet size of 20 mm × 187 mm. A photo tool having a 41-step tablet having a size of 3 mm × 12 mm for each step was brought into close contact. Using a direct drawing machine “DE-1AH” (trade name) manufactured by Hitachi Via Mechanics Co., Ltd. with a 405 nm blue-violet laser diode as a light source, a photo tool and polyethylene terephthalate with an energy amount (exposure amount) of 100 mJ / cm ² Exposure (drawing) was performed with respect to the photosensitive resin composition layer through the film. The illuminance was measured using an ultraviolet illuminometer (trade name “UIT-150” manufactured by USHIO INC.) To which a 405 nm probe was applied.

  After the exposure, the polyethylene terephthalate film was peeled from the laminated substrate, the photosensitive resin composition layer was exposed, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 20 seconds to remove unexposed portions. Thus, the cured film which consists of hardened | cured material of the photosensitive resin composition was formed on the copper surface of a board | substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the number of remaining steps of the step tablet obtained as a cured film. The sensitivity is indicated by the number of steps of the step tablet, and the higher the number of steps, the better the sensitivity. The results are shown in Table 4.

(Evaluation of resolution and adhesion)
<Resolution / Adhesion (L / S = x / x)>
A drawing pattern (line width (L) / space width (S) (hereinafter referred to as “L / S”) is 5/5 to 30/30 (unit: μm) (L / S = x / x) 1), the photosensitive resin composition layer of the laminated substrate was exposed (drawn) with an energy amount such that the number of remaining steps of the 41-step tablet was 12. After the exposure, the same development processing as in the sensitivity evaluation was performed.

  After development, the space portion (unexposed portion) is removed neatly and the line portion (exposed portion) is formed with no meandering or chipping, and the resolution is determined by the smallest value of the line width / space width. -Adhesion was evaluated. A smaller value means better resolution and adhesion. The results are shown in Table 4.

<Adhesion (L / S = x / 3x)>
Using a drawing pattern (see FIG. 2) having an L / S of 5/15 to 30/90 (unit: μm) (L / S = x / 3x), exposure and development processes were performed in the same manner as described above. The adhesion was evaluated based on the smallest value of the line width in which the line portion (exposed portion) was formed without causing meandering or chipping. A smaller minimum value means better adhesion. The results are shown in Table 4.

<Resolution (L / S = 3x / x)>
Using a drawing pattern (see FIG. 3) having an L / S of 15/5 to 90/30 (unit: μm) (L / S = 3x / x), exposure and development processes were performed in the same manner as described above. The resolution was evaluated by the smallest value of the space width in which the space portion (unexposed portion) was removed cleanly. The smaller this minimum value, the better the resolution. The results are shown in Table 4.

(Evaluation of resist shape)
In the evaluation of the resolution and adhesion (L / S = x / x), the obtained resist shape (cross-sectional shape of the resist pattern) was observed using a Hitachi scanning electron microscope S-500A. The results are shown in Table 4. When the resist shape is trapezoidal or inverted trapezoidal, or when there is a tailing of the resist, there is a tendency that a short circuit or disconnection tends to occur in a circuit formed by the subsequent etching process or plating process. Therefore, it is desirable that the resist shape is rectangular (rectangular) and the resist is not skirted.

(Evaluation of peeling properties)
Each photosensitive element was laminated on the copper-clad laminate (substrate) and exposed and developed under the following conditions to produce a test piece (40 mm × 50 mm) having a cured film formed on the substrate. .
<Exposure conditions>
Exposure machine: Direct drawing exposure machine "DE-1AH" manufactured by Hitachi Via Mechanics Co., Ltd. using a 405 nm blue-violet laser diode as a light source
Exposure amount: 100 mJ / cm ²
Size: 40mm x 50mm
<Development conditions>
Developer: 1% by weight Na ₂ CO ₃
Liquid temperature: 30 ° C
Spray

  After leaving this test piece for a whole day and night at room temperature (25 ° C.), it was immersed in a 3 mass% sodium hydroxide aqueous solution (stripping solution) at 50 ° C. and stirred with a stir bar. The peeling characteristics were evaluated by the time (peeling time) from the start of stirring until the cured film was completely peeled and removed from the substrate. The shorter the peeling time, the better the peeling characteristics. The results are shown in Table 4.

(Evaluation of sludge removal)
The photosensitive elements according to Examples 1 to 18 and Comparative Examples 1 to 9 were cut into 0.6 m ² squares, the protective film and the support film were peeled off, dissolved in 1 L of a 1% by mass sodium carbonate aqueous solution, and then developed in a small size. It stirred for 90 minutes, circulating sodium carbonate aqueous solution with a spray circulator. The stirred sodium carbonate aqueous solution was transferred to a plastic bottle, covered and allowed to stand for one week, and then the flow of sludge (sediment) that settled on the bottom of the plastic bottle was observed before and after shaking the plastic bottle. Sludge removability was evaluated in four stages according to the criteria shown in Table 3. It means that it is so favorable that a numerical value is high. The results are shown in Table 4.

＊１…露光量１００ｍＪ／ｃｍ^２におけるステップ段数

* 1: Number of steps at an exposure of 100 mJ / cm ²

  As is clear from Table 4, the photosensitive resin compositions of Examples 1 to 18 all had good sensitivity, resolution, adhesion, resist shape, release characteristics after curing, and sludge removal. On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 9 were inferior in sensitivity, resolution, adhesion, resist shape, release property after curing, or sludge removability as compared with the examples. .

  The photosensitive resin composition of this invention is applied as a material which forms the resist pattern for manufacturing a printed wiring board. In particular, the photosensitive resin composition has excellent sensitivity, resolution, adhesion, resist shape, release characteristics after curing, and sludge removability. It is also preferably used for forming a resist pattern for manufacturing a printed wiring board having a wiring.

  DESCRIPTION OF SYMBOLS 1 ... Drawing pattern (L / S = x / x), 11 ... Line part (exposure part), 12 ... Space part (unexposed part), 13 ... Rectangle pattern used as line width: line length = 1: 5, 14 ... Line width: rectangular line pattern with line length = 1: 3, 15 ... Line width: rectangular line pattern with line length = 1: 2, 16 ... Line width: line length = 1: 1 Square line pattern, 2 ... drawing pattern (L / S = x / 3x), 21 ... line part (exposed part), 22 ... space part (unexposed part), 23 ... line width: line length = 1: 1 A square line pattern, 24 ... a circular line pattern whose line width is a diameter, 3 ... a drawing pattern (L / S = 3x / x), 31 ... a space part (unexposed part), 32 ... a line part (exposed part), 33 ... space width: space length = 1: Become square space pattern, a circular space pattern 34 ... space width is the diameter.

Claims (15)

(A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator containing a compound represented by the following general formula (1), and (D) a compound represented by the following general formula (4). A photosensitive resin composition containing a sensitizing dye.

[In General Formula (1), Z ¹ and Z ² each independently represent a monovalent group represented by the following General Formula (2) or (3). ]

[In General Formula (2) and General Formula (3), R ^{1 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, or an alkoxy group having 1 to 5 carbon atoms, and R ^{1 to} R ^{30 in the} same molecule. When two or more are present, they may be the same or different, and at least one of R ^{1 to} R ³⁰ represents an alkoxy group having 1 to 5 carbon atoms. ]

[In General Formula (4), R ^{31 to} R ³³ each independently represent an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and a plurality of R ^{31 to} R ³³ are present in the same molecule. They may be the same or different and the sum of a, b and c is 1-6. ] R ^{1 to} R ³⁰ of the photopolymerization initiator containing the compound represented by the general formula (1) each independently represent a hydrogen atom, a chlorine atom or a methoxy group, and at least one of R ^{1 to} R ³⁰ is methoxy. The photosensitive resin composition of Claim 1 which is group. Formula R ³¹ to R ³³ of the sensitizing dye containing a compound represented by (4) is independently an isopropyl group or a methoxy group independently, the photosensitive resin composition according to claim 1 or 2.   The photosensitive resin composition in any one of Claims 1-3 whose sum total of a, b, and c of the sensitizing dye containing the compound represented by the said General formula (4) is 1-2.   The photosensitive resin composition in any one of Claims 1-4 in which the said (A) binder polymer contains the structural unit based on (meth) acrylic acid and styrene or a styrene derivative.   The photosensitive resin composition in any one of Claims 1-5 in which the said (B) photopolymerizable compound contains a bisphenol A type (meth) acrylate compound.   The (B) photopolymerizable compound contains a trimethylolpropane tri (meth) acrylate compound having a (poly) oxyethylene chain or a (poly) oxypropylene chain in the molecule. Photosensitive resin composition.   The (B) photopolymerizable compound further comprises a polyalkylene glycol di (meth) acrylate having both a (poly) oxyethylene chain and a (poly) oxypropylene chain in the molecule. The photosensitive resin composition as described in 2.   The photosensitive resin composition in any one of Claims 1-8 whose acid value of the said (A) binder polymer is 80-250 mgKOH / g.   The photosensitive resin composition in any one of Claims 1-9 whose weight average molecular weights of the said (A) binder polymer are 5000-200000.   (E) The photosensitive resin composition in any one of Claims 1-10 which further contains an amine compound.   A photosensitive element provided with a support film and the photosensitive resin composition layer which consists of the photosensitive resin composition in any one of Claims 1-11 formed on this support film. A laminating step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition according to claim 1 on a substrate;
An exposure step of irradiating the predetermined portion of the photosensitive resin composition layer with an actinic ray to expose and cure the predetermined portion;
A development step of forming a resist pattern made of a cured product of the photosensitive resin composition on the substrate by removing portions other than the predetermined portion of the photosensitive resin composition layer from the substrate; A method for forming a resist pattern.   The method of forming a resist pattern according to claim 13, wherein the wavelength of the actinic ray is in a range of 390 to 420 nm.   The manufacturing method of a printed wiring board including the process of etching or plating the board | substrate with which the resist pattern was formed by the formation method of the resist pattern of Claim 13 or 14.

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