JP5435259B2 - Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method - Google Patents

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, the resist pattern which consists of a hardened | cured material of the photosensitive resin composition is formed on a board | substrate by removing (developing) an unexposed part from a board | 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 addition, the photosensitive resin composition is required to have excellent release characteristics after curing. If the resist peeling property is poor, there is a problem that the peeling time becomes long and the production efficiency of the peeling process is lowered. Further, in the high-density package substrate, there is a problem that a peeling residue is generated between the plating lines in the peeling process after the fine wire plating, and the production yield is lowered.

  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.

  Therefore, the present invention is a photosensitive resin composition that is highly sensitive in direct drawing exposure and has good resolution, adhesion, and peeling properties, a photosensitive element using the same, a method for forming a resist pattern, and It aims at providing the manufacturing method of a printed wiring board.

The present invention is a photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator, ) A binder polymer contains a structural unit based on a (meth) acrylic acid benzyl ester or a (meth) acrylic acid benzyl ester derivative, and the (C) photopolymerization initiator comprises (C1) an acridine compound having two acridinyl groups. seen including, to provide a photosensitive resin composition comprising further acridine compound having one (C2) acridinyl group.

  Since the photosensitive resin composition of the present invention has the above-described configuration, it is highly sensitive even in direct drawing exposure, and it is possible to form a resist pattern having good resolution, adhesion, and peeling characteristics.

  Moreover, in the photosensitive resin composition of this invention, it is preferable that the said (C1) component contains the acridine compound represented by following General formula (1).

［一般式（１）中、Ｒ^１は炭素数２〜２０のアルキレン基、炭素数２〜２０のオキサジアルキレン基又は炭素数２〜２０のチオジアルキレン基を示す。］
これにより、本発明の感光性樹脂組成物は、感度、解像度及び密着性が一層優れたものとなる。
また、本発明の感光性樹脂組成物において、前記（Ｃ２）成分は、下記一般式（２）で表されるアクリジン化合物である事が好ましい。

[In General Formula (1), R ¹ represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms. ]
Thereby, the photosensitive resin composition of this invention becomes a thing with much more excellent sensitivity, resolution, and adhesiveness .
Also, in the photosensitive resin composition of the present invention, the component (C2) is preferably from acridine compound represented by the following general formula (2).

［一般式（２）中、Ｒ^２はハロゲン原子、アミノ基、カルボキシル基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基又は炭素数１〜６のアルキルアミノ基を示し、ｍは０〜５の整数を示す。］
これにより、本発明の感光性樹脂組成物は、感度が一層優れたものとなる。
また、本発明の感光性樹脂組成物は、波長３５５ｎｍの活性光線により光硬化されるものであることが好ましい。これにより、本発明の効果がより確実に得られる。
また、本発明の感光性樹脂組成物において、前記（Ａ）バインダーポリマーは、（メタ）アクリル酸に基づく構成単位を含むことが好ましい。これにより、本発明の感光性樹脂組成物は、アルカリ現像性及び解像度が一層優れたものとなる。

[In General Formula (2), R ² represents a halogen atom, an amino group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms, m shows the integer of 0-5. ]
Thereby, the photosensitive resin composition of the present invention is more excellent in sensitivity.
Moreover, it is preferable that the photosensitive resin composition of this invention is photocured with the active light of wavelength 355nm. Thereby, the effect of the present invention can be obtained more reliably.
Moreover, the photosensitive resin composition of this invention WHEREIN: It is preferable that the said (A) binder polymer contains the structural unit based on (meth) acrylic acid. Thereby, the photosensitive resin composition of this invention becomes the thing which was further excellent in alkali developability and the resolution.

  Moreover, in the photosensitive resin composition of this invention, it is preferable that the said (A) binder polymer contains the structural unit based on styrene or a styrene derivative. Thereby, the photosensitive resin composition of this invention becomes the thing which was further excellent in the resolution and adhesiveness.

  In the photosensitive resin composition of the present invention, it is preferable that the photopolymerizable compound (B) having at least one ethylenically unsaturated bond contains a bisphenol A (meth) acrylate compound. Thereby, the photosensitive resin composition of this invention becomes a thing which was further excellent in the sensitivity and the resolution.

  In the photosensitive resin composition of the present invention, the photopolymerizable compound (B) having at least one ethylenically unsaturated bond contains an oxyethylene group (oxyethylene chain) and an oxypropylene group (oxypropylene) in the molecule. It is preferable to include a polyalkylene glycol di (meth) acrylate compound having both chains. Thereby, the adhesive resin composition of this invention becomes a thing with much more excellent adhesiveness and flexibility.

  In the photosensitive resin composition of the present invention, the (B) photopolymerizable compound having at least one ethylenically unsaturated bond preferably contains a compound having one ethylenically unsaturated bond in the molecule. . Thereby, alkali developability, a resist shape, and the peeling characteristic after hardening improve.

  Moreover, in the photosensitive resin composition of this invention, it is preferable that the said (B) photopolymerizable compound which has at least 1 ethylenically unsaturated bond contains the compound represented by following General formula (3).

［一般式（３）中、Ｒ^６は炭素数１〜５のアルキル基、ハロゲン原子又は水酸基を示し、Ｒ^７は水素原子又はメチル基を示し、Ｒ^８は水素原子、メチル基、又はハロゲン化メチル基を示し、ｎは１〜４の整数を示し、ｒは０〜４の整数を示す。なお、ｒが２以上の場合、複数存在するＲ^６は同一でも異なっていてもよい。］
これにより、本発明の感光性樹脂組成物は、感度、解像度及び剥離特性が一層優れたものとなる。

[In General Formula (3), R ⁶ represents an alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a hydrogen atom, a methyl group or a halogenated group. Represents a methyl group, n represents an integer of 1 to 4, and r represents an integer of 0 to 4. When r is 2 or more, a plurality of R ⁶ may be the same or different. ]
Thereby, the photosensitive resin composition of this invention becomes a thing which was further excellent in the sensitivity, the resolution, and the peeling characteristic.

  Moreover, this invention provides a photosensitive element provided with a support body and the photosensitive resin composition layer which consists of a photosensitive resin composition of the said this invention formed on this support body.

  According to the photosensitive element of the present invention, by providing the photosensitive resin composition layer composed of the photosensitive resin composition of the present invention, it is highly sensitive even in direct drawing exposure, and has resolution, adhesion and peeling characteristics. In any case, a good resist pattern can be formed.

  The present invention also includes a laminating step of laminating the photosensitive resin composition layer of the photosensitive element of the present invention on a circuit forming substrate, and irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays. Thus, there is provided a resist pattern forming method comprising: an exposure step of photocuring an exposed portion; and a developing step of forming a resist pattern by removing portions other than the exposed portion.

  According to the method for forming a resist pattern of the present invention, since the photosensitive element of the present invention that is highly sensitive even in direct drawing exposure is used, production efficiency can be improved, and resolution, adhesion, and peeling characteristics are good. A resist pattern can be formed.

  In the method for forming a resist pattern of the present invention, it is preferable that the exposed portion is photocured by irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray having a wavelength of 355 nm in the exposure step. The light source with a wavelength of 355 nm is preferably an actinic ray from a laser. Thereby, it is possible to more efficiently form a resist pattern with better resolution, adhesion and peeling characteristics.

  Moreover, this invention provides the manufacturing method of a printed wiring board which etches or plates the board | substrate for circuit formation in which the resist pattern was formed by the formation method of the resist pattern of the said invention.

  According to the method for producing a printed wiring board of the present invention, since the resist pattern is formed by the resist pattern forming method of the present invention, the printed wiring board can be efficiently produced and the density of the wiring is high. Can be realized.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which is excellent in photosensitivity, resolution, and adhesiveness, and can form the resist pattern which has a favorable resist shape in productive efficiency, and the photosensitive element and resist using this A pattern forming method and a printed wiring board manufacturing method can be provided.

  Hereinafter, the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and The corresponding methacryloyl group is meant.

  The photosensitive resin composition of the present invention contains (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator.

  (A) A binder polymer contains the structural unit based on a (meth) acrylic-acid benzyl ester or a (meth) acrylic-acid benzyl ester derivative.

  (A) The binder polymer can be obtained, for example, by radical polymerization of (meth) acrylic acid benzyl ester or (meth) acrylic acid benzyl ester derivative and another polymerizable monomer.

  As the (meth) acrylic acid benzyl ester derivative, a hydrogen atom in the benzene ring of (meth) acrylic acid benzyl ester is substituted with an arbitrary substituent such as an alkyl group, an alkoxy group, an amino group, or a halogen atom. Can be mentioned.

  Other polymerizable monomers include, for example, polymerizable styrene derivatives substituted with an arbitrary substituent in the α-position or aromatic ring such as styrene, vinyltoluene and α-methylstyrene, diacetone acrylamide, etc. Ethers of vinyl alcohol such as acrylamide, acrylonitrile and vinyl-n-butyl ether, alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl ester (meth) acrylate, dicyclo (meth) acrylate Pentanyl ester, (meth) acrylic acid adamantyl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoro Ethyl (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, maleic acid monoesters such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α- Examples thereof include cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These can be used alone or in combination of two or more.

  The binder polymer as component (A) preferably contains a carboxyl group from the viewpoint of alkali developability, for example, radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. Can be manufactured. As the polymerizable monomer having a carboxyl group, (meth) acrylic acid is preferable, and methacrylic acid is more preferable.

  The carboxyl group content of the binder polymer (A) (the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomer used) is 12 to 50 from the viewpoint of the balance between alkali developability and alkali resistance. It is preferable that it is mass%, It is more preferable that it is 12-40 mass%, It is especially preferable that it is 15-35 mass%, It is very preferable that it is 15-30 mass%. If the carboxyl group content is less than 12% by mass, the alkali developability tends to be inferior and the development time tends to be long, and if it exceeds 50% by mass, the developer resistance tends to be inferior and the adhesion tends to decrease.

  Moreover, it is preferable that the binder polymer which is (A) component in this invention contains the structural unit based on styrene or a styrene derivative from the standpoint of resolution and adhesiveness.

  In the case of including a structural unit based on the above styrene or styrene derivative, the content thereof (ratio of styrene or styrene derivative to the total polymerizable monomer used) is from the standpoint of improving both resolution, adhesion and peelability. (A) It is preferable to contain 0.1-40 mass% with respect to solid content of the whole component, It is more preferable to contain 1-30 mass%, It is especially preferable to contain 3-27 mass%. If this content is less than 0.1% by mass, the adhesion tends to be inferior, and if it exceeds 40% by mass, the peel piece tends to be large and the peel time tends to be long.

  Moreover, it is preferable that the binder polymer which is (A) component in this invention contains the (meth) acrylic-acid alkylester from the viewpoint of the resolution and peeling characteristics.

  As said (meth) acrylic-acid alkylester, for example, general formula (4)

（一般式中、Ｒ^１０は水素原子又はメチル基を示し、Ｒ^１１は炭素数１〜１２のアルキル基を示す）で表される化合物、これらの化合物のアルキル基が水酸基、エポキシ基、ハロゲン基等で置換された化合物などが挙げられる。上記一般式（４）中のＲ^１１で示される炭素数１〜１２のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基及びこれらの構造異性体が挙げられる。

(In the general formula, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms), and the alkyl group of these compounds is a hydroxyl group, an epoxy group, or a halogen group. And the like, and the like. Examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹¹ in the general formula (4) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof can be mentioned.

  Examples of the monomer represented by the general formula (4) 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, (Meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, and the like. These can be used alone or in combination of two or more.

  The content (the ratio of the (meth) acrylic acid alkyl ester to the total polymerizable monomer used) in the case of containing a structural unit based on the above (meth) acrylic acid alkyl ester makes both the resolution and the peeling property good. From a viewpoint, it is preferable to contain 0.1-30 mass% with respect to solid content of the whole (A) component, it is more preferable to contain 1-20 mass%, and it is especially preferable to contain 1-15 mass%. When the content is less than 0.1% by mass, the resolution and the peeling properties tend to be lowered, and when it exceeds 30% by mass, the developer resistance is inferior and the adhesion tends to be lowered.

  (A) The binder polymer which is a component is used individually or in combination of 2 or more types. 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 copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion are used. Examples thereof include a binder polymer.

  The weight average molecular weight of the (A) binder polymer is preferably 20,000 to 100,000, and preferably 20,000 to 80,000 from the viewpoint of the balance of film formability, developer resistance and alkali developability. More preferably, it is more preferably 20,000 to 50,000. If the weight average molecular weight is less than 20,000, it tends to be difficult to form a film, and the developer resistance tends to decrease. If it exceeds 100,000, the development time becomes longer, and the peeling property further decreases. Tend. In addition, the weight average molecular weight in this invention is the value measured by the gel permeation chromatography method, and converted with the analytical curve created using standard polystyrene.

  The content of the (A) binder polymer is preferably 30 to 80 parts by mass, and 40 to 75 parts by mass with respect to 100 parts by mass of the total solid content of the components (A) and (B). Is more preferable, and 50 to 70 parts by mass is particularly preferable. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured product become better.

  Examples of the photopolymerizable compound (B) having at least one ethylenically unsaturated bond include a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, and a bisphenol A-based (meth) acrylate. Compounds, compounds obtained by reacting glycidyl group-containing compounds with α, β-unsaturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond, nonylphenoxytetraethyleneoxy (meth) acrylate, nonylphenoxyocta Examples thereof include ethyleneoxy (meth) acrylate, (meth) acrylic acid alkyl ester, and a compound represented by the above general formula (3). These may be used alone or in combination of two or more.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. Polypropylene glycol di (meth) acrylate being 14, polyethylene polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraeth Xyltri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polypropylene glycol di (meth) having 2 to 14 propylene groups ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These may be used alone or in combination of two or more.

  (B) From the viewpoint of improving the flexibility of the cured product (cured film) of the photosensitive resin composition, the photopolymerizable compound (B) is a photopolymerizable compound having at least one ethylenically unsaturated bond. It is preferable that a polyalkylene glycol di (meth) acrylate compound having both an oxyethylene chain and an oxypropylene chain in the molecule is included. 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 (5), (6) or (7) is particularly preferable. These may be used alone or in combination of two or more.

In the general formulas (5), (6) and (7), 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, n ₁ , n ₂ , n ₃ and n ₄ represent the number of repeating structural units composed of oxypropylene groups, 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) each independently represents an integer of 1 to 30.

In the compound represented by the general formula (5), (6) or (7), 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 to 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.

Further, 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, particularly preferably. Is an integer from 10 to 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 (5), 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 (6), 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 a compound represented by the above general formula (7), a vinyl compound (made by Shin-Nakamura Chemical Co., Ltd., sample) having R = hydrogen atom, m ₄ = 1 (average value), and n ₄ = 9 (average value) Name NK ester HEMA-9P) and the like. These can be used alone or in combination of two or more.

  Examples of the urethane monomer include a (meth) acrylic monomer having a hydroxyl group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups. Examples of the EO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., product name UA-11, and the like. Examples of EO and PO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., product name UA-13, and the like. Examples of tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate include the product name UA-21 manufactured by Shin-Nakamura Chemical Co., Ltd. Among them, UA-21 is preferably 5 to 25% by mass and more preferably 7 to 15% by mass from the viewpoint of further improving the tent tear rate. These may be used alone or in combination of two or more.

  Further, the photopolymerizable compound having at least one ethylenically unsaturated bond as the component (B) preferably contains a bisphenol A (meth) acrylate compound from the viewpoint of improving the photosensitivity and resolution.

  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) acryloxypolyethoxypolypropoxy) phenyl) propane, and the like. From the viewpoint of further improving the resolution, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is more preferable.

  Examples of the 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-((meta ) 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) acryloxynonane) Xyl) 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) acryloxy) Hexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE- It is commercially available as 00 (made by Shin-Nakamura Chemical Co., Ltd., product name) or FA-321M (made by Hitachi Chemical Co., Ltd., product name) and 2,2-bis (4- (methacryloxypentadeca Ethoxy) phenyl) propane is commercially available as BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). These may be used alone or in combination of two or more.

  Examples of the 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-((meta ) 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) a) Liloxynonapropoxy) 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-((meta And acryloxyhexadecapropoxy) phenyl) propane. These may be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane. 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. . These may be used alone or in combination of two or more.

  Moreover, when the (B) component in this invention contains a bisphenol A type (meth) acrylate compound, the content is with respect to the mass of the whole (B) component from the viewpoint of the balance of photosensitivity and resolution. It is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and further preferably 30 to 80% by mass.

  Moreover, it is preferable that (B) component further contains the photopolymerizable compound which has one ethylenically unsaturated bond in a molecule | numerator. (B) When the photopolymerizable compound contains a photopolymerizable compound having one ethylenically unsaturated bond in the molecule, its content improves the resolution, adhesion, resist shape, and release characteristics after curing in a well-balanced manner. From the viewpoint of making the content, the content is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, and even more preferably 10 to 40% by mass with respect to the total amount of the component (B). .

  Examples of the photopolymerizable compound having one ethylenically unsaturated bond in the molecule include the aforementioned nonylphenoxypolyethyleneoxyacrylate, the compound represented by the above general formula (3), and an alkyl (meth) acrylate. Of these, from the viewpoint of improving the photosensitivity and resolution, it is preferable to include a compound represented by the above general formula (3).

In the general formula (3), R ⁶ represents an alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group, and is preferably an alkyl group having 1 to 5 carbon atoms or a halogen atom. R ⁷ represents a hydrogen atom or a methyl group. R ⁸ represents a hydrogen atom, a methyl group, or a halogenated methyl group, and is preferably a hydrogen atom or a halogenated methyl group. Examples of the halogen atom of the halogenated methyl group include Cl, Br, F, and the like. From the viewpoint of obtaining the effect of the present invention more reliably, Cl is preferable. n represents an integer of 1 to 4, and is preferably an integer of 1 to 2, and r represents an integer of 0 to 4, and is preferably an integer of 0 to 2. When r is 2 or more, a plurality of R ⁶ may be the same or different.

  Examples of the compound represented by the general formula (3) include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxy. Examples include ethyl-o-phthalate and β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, among which γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxy. Ethyl-o-phthalate is preferred. γ-Chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (manufactured by Hitachi Chemical Co., Ltd., product name). These are used individually by 1 type or in combination of 2 or more types.

  Moreover, when (B) component in this invention contains the compound represented by the said General formula (3), the content is (B) component from the viewpoint of the balance of a photosensitivity, a peeling characteristic, and coating film property. It is preferable that it is 1-50 mass% with respect to the whole mass, It is more preferable that it is 5-45 mass%, It is further more preferable that it is 10-40 mass%.

  The content of the photopolymerizable compound (B) having at least one ethylenically unsaturated bond is 20 to 60 parts by mass with respect to 100 parts by mass of the total solid content of the component (A) and the component (B). It is preferably 30 to 55 parts by mass, particularly preferably 35 to 50 parts by mass. When the content of the component (B) is within this range, the photosensitivity and coating properties of the photosensitive resin composition become better.

  (C) The photopolymerization initiator includes (C1) an acridine compound having two acridinyl groups. The component (C1) is preferably an acridine compound represented by the general formula (1).

In the general formula (1), R ¹ represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms. From the viewpoint of more reliably obtaining the effects of the present invention, R ¹ is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 4 to 14 carbon atoms.

  Examples of the compound represented by the general formula (1) include 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, and 1,4-bis (9-acridinyl). Butane, 1,5-bis (9-acridinyl) pentane, 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, 14-bis (9-acridinyl) tetradecane, 1,16-bis (9-acridinyl) hexadecane, 1,18-bis (9-acridinyl) octadecane, 1,20- Bis (9-acridinyl) alkanes such as su (9-acridinyl) eicosane, 1,3-bis (9-acridinyl) -2-oxapropane, 1,3-bis (9-acridinyl) -2-thiapropane, 1, 5-bis (9-acridinyl) -3-thiapentane and the like can be mentioned. These are used alone or in combination of two or more.

In the acridine compound represented by the general formula (1), from the viewpoint of improving photosensitivity and resolution, a compound in which R ¹ is a heptylene group in the general formula (1) (for example, manufactured by ADEKA Corporation, Product name "N-1717").

  In the photosensitive resin composition of the present invention, the content of the component (C1) is 0 with respect to 100 parts by mass of the total solid content of the component (A) and the component (B) from the viewpoint of sensitivity, resolution, and adhesion. It is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and even more preferably 0.05 to 1 part by mass.

  The (C) photopolymerization initiator preferably further includes (C2) an acridine compound having one acridinyl group.

  Examples of the (C2) acridine compound having one acridinyl group in the molecule include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, 9- (p- Chlorophenyl) acridine, 9- (m-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine, 9-pentylaminoacridine and the like. These are used alone or in combination of two or more.

  When the (C) photopolymerization initiator contains the component (C2), the content is from the standpoints of sensitivity, resolution, and adhesion, with respect to 100 parts by mass of the total solid content of the components (A) and (B). It is preferable that it is 0.01-3 mass parts, It is more preferable that it is 0.03-1 mass part, It is further more preferable that it is 0.05-0.5 mass part.

  The photosensitive resin composition of the present invention may contain a photopolymerization initiator other than the components (C1) and (C2). Examples of the photopolymerization initiator other than the components (C1) and (C2) include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4. '-Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholino-propanone-1, etc. aromatic ketone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylant Quinones such as quinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone, benzoin methyl ether Benzoin ether compounds such as benzoin ethyl ether and benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5- Diphenylimidazole dimer, and 2- p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzyl derivatives such as benzyldimethyl ketal, 9,10-dimethoxyanthracene, 9,10-di Substituted anthracenes such as ethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene, coumarin compounds, oxazole compounds, pyrazoline compounds, triarylamine compounds, etc. It is done. The substituents of the aryl groups of two 2,4,5-triarylimidazoles of the 2,4,5-triarylimidazole dimer may give the same and symmetric compounds, or differently asymmetric compounds May be given. These are used alone or in combination of two or more. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. These are used alone or in combination of two or more.

  When the photosensitive resin composition contains the above-described photopolymerization initiator, the content thereof is based on 100 parts by mass of the total solid content of the component (A) and the component (B) from the viewpoint of sensitivity and internal photocurability. It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and particularly preferably 0.2 to 5 parts by mass.

  The content of the (C) photopolymerization initiator is 0.01 with respect to 100 parts by mass of the total solid content of the component (A) and the component (B) from the viewpoints of sensitivity, adhesion, and internal photocurability. It is preferably ˜20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass.

  The photosensitive resin composition of the present invention may further contain a polymerization inhibitor for the purpose of improving the resolution.

  The polymerization inhibitor is not particularly limited as long as it has a polymerization inhibiting effect on radical polymerization, and examples thereof include catechols such as t-butylcatechol, hydroquinone, methylhydroquinone, t-butylhydroquinone, and p-methoxy. Examples include hydroquinones such as phenol, alkoxyquinones such as methoquinone, benzoquinones such as p-benzoquinone, methyl-p-benzoquinone, and t-butyl-p-benzoquinone. Among these, catechols are preferable from the viewpoint of light sensitivity and resolution, and t-butylcatechol is more preferable.

  When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content is 0.001 with respect to 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoint of improving the resolution. It is preferable that it is -0.05 mass part, and it is more preferable that it is 0.002-0.01 mass part.

  Further, in the photosensitive resin composition of the present invention, if necessary, dyes such as malachite green, Victoria pure blue, brilliant green, and methyl violet, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline and Photo-coloring agents such as o-chloroaniline, thermo-coloring inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, adhesion-imparting agents, leveling agents, peeling accelerators, oxidation An inhibitor, a fragrance, an imaging agent, a thermal crosslinking agent and the like can be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the component (A) and the component (B). These are used alone or in combination of two or more.

  If necessary, the photosensitive resin composition of the present invention may be a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. It can melt | dissolve in and can apply | coat as a solution of about 30-60 mass% solid content. These are used alone or in combination of two or more.

  The photosensitive resin composition of the present invention is not particularly limited, but a metal surface, for example, an iron-based alloy such as copper, copper-based alloy, nickel, chromium, iron, stainless steel, preferably copper, copper-based alloy, iron-based It is preferable that the surface of the alloy is applied as a liquid resist and dried, and then coated with a protective film if necessary, or used in the form of a photosensitive element.

  The photosensitive element of the present invention comprises a support, and a photosensitive resin composition layer formed by uniformly applying and drying a solution of the photosensitive resin composition on the support. A protective film covering the resin composition layer may be further provided.

  Examples of the support include polymer films having heat resistance and solvent resistance such as polyesters such as polyethylene terephthalate, polypropylene, and polyethylene, and a photosensitive resin composition is applied on the polymer film and dried. Thereby, the photosensitive element in which the photosensitive resin composition layer was formed is obtained. From the viewpoint of transparency, it is preferable to use a polyethylene terephthalate film.

  In addition, these polymer films must be removable from the photosensitive resin composition layer later, and therefore may be subjected to a surface treatment or a material that makes removal impossible. must not. The thickness of these polymer films is preferably 1 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 1 to 30 μm. If this thickness is less than 1 μm, the mechanical strength tends to decrease, and problems such as breakage of the polymer film during coating tend to occur, and if it exceeds 100 μm, the resolution tends to decrease and the price tends to increase.

  One of these polymer films may be laminated on both sides of the photosensitive resin composition layer as a support for the photosensitive resin composition layer, and the other as a protective film for the photosensitive resin composition.

  The protective film preferably has a lower adhesive strength between the photosensitive resin composition layer and the protective film than the photosensitive resin composition layer and the support, and a low fisheye film. Is preferred.

  The application can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater, or a spray coater. Moreover, drying can be performed at 70-150 degreeC and about 5 to 30 minutes. Further, 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 said photosensitive resin composition layer changes with uses, it is preferable that it is 1-200 micrometers by the thickness after drying, It is more preferable that it is 5-100 micrometers, It is especially preferable that it is 10-50 micrometers. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 200 μm, the effect of the present invention is small, the sensitivity decreases, and the photocurability at the bottom of the resist tends to deteriorate.

  The photosensitive element may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, or a gas barrier layer. The photosensitive element thus obtained is stored, for example, in the form of a sheet or wound around a core in a roll shape. An end face separator is preferably installed on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, or ABS resin (acrylonitrile-butadiene-styrene copolymer).

When forming the resist pattern using the photosensitive element, if the protective film is present, after removing the protective film, the photosensitive resin composition layer is heated and pressure-bonded onto the circuit forming substrate. The method of laminating by this is mentioned, It is preferable to laminate | stack under reduced pressure from the standpoint of adhesiveness and followability. The surface to be laminated is usually a metal surface, but is not particularly limited. The heating temperature of the photosensitive resin composition layer is preferably 70 to 130 ° C., and the pressure bonding pressure is preferably about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). There are no particular restrictions on the conditions. In addition, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the circuit forming substrate in advance, but in order to further improve the laminating property, Pre-heat treatment of the substrate can also be performed.

  The photosensitive resin composition layer thus laminated is irradiated with an actinic ray in an image form by a laser direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method. . As the actinic ray light source, a known light source such as a YAG laser having a wavelength of 350 to 410 nm, a semiconductor laser, or a gallium nitride blue-violet laser can be used.

  In order to obtain the effect of the present invention more reliably, the actinic ray irradiated to the photosensitive resin composition layer in the exposure step preferably has a wavelength region of 350 to 360 nm, and more preferably has a wavelength region near 355 nm. preferable.

  Next, after the exposure, when a support is present on the photosensitive resin composition layer, the support is removed, and then the unexposed area is removed and developed by wet development, dry development, or the like. Manufacturing. In the case of wet development, development is performed by a known method such as spraying, rocking immersion, brushing, scraping, or the like, using a developer corresponding to the photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. To do. As the developing solution, a safe and stable solution having good operability such as an alkaline aqueous solution is used.

  Examples of the base of the alkaline aqueous solution include alkali hydroxides such as sodium or potassium hydroxide, alkali carbonates such as sodium, potassium or ammonium carbonate or bicarbonate, alkalis such as potassium phosphate and sodium phosphate. Metal phosphates, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

  Moreover, as alkaline aqueous solution used for image development, 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, A dilute solution of 0.1 to 5% by mass sodium tetraborate is preferred. Moreover, it is preferable to make pH of the alkaline aqueous solution used for image development into the range of 9-11, and the temperature is adjusted according to the 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 accelerating development, and the like may be mixed.

  As said aqueous developing solution, what consists of water or alkaline aqueous solution and 1 or more types of organic solvent is used. Here, as the base of the alkaline aqueous solution, in addition to the above substances, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propane Examples include diol, 1,3-diaminopropanol-2, morpholine and the like. The pH of the developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, more preferably pH 9-10. Further, a small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.

  Examples of the organic solvent include 3-acetone alcohol, 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. And monobutyl ether. These are used alone or in combination of two or more. The concentration of the organic solvent is usually preferably 2 to 90% by mass, and the temperature can be adjusted according to the developability. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvents preferably add water in the range of 1 to 20% by mass in order to prevent ignition. A small amount of a surfactant, an antifoaming agent or the like can be mixed in the water to be added.

In the method for forming a resist pattern of the present invention, two or more kinds of development methods described above may be used in combination as necessary. Development methods include a dip method, a battle method, a spray method, brushing, and slapping, and the high pressure spray method is most suitable for improving the resolution. Moreover, as a process after image development, 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.

  When a printed wiring board is produced using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask.

  For the etching of the metal surface, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or a hydrogen peroxide-based etching solution can be used, but a ferric chloride solution is used because of its good etch factor. It is desirable. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and hard There are gold plating such as gold plating and soft gold plating. A known method can be appropriately used for these.

  Next, the resist pattern can be peeled 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. Examples of the peeling method include a dipping method or a spray method, and these may be used alone or in combination.

  The printed wiring board manufacturing method of the present invention can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole. It is.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

Hereinafter, the present invention will be described in more detail with reference to examples.
(Examples 1-3 and Comparative Examples 1-3)
[Synthesis of Binder Polymer (A-1)]
To a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 400 g of a mixture of methyl cellosolve and toluene having a mass ratio of 6: 4 was added, and stirred while blowing nitrogen gas. Heated to 80 ° C. On the other hand, a solution (hereinafter referred to as “solution a”) in which 125 g of methacrylic acid, 25 g of methyl methacrylate, 125 g of benzyl methacrylate and 225 g of styrene and 1.5 g of azobisisobutyronitrile are mixed as a comonomer. The solution a was added dropwise to the above mixture of methyl cellosolve and toluene having a mass ratio of 6/4 heated to 80 ° C. over 4 hours, and then kept at 80 ° C. with stirring for 2 hours. Furthermore, a solution in which 1.2 g of azobisisobutyronitrile was dissolved in 100 g of a mixture of methyl cellosolve and toluene having a mass ratio of 6/4 was dropped into the flask over 10 minutes. The solution after dropping was kept at 80 ° C. for 3 hours with stirring, and then heated to 90 ° C. over 30 minutes. After incubating at 90 ° C. for 2 hours, the mixture was cooled to obtain a binder polymer (A-1) as component (A).

The nonvolatile component (solid content) of the binder polymer (A-1) was 50% by mass. The weight average molecular weight of the binder polymer (A-1) was 50,000, and the acid value was 163 mgKOH / g. The weight average molecular weight was measured by a gel permeation chromatography method and was 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: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (three in total) [above, manufactured by Hitachi Chemical Co., Ltd.]
Eluent: Tetrahydrofuran Measurement temperature: 25 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI [manufactured by Hitachi, Ltd.]

[Synthesis of Binder Polymer (A-2)]
A binder polymer (A-2) was obtained in the same manner as the binder polymer (A-1) except that the amount of azobisisobutyronitrile added first was changed from 1.5 g to 1.0 g. The nonvolatile component (solid content) was 50% by mass, the weight average molecular weight was 55,000, and the acid value was 163 mgKOH / g.

[Synthesis of Binder Polymer (A-3)]
A binder polymer (A-3) was obtained in the same manner as the binder polymer (A-1) except that 125 g of methacrylic acid, 150 g of methyl methacrylate and 225 g of styrene were used as the comonomer. The nonvolatile component (solid content) was 50 mass%, the weight average molecular weight was 50,000, and the acid value was 163 mgKOH / g.

(Preparation of photosensitive resin composition)
The materials shown in Table 1 were mixed in the blending amounts shown in the same table to obtain a photosensitive resin composition solution.

数値は各成分の固形分配合量（単位：ｇ）

The numerical value is the solid content of each component (unit: g)

The materials shown in Table 1 are as follows.
* 1: Copolymer of methacrylic acid / methyl methacrylate / benzyl methacrylate / styrene (25/5/25/45 (mass ratio)), weight average molecular weight 50,000, acid value 163 mg KOH / g, 50 wt% methyl Cellsolve / toluene = 6/4 (mass ratio) solution * 2: copolymer of methacrylic acid / methyl methacrylate / benzyl methacrylate / styrene (25/5/25/45 (mass ratio)), weight average molecular weight 55 , 000, acid value 163 mg KOH / g, 50 mass% methyl cellosolve / toluene = 6/4 (mass ratio) solution * 3: co-use of methacrylic acid / methyl methacrylate / styrene (25/30/45 (mass ratio)) Polymer, weight average molecular weight 55,000, acid value 163 mg KOH / g, 50 mass% methyl cellosolve / toluene = 6/4 (mass ratio) solution

* 4: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 5: Polyethylene glycol polypropylene glycol diacrylate (modified with 6 moles of oxyethylene chain, 12 moles of oxypropylene chain) (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 6: γ-Chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 7: 1,7-bis (9,9'-acridinyl) heptane (product name, manufactured by ADEKA Corporation)
* 8: 9-phenylacridine (manufactured by Nippon Steel Chemical Co., Ltd., product name)

(Production of photosensitive element)
Next, the solution of the obtained photosensitive resin composition was uniformly applied on a 16 μm thick polyethylene terephthalate film (trade name G2-16, manufactured by Teijin Ltd.), and 10 minutes by a hot air convection dryer at 100 ° C. After drying, it was protected with a polyethylene protective film (trade name: NF-13, manufactured by Tamapoly Co., Ltd.) to obtain a photosensitive element as a photosensitive resin composition laminate. The film thickness after drying of the photosensitive resin composition layer was 25 μm.

(Production of test substrate)
Next, the copper surface of a copper clad laminate (trade name MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness 12 μm) is laminated on both sides, is polished with a brush equivalent to # 600. Polishing using a machine (manufactured by Sankei Co., Ltd.), washing with water and drying with an air stream, the obtained copper-clad laminate is heated to 80 ° C., and the photosensitive resin composition layer is formed on the copper surface. The laminate was laminated at a speed of 1.5 m / min using a 110 ° C. heat roll while peeling off the protective film.

<Evaluation of photosensitivity>
Next, a Hitachi 41-step tablet is placed on the test substrate, and using a direct drawing exposure apparatus (trade name Paragon-9000, manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor laser having a wavelength of 355 nm as a light source, a predetermined energy is obtained. Exposed in quantity. Thereafter, the polyethylene terephthalate film was peeled off, and a 1.0 mass% sodium carbonate aqueous solution was sprayed at 30 ° C. for 45 seconds to remove the unexposed portion, and then the photocured film step tablet formed on the copper clad laminate was removed. The number of steps was measured, the amount of energy (mJ / cm ² ) at which the number of remaining steps after development was 17.0 was determined, and the photosensitivity of the photosensitive resin composition was evaluated. The evaluation of sensitivity indicates that the smaller this value, the higher the sensitivity.

<Evaluation of resolution>
Using phototool data having a wiring pattern with a line width / space width of 5/5 to 47/47 (unit: μm) as a resolution evaluation pattern on the test substrate, after development of a Hitachi 41-step tablet The exposure was performed with an energy amount such that the number of remaining steps was 17.0. Here, the resolution was evaluated based on the value of the smallest space width among the space portions (unexposed portions) that were neatly removed after development processing was performed under the same conditions as the evaluation of the photosensitivity. The smaller the numerical value, the better the resolution evaluation.

<Evaluation of adhesion>
Development of Hitachi 41-step tablet using phototool data having a wiring pattern with a line width / space width of 5/15 to 47/141 (unit: μm) as an adhesion evaluation pattern on the test substrate. The exposure was performed with an energy amount so that the remaining number of remaining steps was 17.0. Here, the adhesion was evaluated based on the smallest line width value among the line portions (exposed portions) that remained clean after the development process was performed under the same conditions as the evaluation of the photosensitivity. The smaller the numerical value, the better the evaluation of adhesion.

<Evaluation of peeling time>
Using the photo tool data having a 60 mm × 45 mm pattern as a peelability evaluation pattern on the test substrate, exposure is performed with an energy amount that the number of remaining step steps after development of the Hitachi 41 step tablet is 17.0. went. After performing development processing under the same conditions as the evaluation of the photosensitivity, it is immersed in a 3.0% by mass aqueous sodium hydroxide solution at 50 ° C., and the time until the resist is completely peeled from the substrate surface (unit: Second) was evaluated as the peeling time. The shorter the peeling time, the better.

<Evaluation of peelability after fine wire plating>
The laminated substrate on which the resist pattern obtained by the resolution evaluation was formed was immersed in a degreasing bath (12.5 parts by mass of PC-455 Conch (Meltex)) for 5 minutes, washed with water, and 10% by mass. Immerse in a sulfuric acid bath for 1 minute. Subsequently, the laminated substrate was subjected to a copper sulfate plating bath (copper sulfate pentahydrate 60 g / L, sulfuric acid 98 mL / L, sodium chloride 100 mg / L, basic leveler capaside (manufactured by Atotech Japan) 20 mL / L, brightener capaside Universal (made by Atotech Japan Co., Ltd., 3 mL / L mixed solution) was subjected to copper sulfate plating at 2 A / dm ² for 35 minutes. After plating, a 3% by mass aqueous sodium hydroxide solution was sprayed for 4 minutes, and the minimum value of the resist line width (width between plating lines) at which the resist could be completely removed was evaluated as peelability after fine wire plating. The smaller this value, the better the peelability after fine wire plating.

  The above results are summarized in Table 2.

Reference Example 1 and Examples 1 and 2 using the photosensitive resin composition of the present invention were both highly sensitive in direct drawing exposure, excellent in adhesion and resolution, and excellent in peeling properties. Examples 1 and 2 were particularly excellent in photosensitivity, and Reference Example 1 and Example 1 were particularly excellent in peeling characteristics. On the other hand, Comparative Examples 1 and 2 had sufficient photosensitivity and peeling properties but poor adhesion and resolution, and Comparative Example 3 had insufficient photosensitivity for direct drawing exposure.

Claims (14)

A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator,
The (A) binder polymer includes a structural unit based on a (meth) acrylic acid benzyl ester or a (meth) acrylic acid benzyl ester derivative,
The (C) photopolymerization initiator, (C1) acridinyl seen containing acridine compound having two, (C2) acridinyl the photosensitive resin composition further comprising an acridine compound having one. The photosensitive resin composition of Claim 1 whose said (C1) component is an acridine compound represented by following General formula (1).

[In General Formula (1), R ¹ represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms. ] The photosensitive resin composition of Claim 1 or 2 whose said (C2) component is an acridine compound represented by following General formula (2).

[In General Formula (2), R ² represents a halogen atom, an amino group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms, m shows the integer of 0-5. ] The photosensitive resin composition as described in any one of Claims 1-3 photocured by the active light of wavelength 355nm. The photosensitive resin composition as described in any one of Claims 1-4 in which the said (A) binder polymer contains the structural unit based on (meth) acrylic acid. The photosensitive resin composition as described in any one of Claims 1-5 in which the said (A) binder polymer contains the structural unit based on styrene or a styrene derivative. (B) the ethylenically unsaturated bond at least one having the photopolymerizable compound comprises a bisphenol A-based (meth) acrylate compound, a photosensitive resin composition according to any one of claims 1-6. The (B) photopolymerizable compound having at least one ethylenically unsaturated bond includes a polyalkylene glycol di (meth) acrylate compound having both an oxyethylene chain and an oxypropylene chain in the molecule. The photosensitive resin composition as described in any one of 7 . The photosensitivity as described in any one of Claims 1-8 in which the (B) photopolymerizable compound which has at least 1 ethylenically unsaturated bond contains the compound which has one ethylenically unsaturated bond in a molecule | numerator. Resin composition. The photosensitive resin composition of Claim 9 in which the compound which has one ethylenically unsaturated bond in the said molecule | numerator contains the compound represented by following General formula (3).

[In General Formula (3), R ⁶ represents an alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydroxyl group, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents a hydrogen atom, a methyl group or a halogenated group. Represents a methyl group, n represents an integer of 1 to 4, and r represents an integer of 0 to 4. When r is 2 or more, a plurality of R ⁶ may be the same or different. ] A photosensitive element provided with a support body and the photosensitive resin composition layer which consists of a photosensitive resin composition as described in any one of Claims 1-10 formed on this support body. A laminating step of laminating the photosensitive resin composition layer of the photosensitive element according to claim 11 on a circuit forming substrate,
An exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photocure an exposed portion; and
A development step of removing a portion other than the exposed portion to form a resist pattern;
A method for forming a resist pattern having The method for forming a resist pattern according to claim 12 , wherein in the exposure step, a predetermined portion of the photosensitive resin composition layer is irradiated with an actinic ray having a wavelength of 355 nm to photocur the exposed portion. A method for manufacturing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 12 or 13 .