JP5470933B2 - Photosensitive resin composition for laser direct drawing exposure, 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 for laser direct drawing exposure, a photosensitive element using the same, a method for forming a resist pattern, and a method for producing a printed wiring board.

  Conventionally, in the field of production of printed wiring boards, as a resist material used for etching and plating, a photosensitive resin composition and a photosensitive element that is laminated on a support and covered with a protective film are widely used. Yes.

  When manufacturing a printed wiring board using a photosensitive element, first, the photosensitive element is laminated on a circuit forming substrate such as an insulating substrate covered with copper foil while peeling the protective film, and a photosensitive resin composition A photosensitive resin composition layer made of a product is laminated on a circuit board. Next, after pattern exposure of the photosensitive resin composition layer through a mask film or the like, a resist pattern is formed by removing an unexposed portion of the photosensitive resin composition layer with a developer. Next, using this resist pattern as a mask, the circuit forming substrate on which the resist pattern is formed is etched or plated to form a circuit pattern, and finally a cured portion (resist pattern) of the photosensitive resin composition layer Is peeled off from the substrate.

  In such a printed wiring board manufacturing method, a laser direct drawing method in which actinic rays are directly irradiated in an image form using digital data without passing through a mask film has been put into practical use. As a light source used in the laser direct drawing method, a YAG laser, a semiconductor laser, or the like is used from the viewpoints of safety and handleability. Recently, a technique using a long-life, high-power gallium nitride blue laser as a light source has been proposed.

  Furthermore, in recent years, along with higher definition and higher density of printed wiring boards, a laser direct drawing exposure method that does not require a mask and has better alignment accuracy than before has been adopted. In general, in the laser direct drawing exposure method, actinic rays having a wavelength of 350 to 410 nm using a YAG laser having a wavelength of 355 nm or a blue-violet semiconductor laser having a wavelength of 405 nm as a light source are used.

  Various photosensitive resin compositions have been studied in order to cope with such a laser direct drawing exposure method. For example, a sensitizer having a maximum absorption at 355 to 430 nm that can correspond to each wavelength of a laser light source is disclosed (for example, see Patent Documents 1 to 3).

JP-A-2005-107191 JP 2005-122123 A JP-A-2005-215142

  However, the laser direct drawing exposure method, in which exposure is performed by moving the laser at high speed, is an object to be exposed using a light source that effectively emits ultraviolet rays, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp. On the other hand, the amount of exposure energy per spot is small and the production efficiency is low as compared with the exposure method that performs batch exposure. Therefore, in the laser direct drawing exposure method, even a photosensitive resin composition containing a sensitizer as described in Patent Documents 1 to 3 cannot be said to have sufficient photosensitivity, and more photosensitivity. High photosensitive resin composition is required.

  In order to improve photosensitivity, increasing the amount of photoinitiator and sensitizer contained in the photosensitive resin composition has also been studied. However, when the amount of photoinitiator or sensitizer in the photosensitive resin composition is increased, the photoreaction proceeds locally at the surface layer portion of the photosensitive resin composition layer, and the curability at the bottom is reduced. Problems such as resolution of resist pattern obtained after photocuring, adhesion and deterioration of resist shape occur.

  Furthermore, if there is an abnormality in the resist shape, such as a mouth bit at the bottom of the resist, or resist floating, peeling or chipping, there is a possibility that a short circuit or disconnection may occur in the circuit formed by the subsequent etching process or plating process.

  Thus, with the conventional photosensitive resin composition, it was difficult to obtain sufficient photosensitivity while maintaining a good resist shape obtained after photocuring.

  The present invention has been made in view of the above-described problems of the prior art, and forms a resist pattern that has high sensitivity in laser direct drawing exposure, excellent resist shape, and good resolution, adhesion, and peelability. It is an object to provide a photosensitive resin composition for laser direct drawing exposure, a photosensitive element, a method for forming a resist pattern, and a method for producing a printed wiring board.

The present invention includes (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond, (C1) an acridine compound, (C2) 2,4,5-triarylimidazole dimer, (D) A photosensitive resin composition for laser direct writing exposure containing a halogen compound and (E) a polymerization inhibitor, wherein the content of the (E) polymerization inhibitor is 20 to 100 ppm by mass. A photosensitive resin composition for exposure is provided.
The photosensitive resin composition of the present invention can form a resist pattern having high sensitivity in laser direct drawing exposure, excellent resist shape, and good resolution, adhesion and peelability by having the above-described configuration. It becomes possible.

  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、レジスト形状、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は、（Ｄ）下記一般式（２）で表される化合物を含むことが好ましい。

[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. ]
As a result, the photosensitive resin composition of the present invention is further excellent in sensitivity, resist shape, resolution and adhesion.
Moreover, it is preferable that the photosensitive resin composition of this invention contains the compound represented by (D) following General formula (2).

［一般式（２）中、Ｘは炭素原子又は窒素原子を示す。Ｒ^２は炭素数１〜５のアルキル基又は炭素数１〜５のアルコキシ基を示し、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立にハロゲン原子又は炭素数１〜５のアルキル基を示し、Ｒ^３、Ｒ^４及びＲ^５のうち少なくとも一つはハロゲン原子を示す。ｎは０〜４の整数を示す。］
これにより、本発明の感光性樹脂組成物は、感度及びレジスト形状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), X represents a carbon atom or a nitrogen atom. R ² represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; R ³ , R ⁴ and R ⁵ each independently represent a halogen atom or an alkyl group having 1 to 5 carbon atoms; ^At least one of ³ , R ⁴ and R ⁵ represents a halogen atom. n shows the integer of 0-4. ]
Thereby, the sensitivity and the resist shape of the photosensitive resin composition of the present invention are further improved.
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.

  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、ｍ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, m 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 with much more excellent sensitivity, resolution, and peelability.

  Moreover, this invention provides the photosensitive element provided with a support body and the photosensitive resin composition layer which consists of a photosensitive resin composition for laser direct drawing exposure 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 in laser direct drawing exposure, has excellent resist shape, resolution, It becomes possible to form a resist pattern with good adhesion and peelability.

  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 resist pattern forming method of the present invention, since the photosensitive element of the present invention having high sensitivity in laser direct drawing exposure is used, production efficiency can be improved, resist shape is excellent, resolution, adhesion and It becomes possible to form a resist pattern with good peelability.

  In the method for forming a resist pattern of the present invention, it is preferable that a predetermined portion of the photosensitive resin composition layer is irradiated with a laser active beam having a wavelength of 355 nm in the exposure step to photocur the exposed portion. As a result, a resist pattern with better resist shape, resolution, adhesion and peelability can be formed more efficiently.

  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 for laser direct drawing exposure which is excellent in photosensitivity, resolution, and adhesiveness, and can form the resist pattern which has a favorable resist shape in productive efficiency, and this were used. A photosensitive element, a resist 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 for laser direct drawing exposure of the present invention comprises (A) a binder polymer, (B) a photopolymerizable compound having at least one ethylenically unsaturated bond, (C1) an acridine compound, (C2) 2, Contains a 4,5-triarylimidazole dimer, (D) a halogen compound, and (E) a polymerization inhibitor.

  Examples of the (A) binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. From the viewpoint of alkali developability, an acrylic resin is preferable. These can be used alone or in combination of two or more.

  The (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted with any substituent in the α-position or aromatic ring such as styrene, vinyl toluene and α-methylstyrene, and acrylamide such as diacetone acrylamide. , Vinyl alcohol ethers such as acrylonitrile and vinyl-n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid cyclohexyl ester, (Meth) acrylic acid dicyclopentanyl ester, (meth) acrylic acid adamantyl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester Steal, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro Maleic acid monoesters such as (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate , Fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. These can be used alone or in combination of two or more.

  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), the alkyl group of these compounds is a hydroxyl group, an epoxy group, And compounds substituted with a halogen group. 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 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 15-30 mass%, It is very preferable that it is 15-25 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.

  The content of the above styrene or styrene derivative as a copolymerization component (ratio of styrene or styrene derivative to the total polymerizable monomer used) is from the viewpoint of improving 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.

  These binder polymers are used alone or in combination of two or more. 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 300,000, and preferably 30,000 to 150,000 from the viewpoint of the balance of film formability, developer resistance and alkali developability. More preferably, it is more preferably 40,000 to 120,000, and particularly preferably 50,000 to 100,000. If the weight average molecular weight is less than 20,000, film formation tends to be difficult, and the developer resistance tends to decrease. If it exceeds 300,000, the development time tends to be long. 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 (4). 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 above formulas (5), (6) and (7), R each 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) 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.

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 a 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.

  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. 10 to 90% by mass, more preferably 20 to 85% by mass, and even more preferably 30 to 80% by mass.

  The photopolymerizable compound having at least one ethylenically unsaturated bond as the component (B) preferably contains the compound represented by the general formula (3) from the viewpoint of improving the photosensitivity and resolution. .

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. m 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 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 weight 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.

  The photosensitive resin composition of the present invention contains (C1) an acridine compound and (C2) 2,4,5-triarylimidazole dimer.

  The (C1) acridine compound is not particularly limited as long as it is an acridine compound having one or two acridinyl groups in the molecule. Examples of the acridine compound having one acridinyl group in the molecule include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, 9- (p-chlorophenyl) acridine, Examples include 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.

  The component (C1) preferably contains an acridine compound having two acridinyl groups in the molecule from the viewpoint of more reliably obtaining the effects of the present invention, and contains an acridine compound represented by the above general formula (1). Is more preferable.

In the general formula (1), R ² 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 ² 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, Asahi Denka Kogyo Co., Ltd.) Product name “N-1717”).

  In the photosensitive resin composition of the present invention, the content of the (C1) acridine compound is based on the balance of sensitivity, resolution, and resist shape with respect to 100 parts by mass of the total solid content of the component (A) and the component (B). The content is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and particularly preferably 0.05 to 1 part by mass.

  Examples of the (C2) 2,4,5-triarylimidazole dimer include 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 etc. are mentioned. Further, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may give the same and symmetric compounds, or differently give asymmetric compounds. These are used alone or in combination of two or more.

  Further, in the photosensitive resin composition, the content of (C2) 2,4,5-triarylimidazole dimer is the total solid content of component (A) and component (B) from the viewpoint of sensitivity and adhesion. The amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass.

  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, benzyl derivatives such as benzyldimethyl ketal, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene Substituted anthracene such as 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene, coumarin compounds, oxazole compounds, pyrazolis Compounds, and triarylamine compounds. 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 photosensitive resin composition of the present invention contains (D) a halogen compound. The (D) halogen compound preferably contains a halogen compound represented by the general formula (2).

  In the general formula (2), X represents a carbon atom or a nitrogen atom, and is preferably a carbon atom from the viewpoint of more reliably obtaining the effects of the present invention.

R ² represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, n represents an integer of 0 to 4, and an integer of 0 to 2 from the viewpoint of more reliably obtaining the effects of the present invention. Is preferred.

R ³ , R ⁴ and R ⁵ each independently represent a halogen atom or an alkyl group having 1 to 5 carbon atoms, at least one of R ³ , R ⁴ and R ⁵ represents a halogen atom, and at least two of them are It preferably represents a halogen atom. Examples of the halogen atom include Cl, Br, and F. From the viewpoint of improving the photosensitivity, Br is preferable. The alkyl group having 1 to 5 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and structural isomers thereof. Moreover, these alkyl groups may have arbitrary substituents in the range which does not inhibit the effect of this invention.

  Examples of the halogen compound represented by the general formula (2) include tribromomethylphenylsulfone, 2-tribromomethylsulfonylpyridine, and the like. These are used alone or in combination of two or more. These compounds may use what is marketed, for example, BMPS, BSP (both Sumitomo Seika Co., Ltd. product name) etc. are commercially available.

  Further, when the photosensitive resin composition of the present invention contains (D) the halogen compound represented by the general formula (2), the content thereof is from the viewpoint of photosensitivity, resolution, and film stability. It is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of solid content total amount of (A) component and (B) component, It is more preferable that it is 0.05-5 mass parts, 0.1 It is especially preferable that it is -3 mass parts. If this content is less than 0.01 parts by mass, the photosensitivity tends to be inferior, and if it exceeds 10 parts by mass, the film tends to turn blue despite being unexposed.

  (E) 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. -Hydroquinones such as -methoxyphenol, alkoxyquinones such as methoquinone, benzoquinones such as p-benzoquinone, methyl-p-benzoquinone, and t-butyl-p-benzoquinone. Among these, hydroquinones are preferable and p-methoxyphenol is more preferable from the viewpoint of effectively improving photosensitivity.

  (E) Content of a polymerization inhibitor is 20-100 mass ppm with respect to the total solid content including the polymerization inhibitor contained in the whole photosensitive resin composition, and 20 from a viewpoint which further improves a photosensitivity. It is preferable that it is -80 mass ppm, and it is more preferable that it is 20-65 mass ppm. If this content is less than 20 ppm by mass, the stability of the photosensitive resin composition tends to be insufficient, and if it exceeds 100 ppm by mass, the sensitivity tends to decrease.

  Although there is no restriction | limiting in particular as a method to adjust content of the (E) polymerization inhibitor in the photosensitive resin composition of this invention, It adds independently at the time of preparation of the photosensitive resin composition as a 1st method (E ) A method for adjusting the amount of polymerization inhibitor, as a second method (E) a method in which the addition amount of polymerization inhibitor is adjusted in advance (A) a method using a binder polymer, or a third method (E) polymerization (B) The method of using the photopolymerizable compound which has an ethylenically unsaturated bond in the molecule | numerator by which the addition amount of the inhibitor was adjusted beforehand is mentioned. It is preferable to use the third method from the viewpoint of obtaining sufficient sensitivity and good resist shape, but (E) combining two or more of the first to third methods according to the desired content of the polymerization inhibitor. Can be used.

  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.

  The support is obtained, for example, by applying and drying a photosensitive resin composition on a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene. 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 acquire the effect of this invention more reliably, it is preferable that the wavelength of the active light irradiated to the photosensitive resin composition layer at an exposure process is 350-360 nm, and it is more preferable that it is 355 nm.

  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.

  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. 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-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.

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 to 3, Comparative Examples 1 to 3 and Reference Example 1)
(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, 200 g of methyl methacrylate, 75 g of ethyl acrylate and 100 g of styrene and 0.8 g of azobisisobutyronitrile were 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 80,000, 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.]

(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 solution of a photosensitive resin composition for laser direct drawing exposure.

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 exposure apparatus shown in Table 1 is as follows.
Paragon-9000: a direct drawing exposure apparatus using a YAG laser having a wavelength of 355 nm as a light source (trade name, manufactured by Nippon Orbotech Co., Ltd.)
HMW-201GX: Batch exposure apparatus using a high-pressure mercury lamp of all wavelengths (maximum wavelengths 365 nm, 405 nm, 430 nm) as a light source (trade name, manufactured by Oak Manufacturing Co., Ltd.)

The materials shown in Table 1 are as follows.
* 1: Copolymer of methacrylic acid / methyl methacrylate / ethyl acrylate / styrene (25/40/17/20 (mass ratio)), weight average molecular weight 80,000, acid value 163 mg KOH / g, 50 mass% methyl Cellsolve / toluene = 6/4 (mass ratio) solution * 2: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd.) containing 70 mass ppm of p-methoxyphenol product name)
* 3: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane containing 220 mass ppm of p-methoxyphenol (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 4: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate containing 100 mass ppm of p-methoxyphenol (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 5: γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate containing 500 mass ppm of p-methoxyphenol (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 6: Polyethylene glycol polypropylene glycol diacrylate containing 220 mass ppm of p-methoxyphenol (modified with 6 mol of oxyethylene chain, 12 mol of oxypropylene chain) (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 7: 1,7-bis (9-acridinyl) heptane (product name, manufactured by Asahi Denka Kogyo Co., Ltd.)
* 8: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (Kurokin Kasei Co., Ltd., product name)
* 9: N, N′-tetraethyl-4,4′-diaminobenzophenone * 10: Tribromomethylphenyl sulfone (product name, manufactured by Sumitomo Seika Co., Ltd.)
* 11: 2-Tribromomethylsulfonylpyridine

(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 resin composition laminate. The film thickness after drying of the photosensitive resin composition layer was 38 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 35 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 Examples 1-3 and Comparative Examples 1-3)
<Sensitivity>
A Hitachi 41-step tablet is placed on the test substrate, and exposure is performed at 15 mJ / cm ² using a direct drawing exposure apparatus (Nippon Orbotech Co., Ltd., trade name Paragon-9000) using a YAG laser with a wavelength of 355 nm as a light source. did. After exposure, the polyethylene terephthalate film is peeled off, and a 1.0% by weight aqueous sodium carbonate solution is sprayed at 30 ° C. for 60 seconds to remove the unexposed portion, and then a photocured film step tablet formed on a copper clad laminate The photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps. The sensitivity is indicated by the number of steps of the step tablet. The higher the number of steps of the step tablet, the higher the sensitivity.

<Contrast>
The photosensitive resin composition layer laminated on the test substrate was exposed with an energy amount such that the number of remaining step steps after development of the Hitachi 41-step tablet was 17.0. One minute after exposure, the color difference (ΔE) between the exposed and unexposed areas is measured with a color difference meter (model name TC-I, manufactured by Tokyo Denshoku Co., Ltd.), and the difference between the ΔE values is obtained. Contrast was evaluated. The contrast evaluation is better as the value is larger.

<Resolution>
Photo tool data having a wiring pattern with a line width / space width of 400/5 to 400/200 (unit: μm) as a resolution evaluation pattern on the test substrate is the number of remaining step stages after development of Hitachi 41-step tablet. Was exposed with an energy amount of 17.0. Here, the resolution was evaluated by the value of the smallest space width among the space portions (unexposed portions) that were cleanly removed 60 seconds after the development processing. The smaller the numerical value, the better the resolution evaluation.

<Adhesion>
Photo tool data having a wiring pattern with a line width / space width of 5/400 to 200/400 (unit: μm) as an adhesion evaluation pattern on the test substrate is used as a remaining step after development of Hitachi 41-step tablet. The exposure was performed with an energy amount of 17.0. Here, the adhesion was evaluated based on the smallest line width value among the line portions (exposed portions) that remained cleanly after 60 seconds of development processing. The smaller the numerical value, the better the evaluation of adhesion.

<Mouse bite>
Using a test substrate on which a resist pattern was formed in the adhesion evaluation, a resist shape of a pattern having a line width / space width of 45/400 (unit: μm) was measured using an S-2100A scanning electron microscope (Co., Ltd.). (Manufactured by Hitachi, Ltd.) and evaluated according to the following criteria.
"None": The mouse bite was not seen in the resist hem.
“Yes”: A mouse bite was seen at the bottom of the resist.

<Bottom of resist>
In the same manner as the above-described evaluation of the mouse bite, the resist bottom surface at the tip portion of the resist pattern was observed and evaluated according to the following criteria.
“Good”: No abnormality was found on the resist bottom of the pattern tip,
“Float”: A pattern in which the bottom of the resist at the tip of the pattern is lifted from the substrate.

<Peelability>
Photo tool data having an exposure pattern of 60 mm × 45 mm as a peeling time measurement pattern on the test substrate was exposed with an energy amount such that the number of remaining step steps after development of the Hitachi 41 step tablet was 17.0. After 60 seconds of development treatment, the film was immersed in a 3 mass% sodium hydroxide aqueous solution (stripping solution) at 50 ° C and stirred with a stirrer. The peelability was evaluated by the time from the start of stirring until the cured film was completely removed from the substrate (peeling time). The evaluation of peelability is better as the peel time is shorter.

(Evaluation of Reference Example 1)
<Sensitivity>
Hitachi 41-step tablet is brought into close contact with the test substrate and exposed at 15 mJ / cm ² using a batch exposure apparatus (trade name HMW-201GX, manufactured by Oak Manufacturing Co., Ltd.) using a high-pressure mercury lamp of all wavelengths as a light source. did. After exposure, the polyethylene terephthalate film is peeled off, and a 1.0% by weight aqueous sodium carbonate solution is sprayed at 30 ° C. for 60 seconds to remove the unexposed portion, and then a photocured film step tablet formed on a copper clad laminate The photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps. The sensitivity is indicated by the number of steps of the step tablet. The higher the number of steps of the step tablet, the higher the sensitivity.

<Contrast>
The photosensitive resin composition layer laminated on the test substrate was exposed with an energy amount such that the number of remaining step steps after development of Hitachi 41-step tablet was 23.0. One minute after exposure, the color difference (ΔE) between the exposed and unexposed areas is measured with a color difference meter (model name TC-I, manufactured by Tokyo Denshoku Co., Ltd.), and the difference between the ΔE values is obtained. Contrast was evaluated. The contrast evaluation is better as the value is larger.

<Resolution>
A phototool having a wiring pattern with a line width / space width of 400/6 to 400/47 (unit: μm) is brought into close contact with the test substrate as a resolution evaluation negative, and the remaining steps after development of Hitachi 41-step tablet The exposure was performed with an energy amount of 23.0. Here, the resolution was evaluated by the value of the smallest space width among the space portions (unexposed portions) that were cleanly removed 60 seconds after the development processing. The smaller the numerical value, the better the resolution evaluation.

<Adhesion>
A phototool having a wiring pattern with a line width / space width of 6/400 to 47/400 (unit: μm) is brought into close contact with the test substrate as a negative for adhesion evaluation, and the remaining after development of the Hitachi 41-step tablet. The exposure was performed with an energy amount at which the number of steps was 23.0. Here, the adhesion was evaluated based on the smallest line width value among the line portions (exposed portions) that remained cleanly after 60 seconds of development processing. The smaller the numerical value, the better the evaluation of adhesion.

<Mouse bite>
Using a test substrate on which a resist pattern was formed in the adhesion evaluation, a resist shape of a pattern having a line width / space width of 45/400 (unit: μm) was measured using an S-2100A scanning electron microscope (Co., Ltd.). (Manufactured by Hitachi, Ltd.) and evaluated according to the following criteria.
"None": The mouse bite was not seen in the resist hem.
“Yes”: A mouse bite was seen at the bottom of the resist.

<Bottom of resist>
The resist shape was observed in the same manner as the above-mentioned evaluation of the mouse bite and evaluated according to the following criteria.
“Good”: No abnormality was found on the resist bottom of the pattern tip,
“Float”: A pattern in which the bottom of the resist at the tip of the pattern is lifted from the substrate.

<Peelability>
A phototool having an exposure pattern of 60 mm × 45 mm as a negative for peeling time measurement was brought into intimate contact with the test substrate, and exposure was performed with an energy amount such that the number of remaining step stages after development of Hitachi 41-step tablet was 23.0. . After 60 seconds of development treatment, the film was immersed in a 3 mass% sodium hydroxide aqueous solution (stripping solution) at 50 ° C and stirred with a stirrer. The peelability was evaluated by the time from the start of stirring until the cured film was completely removed from the substrate (peeling time). The evaluation of peelability is better as the peel time is shorter.

  The above results are summarized in Table 2. The amount of exposure energy in the above-described evaluation of contrast, mouth bite, resist bottom surface, resolution, adhesion and peelability is recommended by the apparatus used (the balance between resolution and adhesion is optimized). It was.

  In Comparative Example 1 having the same composition as Reference Example 1 using a batch exposure apparatus, when a direct drawing exposure apparatus is used, abnormalities are observed in the resist shape, such as a mouse bite and a float on the bottom of the resist, which were not a problem in the batch exposure. It was done. Further, the composition of Comparative Example 2 had low sensitivity, the composition of Comparative Example 3 had low sensitivity, contrast, resolution and adhesion, and generation of mouth bite was also observed. On the other hand, the compositions of Examples 1 to 3 of the present invention had high sensitivity even when used for direct drawing exposure, and had good contrast, resist shape, resolution, adhesion, and peelability.

Claims (10)

(A) a binder polymer,
(B) a photopolymerizable compound having at least one ethylenically unsaturated bond,
(C1) an acridine compound,
(C2) 2,4,5-triarylimidazole dimer,
(D) a photosensitive resin composition for laser direct drawing exposure containing a halogen compound and (E) a polymerization inhibitor,
The component (C1) includes an acridine compound represented by the following general formula (1),
The photopolymerizable compound (B) having at least one ethylenically unsaturated bond includes a compound represented by the following general formula (3),
(E) The photosensitive resin composition for laser direct drawing exposure whose content of the said polymerization inhibitor is 20-100 mass ppm.

[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. ]

[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, m 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. ] The photosensitive resin composition for laser direct drawing exposure according to claim 1, wherein the component (D) contains a halogen compound represented by the following general formula (2).

[In General Formula (2), X represents a carbon atom or a nitrogen atom. R ² represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; R ³ , R ⁴ and R ⁵ each independently represent a halogen atom or an alkyl group having 1 to 5 carbon atoms; ^At least one of ³ , R ⁴ and R ⁵ represents a halogen atom. n shows the integer of 0-4. ] It is photocured by actinic light having a wavelength of 355 nm, a laser direct writing exposure photosensitive resin composition according to claim 1 or 2. The photosensitive resin composition for laser direct drawing exposure as described in any one of Claims 1-3 in which the said (A) binder polymer contains the structural unit based on (meth) acrylic acid. The photosensitive resin composition for laser direct drawing exposure as described in any one of Claims 1-4 in which the said (A) binder polymer contains the structural unit based on styrene or a styrene derivative. The photopolymerizable compound (B) having at least one ethylenically unsaturated bond contains a bisphenol A-based (meth) acrylate compound, and the photosensitivity for laser direct drawing exposure according to any one of claims 1 to 5. Resin composition. A photosensitive element comprising: a support; and a photosensitive resin composition layer comprising the photosensitive resin composition for laser direct drawing exposure according to any one of claims 1 to 6 formed on the support. . A laminating step of laminating the photosensitive resin composition layer of the photosensitive element according to claim 7 on a circuit forming substrate,
An exposure step of irradiating a predetermined part of the photosensitive resin composition layer with a laser active light to photo-cure an exposed portion;
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 8 , wherein in the exposure step, a predetermined portion of the photosensitive resin composition layer is irradiated with a laser active 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 8 .