KR20110005914A - The photosensitive resin composition, the photosensitive element, the formation method of a resist pattern, and the manufacturing method of a printed wiring board using the same - Google Patents

Abstract

<화학식 II>

This invention is the photosensitive resin composition containing (A) binder polymer, the photopolymerizable compound which has at least one (B) ethylenically unsaturated bond, and (C) photoinitiator, The said (C) photoinitiator is It provides a photosensitive resin composition comprising a compound represented by the formula (I) and a compound represented by the following formula (II).
<Formula I>

<Formula II>

Description

PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE ELEMENT WHEREIN SAME IS USED, METHOD FOR FORMING A RESIST-PATTERN, AND METHOD FOR PRODUCING A PRINTED WIRING BOARD}

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

Background Art Conventionally, in the field of manufacturing printed wiring boards, a photosensitive resin composition as a resist material used for etching, plating or the like, or a photosensitive element coated with a protective film by laminating it on a support has been widely used.

In the case of manufacturing a printed wiring board using the photosensitive element, first, the photosensitive element is laminated on a circuit forming substrate such as a copper substrate, passed through a mask film or the like and subjected to pattern exposure, and then the unexposed part of the photosensitive element is removed with a developer. As a result, a resist pattern is formed. Subsequently, 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, the cured portion of the photosensitive element is peeled off from the substrate.

In the manufacturing method of such a printed wiring board, the laser direct drawing method which irradiates actinic light directly on an image using digital data in recent years without using a mask film has been put into practical use. As a light source used for the direct drawing method, a YAG laser, a semiconductor laser, etc. are used from a viewpoint of safety | security and handleability, etc. In recent years, the technique using the gallium nitride system blue laser etc. which have a long lifetime and a high output is proposed.

Moreover, in recent years, the direct drawing method called the DLP (Digital Light Processing) exposure method which can form a fine pattern from the past with the high precision and high density in a printed wiring board is introduced. In general, in the DLP exposure method, active light having a wavelength of 390 to 430 nm using a blue violet semiconductor laser as a light source is used. Moreover, the exposure method using the polygonal multibeam of wavelength 355nm which used the YAG laser as a light source which is compatible with a small quantity of various products mainly in the printed wiring board which is mainly used is also used. Therefore, in order to respond | correspond to each wavelength, various sensitizers are examined in the photosensitive resin composition (for example, refer patent document 1, 2).

Japanese Patent Laid-Open No. 2004-301996 Japanese Patent Laid-Open No. 2005-107191

By the way, the direct drawing method of moving a laser at high speed and exposing it is conventional exposure method which collectively exposes using a light source which effectively radiates 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, and the like. In comparison, the amount of exposure energy per spot is small, and the production efficiency is low. For this reason, in the direct drawing method, a more sensitive photosensitive resin composition is calculated | required.

However, when the photoinitiator and the sensitizer contained in the photosensitive resin composition are increased in order to improve the light sensitivity, the photoreaction proceeds locally at the top of the photosensitive resin composition layer, and thus the curability of the bottom portion is lowered, so that the photoinitiator is obtained after photocuring. It causes a decrease in resolution and deterioration of the resist shape (historical trapezoid). The problem of resist shape becomes serious with high resolution and high density of a resist pattern, and since a resist shape is an inverted trapezoid, there exists a possibility that it may cause defects, such as a disconnection and a short circuit, after an etching or plating process. As described above, it is difficult to sufficiently achieve the required light sensitivity, resolution, and resist shape with the conventional photosensitive resin composition.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and is excellent in light sensitivity and resolution, and even when a direct drawing method is used, a photosensitive resin composition capable of forming a resist pattern having a good resist shape, and the formation of a photosensitive element and a resist pattern using the same It aims at providing the method and the manufacturing method of a printed wiring board.

This invention is the photosensitive resin composition containing (A) binder polymer, the photopolymerizable compound which has at least one (B) ethylenically unsaturated bond, and (C) photoinitiator, The said (C) photoinitiator is It provides a photosensitive resin composition comprising a compound represented by the formula (I) and a compound represented by the following formula (II).

<Formula I>

[In formula, R <^1> represents a C2-C20 alkylene group, a C2-C20 oxadialkylene group, or a C2-C20 thiodialkylene group.]

<Formula II>

[Wherein, R ² represents an aryl group which may have a substituent]

The photosensitive resin composition of this invention is excellent in light sensitivity and a resolution by having the said structure. Moreover, according to the photosensitive resin composition of this invention, even when the direct drawing method is used, the resist pattern which has a favorable resist shape can be formed. The resist pattern with a good resist shape does not generate defects such as disconnection and short circuit after etching or plating treatment, and is effective for forming a printed wiring board having a fine pattern with high precision and high density.

It is preferable that the said (C) photoinitiator further contains the compound represented by following formula (III). Thereby, the photosensitive resin composition of this invention becomes further excellent in light sensitivity and resolution, and can be used suitably for formation of the resist pattern by the direct drawing method.

<Formula III>

Moreover, this invention provides the photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on this support body. According to the photosensitive element of this invention, a photosensitive resin composition layer can be easily laminated | stacked on a board | substrate etc .. Moreover, the photosensitive element of this invention is excellent in light sensitivity and resolution, and the resist pattern formed using this photosensitive element has a favorable resist shape.

Moreover, this invention irradiates actinic light to the predetermined part of the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on the board | substrate for circuit formation, and irradiates an optical part of an exposure part, and it is other than the predetermined part of the said photosensitive resin composition layer. A method of forming a resist pattern is provided that includes a removal process for removing a portion from a substrate. Since the resist pattern formed by the formation method of this invention uses the photosensitive resin composition of the said invention, it has a favorable resist shape.

Moreover, this invention irradiates actinic light to an image image by direct drawing to the predetermined part of the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on the board | substrate for circuit formation, and the photocuring process, and the said Provided is a method of forming a resist pattern including a removing step of removing portions other than predetermined portions of the photosensitive resin composition layer from the substrate. The formation method of this invention can easily form a high-precision and high-density resist pattern by employ | adopting the direct drawing method as an irradiation method in the said irradiation process. Moreover, according to the formation method of this invention, since the photosensitive resin composition of the said invention is used, even when irradiating actinic light by the direct drawing method, the resist pattern with a favorable resist shape is obtained.

The present invention also provides a method of manufacturing a printed wiring board for etching or plating a circuit forming substrate on which a resist pattern is formed by the method of forming a resist pattern. According to this manufacturing method, a high precision and high density printed wiring board is obtained with good production efficiency.

According to the present invention, a photosensitive resin composition having excellent light sensitivity and resolution and capable of forming a resist pattern having a good resist shape even when a direct drawing method is used, a method of forming a photosensitive element, a resist pattern, and a printed wiring board using the same It may provide a method.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows preferable one Embodiment of the photosensitive element of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. In the present invention, (meth) acrylic acid refers to acrylic acid or methacrylic acid, (meth) acrylate means acrylate or methacrylate corresponding thereto, and (meth) acryloyl group corresponds to acryloyl group or the like It means a methacryloyl group.

(Photosensitive resin composition)

First, the photosensitive resin composition which concerns on this embodiment is demonstrated. The photosensitive resin composition which concerns on this embodiment is (A) binder polymer (henceforth called "(A) component"), and (B) photopolymerizable compound which has at least one ethylenically unsaturated bond (henceforth According to the present invention, the term "component (B)" and (C) photoinitiator (hereinafter, sometimes referred to as "component (C)") are included.

Examples of the component (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenolic resins, which may be used alone or in combination of two or more thereof. Can be. Since the alkali developability of the photosensitive resin composition becomes favorable (A) component, it is preferable that it is acrylic resin.

(A) component can be manufactured by radically polymerizing a polymerizable monomer, for example. Examples of the polymerizable monomer include styrene; Polymerizable styrene derivatives having a substituent at an α-position or an aromatic ring such as vinyltoluene and α-methylstyrene; Acrylamides such as diacetone acrylamide; Acrylonitrile; Esters of vinyl alcohol such as vinyl-n-butyl ether; (Meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid dicyclopentanyl ester, (meth) acrylic acid adamantyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (Meth) acrylic acid furfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylic acid Rate, 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, maleic acid monoesters such as β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, Itaconic acid, crotonic acid, And the like can be ropi olsan. These can be used individually or in combination of 2 or more types.

As said (meth) acrylic-acid alkylester, the compound represented by following formula (IV) is mentioned, for example.

<Formula IV>

In said formula, R <^3> represents a hydrogen atom or a methyl group, R <^4> represents the C1-C12 alkyl group which may have a substituent. As a substituent, a hydroxyl group, an epoxy group, a halogen group, etc. are mentioned here. In addition, the alkyl group having 1 to 12 carbon atoms represented by R ⁴ may be linear or branched, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or furnace And a silyl group, a decyl group, an undecyl group, a dodecyl group, and these structural isomers.

Examples of the polymerizable monomer represented by Formula IV include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid isopropyl ester, (meth) acrylic acid butyl ester, and (meth) Acrylic acid t-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, etc. are mentioned. These can be used individually or in combination of 2 or more types.

In addition, since the alkali developability of the photosensitive resin composition improves (A) component, it is preferable that it is a binder polymer (henceforth "a carboxyl group-containing polymer") which has a carboxyl group. A carboxyl group-containing polymer can be manufactured by radically polymerizing the polymerizable monomer which has a carboxyl group, and another polymerizable monomer, for example. As a polymerizable monomer which has the said carboxyl group, (meth) acrylic acid is preferable and especially, methacrylic acid is more preferable.

As for a carboxyl group-containing polymer, it is preferable that content (henceforth "carboxyl group content rate") of the repeating unit derived from the polymerizable monomer which has a carboxyl group is 12-50 mass% on the basis of whole quantity of a carboxyl group-containing polymer, 12-40 mass% It is more preferable that it is, It is further more preferable that it is 15-30 mass%, It is especially preferable that it is 15-25 mass%. The photosensitive resin composition containing such a carboxyl group-containing polymer is not only excellent in alkali developability, but also excellent in alkali resistance after curing. If the carboxyl group content is less than 12 mass%, alkali developability tends to be inferior, and if it exceeds 50 mass%, alkali resistance tends to be inferior.

Moreover, since adhesiveness and peeling characteristic to the board | substrate etc. of the photosensitive resin composition layer which consist of a photosensitive resin composition improve, (A) component is a binder polymer containing styrene or a styrene derivative as a polymerizable monomeric unit.

It is preferable that content of the repeating unit derived from styrene or a styrene derivative is 0.1-30 mass% on the basis of whole quantity of a binder polymer, It is more preferable that it is 1-28 mass%, It is further more preferable that it is 1.5-27 mass%. When content is less than 0.1 mass%, there exists a tendency for adhesiveness to be inferior, and when it exceeds 30 mass%, a peeling piece becomes large and there exists a tendency for peeling time to become long.

It is preferable that the weight average molecular weights of (A) component are 20000-300000, It is more preferable that it is 30000-150000, It is still more preferable that it is 40000-120000, It is especially preferable that it is 50000-110000. When the weight average molecular weight of (A) component is the said range, the alkali developability of the photosensitive resin composition and the mechanical strength of a photocured material become more favorable. When the weight average molecular weight of (A) component is less than 20000, there exists a tendency for the developing solution resistance of the hardened | cured material of the photosensitive resin composition to fall, and when it exceeds 300000, the time required for image development will become long. In addition, the weight average molecular weight in this invention is the value measured by the gel permeation chromatography method, and converted by the analytical curve manufactured using standard polystyrene.

As the component (A), the binder polymer described above can be used alone or in combination of two or more thereof. As the 2 or more types of combination, the combination of 2 or more types of binder polymers containing a different copolymerization component, the combination of 2 or more types of binder polymers of a different weight average molecular weight, the combination of 2 or more types of binder polymers of different dispersion degrees, etc. are mentioned. .

Component (B) is a photopolymerizable compound having at least one ethylenically unsaturated bond. As the component (B), a compound obtained by the reaction of a polyhydric alcohol and an α, β-unsaturated carboxylic acid, a bisphenol A-based (meth) acrylate compound, a glycidyl group-containing compound and an α, β-unsaturated carboxylic acid Compound obtained by the following, urethane monomer (for example, (meth) acrylate compound which has a urethane bond), nonylphenoxy polyalkyleneoxy (meth) acrylate, (gamma)-chloro- (beta)-hydroxypropyl (beta) '- (Meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β'-(meth) acryloyl Oxyethyl-o-phthalate, (meth) acrylic acid alkyl ester, etc. are mentioned. These are used individually or in combination of 2 or more types.

As a compound obtained by reaction of the said polyhydric alcohol and (alpha), (beta)-unsaturated carboxylic acid, the polyethyleneglycol di (meth) acrylate whose number of ethylene groups is 2-14, and the polypropylene glycol di whose number of propylene groups is 2-14. (Meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, and polypropylene glycol di (meth) acrylic having 2 to 14 propylene groups Rate, trimethylolpropanedi (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropaneethoxytri (meth) acrylate, trimethylolpropanediethoxytri (meth) acrylate, trimethylolpropanetripoly Ethoxytri (meth) acrylate, trimethylolpropane polypropoxytri (meth) acrylate, trimethylolpropanepolyethoxy Cipolypropoxytrimethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol polyethoxytetra (meth) acrylate, dipentaerythritol penta ( Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These are used individually or in combination of 2 or more types.

Since the (B) component is further excellent in the light sensitivity and the resolution of the photosensitive resin composition, it is preferable to contain a bisphenol-A (meth) acrylate compound.

Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolyprop Foxy) phenyl) propane, 2, 2-bis (4- ((meth) acryloxy polyethoxy polypropoxy) phenyl) propane, etc. are mentioned.

Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy ) Phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxytetrade Ethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl Propane etc. are mentioned. In addition, 2, 2-bis (4- (methacryloxy pentaethoxy) phenyl) propane is BPE-500 (made by Shin-Nakamura Kagaku Kogyo Co., Ltd., product name) or FA-321M (made by Hitachi Kasei Kogyo Co., Ltd.) 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd., product name). It is available. These are used individually or in combination of 2 or more types.

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-(( (Meth) acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaf Loxyoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonapropoxy) phenyl) propane , 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecpropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxyhexadecapropoxy) phenyl) propane etc. are mentioned. These are used individually or in combination of 2 or more types.

As said 2, 2-bis (4- ((meth) acryloxy polyethoxy polypropoxy) phenyl) propane, 2, 2-bis (4- ((meth) acryloxy diethoxy octapropoxy) phenyl) propane , 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane Etc. can be mentioned. These are used individually or in combination of 2 or more types.

Since the (B) component further improves the light sensitivity and resolution of the photosensitive resin composition, it is preferable to include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2, It is more preferable to include 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (for example, Hitachi Kasei Kogyo Co., Ltd. product name "FA-321M").

When (B) component contains a bisphenol-A (meth) acrylate compound, it is preferable that the content is 10-50 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and is 15-40 It is more preferable that it is a mass part. When content of a bisphenol-A (meth) acrylate compound exists in the said range, the optical sensitivity and resolution of the photosensitive resin composition will improve in balance.

(B) It is preferable that a component contains a urethane monomer, since the flexibility and tentability of the cured film of the photosensitive resin composition improve. Here, a urethane monomer represents the photopolymerizable compound which has at least one ethylenically unsaturated bond and a urethane bond.

As a urethane monomer, (meth) acrylic monomer which has a hydroxyl group in (beta) position, diisocyanate, such as isophorone diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, 1, 6- hexamethylene diisocyanate, etc. Addition reactants with compounds; A compound represented by the following formula (V); EO modified urethane di (meth) acrylate; EO, PO modified urethane di (meth) acrylate, etc. are mentioned. In addition, EO represents ethylene oxide, and the EO modified compound has a block structure of an ethylene oxide group. In addition, PO represents propylene oxide, and the PO modified compound has a block structure of propylene oxide group. As EO modified urethane di (meth) acrylate, Shin-Nakamura Chemical Industries, Ltd. make, product name UA-11 is mentioned, for example. Moreover, as EO and PO modified urethane di (meth) acrylate, Shin-Nakamura Chemical Industries, Ltd. make, a product name UA-13 is mentioned, for example. (B) It is preferable that a component contains the compound represented by following formula (V) as a urethane monomer.

(V)

In the above formula, R ⁵ represents a divalent organic group, R ⁶ represents a group represented by the following general formula (VI), and a plurality of R ^{5 's} may be the same or different from each other, and a plurality of R ^{6' s} may be the same or different from each other. It may be.

<Formula VI>

In said formula, R <^7> represents a hydrogen atom or a methyl group, X represents an ethylene group or a propylene group, m represents the integer of 1-14, and m existing X may be same or different from each other. In addition, a propylene group includes a 1-methylethylene group and a 2-methylethylene group.

As a compound represented by the said Formula (V), UA-21 (In formula (V), R <^7> is a methyl group, X is an ethylene group, m is a 4 (average value), R <^5> is a hexamethylene group, Shin-Nakamura Chemical Industries. UA-41 (compound V), R ⁷ is a methyl group, X is a propylene group, m is 5 (average value), a compound in which R ⁵ is a hexamethylene group, Shin-Nakamura Chemical Co., Ltd. UA-42 (In formula (V), a compound whose R <^7> is a methyl group, X is a propylene group, m is 9 (average value), R <^5> is a hexamethylene group, Shin-Nakamura Chemical Co., Ltd. brand name), UA-44 (Formula V) Among these, a compound in which R ⁷ is a hydrogen atom, X is a propylene group, m is 6 (average value), R ⁵ is a hexamethylene group, and Shin-Nakamura Chemical Co., Ltd. These are used individually or in combination of 2 or more types.

In said Formula (V), it is preferable that R <^5> is a C1-C12 alkylene group. In formula (VI), X is preferably an ethylene group. The cured product of the photosensitive resin composition containing such a component (B) is more excellent in flexibility and tentability.

When (B) component contains the compound represented by the said Formula (V), it is preferable that its content is 5-25 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and is 7-15 mass parts It is more preferable. When content of the compound represented by the said Formula (V) is in the said range, the flexibility and tentability of the hardened | cured material of the photosensitive resin composition improve further.

The component (B) preferably contains nonylphenoxypolyalkyleneoxy (meth) acrylate. Thereby, the peeling characteristic of the resist which consists of hardened | cured material of the photosensitive resin composition improves.

Nonylphenoxypolyalkyleneoxy (meth) acrylates include nonylphenoxypolyethyleneoxy (meth) acrylates, nonylphenoxypolypropyleneoxy (meth) acrylates, and nonylphenoxypolybutyleneoxy (meth) acrylates. Can be mentioned. These are used individually or in combination of 2 or more types.

Nonylphenoxy polyethyleneoxy (meth) acrylates include nonylphenoxyethyleneoxy (meth) acrylates, nonylphenoxydiethyleneoxy (meth) acrylates, nonylphenoxytriethylethylene (meth) acrylates, and nonylphenoxytetra Ethyleneoxy (meth) acrylate, nonylphenoxypentaethyleneoxy (meth) acrylate, nonylphenoxyhexaethyleneoxy (meth) acrylate, nonylphenoxyheptaethyleneoxy (meth) acrylate, nonylphenoxyoctaethyleneoxy (Meth) acrylate, nonylphenoxy nonaethyleneoxy (meth) acrylate, nonylphenoxy decaethyleneoxy (meth) acrylate, etc. are mentioned. These are used individually or in combination of 2 or more types.

Nonylphenoxypolypropyleneoxy (meth) acrylates include nonylphenoxypropyleneoxy (meth) acrylates, nonylphenoxydipropyleneoxy (meth) acrylates, nonylphenoxytripropylenepropylene (meth) acrylates, and nonylphenoxy. Tetrapropyleneoxy (meth) acrylate, nonylphenoxypentapropyleneoxy (meth) acrylate, nonylphenoxy hexapropyleneoxy (meth) acrylate, nonylphenoxyheptapropyleneoxy (meth) acrylate, nonylphenoxyoctapropylene Oxy (meth) acrylate, nonylphenoxy nonapropyleneoxy (meth) acrylate, nonylphenoxy decapropyleneoxy (meth) acrylate, etc. are mentioned. These are used individually or in combination of 2 or more types.

It is preferable that (B) component contains nonylphenoxy polyethyleneoxy (meth) acrylate, and nonylphenoxy tetraethyleneoxy (meth) acrylate (for example, Toagosei Co., Ltd. make, a product name "M-113 ") Or nonylphenoxyoctaethyleneoxy (meth) acrylate (for example, Kyoeisha Chemical Co., Ltd. make, product name" NP-8EA ") is more preferable. When (B) component contains these compounds, the peeling characteristic of the resist which consists of hardened | cured material of the photosensitive resin composition becomes further favorable.

When (B) component contains nonylphenoxy polyalkylene oxy (meth) acrylate, it is preferable that the content is 3-40 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, It is more preferable that it is 5-30 mass parts, and it is still more preferable that it is 5-20 mass parts. When content of nonylphenoxy polyalkyleneoxy (meth) acrylate is in the said range, the peeling characteristic of the resist which consists of hardened | cured material of the photosensitive resin composition will become more favorable.

It is preferable that (B) component contains the compound represented by following formula (VII) in order to make the peeling characteristic of the resist which consists of the resolution of the photosensitive resin composition and the hardened | cured material of the photosensitive resin composition more favorable.

<Formula VII>

In the formula VII, R ⁸ is a hydrogen atom or a methyl group, R ⁹ is a hydrogen atom, a methyl group or a halogenated methyl group, R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or a hydroxyl group, n is 0 to 4; Represents an integer. n pieces of R ¹⁰ may be identical to or different from each other.

Examples of the compound represented by the formula (VII) include γ-chloro-β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyl Oxyethyl-o-phthalate, β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, and the like. Among these, γ-chloro-β-hydroxypropyl-β'-( Preferred is meth) acryloyloxyethyl-o-phthalate. γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (manufactured by Hitachi Kasei Kogyo Co., Ltd., product name). These are used individually by 1 type or in combination of 2 or more types.

When (B) component contains the compound represented by the said Formula (VII), it is preferable that its content is 3-20 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and is 5-15 mass parts It is more preferable. When content of the compound represented by the said general formula (VII) is in the said range, the resolution of the photosensitive resin composition is further excellent. Moreover, the peeling characteristic of the resist which consists of hardened | cured material of the photosensitive resin composition becomes more favorable.

The photoinitiator which is (C) component contains the compound represented by the said Formula (I), and the compound represented by the said Formula (II).

In said Formula (I), R <^1> is preferably a C2-C20 alkylene group, It is more preferable that it is a C4-C14 alkylene group, It is more preferable that it is a C7 alkylene group. The photosensitive resin composition containing such a compound improves light sensitivity and resolution in a balanced manner. And according to this photosensitive resin composition, the resist pattern which has a more favorable resist shape can be formed. Moreover, as a compound whose R <^1> is a C7 alkylene group, Asahi Denka Kogyo Co., Ltd. make, a product name "N-1717" is mentioned, for example.

It is preferable that it is 0.01-20 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and, as for content of the compound represented by the said Formula (I) in the photosensitive resin composition, it is more preferable that it is 0.1-10 mass parts, It is more preferable that it is 0.2-5 mass parts. When the content of the compound represented by the formula (I) is less than 0.01 part by mass, the light sensitivity of the photosensitive resin composition tends to be low, and when it exceeds 20 parts by mass, it is difficult to obtain a good resist shape, thereby decreasing the adhesion and resolution of the resist. have.

In said Formula (II), it is preferable that R <^2> is a phenyl group which may have a substituent, and it is more preferable that it is a phenyl group. As a substituent here, a C1-C6 alkyl group, a halogen atom, a hydroxyl group, an amino group is mentioned, for example. The photosensitive resin composition containing such a compound is further excellent in light sensitivity and resolution. Moreover, as a compound whose R <^2> is a phenyl group, Shin-Nudetsu Chemical Co., Ltd. make, a product name "9-PA" is mentioned, for example.

It is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and, as for content of the compound represented by the said Formula (II) in the photosensitive resin composition, it is more preferable that it is 0.05-5 mass parts, It is especially preferable that it is 0.07-3 mass parts. When the content of the compound represented by the formula (II) is less than 0.01 parts by mass, the light sensitivity of the photosensitive resin composition tends to be low, and when it exceeds 10 parts by mass, it is difficult to obtain a good resist shape, and the adhesion and resolution of the resist tend to be lowered. have.

It is preferable that (C) component further contains the compound represented by the said General formula (III). The compound represented by general formula (III) can be obtained as N-phenylglycine (made by Mitsui Chemicals, make, product name), for example. The photosensitive resin composition containing such a compound is further excellent in light sensitivity and resolution.

When (C) component contains the compound represented by the said Formula (III), its content is preferably 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and is 0.05-5 mass parts It is more preferable, and it is still more preferable that it is 0.07-3 mass parts. When content of the compound represented by the said general formula (III) is in the said range, the light sensitivity and the resolution of the photosensitive resin composition are further excellent.

The component (C) may further contain other photopolymerization initiators. Other photoinitiators include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Mihiler ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone , 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methyl Aromatic ketones such as thio) phenyl] -2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di Phenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl 1,4-naphthoquinone, 2,3-dimethylanthraquinone Quinones such as these; Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; Benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; Benzyl derivatives such as benzyl dimethyl ketal; Substituted anthracenes such as 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxycanthracene, 9,10-dibutoxyanthracene and 9,10-dipentoxyanthracene; 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, 2- (p-methoxyphenyl) -4 2,4,5-triarylimidazole dimers, such as, 5-diphenylimidazole dimer; Coumarin compound; Oxazole compounds; And pyrazoline compounds. The 2,4,5-triarylimidazole dimer may be a dimer of two 2,4,5-triarylimidazoles in which the substituents of the aryl groups are identical to each other, or two different substituents of the aryl groups. It may also be a dimer of 2,4,5-triarylimidazole. The former is a symmetric compound and the latter is asymmetric compound. Like the combination of diethyl thioxanthone and dimethylaminobenzoic acid, a thioxanthone compound and a tertiary amine compound can also be used in combination as a photoinitiator. These are used individually or in combination of 2 or more types.

It is preferable that content of (A) component in the photosensitive resin composition is 30-80 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, It is more preferable that it is 40-75 mass parts, 50-70 It is especially preferable that it is a mass part. When content of (A) component is this range, the coating film property of the photosensitive resin composition and the intensity | strength of a photocured material become more favorable.

It is preferable that content of (B) component in the photosensitive resin composition is 20-60 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, It is more preferable that it is 30-55 mass parts, 35-50 It is especially preferable that it is a mass part. When content of (B) component is this range, the optical sensitivity and coating film property of the photosensitive resin composition become more favorable.

It is preferable that content of (C) component in the photosensitive resin composition is 0.01-20 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, It is more preferable that it is 0.1-10 mass parts, 0.2-5 It is especially preferable that it is a mass part. When content of (C) component is this range, the optical sensitivity of the photosensitive resin composition and the photocurability inside the photosensitive resin composition layer become more favorable.

As for the photosensitive resin composition, if necessary, dyes, such as malachite green, Victoria pure blue, brilliant green, methyl violet; Photochromic agents such as tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, o-chloroaniline; Thermochromic agents; plasticizers such as p-toluenesulfonamide; Pigments; Fillers; Antifoam; Flame retardant; Adhesion imparting agent; Leveling agents; Peel accelerators; Antioxidants; Spices; Imaging agents; You may contain a thermal crosslinking agent etc. about 0.01-20 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, respectively. These are used individually or in combination of 2 or more types.

The photosensitive resin composition 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 the like as necessary. It can melt | dissolve in a mixed solvent and can apply | coat as a solution of about 30-60 mass% of solid content. These are used individually or in combination of 2 or more types.

Although the photosensitive resin composition does not have a restriction | limiting in particular, It is preferable to apply | coat and dry as a liquid resist on a metal surface, to coat a protective film as needed, or to use it in the form of the photosensitive element mentioned later. As said metal surface, the metal surface containing iron type alloys, such as copper, a copper type alloy, nickel, chromium, iron, or stainless steel, is used, Preferably the metal containing copper, a copper type alloy, or an iron type alloy Cotton is used.

(Photosensitive element)

Next, the photosensitive element which concerns on this embodiment is demonstrated. The photosensitive element which concerns on this embodiment is equipped with a support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on this support body.

Here, FIG. 1: is a schematic cross section which shows preferable one Embodiment of the photosensitive element of this invention. The photosensitive element 1 shown in FIG. 1 is comprised from the support body 10 and the photosensitive resin composition layer 14 provided on this support body 10. As shown in FIG. The photosensitive resin composition layer 14 is a layer which consists of the photosensitive resin composition of this embodiment mentioned above. In addition, the photosensitive element 1 of this embodiment can also coat the surface F1 on the opposite side to the support body 10 on the photosensitive resin composition layer 14 with a protective film.

As the support body 10, the polymer film which has heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, polyester, is mentioned, for example. The photosensitive element 1 is obtained by apply | coating and drying the photosensitive resin composition on these polymer films. Since the support 10 is excellent in transparency, it is preferable to use a polyethylene terephthalate film.

These polymer films need to be removable later on the photosensitive resin composition layer 14. The film on which the surface treatment which removes from the photosensitive resin composition layer 14 becomes easy, and the film which is a material which becomes easy to remove can be used suitably as the support body 10. It is preferable that the thickness of the said polymer film is 1-100 micrometers, It is more preferable that it is 1-50 micrometers, It is especially preferable that it is 1-30 micrometers. If the thickness of the polymer film is less than 1 μm, the mechanical strength decreases, and there is a tendency that problems such as tearing of the polymer film during the coating tend to occur. If the thickness of the polymer film exceeds 100 μm, the photosensitive resin composition layer (14) is passed through the polymer film. In the case of irradiating actinic light), resolution tends to be lowered. Moreover, the support body whose thickness exceeds 100 micrometers tends to be inexpensive.

The said polymer film can also be used as a protective film, and the surface on the opposite side to the support body 10 of the photosensitive resin composition layer 14 can also be coat | covered with a polymer film.

It is preferable that the adhesive force of the said protective film with the photosensitive resin composition layer 14 is smaller than the adhesive force of the photosensitive resin composition layer 14 and the support body 10. As shown in FIG. In addition, the protective film is preferably a low fisheye film. In addition, "fisheye" means that foreign materials, undissolved matters, oxidative thermal decomposing materials, etc. of the material are introduced into the film when the material is thermally melted and kneaded, extruded, biaxially stretched, cast or the like.

As a method of apply | coating the solution of the photosensitive resin composition on the support body 10, methods, such as a roll coater, a coater coater, a gravure coater, an air knife coater, a die coater, a bar coater, a spray coater, are mentioned. Moreover, as conditions which dry the solution of the photosensitive resin composition apply | coated on the support body 10, the conditions of a drying temperature of 70-150 degreeC and a drying time of about 5 to 30 minutes are mentioned, for example. In order that the amount of the residual organic solvent in the photosensitive resin composition layer 14 may prevent the diffusion of the organic solvent in a subsequent process, it is preferable to set it as 2 mass% or less on the basis of whole quantity of the photosensitive resin composition layer 14.

Although the thickness of the photosensitive resin composition layer 14 changes with a use, it is preferable that it is 1-200 micrometers in thickness after drying, It is more preferable that it is 5-100 micrometers, It is especially preferable that it is 10-50 micrometers. When this thickness is less than 1 micrometer, there exists a tendency for industrial coating to be difficult, and when it exceeds 200 micrometers, the effect of this invention is small and there exists a tendency for the photocurability of the resist bottom part to deteriorate.

The photosensitive element 1 may further be equipped with intermediate layers, such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. Moreover, the obtained photosensitive element 1 can be wound up as a sheet form or wound up to the core in roll shape, and can be stored. In the end face of the roll-shaped photosensitive element roll, it is preferable to provide an end face separator for end face protection. In addition, it is preferable to provide a moisture proof end face separator on the end face of the photosensitive element roll for inner edge fusion. As said core, the core which consists of plastics, such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, and ABS (acrylonitrile- butadiene-styrene copolymer), is mentioned, for example.

(Formation method of resist pattern)

Next, the formation method of the resist pattern which concerns on this embodiment is demonstrated. The formation method of the resist pattern which concerns on this embodiment irradiates actinic light to the predetermined part of the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on the board | substrate for circuit formation, and the photosensitive process irradiates an exposure part, and the said photosensitive property The removal process of removing parts other than the predetermined part of a resin composition layer from the said board | substrate is included. In addition, a circuit formation board means the board | substrate provided with the insulating layer and the conductive layer formed on the insulating layer.

Lamination | stacking of the photosensitive resin composition layer on the board | substrate for circuit formation apply | coats the photosensitive resin composition on the board | substrate for circuit formation by methods, such as a screen printing method, a spray method, a roll coating method, a curtain coating method, and an electrostatic coating method, for example. And it can carry out by drying a coating film at 60-110 degreeC.

Moreover, lamination | stacking of the photosensitive resin composition layer on a board | substrate can also be performed using the photosensitive element mentioned above. In that case, as a lamination | stacking method, when a photosensitive element is equipped with a protective film, after removing a protective film, about 0.1 MPa-about 1 MPa (1 kgf / cm <2>-) to a board | substrate, heating a photosensitive resin composition layer about 70 to 130 degreeC And a method of pressing at a pressure of about 10 kgf / cm 2). It is preferable to perform this method under reduced pressure from the standpoint of adhesiveness and followability. In addition, in order to further improve lamination, it is also possible to perform a thermal treatment of the circuit forming substrate before crimping. The surface of the substrate on which the photosensitive resin composition layer is laminated is usually a metal surface, but is not particularly limited.

As a formation method using a photosensitive element, a photosensitive resin composition layer and a support body are laminated | stacked sequentially on the board | substrate for circuit formation. When a support body has transparency, actinic light may be irradiated from the support body in an irradiation process, and the photosensitive resin composition may be exposed. In addition, when transparency of a support body is low, a support body can be removed from a possibility resin composition layer, and actinic light can be irradiated directly to the photosensitive resin composition.

In the irradiation step, the active light is irradiated onto the image through, for example, a negative or positive mask pattern called artwork. As the light source of the active light beam, for example, effectively radiating ultraviolet rays such as carbon arc lamp, mercury vapor arc lamp, ultrahigh pressure mercury lamp, high pressure mercury lamp, xenon lamp or visible light such as flat light bulb for photo, solar lamp You can use spinning.

As an irradiation method of an actinic light, you may employ | adopt the method of irradiating an actinic light on an image by the laser direct drawing method, such as a DLP (digital light source processing) exposure method. In this method, a light source such as a YAG laser, a semiconductor laser, or a gallium nitride-based blue violet laser can be used as the light source of the active light.

In a removal process, parts other than the part which irradiated the active light of the photosensitive resin composition layer are removed from the said board | substrate. In the removal process, when a support body exists on the photosensitive resin composition layer, after removing a support body, a unexposed part can be removed by methods, such as a wet image development, a dry image development, and a resist pattern can be manufactured. As wet development, image development can be performed by methods, such as spraying, shaking immersion, brushing, and scraping, using developing solutions, such as alkaline aqueous solution, an aqueous developing solution, and an organic solvent. As the developing solution used in the wet development, those having high safety and stability such as alkaline aqueous solution and having good operability are used.

The alkaline aqueous solution is an aqueous solution containing a base, and examples of the base include alkali hydroxides such as hydroxides of lithium, sodium or potassium; Alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium; Alkali metal phosphates such as potassium phosphate and sodium phosphate; Alkali metal pyrroline salts, such as sodium pyrrolate and potassium pyrrolate, etc. can be used.

In addition, as an alkaline aqueous solution used for image development, the lean solution of 0.1-5 mass% sodium carbonate, the lean solution of 0.1-5 mass% potassium carbonate, the lean solution of 0.1-5 mass% sodium hydroxide, and the 0.1-5 mass% sodium tetraborate Lean solutions and the like are preferred. Moreover, it is preferable that pH of the alkaline aqueous solution used for image development is 9-11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. In the alkaline aqueous solution, a surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting the development, and the like can also be mixed.

As the aqueous developing solution, one containing water or an alkaline aqueous solution and at least one organic solvent is used. As the base contained in the alkaline aqueous solution, the above-mentioned base, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propane Diol, 1,3-diaminopropanol-2, morpholine, and the like. It is preferable to make pH of an aqueous developing solution as small as possible in the range which can develop a resist, It is preferable to set it as pH 8-12, and it is more preferable to set it as pH 9-10.

Examples of the organic solvent include 3-acetone alcohol, acetone, ethyl acetate, alkoxy ethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether and the like. These are used individually or in combination of 2 or more types. It is preferable that the density | concentration of the organic solvent shall be 2 to 90 weight% normally, and the temperature can be adjusted according to developability. Moreover, a small amount of surfactant, an antifoamer, etc. can also be mixed in an aqueous developing solution. As an organic solvent developer used alone, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, etc. Can be mentioned. These organic solvents are preferably added with water in the range of 1 to 20% by weight in order to prevent ignition.

Moreover, the above 2 or more types of image development methods can also be used together as needed. Development methods include dip, puddle, spray, brushing and scraping, and high pressure spray is most suitable for improving resolution. As a process after image development, a resist pattern can further be hardened | cured and used by heating about 60-250 degreeC or exposure about 0.2-10 mJ / cm <2> as needed.

(Manufacturing method of a printed wiring board)

Next, the manufacturing method of the printed wiring board which concerns on this embodiment is demonstrated. The manufacturing method of the printed wiring board which concerns on this embodiment is characterized by etching or plating the board | substrate for circuit formation in which the resist pattern was formed by the formation method of the resist pattern mentioned above.

In the above manufacturing method, the surface of the circuit forming substrate is etched or plated using the developed resist pattern as a mask. As a result, a conductor pattern based on the resist pattern is formed on the circuit forming substrate.

For the etching, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide etching solution, or the like can be used. Among them, it is preferable to use a ferric chloride solution from the viewpoint that the etch factor is good. As said plating method, Copper plating, such as copper sulfate plating and copper pyrolate plating; Solder plating such as high-slow solder plating; Nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating; Gold plating, such as hard gold plating and soft gold plating, etc. are mentioned. These can use a well-known method suitably.

After completion of etching or plating, the resist pattern can be peeled, for example, with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. As this strongly alkaline aqueous solution, 1-10 mass% sodium hydroxide aqueous solution, 1-10 mass% potassium hydroxide aqueous solution, etc. are used. An immersion system, a spray system, etc. are mentioned as a peeling system, These may be used independently and may be used together.

Moreover, the manufacturing method of the said printed wiring board is applicable to manufacture of a multilayer printed wiring board as well as a single layer printed wiring board, and is applicable also to manufacture of a printed wiring board etc. which have a small diameter through-hole.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to said embodiment at all.

<Examples>

Hereinafter, the present invention will be described in more detail by way of examples.

First, the binder polymer shown in Table 1 was synthesize | combined according to the synthesis example 1.

Synthesis Example 1

To a flask equipped with a stirrer, a reflux cooler, 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 (methylcellosolve / toluene) was added, and the nitrogen gas was blown in. It stirred and heated to 80 degreeC. On the other hand, a solution obtained by mixing 100 g of methacrylic acid, 250 g of methyl methacrylate, 100 g of ethyl acrylate, and 50 g of styrene and 0.8 g of azobisisobutyronitrile as a copolymerization monomer (hereinafter referred to as "solution a") Was prepared, and solution a was added dropwise to the above-mentioned mixture of methyl cellosolve and toluene having a mass ratio of 6/4 heated to 80 ° C. over 4 hours, and then kept warm at 80 ° C. while stirring for 2 hours. In addition, 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 added dropwise into the flask over 10 minutes. The solution after dropping was kept at 80 ° C for 3 hours with stirring, and then warmed to 90 ° C over 30 minutes. After warming at 90 ° C. for 2 hours, the mixture was cooled to obtain a binder polymer solution as component (A). Acetone was added to this binder polymer solution, and it adjusted so that a non volatile component (solid content) might be 50 mass%. The weight average molecular weight of the binder polymer was 80000. In addition, the weight average molecular weight was measured by gel permeation chromatography (GPC) method, and it derived by converting using the analytical curve of standard polystyrene. The conditions of GPC are shown below.

(GPC condition)

Pump: Hitachi L-6000 type (manufactured by Hitachi Seisakusho)

Column: Gelpack GL-R420 + Gel Pack GL-R430 + Gel Pack GL-R440 (3 in total) [above, Hitachi Kasei Kogyo Co., Ltd., product name]

Eluent: tetrahydrofuran

Measuring temperature: 25 ℃

Flow rate: 2.05 ml / min

Detector: Hitachi L-3300 type RI [manufactured by Hitachi Seisakusho, product name]

(Examples 1 to 5, Comparative Examples 1 to 3)

The material was mix | blended with the compounding quantity (g) shown in Table 1, and the solution of the photosensitive resin composition was obtained.

In the table, the compounding quantity of each (B) component shows solid content (g).

* 1: Methacrylic acid / methyl methacrylate / ethyl acrylate / styrene = 20/50/20/10 (mass ratio), weight average molecular weight = 80000, 50 mass% methyl cellosolve / toluene = 6/4 (mass ratio) solution

* 2: 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane [Hitachi Kasei Kogyo Co., Ltd. make, product name]

* 3: Tris (methacryloyloxy tetraethylene glycol isocyanate hexamethylene) isocyanurate [Shin-Nakamura Chemical Co., Ltd. make, product name]

* 4: gamma-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (manufactured by Hitachi Kasei Kogyo Co., Ltd., product name)

* 5: nonylphenoxy tetraethylene oxyacrylate [product made from Toagosei Co., Ltd., product name]

* 6: nonylphenoxy octaethylene oxyacrylate [manufactured by Kyoeisha Chemical Co., Ltd., product name]

* 7: 1,7-bis (9,9-acridinyl) heptane [Asahi Denka Kogyo Co., Ltd. make, product name]

* 8: 9-phenylacridine (manufactured by Shin-Nitetsu Chemical Co., Ltd., product name)

* 9: N-phenylglycine [manufactured by Mitsui Chemical Industries, Ltd., product name]

Next, the solution of the obtained photosensitive resin composition was apply | coated uniformly on the 16-micrometer-thick polyethylene terephthalate film (made by Teijin Co., Ltd., product name "G2-16"), and dried for 10 minutes by the hot air convection type dryer of 100 degreeC. Then, it protected with the protective film made from polyethylene (The Tamapori Co., Ltd. make, product name "NF-13"), and obtained the photosensitive resin composition laminated body (photosensitive element). The film thickness after drying of the photosensitive resin composition layer was 30 micrometers.

Subsequently, the copper surface of the copper clad laminated board (Hitachi Kasei Kogyo Co., Ltd. product name "MCL-E-67") which is a glass epoxy material which laminated | stacked copper foil (35 micrometers in thickness) on both surfaces, The grinder which has a brush equivalent to # 600 ( It was polished and washed with Sanke Co., Ltd. and dried in air. The obtained copper clad laminate is heated to 80 ° C, and the photosensitive resin composition layer is laminated at a speed of 1.5 m / min using a 110 ° C heat roll while peeling off the protective film of the photosensitive resin composition laminate on the copper surface thereof. A test substrate was obtained.

<Evaluation of light sensitivity>

A Hitachi 41-stage step tablet was placed on the test substrate, and a 17 mJ / L L exposure apparatus (product name "Paragon-9000 m" manufactured by Nippon Orbotech Co., Ltd., product name "Paragon-9000 m") using a semiconductor laser as a light source was used. It exposed at 2 cm <2>. Subsequently, the polyethylene terephthalate film was peeled off, sprayed with 1.0 mass% sodium carbonate aqueous solution at 30 ° C. for 60 seconds to remove the unexposed portion, and then the number of steps of the step tablet of the photocured film formed on the copper clad laminate was measured to thereby light the photosensitive resin composition. Sensitivity was evaluated. The light sensitivity is expressed by the number of steps of the step tablet, and the higher the number of steps of the step tablet, the higher the light sensitivity.

<Evaluation of resolution>

Residual after development of the Hitachi 41-stage step tablet, using drawing data having a wiring pattern having a line width / space width of 5/5 to 47/47 (unit: μm) as a pattern for resolution evaluation on the test substrate after the lamination. Exposure was performed with the amount of energy of step number 20.0. After the development treatment is carried out under the same conditions as the evaluation of the light sensitivity, the resist pattern can be observed using an optical microscope, and the unexposed portions can be completely removed, and the lines between the generated line widths without meandering or defects are generated. The minimum value of the space width of was evaluated as the resolution. The smaller this value, the better the resolution.

Evaluation of Tensile

For evaluation of tentability, a 1.6 mm thick copper clad laminate having 24 holes of 6 mm in diameter was used. The copper clad laminate is a copper epoxy laminated glass plate (Hitachi Kasei Kogyo Co., Ltd., product name "MCL-E-67"), which is a glass epoxy material obtained by laminating copper foil (35 μm thick) on both sides. The protruding portion generated when the dog was produced and the hole was manufactured was removed using a polishing machine (manufactured by Sanke Chemical Industries, Ltd.) having a brush equivalent to # 600, and this was used as a substrate for tentability evaluation. The said photosensitive element was laminated on both surfaces of the said board | substrate for evaluation of tentability, and whole surface exposure was carried out at 17 mJ / cm <2> using the said LDI exposure machine. Subsequently, the polyethylene terephthalate film was peeled off, and spray development was performed twice for 60 seconds with a 1.0 mass% sodium carbonate aqueous solution at 30 ° C. After development, the number of collapsed holes was visually measured and evaluated as the tent collapse rate, which was defined as tentability. The lower the tent collapse rate, the higher the tentability is, and preferably zero.

<Evaluation of Peelability>

On the test substrate after the lamination, exposure data having a pattern of 60 mm x 45 mm was used as the pattern for peelability evaluation, and the exposure was performed with an energy amount such that the remaining step number after development of the Hitachi 41 step tablet was 20.0. It was. After the development treatment was carried out under the same conditions as the evaluation of the optical sensitivity and resolution described above, the beaker was immersed in a 3.0 mass% sodium hydroxide aqueous solution at 50 ° C., and the time (unit: second) until the resist was completely peeled off from the substrate surface was peeled off. It evaluated as time and made it peelable. The shorter the peeling time, the better the peelability.

<Evaluation of Resist Shape>

After development of the Hitachi 41-stage step tablet, using drawing data having a wiring pattern having a line width / space width of 5/5 to 47/47 (unit: µm) as a pattern for resist shape evaluation on the test substrate after the lamination. Exposure was performed by the amount of energy which the remaining step number becomes 20.0. After developing on the conditions similar to the said evaluation of the said light sensitivity, the resist shape was observed using the S-2100A type | mold scanning electron microscope by the Hitachi Seisakusho company.

In the resist shape, if the pattern cross section is trapezoidal or inverted trapezoidal, a problem arises that a wiring pattern of design width cannot be obtained after etching or plating treatment, so that the pattern cross section is preferably rectangular.

The said evaluation result performed about the photosensitive element or test board | substrate of Examples 1-5 and Comparative Examples 1-3 is shown in following Table 2.

As shown in Table 2, in Examples 1-5, it was confirmed that it was excellent in the light sensitivity, the resolution, and the resist shape, and had sufficient peelability. In addition, Examples 1, 3 to 5 showed more excellent tenting property.

1: photosensitive element
10: support
14: photosensitive resin composition layer

Claims (6)

It is a photosensitive resin composition containing (A) binder polymer, the photopolymerizable compound which has at least one (B) ethylenically unsaturated bond, and (C) photoinitiator,
The photosensitive resin composition in which the said (C) photoinitiator contains the compound represented by following formula (I), and the compound represented by following formula (II).
<Formula I>

[In formula, R <^1> represents a C2-C20 alkylene group, a C2-C20 oxadialkylene group, or a C2-C20 thiodialkylene group.]
<Formula II>

[Wherein, R ² represents an aryl group which may have a substituent] The photosensitive resin composition of claim 1, wherein the photopolymerization initiator (C) further comprises a compound represented by the following general formula (III).
<Formula III>

The photosensitive element provided with a support body and the photosensitive resin composition layer which consists of the photosensitive resin composition of Claim 1 or 2 formed on this support body. An irradiation step of irradiating active light to a predetermined portion of the photosensitive resin composition layer made of the photosensitive resin composition according to claim 1 or 2 formed on the circuit forming substrate, and curing the exposed portion;
A method of forming a resist pattern comprising a removing step of removing portions other than predetermined portions of the photosensitive resin composition layer from the substrate. Irradiation process which irradiates active part to image part by direct drawing to image-cured by the direct drawing method to the predetermined part of the photosensitive resin composition layer which consists of a photosensitive resin composition of Claim 1 or 2 formed on the board | substrate for circuit formation. and,
A method of forming a resist pattern comprising a removing step of removing portions other than predetermined portions of the photosensitive resin composition layer from the substrate. The manufacturing method of the 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 Claim 4 or 5.

Images