JP2009003000A - Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, method for manufacturing printed wiring board and method for removing photocured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of obtaining a resist pattern which is superior, particularly in sensitivity, resolution and stripping property of resist, and to provide a photosensitive element that uses the same, resist pattern forming method, method for manufacturing printed wiring board and method for removing photocured products. <P>SOLUTION: The photosensitive resin composition comprises: (A) a radical polymerizable polymer including a constitutional unit of an unsaturated double bond-containing compound having a bond which can be decomposed by the action of an acid and/or by heat at 130-250°C; (B) a photopolymerizable compound; and (C) a photopolymerization initiator. There are also provided the photosensitive element that uses the same, the resist pattern forming method, the method for manufacturing a printed wiring board and the method for removing a photocured product. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  In the field of manufacturing printed wiring boards, as a resist material used for etching, plating, etc., a photosensitive resin composition or a layer made of this photosensitive resin composition (hereinafter referred to as “photosensitive resin composition layer”) is used. Photosensitive elements (laminates) formed on a support film and having a structure in which a protective film is disposed on a photosensitive resin composition layer are widely used.

  Conventionally, a printed wiring board is manufactured by the following procedure, for example, using the photosensitive element. That is, first, the photosensitive resin composition layer of the photosensitive element is laminated on a circuit forming substrate such as a copper-clad laminate.

  At this time, the surface opposite to the surface of the photosensitive resin composition layer in contact with the support film (hereinafter referred to as the “lower surface” of the photosensitive resin composition layer) (hereinafter referred to as the “upper surface of the photosensitive resin composition layer”). ") In close contact with the surface of the circuit forming substrate on which the circuit is to be formed.

  Therefore, when a protective film is disposed on the upper surface of the photosensitive resin composition layer, this lamination operation is performed while removing the protective film, and then the photosensitive resin composition layer is heated to the underlying circuit forming substrate. Crimp (normal pressure lamination method).

  Next, pattern exposure is performed through a mask film or the like. At this time, the support film is peeled off at any timing before or after exposure, and then the unexposed portion is dissolved or dispersed and removed with a developer. Furthermore, an etching process or a plating process is performed to form a pattern, and finally the cured portion is peeled and removed.

Here, the etching treatment is a method of removing a resist after etching away a metal surface not covered with a cured resist formed after development.
On the other hand, the plating process is a method in which a metal surface not covered with a hardened resist formed after development is subjected to a plating process such as copper and solder and then the resist is removed and the metal surface covered with the resist is etched. .

  Conventionally, the above-described pattern exposure is performed through a photomask using a mercury lamp as a light source. However, a direct drawing exposure method in which digital data of a pattern is directly drawn on a resist has been proposed. The direct writing exposure method has been introduced for the production of a high-density package substrate because it has better alignment accuracy than a photomask exposure and can obtain a fine pattern.

  In addition, when using a photosensitive element having the same sensitivity in the direct drawing exposure method, generally, a lot of exposure time is required. Therefore, it is necessary to shorten the exposure time as much as possible in order to improve production throughput. For this purpose, it is necessary to increase the illuminance on the exposure apparatus side, increase the sensitivity of the resist, and the like.

  However, when the conventional photosensitive resin composition is applied to the direct drawing exposure method, the sensitivity, resolution, and resist stripping properties are not sufficient. In order to improve the sensitivity, resolution, and resist release characteristics, various studies have been made on binder resins, photopolymerization initiators, and the like (see, for example, Patent Document 1 and Patent Document 2).

  However, even if the photosensitive resin compositions described in Patent Documents 1 and 2 are used, the sensitivity, resolution, and resist stripping characteristics are still insufficient.

JP 2006-234959 A JP 2005-122123 A

  The present invention relates to a photosensitive resin composition capable of obtaining a resist pattern particularly excellent in sensitivity, resolution and resist peeling characteristics, a photosensitive element using the same, a method for forming a resist pattern, a method for producing a printed wiring board, and It aims at providing the removal method of photocured material.

  It is effective to increase the phenolic hydroxyl group and carboxylic acid copolymerized with the binder polymer in order to improve the releasability of the resist. However, if the ratio is increased too much, the resist swells greatly during development after photocuring and is good. I can't get a pattern.

  On the other hand, it is effective to reduce the phenolic hydroxyl group and carboxylic acid copolymerized with the binder polymer for high resolution and high adhesion of the resist, but if it is too small, the development time with an alkaline developer may become long, There exists a tendency for developability and peelability to fall, such as peeling time extending with respect to alkaline stripping solution.

  The present invention has been made in view of such a situation, and when the above bond is cut by heat and acid and / or 130 ° C. to 250 ° C. before or after peeling after photocuring and development, It was confirmed that phenolic hydroxyl groups and / or carboxylic acids were generated, and the releasability was drastically improved with respect to the alkaline stripping solution. That is, the present inventors have found a photosensitive resin composition that achieves both resolution and adhesion at the time of pattern formation and releasability from alkali after etching or plating, and has completed the present invention.

  The present invention includes (A) a radically polymerizable polymer containing a structural unit comprising an unsaturated double bond-containing compound having a bond decomposable by the action of an acid and / or heat at 130 ° C. to 250 ° C., (B) photopolymerization The present invention relates to a photosensitive resin composition comprising a photosensitive compound and (C) a photopolymerization initiator.

  In the present invention, the structural unit comprising an unsaturated double bond-containing compound having a bond capable of decomposing by the action of (A) acid and / or heat at 130 ° C. to 250 ° C. is represented by the following general formula (I) and / or It relates to the above photosensitive resin composition represented by (II).

、

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（ここでＲ^１はそれぞれ独立に水素原子又は炭素数1〜３のアルキル基を表し、Ｒ^２はそれぞれ独立に炭素数１〜３のアルキル基又はアルコキシ基、ＯＨ基、ハロゲンを表す。ｍは０〜４の整数である。Ｒ^３はそれぞれ独立に炭素数４以上の三級アルキル基、トリフェニルアルキル基、三級アルコキシカルボニル基、アルコキシアルキルアセタール基、フェノキシアルキルアセタール基、テトラヒドロピラニル基、トリアルキルシリル基、三級炭素を介して結合しているシクロアルキル基、三級炭素を介して結合しているアダマンチル基、三級炭素を介して結合しているラクトン基、三級炭素を介して結合しているビシクロアルキル基、三級炭素を介して結合しているトリシクロアルキル基を表す。Ｘは水素原子又はカルボン酸、エステル基、アミド基、ウレタン基を表す。）

(Here, R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² independently represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group, an OH group, or a halogen. R ³ is an integer of 0 to 4. R ³ is independently a tertiary alkyl group having 4 or more carbon atoms, a triphenylalkyl group, a tertiary alkoxycarbonyl group, an alkoxyalkylacetal group, a phenoxyalkylacetal group, a tetrahydropyranyl group, A trialkylsilyl group, a cycloalkyl group bonded via a tertiary carbon, an adamantyl group bonded via a tertiary carbon, a lactone group bonded via a tertiary carbon, via a tertiary carbon Represents a bicycloalkyl group bonded to each other and a tricycloalkyl group bonded via a tertiary carbon, where X is a hydrogen atom, a carboxylic acid, or an ester group. Represents an amide group or a urethane group.)

Moreover, this invention relates to said photosensitive resin composition whose (C) photoinitiator is a hexaaryl biimidazole derivative.
Moreover, this invention relates to the photosensitive resin composition formed by further containing (D) sensitizing dye in said photosensitive resin composition.

The present invention also relates to a photosensitive resin composition obtained by further containing (E) an amine compound in the above-described photosensitive resin composition.
Moreover, this invention relates to the photosensitive resin composition formed by containing the compound which generate | occur | produces an acid by (F) light further in said photosensitive resin composition.

Moreover, this invention relates to the photosensitive element provided with the photosensitive resin composition layer which consists of said photosensitive resin composition formed on the support film and this support film.
In the present invention, a photosensitive resin composition layer comprising the above-described photosensitive resin composition is laminated on a circuit forming substrate, and exposure is performed by irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays. The present invention relates to a method for forming a resist pattern, characterized in that a portion is photocured and then portions other than the exposed portion are removed.

  The present invention also relates to a method for manufacturing a printed wiring board, wherein the circuit forming substrate on which the resist pattern is formed is etched or plated by the above-described resist pattern forming method.

  Further, in the present invention, a circuit forming substrate on which a resist pattern is formed by the above resist pattern forming method is etched or plated to form a circuit, and then the resist pattern is heated to 130 ° C. to 250 ° C. It is related with the manufacturing method of the printed wiring board characterized by removing from the said circuit formation board | substrate after or heating.

  The present invention also provides a photocured product obtained by laminating a photosensitive resin composition layer comprising the above photosensitive resin composition on a support substrate, and irradiating actinic rays to photocure the photosensitive resin composition layer. It is related with the removal method of the photocured material characterized by removing from the said support substrate after heating to 130 to 250 degreeC or heating.

  Furthermore, the present invention provides a photocured product obtained by laminating the photosensitive resin composition layer in the above photosensitive element on a support substrate and irradiating actinic rays to photocur the photosensitive resin composition layer. It is related with the removal method of the photocured material characterized by removing from the said support substrate, after heating to 250-250 degreeC or heating.

  According to the present invention, a photosensitive resin composition excellent in sensitivity, resolution, and resist peeling characteristics, a photosensitive element using the same, a resist pattern forming method, a printed wiring board manufacturing method, and a photocured material removing method are provided. It became possible to provide.

  Hereinafter, the best mode for carrying out the invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or a corresponding methacrylate, and (meth) acryloyl group means acryloyl group or methacryloyl group. Means.

(Photosensitive resin composition)
First, the photosensitive resin composition used as the constituent material of the photosensitive resin composition layer of the photosensitive element of this invention is demonstrated.
This photosensitive resin composition is a photosensitive resin composition layer of a photosensitive element having at least a support film and a protective film made of a synthetic resin, and a photosensitive resin composition layer disposed between the support film and the protective film. A photosensitive resin composition as a constituent material of (A), comprising (A) a constituent unit comprising an unsaturated double bond-containing compound having a bond that can be decomposed by the action of an acid and / or heat at 130 ° C. to 250 ° C. A photosensitive resin composition comprising a radical polymerizable polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator.

  In addition, as the structural unit containing an unsaturated double bond-containing compound having a bond decomposable by the action of acid (A) and / or heat at 130 ° C. to 250 ° C., the following general formula (I) and / or (II It is said photosensitive resin composition represented by this.

、

,

（ここでＲ^１はそれぞれ独立に水素原子又は炭素数1〜３のアルキル基を表し、Ｒ^２はそれぞれ独立に炭素数１〜３のアルキル基又はアルコキシ基、ＯＨ基、ハロゲンを表す。ｍは０〜４の整数である。Ｒ^３はそれぞれ独立に炭素数４以上の三級アルキル基、トリフェニルアルキル基、三級アルコキシカルボニル基、アルコキシアルキルアセタール基、フェノキシアルキルアセタール基、テトラヒドロピラニル基、トリアルキルシリル基、三級炭素を介して結合しているシクロアルキル基、三級炭素を介して結合しているアダマンチル基、三級炭素を介して結合しているラクトン基、三級炭素を介して結合しているビシクロアルキル基、三級炭素を介して結合しているトリシクロアルキル基を表す。Ｘは水素原子又はカルボン酸、エステル基、アミド基、ウレタン基を表す。）

(Here, R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² independently represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group, an OH group, or a halogen. R ³ is an integer of 0 to 4. R ³ is independently a tertiary alkyl group having 4 or more carbon atoms, a triphenylalkyl group, a tertiary alkoxycarbonyl group, an alkoxyalkylacetal group, a phenoxyalkylacetal group, a tetrahydropyranyl group, A trialkylsilyl group, a cycloalkyl group bonded via a tertiary carbon, an adamantyl group bonded via a tertiary carbon, a lactone group bonded via a tertiary carbon, via a tertiary carbon Represents a bicycloalkyl group bonded to each other and a tricycloalkyl group bonded via a tertiary carbon, where X is a hydrogen atom, a carboxylic acid, or an ester group. Represents an amide group or a urethane group.)

  First, the binder polymer (radical polymerizable polymer) as the component (A) will be described. (A) The unsaturated double bond-containing compound having an acid action and / or a bond decomposable by heat at 130 ° C. to 250 ° C. includes a phenolic hydroxyl group and a compound obtained by protecting a carboxylic acid with a protecting group. .

  Examples of the protecting group for the phenolic hydroxyl group include a tert-butoxycarbonyl group, a tetrahydropyranyl group, an ethoxymethyl group, an ethoxyethyl group, a phenoxyethyl group, and a trimethylsilyl group.

  Examples of the compound in which the carboxylic acid is protected with a protecting group include a tert-butyl group, a tetrahydropyranyl group, an ethoxymethyl group, an ethoxyethyl group, a phenoxyethyl group, and a trimethylsilyl group.

  Examples of the polymerizable monomer having the general formula (I) as a structural unit include t-butoxycarbonyloxystyrene, p-tetrahydropyranyloxystyrene, p-ethoxymethoxystyrene, p-ethoxy-1-ethoxystyrene, and p-phenoxy. Examples include 1-ethylstyrene and trimethylsilyloxystyrene.

  As the polymerizable monomer having the general formula (II) as a structural unit, tetrahydropyranyl (meth) acrylate, tert-butyl (meth) acrylate, triphenylmethyl (meth) acrylate, ethoxy (meth) acrylate Examples include methyl, ethoxy-1-ethyl (meth) acrylate, t-butoxycarbonyl (meth) acrylate, trimethylsilyl (meth) acrylate, adamantyl (meth) acrylate, and the like.

  From the viewpoint of the peeling property and developability of the resist with respect to the circuit-forming substrate of the photosensitive resin composition layer comprising the photosensitive resin composition as the constituent material, the constituent unit of the general formula (I) or (II) is the entire binder polymer molecule. It is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, still more preferably 15 to 45% by mass, and particularly preferably 20 to 40% by mass with respect to mass. preferable.

In the (A) binder polymer (radically polymerizable polymer) used in the present invention, if the content of the structural unit of the general formula (I) is less than 5% by mass, the alkali solubility is inferior, the peeled piece becomes large, and the peeling time is increased. There exists a tendency which becomes long, and when these content exceeds 60 mass%, there exists a tendency for resolution to fall.
In the present invention, the “styrene derivative” refers to a compound in which a hydrogen atom in styrene is substituted with a substituent (an organic group such as an alkyl group or a halogen atom).

When forming the photosensitive resin composition layer using this binder polymer, one type of binder polymer may be used alone, or two or more types of binder polymers may be used in any combination. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components (including different repeating units as constituent components), two or more types of binders having different weight average molecular weights Examples thereof include polymers and two or more types of binder polymers having different degrees of dispersion.
In addition, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.

  The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder polymer can be measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene).

  According to this measurement method, the Mw of the binder polymer is preferably 5,000 to 300,000, and more preferably 40,000 to 150,000. When the Mw is less than 5,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

  The (A) binder polymer (radical polymerizable polymer) preferably has a dispersity (Mw / Mn) of 1.0 to 3.0, and more preferably 1.0 to 2.0. When the degree of dispersion exceeds 3.0, the adhesion and resolution tend to decrease.

The (A) binder polymer may be used in combination with a styrene resin, an epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, or a phenol resin.
The (A) binder polymer used in the present invention can be produced, for example, by radical polymerization of a polymerizable monomer.

Moreover, (A) binder polymer used by this invention can also use together polymerizable monomers other than the polymerizable monomer for comprising the said general formula (I)-(II). Examples of the polymerizable monomer other than the polymerizable monomer for constituting the general formulas (I) to (II) include the (meth) acrylic acid alkyl ester, for example, the following general formula (III). And compounds in which a hydroxyl group, an epoxy group, a halogen group or the like is substituted on the alkyl group of these compounds. However, in the following general formula (III), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a hydroxyalkyl group.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁵ in the general formula (III) 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, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid- 2-hydroxypropyl, (meth) acrylic acid-3-hydro Shipuropiru include (meth) -4-hydroxybutyl acrylic acid. These may be used alone or in any combination of two or more.

  In addition, acrylamide such as styrene, α-methylstyrene, diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, tetrahydrofurfuryl ester of (meth) acrylate, dimethylaminoethyl (meth) acrylate Ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, ( (Meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, malein Monomethyl acid, monoethyl maleate And maleic acid monoesters such as monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. These may be used alone or in any combination of two or more.

  The (A) binder polymer in the present invention is preferably composed of one or more kinds of polymers having a carboxyl group from the viewpoint of developability when alkali development is performed using an alkaline solution. Such a (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer.

  (A) It is preferable that the acid value of a binder polymer is 30-200 mgKOH / g, and it is more preferable that it is 45-150 mgKOH / g. When the acid value is less than 30 mg KOH / g, the development time tends to be long, and when it exceeds 200 mg KOH / g, the developer resistance of the photocured resist tends to be lowered.

Moreover, when performing solvent image development as a image development process, it is preferable to prepare the polymerizable monomer which has a carboxyl group in a small quantity.
In addition, (A) the binder polymer may have a characteristic group having photosensitivity in the molecule as necessary.

  (A) As content of binder polymer, it is preferable to set it as 30-70 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, and it is more preferable to set it as 35-65 weight part. 40 to 60 parts by weight is more preferable. If this content is less than 30 parts by weight, there is a tendency that a good shape cannot be obtained, and if it exceeds 70 parts by weight, good sensitivity and resolution tend not to be obtained. These may be used alone or in combination of two or more.

Next, the photopolymerizable compound as the component (B) will be described.
Examples of the photopolymerizable compound (B) used in the present invention include compounds obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, bisphenol A (meth) acrylate compounds, and glycidyl group-containing compounds. A compound obtained by reacting an α, β-unsaturated carboxylic acid with a monomer, a urethane monomer such as a (meth) acrylate compound having a urethane bond in the molecule, nonylphenoxypolyethyleneoxyacrylate, a phthalic acid compound, (meth) acrylic acid Examples include alkyl esters. These may be used alone or in combination of two or more.

  From the viewpoint of plating resistance and adhesion, it is preferable to use a bisphenol A (meth) acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule as an essential component.

  Also, a photopolymerizable unsaturated compound having one polymerizable ethylenically unsaturated bond in the molecule and a photopolymerizable unsaturated compound having two or more polymerizable ethylenically unsaturated bonds in the molecule. Use in combination is preferable from the viewpoint of obtaining the effect of the present invention more reliably.

  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. 14 polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. These may be used alone or in combination of two or more.

Here, “EO” represents ethylene oxide, and an EO-modified compound represents one having a block structure of an ethylene oxide group.
“PO” represents propylene oxide, and the PO-modified compound has a propylene oxide group block structure.

  Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis [4-[(meth) acryloxypolyethoxy] phenyl] propane and 2,2-bis [4- (meth) acryloxypolypropoxy] phenyl. ] Propane, 2,2-bis [4-[(meth) acryloxypolybutoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxypolyethoxypolypropoxy] phenyl] propane and the like. .

  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) acryloxynonae 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.

  2,2-bis [4- (methacryloxypentaethoxy) phenyl] propane is BPE-500 [trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.], FA-321M [trade name, manufactured by Hitachi Chemical Co., Ltd. 2,2-bis [4- (methacryloxypentadecaethoxy) phenyl] propane is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). It is available.

  The number of ethylene oxide groups in one molecule of the 2,2-bis [4-[(meth) acryloxypolyethoxy] phenyl] propane is preferably 4-20, and more preferably 8-15. . These may be used alone or in any combination of two or more.

  Examples of the (meth) acrylate compound having a urethane bond in the molecule include, for example, a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate). , 1,6-hexamethylene diisocyanate, etc.), tris [(meth) acryloxytetraethylene glycol isocyanate] hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate Etc.

Examples of the EO-modified urethane di (meth) acrylate include UA-11 [trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.].
Examples of the EO and PO-modified urethane di (meth) acrylate include UA-13 [trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.]. These may be used alone or in combination of two or more.

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

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o-phthalate. Etc. These may be used alone or in any combination of two or more.

  The component (B) used in the present invention preferably contains a bisphenol A (meth) acrylate compound from the viewpoint of improving sensitivity and resolution. From the viewpoint of shortening the peeling time, one ethylenic group is not contained in the molecule. It is preferable to include a compound having a saturated group.

  The component (B) used in the present invention includes polyalkylene glycol di (meth) acrylate having both an ethylene glycol chain and a propylene glycol chain in the molecule from the viewpoint of improving the flexibility of the cured film. Preferably it is.

  This (meth) acrylate is not particularly limited as long as it has both an ethylene glycol chain and a propylene glycol chain (n-propylene glycol chain or isopropylene glycol chain) as alkylene glycol chains in the molecule.

  In addition, this (meth) acrylate further includes an n-butylene glycol chain, an isobutylene glycol chain, an n-pentylene glycol chain, a hexylene glycol chain, an alkylene glycol chain having about 4 to 6 carbon atoms such as a structural isomer thereof. You may have.

When there are a plurality of ethylene glycol chains and propylene glycol chains, the plurality of ethylene glycol chains and propylene glycol chains need not be continuously present in blocks, and may be present randomly.
In the isopropylene glycol 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.

  Intramolecular of polyalkylene glycol di (meth) acrylate having at least one polymerizable ethylenically unsaturated bond in these components (B) and having both ethylene glycol chain and propylene glycol chain in the molecule The alkylene glycol chain of, for example, a compound represented by the general formula (IV),

（式中、２つのＲは各々独立に水素原子又は炭素数１〜３のアルキル基を示し、ＥＯはエチレングリコール鎖を示し、ＰＯはプロピレングリコール鎖を示し、ｍ^１、ｍ^２及びｎ^１は各々独立に１〜３０の整数である。）
一般式（Ｖ）で表される化合物

(In the formula, two R's each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO represents an ethylene glycol chain, PO represents a propylene glycol chain, and m ¹ , m ² and n ¹ are Each is independently an integer of 1 to 30.)
Compound represented by general formula (V)

（式中、２つのＲは各々独立に水素原子又は炭素数１〜３のアルキル基を示し、ＥＯはエチレングリコール鎖を示し、ＰＯはプロピレングリコール鎖を示し、ｍ^３、ｎ^２及びｎ^３は各々独立に１〜３０の整数である。）
及び一般式（ＶＩ）で表される化合物等が挙げられる。

(In the formula, two Rs each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO represents an ethylene glycol chain, PO represents a propylene glycol chain, and m ³ , n ² and n ³ are Each is independently an integer of 1 to 30.)
And compounds represented by formula (VI).

（式中、２つのＲは各々独立に水素原子又は炭素数１〜３のアルキル基を示し、ＥＯはエチレングリコール鎖を示し、ＰＯはプロピレングリコール鎖を示し、ｍ^４及びｎ^４は各々独立に１〜３０の整数である。）

(In the formula, two Rs each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, EO represents an ethylene glycol chain, PO represents a propylene glycol chain, and m ⁴ and n ⁴ each independently represent It is an integer from 1 to 30.)

These may be used alone or in combination of two or more.
Examples of the alkyl group having 1 to 3 carbon atoms in the general formula (IV), the general formula (V), and the general formula (VI) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

The total number (m ¹ + m ² , m ³ and m ⁴ ) of ethylene glycol chain repeats in the above general formula (IV), general formula (V) and general formula (VI) is each independently an integer of 1 to 30. It is preferably an integer of 1 to 10, more preferably an integer of 4 to 9, and further preferably an integer of 5 to 8. If the number of repetitions exceeds 30, the tent reliability and the resist shape tend to deteriorate.

The total number (n ¹ , n ² + n ³ and n ⁴ ) of propylene glycol chains in the general formula (IV), general formula (V) and general formula (VI) is an integer of 1 to 30 each independently. , Preferably an integer of 5 to 20, more preferably an integer of 8 to 16, and even more preferably an integer of 10 to 14. If the number of repetitions exceeds 30, the resolution deteriorates and sludge tends to be generated.

Specific examples of the compound represented by the general formula (IV) include, for example, vinyl compounds [Hitachi Chemical Co., Ltd.] wherein R = methyl group, m ¹ + m ² = 4 (average value), and n ¹ = 12 (average value). Kogyo Co., Ltd., trade name FA-023M].

Specific examples of the compound represented by the general formula (V) include vinyl compounds [Hitachi Chemical Co., Ltd.] wherein R = methyl group, m ³ = 6 (average value), and n ² + n ³ = 12 (average value). Kogyo Co., Ltd. product name FA-024M].

Specific examples of the compound represented by the general formula (VI) include, for example, R = hydrogen atom, m ⁴ = 1 (average value), n ⁴ = 9 (average value) vinyl compound [Shin Nakamura Chemical Co., Ltd. Co., Ltd., sample name NK ester HEMA-9P] and the like. These may be used alone or in combination of two or more.

  As content of the photopolymerizable compound of (B) component, it is preferable to set it as 30-70 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, and it is 35-65 weight part. More preferably, the amount is 40 to 60 parts by weight. If the content is less than 30 parts by weight, good sensitivity and resolution tend not to be obtained, and if it exceeds 70 parts by weight, a good shape tends not to be obtained. These may be used alone or in combination of two or more.

  Next, as the photopolymerization initiator as the component (C), for example, 4,4′-bis (diethylamino) benzophenone, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone— Aromatic ketones such as 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, quinones such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ether, benzoin, alkylbenzoin Benzoin compounds such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole 2-mer, 2- (o-fluorophenyl) -4,5 2,4,5 such as diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer -Acridine derivatives such as -triarylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, and the like.

Further, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound.
From the viewpoint of adhesion and sensitivity, 2,4,5-triarylimidazole dimer is more preferable. These may be used alone or in combination of two or more.

  As content of the photoinitiator of (C) component, it is preferable to set it as 0.1-10 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, 2-6 weight part More preferably, the content is 3.5 to 5 parts by weight. If this content is less than 0.1 part by weight, good sensitivity and resolution tend not to be obtained, and if it exceeds 10 parts by weight, a good shape tends not to be obtained. These may be used alone or in combination of two or more.

  The sensitizing dye of component (D) in the present invention can effectively utilize the absorption wavelength of the active light to be used. As the sensitizing dye, a compound having a maximum absorption wavelength of 370 nm to 420 nm is preferable.

  In the present invention, by using such a sensitizing dye, it becomes possible to have a sufficiently high sensitivity to the exposure light of the direct drawing exposure method. If the maximum absorption wavelength of the sensitizing dye is less than 370 nm, the sensitivity to direct drawing exposure light tends to decrease, and if it is 420 nm or more, the stability tends to decrease even in a yellow light environment.

  Examples of the sensitizing dye (D) used in the present invention include pyrazolines, anthracenes, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, and triazines. , Thiophenes, naphthalimides and the like.

  (D) The content of the sensitizing dye is preferably 0.01 to 10 parts by weight, and 0.05 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). More preferably, the content is 0.1 to 2 parts by weight. If this amount is less than 0.01 part by weight, good sensitivity and resolution tend not to be obtained, and if it exceeds 10 parts by weight, a good shape tends not to be obtained. These may be used alone or in combination of two or more.

  Examples of the (E) amine compound used in the present invention include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leucocrystal violet.

  (E) The content of the amine compound is preferably 0.01 to 10 parts by weight, and 0.05 to 5 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). More preferably, the content is 0.1 to 2 parts by weight. If the blending amount is less than 0.01 parts by weight, good sensitivity tends not to be obtained, and if it exceeds 10 parts by weight, there is a tendency to deposit as foreign matter after film formation. These may be used alone or in combination of two or more.

  If necessary, the photosensitive resin composition may include a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, a dye such as malachite green, Photochromic agents such as bromophenylsulfone and leucocrystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents , Peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, 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 amount of component (A) and component (B). . These may be used alone or in combination of two or more.

  The photosensitive resin composition according to the present invention is soluble in 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. And it is good also as a solution about 30-60 mass% of solid content. This solution can be used as a coating solution for forming the photosensitive resin composition layer of the photosensitive element.

  In addition, the above coating solution may be used for forming a photosensitive resin composition layer of a photosensitive element by coating and drying on a support film described later, for example, the surface of a metal plate, for example, Apply a liquid resist on the surface of an iron-based alloy such as copper, copper-based alloy, nickel, chromium, iron, stainless steel, preferably copper, copper-based alloy, iron-based alloy, and dry, and then coat the protective film It may be used.

  Moreover, although the layer thickness of the photosensitive resin composition layer changes with uses of the photosensitive element, it is preferable that it is about 1-100 micrometers by the thickness after drying. In the case where the above-described liquid resist is used after being coated with a protective film, examples of the protective film include polymer films such as polyethylene and polypropylene.

(Photosensitive element)
Next, the photosensitive element according to the present invention will be described.
The photosensitive element according to the present invention has at least a support film, a protective film made of a synthetic resin, and a photosensitive resin composition layer disposed between the support film and the protective film.

  As the support film, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.

  The support film (polymer film) preferably has a thickness of 1 to 100 μm. If the thickness is less than 1 μm, the support film tends to be broken when the support film is peeled off before development, and if it exceeds 100 μm, the resolution tends to decrease. From this viewpoint, 5 to 25 μm is preferable. One polymer film is used as a support for the photosensitive resin composition layer, and the other is used as a protective film for the photosensitive resin composition, laminated on both sides of the photosensitive resin composition layer. Also good.

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

  "Fish eye" means that when a material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidized degradation products, etc. It is taken in.

  As the protective film, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.

  Examples of commercially available products include, for example, Oji Paper Co., Ltd., trade name: Alphan MA-410, E-200C, Shin-Etsu Film Co., Ltd., polypropylene film, Teijin Limited, trade name: PS-25, PS series. Examples thereof include, but are not limited to, polyethylene terephthalate films.

  The protective film preferably has a thickness of 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. If the thickness is less than 1 μm, the protective film tends to be broken during lamination, and if it exceeds 100 μm, the cost tends to be inferior.

  The photosensitive resin composition layer is prepared by dissolving the photosensitive resin composition of the present invention in a solvent as described above to obtain a solution (coating solution) having a solid content of about 30 to 60% by mass, and then applying the solution (coating solution). (Liquid) is preferably applied on a support film and dried.

The coating 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, or a bar coater.
Moreover, drying can be performed at 70-150 degreeC and about 5 to 30 minutes.
In addition, it is preferable that the amount of the residual organic solvent in the photosensitive resin composition shall be 2 mass% or less from the point which prevents the spreading | diffusion of the organic solvent in a next process.

  Moreover, although the thickness of the photosensitive resin composition layer changes with uses, it is preferable that it is 1-100 micrometers by the thickness after drying, and it is more preferable that it is 1-50 micrometers. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the effect of the present invention is reduced, and the adhesive force and resolution tend to decrease.

Moreover, it is preferable that the transmittance | permeability with respect to the ultraviolet-ray with a wavelength of 365 nm is 5 to 75%, as for the photosensitive resin composition layer, it is more preferable that it is 7 to 60%, and it is further more preferable that it is 10 to 40%. If the transmittance is less than 5%, the adhesion tends to be inferior, and if it exceeds 75%, the resolution tends to be inferior.
The transmittance can be measured by a UV spectrometer, and examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

The photosensitive element according to the present invention may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.
Moreover, the obtained photosensitive element can be wound up and stored in a roll shape around a sheet shape or a core. In addition, it is preferable to wind up so that a support body may become the 1st outer side at this time.

  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.

Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability.
Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

(Method for forming resist pattern)
Next, a resist pattern forming method according to the present invention will be described.
The method for forming a resist pattern according to the present invention is a method in which the above-described protective film of the photosensitive element of the present invention is gradually peeled off from the photosensitive resin composition layer and simultaneously exposed to the photosensitive resin composition layer. A first step of laminating the photosensitive resin composition layer on the circuit forming substrate by bringing the surface portion into close contact with the surface of the circuit forming substrate on which the circuit is to be formed, exposure of the photosensitive resin composition layer It includes at least a second step of irradiating a predetermined portion to be irradiated with actinic rays to form an exposed portion, and then a third step of removing an unexposed portion other than the exposed portion. The “circuit forming substrate” refers to a substrate including an insulating layer and a conductor layer formed on the insulating layer.

  As a method of laminating the photosensitive resin composition layer on the circuit forming substrate in the first step, after removing the protective film, the photosensitive resin composition layer is used for circuit formation while heating the photosensitive resin composition layer. The method of laminating | stacking by crimping | bonding to a board | substrate is mentioned. In addition, it is preferable to laminate | stack this operation under pressure reduction from the viewpoint of adhesiveness and followable | trackability.

In the lamination of the photosensitive element, the photosensitive resin composition layer and / or the circuit forming substrate is preferably heated to 70 to 130 ° C., and the pressure bonding pressure is about 0.1 to 1.0 MPa (1 to 10 kgf / cm). it is preferably about ^2), but not particularly limited to these conditions.

  Further, 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.

  Examples of the method for forming the exposed portion in the second step include a method of irradiating an image with active light through a negative or positive mask pattern called an artwork (mask exposure method).

At this time, when the support film present on the photosensitive resin composition layer is transparent to the active light, the active light can be irradiated through the support film, and when the support film is light-shielding After removing the support film, the photosensitive resin composition layer is irradiated with actinic rays.
Further, a method of irradiating actinic rays in an image form by a direct drawing method such as a laser direct drawing exposure method or a DLP (Digital Light Processing) exposure method may be adopted.

  As a light source of actinic light, known light sources such as carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid state lasers such as YAG lasers, ultraviolet rays such as semiconductor lasers, visible light, etc. That effectively radiate are used.

  Next, after the exposure, as a method of removing the portion other than the exposed portion in the third step, first, when the support film is present on the photosensitive resin composition layer, the support film is removed, and then Examples include a method in which a portion other than the exposed portion is removed by wet development, dry development, or the like. Thereby, a resist pattern is formed.

  For example, in the case of wet development, using a developer corresponding to a photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, an organic solvent developer, etc., for example, spraying, rocking immersion, brushing, scraping, etc. Development is performed by a known method.

  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 lithium, sodium, and potassium hydroxide, alkali carbonates such as lithium, sodium, potassium, and ammonium carbonate or bicarbonate, potassium phosphate, and phosphoric acid. Alkali metal phosphates such as sodium and 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.
Further, 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.

  Examples of the aqueous developer include a developer composed of water or an alkaline aqueous solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1, Examples include 3-propanediol, 1,3-diaminopropanol-2, morpholine and the like.

The pH of the developer is desirably as small as possible within a range where the resist can be sufficiently developed, and is preferably pH 8-12, more preferably pH 9-10.
Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. It is done. These may be 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.
Moreover, you may use together 2 or more types of image development methods as needed. 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.

As processing after development, the resist pattern may be further cured and used by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary.
For the etching of the metal surface performed after development, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used.

(Printed wiring board manufacturing method)
Next, the manufacturing method of the printed wiring board which becomes this invention is demonstrated.
The method for producing a printed wiring board according to the present invention comprises etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern of the present invention.

  Etching and plating of the circuit forming substrate is performed on a conductor layer or the like of the circuit forming substrate using the formed resist pattern as a mask. Etching solutions used for etching include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution, etc., and among these, chloride chloride is used because of its good etch factor. It is preferable to use a diiron solution.

  Moreover, as a plating method in the case of plating, for example, copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate, etc. Nickel plating, hard gold plating, and gold plating such as soft gold plating.

  After completion of the etching or plating, the resist pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As this strongly alkaline aqueous solution, for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used.

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

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to these Examples.
[Synthesis of Binder Polymer (A-1)]
To a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet tube, 450 g of propylene glycol monomethyl ether and toluene in a mass ratio of 3: 2 are added, and stirred while blowing nitrogen gas. And heated to 80 ° C.

  On the other hand, a solution in which 125 g of methacrylic acid, 125 g of methyl methacrylate, 125 g of t-butyl methacrylate and 125 g of styrene, and 9.0 g of azobisisobutyronitrile are mixed as a comonomer (hereinafter referred to as “solution a”). The solution a was added dropwise to the above blend of propylene glycol monomethyl ether and toluene having a mass ratio of 3: 2 heated to 80 ° C. over 4 hours, and then kept at 80 ° C. for 2 hours with stirring. .

  Further, a solution prepared by dissolving 1.2 g of azobisisobutyronitrile in 100 g of a propylene glycol monomethyl ether and toluene mixture having a mass ratio of 3: 2 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. The mixture was kept at 90 ° C. for 2 hours and then cooled to obtain a binder polymer (A-1).

  The nonvolatile content (solid content) of the binder polymer (A-1) was 47.8% by mass, and the weight average molecular weight was 40,000. 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 (manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (3 in total) [above, product name, manufactured by Hitachi Chemical Co., Ltd.]
-Eluent: Tetrahydrofuran-Measurement temperature: 40 ° C
-Flow rate: 2.05 mL / min-Detector: Hitachi L-3300 type RI [manufactured by Hitachi, Ltd.]

Synthesis of binder polymers (A-2) to (A-6) Binder polymers (A-2) to (A-6) were synthesized in the same manner as (A-1) with the following comonomer composition. .

プロピレングリコールモノメチルエーテル／トルエン（３／２）溶液（固形分濃度：４７．８％）

Propylene glycol monomethyl ether / toluene (3/2) solution (solid content concentration: 47.8%)

(B) Photopolymerizable compound (B-1): FA-321M [manufactured by Hitachi Chemical Co., Ltd., trade name]; 2,2-bis [4-[(methacryloxypentaethoxy) phenyl] propane]
(B-2): FA-024M (trade name, manufactured by Hitachi Chemical Co., Ltd.); in the compound represented by the general formula (V), R = methyl group, m ³ = 6 (average value), n Compound in which ² + n ³ = 12 (average value)
(B-3): M-114 [trade name, manufactured by Toagosei Co., Ltd.]; 4-normalnonylphenoxyoctaethylene glycol acrylate

(C) Photopolymerization initiator (C-1): BCIM (trade name, manufactured by Hampford); 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole
(D) Sensitizing dye: DBA: [trade name, manufactured by Kawasaki Kasei Kogyo Co., Ltd.]; 9,10-dibutoxyanthracene (E) color former (amine compound): leuco crystal violet
(F) Photoacid generator; NAI-105 [manufactured by Midori Chemical Co., Ltd.]

＊ 固形分量

* Solid content

  Next, the solution of the photosensitive resin composition was uniformly applied onto a 16 μm thick polyethylene polyethylene terephthalate film and dried with a hot air convection dryer at 70 ° C. and 110 ° C. to obtain a photosensitive element. The film thickness of the photosensitive resin composition layer was 25 μm.

  On the other hand, the copper surface of a copper-clad laminate [made by Hitachi Chemical Co., Ltd., trade name MCL-E-67], which is a glass epoxy material laminated with copper foil (thickness 35 mm) on both sides, is a brush equivalent to # 600. Polishing was performed using a polishing machine (manufactured by Sankei Co., Ltd.), washed with water, and dried with an air flow to obtain a copper-clad laminate (substrate).

Next, after heating to a copper clad laminate 80 ° C., each photosensitive resin (each photosensitive resin while removing the protective films of Examples 1 to 3 and Comparative Examples 1 and 2 on the copper clad laminate) The composition layer was laminated (laminated) at 120 ° C. under a pressure of 4 kgf / cm ² so that the composition layer was in close contact with the surface of the copper-clad laminate.

  Next, when the copper clad laminate on which each photosensitive element is laminated is cooled to 23 ° C., the polyethylene terephthalate surface has a concentration region of 0.00 to 2.00, a concentration step of 0.05, and a tablet size. A phototool having a 41-step tablet having a length of 20 mm × 187 mm and a size of each step of 3 mm × 12 mm was adhered.

Using a direct drawing machine DE-1AH manufactured by Hitachi Via Mechanics Co., Ltd. using a 405 nm blue-violet laser diode as a light source, drawing was performed at a predetermined exposure amount, and the number of remaining step steps after development of the 41-step tablet was obtained. .
In addition, a drawing pattern having a line width / space width of 6/6 to 22/22 (unit: mm) was used, and the minimum dimension at which resolution adhesion was obtained after development was defined as the resolution.

The number of remaining steps when 70 mJ / cm ² was exposed was shown as sensitivity. The illuminance was measured using an ultraviolet illuminometer (trade name: “UIT-150” manufactured by USHIO INC.) To which a 405 nm probe was applied.

  Next, the polyethylene terephthalate film was peeled off, and a 1% by mass sodium carbonate aqueous solution was sprayed at 30 ° C. for 24 seconds to remove unexposed portions. Then, the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablet of the photocured film formed on the copper-clad laminate. The results are shown in Table 4 below. The photosensitivity is indicated by the number of steps of the step tablet, and the higher the number of steps of the step tablet, the higher the photosensitivity.

  Resolution adhesion was evaluated based on the smallest value of equal width lines / spaces in which unexposed portions could be removed cleanly by development processing, and the lines were generated without meandering or chipping. The evaluation of sensitivity and resolution is better as the numerical value is smaller. The results are shown in Table 4 below.

The resist shape after development was observed using a Hitachi scanning electron microscope S-500A. The resist shape is preferably close to a rectangle.
For the peelability, a photocured film having a size of 40 mm × 50 mm was prepared under the conditions shown in Table 3, and peeling was performed using a 3% by mass aqueous sodium hydroxide solution. The time when the film finished peeling from the substrate was defined as the peeling time.
Moreover, the size of the peeling piece after peeling completion was observed visually.

*露光量７０ｍJ／ｃｍ^２でのステップ段数

* Number of steps at exposure 70mJ / cm ²

  As shown in Table 4, in the compositions of Examples 1 to 4, the resolution adhesion (L / S) is as good as 12 μm, the peeling time is short, the peel piece size is small, and the resolution and peelability are good. It is clear that there is a balance. On the other hand, in Comparative Examples 1 and 2, it is clear that although the peelability is good, the resolution adhesion is low.

Claims (12)

  (A) a radically polymerizable polymer comprising a structural unit composed of an unsaturated double bond-containing compound having an acid action and / or a bond decomposable by heat at 130 ° C. to 250 ° C., (B) a photopolymerizable compound and ( C) A photosensitive resin composition containing a photopolymerization initiator. (A) A structural unit composed of an unsaturated double bond-containing compound having a bond decomposable by the action of an acid and / or heat at 130 ° C. to 250 ° C. is represented by the following general formula (I) and / or (II): The photosensitive resin composition according to claim 1.

,

(Here, R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² independently represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group, an OH group, or a halogen. R ³ is an integer of 0 to 4. R ³ is independently a tertiary alkyl group having 4 or more carbon atoms, a triphenylalkyl group, a tertiary alkoxycarbonyl group, an alkoxyalkylacetal group, a phenoxyalkylacetal group, a tetrahydropyranyl group, A trialkylsilyl group, a cycloalkyl group bonded via a tertiary carbon, an adamantyl group bonded via a tertiary carbon, a lactone group bonded via a tertiary carbon, via a tertiary carbon Represents a bicycloalkyl group bonded to each other and a tricycloalkyl group bonded via a tertiary carbon, where X is a hydrogen atom, a carboxylic acid, or an ester. ,. To an amide group, a urethane group)   The photosensitive resin composition according to claim 1 or 2, wherein (C) the photopolymerization initiator is a hexaarylbiimidazole derivative.   A photosensitive resin composition comprising the photosensitive resin composition according to claim 1, 2 or 3 and further containing (D) a sensitizing dye.   A photosensitive resin composition obtained by further containing (E) an amine compound in the photosensitive resin composition according to claim 1.   The photosensitive resin composition formed by containing the compound which generate | occur | produces an acid by the (F) light further in the photosensitive resin composition in any one of Claims 1-5.   The photosensitive element provided with the photosensitive resin composition layer which consists of a photosensitive resin composition in any one of Claims 1-6 formed on the support film and this support film.   A photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 6 is laminated on a circuit forming substrate, and a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays. Then, the exposed portion is photocured, and then a portion other than the exposed portion is removed.   A method for producing 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.   A circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 8 is etched or plated to form a circuit, and then the resist pattern is heated to 130 ° C to 250 ° C or after heating. However, the printed wiring board manufacturing method is characterized in that the printed wiring board is removed from the circuit forming substrate.   The photosensitive resin composition layer which consists of the photosensitive resin composition in any one of Claims 1-6 was laminated | stacked on the support substrate, the active ray was irradiated, and the said photosensitive resin composition layer was photocured. A method for removing a photocured product, comprising: removing the photocured product from the support substrate after heating to 130 ° C to 250 ° C or while heating.   A photocured product obtained by laminating the photosensitive resin composition layer in the photosensitive element according to claim 7 on a support substrate and irradiating actinic light to photocure the photosensitive resin composition layer is 130 ° C to 250 ° C. A method for removing a photocured product, comprising: removing from the support substrate after heating to ° C or while heating.