JP2008216876A - Photosensitive resin composition, photosensitive element, resist pattern forming method, method for manufacturing printed wiring board and method for removing photocured object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having improved removability while retaining excellent resolution, a photosensitive element, a resist pattern forming method, a method for manufacturing a printed wiring board and a method for removing a photocured object. <P>SOLUTION: The photosensitive resin composition comprises (A) a compound having a conjugated diene moiety and a compound having a dienophilic moiety and (B) a photopolymerization initiator for initiating a photopolymerization reaction of a photoradical polymerizable compound, wherein one or both of (A) the compound having the conjugated diene moiety and the compound having the dienophilic moiety are a compound having a photoradical polymerizable ethylenically unsaturated bond within a molecule or a compound having a ring structure by the Diels-Alder reaction. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  Conventionally, in the field of manufacturing printed wiring boards, as a resist material used for etching, plating, etc., a photosensitive resin composition and a photosensitive element obtained by using a support and a protective film are widely used. The printed wiring board is formed by laminating the photosensitive resin composition on the copper substrate, exposing the pattern, removing the uncured portion with a developer, performing etching or plating treatment, forming a pattern, and then curing. It is manufactured by a method in which the part is peeled off from the substrate. Development is performed using an alkaline aqueous solution. Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, and the like. The main purpose of the development process is to remove the unexposed part, that is, the uncured part by dissolution. The swelling of the hardened portion causes poor adhesion of the resist pattern and thickening of the line width, and is regarded as a main factor for lowering the resolution. That is, in order to improve the resolution, a composition design that is difficult to swell in an alkaline aqueous solution is effective.

  On the other hand, the resist pattern is peeled and removed with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. As said strong alkaline aqueous solution, 1-10 weight% sodium hydroxide aqueous solution, 1-10 weight% potassium hydroxide aqueous solution, etc. are used, for example. The principle of removal is the generation of stress due to swelling and a decrease in adhesion to the substrate. That is, in order to improve the removability, a composition design that is easy to swell in an alkaline aqueous solution is effective. In recent years, the photosensitive resin composition disclosed in Non-Patent Document 1 and the thermosetting resin composition disclosed in Non-Patent Document 2 have been proposed in order to improve the removability of cured products having a crosslinked structure formed by light or heat. Is being considered.

JP 11-327137 A Masamitsu Shirai, “Future Materials” Vol. 2, No. 9, p. 20-25, 2002 Hideyuki Otsuka et al., “Proceedings of the Society of Polymer Science,” Vol. 48, No. 8, p. 1635-1636, 1999

  With the recent increase in the density of printed wiring boards, the resist material is required to have higher resolution. However, as described above, the resist material having high resolution has poor removability. The photosensitive resin composition disclosed in Non-Patent Document 1 is an epoxy monomer, and is difficult to use for circuit formation of a printed wiring board from the viewpoint of sensitivity, resolution, developability, and the like. The composition disclosed in Non-Patent Document 2 is a thermosetting resin composition and cannot be used as a resist material because it is not photocured. The present invention has been made in view of the above, and provides a photosensitive resin composition having excellent removability, a photosensitive element, a resist pattern forming method, a printed wiring board manufacturing method, and a photocured product removing method. The purpose is to do.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a photosensitive resin containing a photopolymerizable compound having a specific structure and decomposing at a specific heating temperature, and a photopolymerization initiator. The present inventors have found that the above object can be achieved with a composition, and have completed the present invention.

That is, the present invention relates to the following.
1. (A) a photosensitive resin composition containing a compound having a conjugated diene moiety and a compound having a diene moiety, and (B) a photopolymerization initiator that initiates a photopolymerization reaction of a photoradically polymerizable compound, A) A compound having a conjugated diene moiety and a compound having a diene moiety, one or both of which has a photoradically polymerizable ethylenically unsaturated bond in the molecule or a ring wound by Diels-Alder reaction A photosensitive resin composition, which is a compound having a conventional structure.
2. (A) A compound having a conjugated diene moiety and a compound having a diene moiety are represented by the following general formula (1), the following general formula (2), and the following general formula (3). Item 2. The photosensitive resin composition according to Item 1, which is any one or more of the following compounds.

［式（１）〜（３）中、Ｒ_１、Ｒ_２の一方、又は両方にエチレン性不飽和結合を含む］

[In Formulas (1) to (3), _one or both of R ₁ and R ₂ contain an ethylenically unsaturated bond]

3. Item 3. A photosensitive element using a photosensitive resin composition layer obtained by coating the photosensitive resin composition according to item 1 or 2 on a support film while heating at 60 ° C to 120 ° C.
4). A photosensitive resin composition layer comprising the photosensitive resin composition according to item 1 or 2 is laminated on a circuit forming substrate, heated at 60 ° C. to 120 ° C., and then applied to a predetermined portion of the photosensitive resin composition layer. A method for forming a resist pattern, comprising irradiating actinic rays to photocure an exposed portion and then removing portions other than the exposed portion.
5. Laminating the photosensitive resin composition layer in the photosensitive element according to item 3 on a circuit forming substrate, irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays, and photocuring the exposed portion, Next, a resist pattern forming method, wherein a portion other than the exposed portion is removed.
6). The circuit forming step of etching or plating the circuit forming substrate on which the resist pattern is formed by the method for forming a resist pattern according to Item 4 or 5, and while heating the resist pattern at a temperature of 130 to 250 ° C. or And a removing step of removing the substrate from the circuit forming substrate after heating.
7). A photocured product obtained by laminating a photosensitive resin composition layer comprising the photosensitive resin composition according to Item 1 or 2 on a support substrate and irradiating actinic rays to photocur the photosensitive resin composition layer, A method for removing a photocured product, comprising: removing from the support substrate while heating under a temperature condition of 130 to 250 ° C. or after heating.
8). The photocured material obtained by laminating the photosensitive resin composition layer in the photosensitive element according to Item 3 on a support substrate and irradiating actinic light to photocur the photosensitive resin composition layer is 130 to 250 ° C. A method for removing a photocured product, comprising: removing from the support substrate while heating under the following temperature conditions or after heating.

  According to the present invention, a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, a method for producing a printed wiring board, and a photocured product capable of sufficiently improving removability while maintaining excellent resolution. Can be provided.

  The photosensitive resin composition of the present invention contains (A) a compound having a conjugated diene moiety and a compound having a diene moiety, and (B) a photopolymerization initiator that initiates a photopolymerization reaction of the photoradical polymerizable compound. A photosensitive resin composition, (A) a compound having a conjugated diene moiety and a compound having a diene moiety, one or both of which has an ethylenically unsaturated bond capable of photoradical polymerization in the molecule Or a compound having a structure in which a ring is wound by a Diels-Alder reaction.

  In the present invention, the compound represented by the following general formula (1) and the compound represented by the following general formula (2) are preferably used as the compound having the above-mentioned (A) conjugated diene moiety and diene moiety. One or both of them has an ethylenically unsaturated bond capable of photoradical polymerization in the molecule. Further, the compound of the following general formula (1) or the following general formula (2) may be a compound having a structure in which a ring is wound by a Diels-Alder reaction (the following general formula (3))], (B) A photosensitive resin composition containing a photopolymerization initiator that initiates a photopolymerization reaction of a photoradical polymerizable compound.

［式（１）〜（３）中、Ｒ_１、Ｒ_２の一方、又は両方にエチレン性不飽和結合を含む］

[In Formulas (1) to (3), _one or both of R ₁ and R ₂ contain an ethylenically unsaturated bond]

  Moreover, this invention bridge | crosslinks the compound represented by the said General formula (1) and the compound represented by the said General formula (2) by heating at 60 degreeC-120 degreeC, and the said General formula (3) It is preferable that the represented compound is produced. Usually, the compound represented by the general formula (3) is insolubilized in the developer by radical polymerization of ethylenically unsaturated bonds by light irradiation. Then, after metal wiring is formed by plating, etching, etc., when heated at 130 to 250 ° C., the structure of the general formula (3) is decrosslinked, and the general formula (1) and the general formula (2) are regenerated to generate alkali. Removability is improved with respect to a stripping solution such as.

  With such a photosensitive resin composition, it is possible to form a photocured product that has high adhesion to the substrate and hardly swells with respect to the developer, and an excellent resolution can be obtained. And about the removability of the formed photocured material, since the above-mentioned photopolymerizable compound is used, the photocured material can be decomposed by heating at a predetermined temperature, thereby reducing the adhesion to the substrate. The solution for removing the cured product can be easily swollen. At this time, if it is the photosensitive resin composition of this invention, the progress speed of decomposition | disassembly by heating can be increased greatly with respect to the progress speed of superposition | polymerization by the heating of photocured material, and the removability of photocured material Can be dramatically improved. That is, according to the photosensitive resin composition of the present invention, it is possible to eliminate the trade-off relationship between resolution and removability and sufficiently improve removability while maintaining excellent resolution. In particular, it is possible to simultaneously obtain excellent resolution capable of forming a resist pattern having a space width or line width (resolution) of 20 μm or less and excellent removability capable of reliably removing the resist pattern. it can.

  As a result of the cleavage of the characteristic group, the photocured product is likely to swell with respect to the solution for removing the photocured product such as an alkaline aqueous solution, and the removability of the photocured product is dramatically improved.

  The present invention also provides a photosensitive element comprising a support film and a photosensitive resin composition layer formed of the photosensitive resin composition formed on the support film.

  Since such a photosensitive element includes the photosensitive resin composition layer made of the photosensitive resin composition of the present invention that exhibits the above-described effects, the resolution and removability can be achieved at a high level, and the photosensitive element can be used. The workability and yield when manufacturing a printed wiring board using a conductive element can be improved.

  In the present invention, a photosensitive resin composition layer made of the photosensitive resin composition or a photosensitive resin composition layer in the photosensitive element is further laminated on a circuit forming substrate, and a predetermined photosensitive resin composition layer is formed. Provided is a method for forming a resist pattern, which comprises irradiating a portion with an actinic ray to photocure an exposed portion and then removing the portion other than the exposed portion.

  According to such a resist pattern forming method, since the photosensitive resin composition of the present invention or the photosensitive element of the present invention having the effects described above is used, an excellent resolution can be obtained and a resist pattern having excellent removability can be obtained. Can be formed.

  The present invention also provides a circuit forming step of etching or plating a circuit forming substrate on which a resist pattern has been formed by the method for forming a resist pattern, and after or after heating the resist pattern to 130 to 250 ° C., And a removing step of removing from the circuit forming substrate. A method of manufacturing a printed wiring board is provided.

  According to this manufacturing method, when removing the resist pattern formed using the photosensitive resin composition of the present invention, photopolymerization is carried out by removing after heating to 130 to 250 ° C. or while heating. Bonds in the above-mentioned characteristic groups in the functional compound can be easily broken by heating, reducing the adhesion of the resist pattern to the circuit forming substrate and making it easier to swell against the developer, making the resist pattern easier In addition, it can be removed reliably. In particular, when a resist pattern having a space width or line width of 20 μm or less is formed, it can be surely removed.

  Here, from the viewpoint of obtaining the above effect more reliably, the removal of the resist pattern in the removing step is preferably performed using an alkaline aqueous solution, and the heating time of the resist pattern is 1 minute or more. preferable.

  In the present invention, the photosensitive resin composition layer comprising the photosensitive resin composition or the photosensitive resin composition in the photosensitive element is laminated on a support substrate, and the photosensitive resin composition is irradiated with actinic rays. A method for removing a photocured product, comprising: removing a photocured product obtained by photocuring a material layer from a supporting substrate after heating to 130 to 250 ° C. or while heating.

  Such a method for removing a photocured product is not limited to application to the above-described method for producing a printed wiring board, and is applied without particular limitation to applications in which the photosensitive resin composition needs to be removed after photocuring. be able to. And according to the removal method of this photocured material, since it uses the photosensitive resin composition of the present invention or the photosensitive element of the present invention having the above-mentioned effects, it is heated after being heated to 130 to 250 ° C. By performing the removal while removing, it can be easily and reliably removed from the support substrate.

  Here, from the viewpoint of obtaining the above effect more reliably, the removal of the photocured product is preferably performed using an alkaline aqueous solution, and the heating time of the photocured product is preferably 1 minute or longer. .

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

(Photosensitive resin composition)
A compound containing a conjugated diene moiety and a diene moiety, one or both of which has an ethylenically unsaturated bond capable of photoradical polymerization in the molecule, provided that the above two compounds are Diels-Alder reactions A compound having a structure in which a ring is wound may be used.

  The compound (A) is a compound having the above-described configuration. For example, when the compound is heated at a temperature of 60 ° C. to 120 ° C., the Diels-Alder reaction proceeds and a ring structure is generated. Further, when this structure is heated at a temperature of 130 to 250 ° C., the bond in this characteristic group is cleaved by the reverse Diels-Alder reaction, and the original conjugated diene site and the diophile site are regenerated. Examples of the compound having a conjugated diene include 1,3-diene compounds such as butadiene, hexadiene, cyclopentadiene and cyclohexadiene, polycyclic aromatic compounds such as naphthalene, anthracene and tetracene, and heterocyclic groups such as furan, thiophene and pyrrole. Examples of the conjugated diene compound further having a photoradically polymerizable ethylenically unsaturated bond in the molecule include furfuryl methacrylate. Examples of the diene compound include maleic anhydride, maleic acid methyl ester, maleic acid dimethyl ester, m-phenylene bismaleimide, 4,4-diphenylmethane bismaleimide, 4,4-diphenyl ether bismaleimide, 1,3-bis (4 -Maleimidophenoxy) Maleimides such as benzene, and derivatives such as acrolein, dicyanoethylene, and tetracyanoethylene.

  The photosensitive resin composition of the present invention may contain a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule as long as the effects of the present invention are not impaired. , Β-unsaturated carboxylic acid compound, bisphenol A (meth) acrylate compound, glycidyl group-containing compound and α, β-unsaturated carboxylic acid compound, urethane bond in the molecule And urethane monomers such as (meth) acrylate compounds, nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, (meth) acrylic acid alkyl esters, and the like.

  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 and / or PO modified trimethylolpropane tri (meth) acrylate, tetramethylol methane Examples include li (meth) acrylate, tetramethylolmethanetetra (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. In the above, EO represents ethylene oxide, and the EO-modified compound has an ethylene oxide group block structure. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups.

  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 It is done. 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) acryloxynona) Toxi) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is a BPE 500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (Shin-Nakamura Chemical Co., Ltd.). It is commercially available as a product name). 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. .

  Examples of the (meth) acrylate compound having a urethane bond in the molecule include (meth) acrylic monomers having an OH group at the β-position and diisocyanate compounds (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 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Examples of the EO and PO-modified urethane di (meth) acrylate include UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).

  Examples of the nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethylene Examples include oxyacrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxyalkyl-o-phthalate, and the like. Is mentioned.

  Examples of the photopolymerization initiator include benzophenone, N, N′-tetraalkyl-4,4′-diaminobenzophenone, such as N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), 2- Aromatic ketones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones Quinones such as, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2 -(O-chlorophenyl) -4,5-di (methoxy) Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- Acridine such as 2,4,5-triarylimidazole dimer such as methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane Derivatives, N-phenylglycine, N-phenylglycine derivatives, coumarin compounds and the like can be mentioned. 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. These are used alone or in combination of two or more.

  The photosensitive resin composition of the present invention may contain a compound that generates an acid by heating or irradiation with active energy rays (hereinafter referred to as “acid generator”) within a range that does not impair the effects of the present invention. Onium salts such as diazonium salt, iodonium salt, bromonium salt, chloronium salt, sulfonium salt, selenonium salt, pyrylium salt, thiapyrylium salt, pyridinium salt; halogenated compounds such as tris (trihalomethyl) -s-triazine and derivatives thereof; 2-nitrobenzyl ester of sulfonic acid; iminosulfonate; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivative; N-hydroxyimide sulfonate; tri (methanesulfonyloxy) benzene derivative; bissulfonyldiazomethanes; sulfonylcarbonyl Alkanes E sulfonyl carbonyl diazomethanes; disulfone compounds and the like.

  The photosensitive resin composition of the present invention may contain a polymer binder as long as it does not inhibit the curing of the present invention. For example, acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy Resin, alkyd resin, phenol resin and the like. From the viewpoint of alkali developability, an acrylic resin is preferable. These can be used alone or in combination of two or more.

  The polymer binder can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, and p-ethyl styrene, vinyl such as acrylamide, acrylonitrile, and vinyl-n-butyl ether. Esters of alcohol, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl 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, monoester maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanosilicic acid Cinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. These may be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof. These can be used alone or in combination of two or more.

  The polymer binder preferably has a carboxyl group from the viewpoint of alkali developability. For example, the polymer binder is produced by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer. Can do. As the polymerizable monomer having a carboxyl group, methacrylic acid is preferable. The polymer binder preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of flexibility.

  In order to improve both adhesion and removal characteristics using the styrene or styrene derivative as a copolymerization component, it is preferable to contain 3 to 30% by weight, more preferably 4 to 28% by weight, and more preferably 5 to 27% by weight. It is particularly preferable to include it. If this content is less than 3% by weight, the adhesion tends to be inferior, and if it exceeds 30% by weight, the removal time tends to be long.

  The acid value of the polymer binder is preferably 30 to 200 mgKOH / g, and more preferably 45 to 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.

  The weight average molecular weight of the polymer binder (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) is preferably 20,000 to 300,000, and 25,000. More preferably, it is ˜150,000. When the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

Moreover, the said polymer binder may have a photosensitive group as needed.
These polymer binders are used alone or in combination of two or more. Examples of the polymer binder when two or more types are used in combination include, for example, two or more types of polymer binders composed of different copolymerization components, two or more types of polymer binders having different weight average molecular weights, and different dispersions. 2 or more types of polymer binders. A polymer having a multimode molecular weight distribution described in JP-A-11-327137 can also be used.

  The photosensitive resin composition may include a dye such as malachite green, a photochromic agent such as tribromophenyl sulfone or leuco crystal violet, a thermochromic inhibitor, a plasticizer such as p-toluenesulfonamide, or a pigment, if necessary. , Fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, antioxidants, fragrances, imaging agents, thermal crosslinking agents, and the like. These may be used alone or in combination of two or more.

  The photosensitive resin composition is dissolved 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 as necessary. Then, it can be applied as a solution having a solid content of 30 to 60% by weight.

  The photosensitive resin composition is not particularly limited, but is coated as a liquid resist on a metal surface such as copper, a copper-based alloy, iron, and an iron-based alloy, dried, and then covered with a protective film as necessary. Or used in the form of a photosensitive element.

  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. In the case of using a liquid resist coated with a protective film, examples of the protective film include polymer films such as polyethylene and polypropylene.

  The photosensitive element can be obtained, for example, by applying and drying a photosensitive resin composition on a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester as a support. The application can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater. Moreover, drying can be normally performed at 70-150 degreeC * 5-30 minutes, Preferably it is 60-120 degreeC * 5-30 minutes. Further, the amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 2% by weight or less from the viewpoint of preventing the organic solvent from diffusing in the subsequent step.

  The thickness of these polymer films is preferably 1 to 100 μm. One of these polymer films may be laminated on both sides of the photosensitive resin composition layer as a support for the photosensitive resin composition layer, and the other as a protective film for the photosensitive resin composition. As the protective film, those having a smaller adhesive force between the photosensitive resin composition layer and the protective film than the adhesive force between the photosensitive resin composition layer and the support are preferable, and a film having a low fish eye is preferable.

  In addition to the photosensitive resin composition layer, the support and the protective film, the photosensitive element may have an intermediate layer or protective layer such as a cushion layer, an adhesive layer, a light absorption layer, or a gas barrier layer. .

  The photosensitive element is stored, for example, as it is or by further laminating a protective film on the other surface of the photosensitive resin composition layer and winding it around a cylindrical 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. Further, 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).

In producing a resist pattern using the photosensitive element, if the protective film is present, the photosensitive resin composition layer is usually 60 to 130 ° C., preferably 60, after removing the protective film. Examples include a method of laminating by pressure bonding to a circuit forming substrate at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ) while heating to ~ 120 ° C, and it is also possible to laminate under a reduced pressure. It is. The surface to be laminated is usually a metal surface, but is not particularly limited.

  The photosensitive resin composition layer thus laminated is irradiated with active energy rays in an image form through a mask pattern. As the light source of the active energy ray, a known light source, for example, one that effectively emits ultraviolet light, visible light, etc., such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, and a xenon lamp is used. In addition, a direct drawing method such as a laser direct drawing exposure method or a DLP (Digital Light Processing) exposure method that is an exposure method that does not use a mask pattern is also used.

  Next, after exposure, when a support is present on the photosensitive resin composition layer, the support is removed, and then wet development or dry development with a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. The resist pattern can be manufactured by removing the unexposed portion with development or the like and developing. Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, and the like. It is done. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent, or the like may be mixed in the alkaline aqueous solution. Examples of the development method include a dip method, a spray method, brushing, and slapping.

As a process after development, the resist pattern may be further cured and used by performing exposure at about 0.2 to 10 J / cm ² as necessary.

  When producing a printed wiring board using the photosensitive resin composition of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating. For the etching of the metal surface, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used.

  In the present invention, heating is performed before and / or while removing the photocured product. As heating temperature, 130 to 250 degreeC is preferable, 140 to 220 degreeC is more preferable, 150 to 200 degreeC is especially preferable. The heating time is preferably 30 seconds to 1 hour, more preferably 1 minute to 30 minutes, and particularly preferably 5 minutes to 20 minutes. Moreover, you may irradiate an active energy ray before a heating. As the light source of the active energy ray, a known light source, for example, one that effectively emits ultraviolet light, visible light, etc., such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, and a xenon lamp is used.

  Then, according to the present invention, the resist pattern comprises an aqueous solution of 0.1-10 wt% sodium carbonate, an aqueous solution of 0.1-10 wt% potassium carbonate, an aqueous solution of 0.1-10 wt% sodium hydroxide, 0 It is removed by an alkaline aqueous solution which may contain an organic amine or an organic solvent, such as a 1 to 10% by weight aqueous potassium hydroxide solution. Examples of the removal method include an immersion method and a spray method.

Hereinafter, the present invention will be described with reference to examples.
(Example 1)
4 g (24 mmol) of furfuryl methacrylate and 4.3 g (12 mmol) of 4,4-diphenylmethane bismaleimide on 10 g of a 40% toluene solution of methacrylic acid / methyl methacrylate / styrene = 25/50/25 wt% copolymer, 2 0.5 g of benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by Ciba Specialty) was added to prepare a photosensitive resin solution. The film was applied on a PET film using an applicator and dried at 80 ° C. for 30 minutes to obtain a film having a thickness of 30 μm. This film was laminated on a copper substrate under the conditions of 110 ° C., 0.4 MP, and 1.5 m / min. It was irradiated with 300 mJ / cm ^{2 of} mercury lamp 365 nm light source through a photomask, and then developed with 1 wt% sodium carbonate, 30 ° C., 30 s. The pattern remained only in the light irradiated part. Thereafter, the film was heated at 150 ° C. for 30 minutes, peeled at 3% by weight caustic soda and 50 ° C., and the pattern was peeled off in 20 s.

(Comparative Example 1)
10 g of 40% toluene solution of methacrylic acid / methyl methacrylate / styrene = 25/50/25 wt% copolymer, 4 g of bisphenol A dimethacrylate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1 (manufactured by Ciba Specialty) was added to prepare a photosensitive resin solution. The film was applied on a PET film using an applicator and dried at 80 ° C. for 30 minutes to obtain a film having a thickness of 30 μm. This film was laminated on a copper substrate under the conditions of 110 ° C., 0.4 MP, and 1.5 m / min. It was irradiated with 300 mJ / cm ^{2 of} mercury lamp 365 nm light source through a photomask, and then developed with 1 wt% sodium carbonate, 30 ° C., 30 s. The pattern remained only in the light irradiated part. Thereafter, heating at 150 ° C. for 30 minutes and peeling at 3 ° C. caustic soda and 50 ° C. took 180 s for the pattern to peel off.

  According to the present invention, a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, a method for producing a printed wiring board, and removal of a photocured product capable of sufficiently improving removability while maintaining excellent resolution. It has been found that a method can be provided.

Claims (8)

  (A) a photosensitive resin composition containing a compound having a conjugated diene moiety and a compound having a diene moiety, and (B) a photopolymerization initiator that initiates a photopolymerization reaction of a photoradically polymerizable compound, A) In a compound having a conjugated diene site and a compound having a diene site, one or both of them has a compound having an ethylenically unsaturated bond capable of photoradical polymerization, or a ring is wound by Diels-Alder reaction. A photosensitive resin composition, which is a compound having a conventional structure. (A) A compound having a conjugated diene moiety and a compound having a diene moiety are represented by the following general formula (1), the following general formula (2), and the following general formula (3). The photosensitive resin composition of Claim 1 which is any 1 or more types of the compound to be made.

[In Formulas (1) to (3), _one or both of R ₁ and R ₂ contain an ethylenically unsaturated bond]   The photosensitive element using the photosensitive resin composition layer formed by coating the photosensitive resin composition of Claim 1 or 2 on a support film, heating at 60 to 120 degreeC.   A photosensitive resin composition layer comprising the photosensitive resin composition according to claim 1 or 2 is laminated on a circuit forming substrate, heated at 60 ° C to 120 ° C, and then a predetermined portion of the photosensitive resin composition layer. A method for forming a resist pattern, comprising: irradiating actinic rays to photo-curing an exposed portion, and then removing portions other than the exposed portion.   The photosensitive resin composition layer in the photosensitive element according to claim 3 is laminated on a circuit forming substrate, and a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays to photocure the exposed portion. Then, a method for forming a resist pattern, wherein a portion other than the exposed portion is removed.   A circuit forming step of etching or plating a circuit forming substrate on which a resist pattern has been formed by the resist pattern forming method according to claim 4 or 5, and while heating the resist pattern at a temperature of 130 to 250 ° C. Or a removing step of removing the substrate from the circuit forming substrate after heating.   A photocured product obtained by laminating a photosensitive resin composition layer comprising the photosensitive resin composition according to claim 1 or 2 on a support substrate, and irradiating actinic rays to photocure the photosensitive resin composition layer. The method for removing a photocured product, comprising removing from the support substrate while heating at 130 to 250 ° C. or after heating.   A photocured product obtained by laminating the photosensitive resin composition layer in the photosensitive element according to claim 3 on a support substrate and irradiating actinic rays to photocur the photosensitive resin composition layer, 130 to 250. A method for removing a photocured product, comprising: removing from the support substrate while heating under a temperature condition of ° C. or after heating.