JP2006039193A - Photosensitive resin composition, photosensitive element using the same, resist pattern producing method and method for manufacturing printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having good sensitivity, resolution, adhesion and tent reliability, and excellent in scum dispersibility and suppression of occurrence of sludge in a developer, and also to provide a photosensitive element using the same, a resist pattern forming method, and a method for manufacturing a printed wiring board. <P>SOLUTION: The photosensitive resin composition contains: (A) a binder polymer in which 10-40 wt.% of a copolymerized component is butyl acrylate or butyl methacrylate; (B) a photopolymerizable compound including a compound having at least one polymerizable ethylenically unsaturated group and a propylene glycol chain per molecule; and (C) a photopolymerization initiator. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  Conventionally, as a resist material used for etching, plating, etc. in the field of manufacturing printed wiring boards, a photosensitive resin composition layer is coated and dried on a support, and the photosensitive resin composition on the side opposite to the support is used. Photosensitive elements obtained by laminating a protective film so as to be in contact with these layers are widely used. The printed wiring board is formed by laminating a photosensitive element on a copper substrate, exposing the pattern, removing the unexposed portion with a developer, performing etching or plating, and forming a pattern. It is manufactured by a method of peeling off from above.

  With recent increases in the density of printed wiring boards, photosensitive resin compositions and photosensitive elements are required to have excellent resolution and adhesion. In the tenting method, tent reliability is also required with respect to irregular formation of through holes, narrowing of through hole lands, and the like.

  In recent years, resolution and adhesion have been improved by incorporating hexaarylbiimidazoles and derivatives thereof and N, N′-tetraalkyl-4,4′-diaminobenzophenone into the photopolymerization initiator. In addition, tent reliability has been improved by using propylene oxide-modified monomers. However, when hexaarylbiimidazole and its derivatives and a propylene oxide-modified monomer are used in combination, there is a problem that scum (oil) is easily generated in the developer, and sludge (precipitate) accumulates at the bottom of the developing machine. It was.

  Patent Document 1 discloses a photosensitive resin composition containing a hexaarylbiimidazole compound having at least one hydrophilic group as an attempt to solve the sludge problem. However, this photosensitive resin composition does not always have satisfactory characteristics with respect to scum dispersibility in a developer.

Japanese Patent No. 3479510

  An object of the present invention is a photosensitive resin composition having good sensitivity, resolution, adhesion, and tent reliability, and excellent in scum dispersibility and sludge removal in a developer, a photosensitive element using the same, and a resist pattern It is to provide a manufacturing method and a manufacturing method of a printed wiring board.

  In order to solve the above-mentioned problems, the present invention provides (A) a binder polymer in which 10 to 40% by weight of the copolymerization component is butyl acrylate or butyl methacrylate, and (B) at least one polymerizable in the molecule. The present invention relates to a photopolymerizable compound containing a compound having an ethylenically unsaturated group and a propylene glycol chain, and (C) a photosensitive resin composition containing a photopolymerization initiator.

  Moreover, the compounding quantity of (A) component, (B) component, and (C) component is 40-80 weight part of (A) component with respect to 100 weight part of total amounts of (A) component and (B) component, (B) It is preferable that a component is 20-60 weight part and (C) component is 0.001-10 weight part.

  Moreover, this invention relates to the photosensitive element formed by apply | coating and drying the layer of the said photosensitive resin composition on a support body.

  In addition, the present invention provides a photosensitive film obtained by coating and drying a photosensitive resin composition layer on a support and drying a protective film so as to be in contact with the photosensitive resin composition layer on the opposite side of the support. Related to sex elements.

  The present invention also provides a method of laminating the photosensitive element on a circuit forming substrate so that the layer of the photosensitive resin composition is in close contact with the circuit forming substrate while peeling off a protective film present in some cases. Further, the present invention relates to a method for producing a resist pattern, characterized by irradiating actinic rays in an image, photocuring an exposed portion, and removing an unexposed portion by development.

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

  The photosensitive resin composition of the present invention, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board have improved sensitivity, resolution, adhesion and tent reliability, and scum dispersion in a developer. The effect which improves the property and sludge removal property is produced.

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

  The photosensitive resin composition of the present invention comprises (A) a binder polymer in which 10 to 40% by weight of the copolymer component is butyl acrylate or butyl methacrylate, and (B) at least one polymerizable ethylene in the molecule. A photopolymerizable compound containing a compound having a polymerizable unsaturated group and a propylene glycol chain, and (C) a photopolymerization initiator.

  The binder polymer as the component (A) in the present invention can be produced, for example, by radical polymerization of a polymerizable monomer. The polymerizable monomer contains butyl acrylate ester or butyl methacrylate ester.

  Examples of the polymerizable monomer other than the polymerizable monomer include styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, p-ethyl styrene, p-methoxy styrene, p-ethoxy styrene, p- Polymerizable styrene derivatives such as chlorostyrene and p-bromostyrene, esters of vinyl alcohol such as acrylamide, acrylonitrile and vinyl-n-butyl ether, alkyl (meth) acrylates other than (meth) acrylic acid butyl 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 -(Meth) acrylic acid esters such as 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, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and other polymerizable monomers having a carboxyl group And maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate.

  Examples of (meth) acrylic acid alkyl esters other than the above (meth) acrylic acid butyl ester include, for example, compounds represented by the following general formula (I), alkyl groups of these compounds, hydroxyl groups, epoxy groups, halogen groups and the like. Examples include substituted compounds.

（一般式（Ｉ）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は炭素数１〜３又は５〜１２のアルキル基を示す）

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 3 or 5 to 12 carbon atoms)

Examples of the alkyl group having 1 to 3 or 5 to 12 carbon atoms represented by R ² in the general formula (I) include a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof. Examples of the monomer represented by the general formula (I) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl 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, Examples include (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, and the like. These are used alone or in combination of two or more.

  The binder polymer preferably contains a carboxyl group from the viewpoint of alkali developability. For example, the binder polymer is produced by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer. be able to. As the polymerizable monomer having a carboxyl group, methacrylic acid is preferable.

  The binder polymer preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of adhesion and developer resistance.

  The polymerizable monomer having a carboxyl group is preferably included as a copolymerization component in an amount of 15 to 35% by weight, and more preferably 20 to 30% by weight from the viewpoint of developability and flexibility. When the content is less than 15% by weight, the developability tends to be inferior, and when it exceeds 35% by weight, the flexibility tends to decrease.

  Further, from the viewpoint of scum dispersibility in the developer, it is necessary to contain 10 to 40% by weight, preferably 10 to 30% by weight, of the butyl acrylate or butyl methacrylate as a copolymerization component. More preferably, it contains 20 to 25% by weight. When the content is less than 10% by weight, the scum dispersibility in the developer is lowered, and when it exceeds 40% by weight, the foamability in the developer is increased.

  Furthermore, from the viewpoint of adhesion and developer resistance, the styrene or styrene derivative is preferably contained as a copolymerization component in an amount of 2 to 30% by weight, more preferably 2 to 28% by weight, and more preferably 2 to 27% by weight. It is particularly preferable to include it. When the content is less than 2% by weight, the adhesion tends to be inferior, and when it exceeds 30% by weight, the peel piece tends to be large and the peel time tends to be long.

  These binder polymers are used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion are used. A binder polymer etc. are mentioned. A polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.

  The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, and more preferably 40,000 to 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. However, the weight average molecular weight in the present invention is a value measured by gel permeation chromatography and converted to standard polystyrene.

  The acid value of the binder polymer is preferably 100 to 500 mgKOH / g, and more preferably 100 to 300 mgKOH / g. When the acid value is less than 100 mgKOH / g, the development time tends to be long, and when it exceeds 500 mgKOH / g, the developer resistance of the photocured resist tends to be lowered.

  The photopolymerizable compound as the component (B) in the present invention contains a compound having at least one polymerizable ethylenically unsaturated group and a propylene glycol chain in the molecule from the viewpoint of tent reliability.

  Examples of the compound having at least one polymerizable ethylenically unsaturated group and propylene glycol chain in the molecule include compounds represented by the following general formula (II) or the following general formula (III). It is done.

（一般式（II）中、ＰＯはプロピレンオキシドを示し、ＥＯはエチレンオキシドを示し、Ｒ^３は水素原子又はメチル基を示し、ｍ^１は２〜３０の整数であり、ｎ^１は０〜１０の整数である。）

(In General Formula (II), PO represents propylene oxide, EO represents ethylene oxide, R ³ represents a hydrogen atom or a methyl group, m ¹ is an integer of 2 to 30, and n ¹ is 0 to 10 (It is an integer.)

（一般式（III）中、ｍ^２は２〜３０の整数であり、ｎ^２は１〜１０の整数である。）

(In the general formula (III), ^{m 2} is an integer from 2 to 30, ^{n 2} is an integer of from 1 to 10.)

Examples of the compound represented by the general formula (II) or the general formula (III) include heptapropylene glycol-modified di (meth) acrylate, octapropylene glycol-modified di (meth) acrylate, and nonapropylene glycol-modified di Polypropylene glycol-modified di (meth) acrylates such as (meth) acrylate, decapropylene glycol-modified di (meth) acrylate, hendecapropylene glycol-modified di (meth) acrylate, dodecapropylene glycol-modified di (meth) acrylate, and ethylene oxide / propylene Examples thereof include oxide-modified urethane dimethacrylate. Examples of the ethylene oxide / propylene oxide modified urethane dimethacrylate include UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) in which m ² = 9 and n ² = 1 in the general formula (III). It is done. These may be used alone or in combination of two or more.

  Examples of the photopolymerizable compound other than the compound having at least one polymerizable ethylenically unsaturated group and propylene glycol chain in the molecule can be obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol. 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis Bisphenol A-based (meth) acrylate compounds such as (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, glycidyl A compound obtained by reacting a group-containing compound with an α, β-unsaturated carboxylic acid, having a urethane bond in the molecule (meta Urethane monomers such as acrylate compounds, nonylphenoxypolyethyleneoxyacrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloyloxyalkyl Phthalic acid compounds such as -o-phthalate, (meth) acrylic acid alkyl esters other than (meth) acrylic acid butyl ester, and the like, but bisphenol A (meth) acrylate compounds or having urethane bonds in the molecule ( It is preferable to contain a (meth) acrylate compound. These may be used alone or in combination of two or more.

  The compounding amount of the compound having at least one polymerizable ethylenically unsaturated group and propylene glycol chain in the molecule is preferably 20% by weight or more in the component (B), and 30% by weight or more. More preferably, it is particularly preferably 40% by weight or more. If the blending amount is less than 20% by weight, the tent reliability tends to deteriorate.

  Examples of the photopolymerization initiator as the component (C) in the present invention include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4 ′. -Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl Aromatic ketones such as 2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2- Phenylanthraquinone, 2,3-diphenylanthra Non-quinones such as 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether, Benzoin ether compounds such as benzoin ethyl ether and benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-dipheny 2,4,5-triarylimidazole dimer such as imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9 , 9'-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, coumarin compounds and the like. Further, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may give the same and symmetric compounds, or differently give asymmetric compounds. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. Further, 2,4,5-triarylimidazole dimer is preferable from the viewpoint of adhesion and sensitivity. These are used alone or in combination of two or more.

  The blending amount of the component (A) is preferably 40 to 80 parts by weight and more preferably 45 to 70 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). . If this blending amount is less than 40 parts by weight, the photocured product tends to be brittle, and when used as a photosensitive element, the coating property tends to be inferior, and if it exceeds 80 parts by weight, the photosensitivity tends to be insufficient. is there.

  The blending amount of the component (B) is preferably 20 to 60 parts by weight and more preferably 30 to 55 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). . If this amount is less than 20 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 60 parts by weight, the photocured product tends to be brittle. Further, from the viewpoint of tent reliability, 1 to 60 parts by weight of a photopolymerizable compound containing a compound having at least one polymerizable ethylenically unsaturated group and a propylene glycol chain in the molecule as component (B). It is preferable to include.

  The blending amount of the component (C) is preferably 0.01 to 5 parts by weight, and 0.1 to 3 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). It is more preferable. If this amount is less than 0.01 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 5 parts by weight, absorption on the surface of the layer of the photosensitive resin composition increases during exposure, and the internal There is a tendency for photocuring to be insufficient.

  In addition, the photosensitive resin composition of the present invention may contain a photopolymerization compound having a cyclic ether group capable of at least 12 cationic polymerization in the molecule, a cationic polymerization initiator, a dye such as malachite green, Photochromic agents such as bromomethylphenylsulfone and leucocrystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling Agent, exfoliation accelerator, antioxidant, perfume, imaging agent, thermal crosslinking agent, etc., each containing about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of component (A) and component (B). Can do. These are used alone or in combination of two or more.

  The photosensitive resin composition of the present invention is, for example, a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or the like as necessary. It can melt | dissolve in a mixed solvent and can apply | coat as a solution of about 30-60 weight% of solid content.

  The photosensitive resin composition of the present invention is preferably applied as a liquid resist on a metal surface and dried, and then coated with a protective film as necessary, or used in the form of a photosensitive element. Examples of the metal include copper, copper-based alloys, iron-based alloys such as nickel, chromium, iron, and stainless steel, but copper, copper-based alloys, or iron from the standpoints of adhesion to a resist and electron conductivity. It is preferable that it is a system alloy.

  Moreover, although the thickness of the layer of the photosensitive resin composition 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 adhesive force and resolution tend to decrease.

  When used as the photosensitive element, the support preferably has a thickness of 5 to 25 μm, more preferably 8 to 20 μm, and particularly preferably 10 to 16 μm. If the thickness is less than 5 μm, the layer of the photosensitive resin composition tends to be broken when the support is peeled off before development, and if it exceeds 25 μm, the resolution tends to be lowered.

  Examples of the support include polymer films having heat resistance and solution resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester.

  When used as the photosensitive element, the protective film preferably has a thickness of 5 to 30 μm, more preferably 10 to 28 μm, and particularly preferably 15 to 25 μm. If this thickness is less than 5 μm, the protective film tends to be broken during lamination, and if it exceeds 30 μm, the cost tends to be inferior.

  Examples of the protective film include polymer films such as polyethylene and polypropylene.

  In addition, since these support and protective film must be removable from the layer of the photosensitive resin composition later, they must be subjected to a surface treatment that makes removal impossible. You may perform the process which can be removed as needed. Furthermore, these supports and protective films may be subjected to antistatic treatment as necessary.

  Moreover, the said photosensitive element may have intermediate | middle layers, such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer, and a protective layer other than the photosensitive resin composition, a support body, and a protective film.

  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 winding core. In addition, it is preferable to wind up in this case so that a support body may become the outermost side. 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 more preferably a moisture-proof end face separator is installed from the viewpoint of edge fusion resistance.

  Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

As a method for producing a resist pattern using a photosensitive element in the previous period, for example, when the protective film is present, after the protective film is removed, the layer of the photosensitive resin composition is overheated for circuit formation. Examples of the method include laminating by pressure bonding to a substrate, and the laminating is preferably performed under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually a metal surface, but is not particularly limited. The heating temperature of the photosensitive resin composition layer is preferably 70 to 130 ° C., and the pressure bonding pressure is preferably about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ). There is no particular restriction. In addition, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to preheat the circuit forming substrate in advance, but in order to further improve the laminating property, Substrate heat treatment can also be performed.

  The photosensitive resin composition layer thus laminated is irradiated with actinic rays on the screen through a negative or positive mask pattern called artwork. Under the present circumstances, when the support body which exists on the layer of the photosensitive resin composition is transparent, you may irradiate actinic light as it is, and when opaque, it is preferable to remove. Examples of the active light source include known light sources that effectively emit ultraviolet rays, such as carbon arc lamps, mercury vapor arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, and xenon lamps. In addition, those that effectively emit visible light, such as a photographic flood bulb and a solar lamp, can be used.

  Next, after the exposure, when a support is present on the layer of the photosensitive resin composition, after removing the support, the unexposed portion is removed and developed by wet development, dry development, etc. Manufacture a pattern. In the case of wet development, development is performed by a known method such as spraying, rocking immersion, brushing, scraping, or the like, using a developer corresponding to the photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. To do. The developer is preferably a safe and stable solution having good operability, such as an alkaline aqueous solution. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium, or 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. Examples of the alkaline aqueous solution used for development 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, A dilute solution of 0.1 to 5% by weight 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 layer of the photosensitive resin composition. 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.

  The aqueous developer comprises water or an alkaline aqueous solution and one or more organic solvents. Examples of the alkaline substance include borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1 , 3-diaminopropanol-2, morpholine and the like. The pH of the developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, more preferably pH 9-10. Examples of the organic solvent include 3 acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono And butyl ether. These are used alone or in combination of two or more. The concentration of the organic solvent is usually preferably 2 to 90% by weight, 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 developer 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 weight in order to prevent ignition. Moreover, you may use together 2 or more types of image development methods as needed. Examples of the development method 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 the treatment 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 alkali etching solution, a hydrogen peroxide-based etching solution, etc. can be used. It is preferable to use a ferric chloride solution.

  When a printed wiring board is produced using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask. Examples of the plating method include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate plating, and hard Examples thereof include gold plating such as gold plating and soft gold plating. Next, the resist pattern can be peeled with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As this strongly alkaline aqueous solution, for example, a 1 to 10% by weight sodium hydroxide aqueous solution, a 1 to 10% by weight 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. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board.

Hereinafter, the present invention will be described with reference to examples.
(Examples 1-3 and Comparative Examples 1-2)
The materials shown in Table 1 and Table 2 were blended to obtain a photosensitive resin composition solution.

In addition, the material used in Table 1 and Table 2 is shown below.
UA-13: Ethylene oxide / propylene oxide modified urethane dimethacrylate (product name) manufactured by Shin-Nakamura Chemical Co., wherein m ² = 9 and n ² = 1 in the general formula (III)
BPE-500: In the following general formula (IV), m ³ and n ³ are each independently a positive integer, and m ³ + n ³ = 10 (average value) (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)

Moreover, the weight average molecular weight of the copolymer in Table 2 is measured by gel permeation chromatography, and a value converted to standard polystyrene is used. The conditions for gel permeation chromatography are shown below.
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name)
Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (3 in total) (manufactured by Hitachi Chemical Co., Ltd., product name)
Eluent: Tetrahydrofuran Measurement temperature: Room temperature Flow rate: 2.05 ml / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

  Subsequently, the obtained photosensitive resin composition solution was uniformly applied onto a 16 μm-thick polyethylene terephthalate film (product name: G2-16, manufactured by Teijin Ltd.), and the solution was 10 in a 100 ° C. hot air convection dryer. After drying for a minute, it was protected with a polyethylene protective film (product name: NF-13, manufactured by Tamapoly Co., Ltd.) to obtain a photosensitive element. The film thickness after drying of the photosensitive resin composition layer was 40 μm.

  Next, the copper surface of a copper clad laminate (product name: MCL-E-61, manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness 35 μm) is laminated on both sides, has a brush equivalent to # 600. Polishing using a polishing machine (manufactured by Sankei Co., Ltd.), washing with water, and drying with an air stream, the obtained copper-clad laminate is heated to 80 ° C., and the photosensitive resin composition is formed on the copper surface. The product layer was laminated at a speed of 1.5 m / min using a 120 ° C. heat roll while peeling off the protective film.

Next, using an exposure machine (product name: HMW-201B, manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp lamp, a 21-step stove tablet as a negative is placed on the test piece and exposed at 60 mJ / cm ² . did.

  Next, the polyethylene terephthalate film is peeled off, sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. for 60 seconds to remove unexposed portions, and then the number of steps of the step tablet of the photocured film formed on the copper clad laminate Was measured to evaluate the photosensitivity of the photosensitive resin composition. 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.

  Further, the time taken for the unexposed portion of the resist to be completely removed by the development process was measured, and this was defined as the minimum development time.

  As for resolution, a photo tool having a stove 21-step tablet and a photo tool having a wiring pattern with a space width / line width of 30/400 to 200/400 (unit: μm) are closely attached as a negative for resolution evaluation. In a fur 21-step tablet, exposure was carried out with an energy amount such that the number of remaining step steps after developing in twice the minimum development time was 8.0. Here, the resolution was evaluated based on the smallest value of the line width that did not peel off by the development process and had no resist residue between the resist patterns. The smaller the numerical value, the better the resolution evaluation.

  Adhesion is achieved by adhering a photo tool having a 21-step tablet of Stoffer and a photo tool having a wiring pattern with a line width / space width of 8/400 to 47/400 (unit: μm) as a negative for adhesion evaluation. Then, the exposure was carried out with an energy amount such that the number of remaining step steps after developing in a stove 21-step step tablet in a time twice as long as the minimum development time was 8.0. Here, the adhesion was evaluated based on the smallest value of the line width that did not cause chipping, peeling, or twisting of the line by development processing. The smaller the numerical value, the better the evaluation of adhesion.

Scum dispersibility, photosensitive film dissolution amount, the developing solution (1 weight photosensitive film 0.6mil · ^{m 2} / l, which corresponds to 1.5 times the 0.4mil · ^{m 2} / l in a developer % Na ₂ CO ₃ aqueous solution), this solution was circulated and stirred for 90 minutes with a small developer machine, the bubble height of the solution was measured, and the amount of scum (oil) generated on the surface was determined based on the criteria in Table 3. evaluated.

  The sludge removability is determined by transferring the liquid after stirring to a plastic bottle and leaving it for 7 days, then shaking the plastic bottle 10 times to dissolve and disperse the sludge (precipitate) in the developer, and then remain at the bottom. The amount of attached sludge was observed. Sludge removability was evaluated according to the criteria shown in Table 4.

The tent reliability is obtained by laminating a photosensitive resin composition with a film thickness after drying of 40 μm on a tent substrate having the following three irregularly shaped holes, and the number of remaining step stages after development in a stove 21-step tablet is 8.0. After the exposure with the amount of energy to become, it was evaluated from the tearing rate of the layer of the photosensitive resin composition when developed in 4 times the minimum development time.
Triple irregular holes: 6 irregular holes with 6mmφ holes,
Deformed hole with three 3mmφ holes (12)
The tent reliability was calculated from the following formula. The evaluation of the tent reliability is better as the numerical value is smaller.

The results are summarized in Table 5.

As is apparent from Table 5, Examples 1, 2, and 3 have good sensitivity, resolution, adhesion, and tent reliability, and are excellent in scum dispersibility and sludge removability in the developer.

Claims (6)

  (A) A binder polymer in which 10 to 40% by weight of the copolymer component is butyl acrylate or butyl methacrylate, (B) at least one polymerizable ethylenically unsaturated group and a propylene glycol chain in the molecule. The photosensitive resin composition containing the photopolymerizable compound containing the compound which has, and (C) photoinitiator.   Component (A), Component (B), and Component (C) are blended in an amount of 40 to 80 parts by weight of component (A) with respect to 100 parts by weight of the total amount of component (A) and component (B). The photosensitive resin composition according to claim 1, wherein the component is 20-60 parts by weight and the component (C) is 0.001-10 parts by weight.   A photosensitive element formed by applying and drying a layer of the photosensitive resin composition according to claim 1 or 2 on a support.   A photosensitive resin composition obtained by applying and drying a layer of the photosensitive resin composition according to claim 1 or 2 on a support, and further laminating a protective film so as to be in contact with the layer of the photosensitive resin composition opposite to the support. Sex element.   The photosensitive element according to claim 3 or 4 is laminated on the circuit forming substrate so that the layer of the photosensitive resin composition is in close contact with the circuit forming substrate while peeling off the protective film present in some cases. A method for producing a resist pattern, which comprises irradiating an actinic ray in an image, photocuring an exposed portion, and removing an unexposed portion by development. A method for producing a printed wiring board, comprising etching or plating a circuit forming substrate on which a resist pattern is produced by the method for producing a resist pattern according to claim 5.