KR20070086618A - Photosensitive composition and process for production of printed wiring boards with the same - Google Patents

Abstract

A photosensitive resin composition characterized by containing at least one resin which has photopolymerizable ethylenically unsaturated groups on the side chains and a photosensitive compound which has three or more ethylenically unsaturated groups and exhibits a viscosity of 2000mPa s or above at 25°C under one atm; and a process for the production of wiring boards with the same.

Description

The photosensitive composition and the manufacturing method of the printed wiring board using the same {PHOTOSENSITIVE COMPOSITION AND PROCESS FOR PRODUCTION OF PRINTED WIRING BOARDS WITH THE SAME}

This invention relates to the photosensitive resin composition and the manufacturing method of the printed wiring board using the same.

In order to manufacture a printed wiring board having a fine and dense conductor pattern simply and reliably, a photosensitive resist liquid which is essentially excellent in performance such as resolution is applied directly to the metal conductor layer on the surface of the insulating substrate to form an etching resist layer. The dipping method for forming this etching resist layer into a predetermined resist pattern is widely known. This method is simple and is effective when a relatively thin film thickness of several micrometers to 20 micrometers is required because pinholes do not occur in the etching resist layer formed.

However, the etching resist layer formed by the photosensitive resist liquid used so far, especially when 3 or more ethylenically unsaturated groups are used and the photosensitive compound whose viscosity is 2000 mPa * s or more under 25 degreeC and 1 atmosphere is used, The adhesion disappeared, but the exposure sensitivity was low, and a large amount of light was required. If a large amount of light is required, the exposure time is long, productivity is poor, and there is a problem that it is difficult to be practically used.

Disclosure of the Invention

In view of the above problems, an object of the present invention is to provide a material for forming an etching resist layer having excellent exposure sensitivity without sticking of etching resist layers.

MEANS TO SOLVE THE PROBLEM The present inventors came to this invention as a result of earnestly examining.

In other words,

The first invention has a resin having at least one kind and three or more ethylenically unsaturated groups having a resin having a photopolymerizable ethylenically unsaturated group in a side chain thereof, and containing a photosensitive compound having a viscosity of at least 2000 mPa · s at 25 ° C. and 1 atmosphere. It is a photosensitive resin composition characterized by the above-mentioned.

It is preferable that the ethylenically unsaturated group equivalent of resin which has a photopolymerizable ethylenically unsaturated group in a side chain in the molecule | numerator contained in the said photosensitive resin composition is 100-1000 g / eq.

Moreover, the resin composition of this invention is a resin which is soluble in aqueous alkali solution, Comprising: It is a preferable aspect from alkali developability viewpoint to further contain resin whose weight average molecular weight is 5000-200,000, and acid value is 20 mgKOH / g-300 mgKOH / g. .

Moreover, it is a preferable aspect that the solvent contained in the said photosensitive resin composition is 30 to 95 weight%.

According to a second aspect of the present invention, after the substrate having a metal conductor layer formed on the surface of the insulating substrate is immersed in the photosensitive resin composition, the photosensitive composition is applied to the surface of the substrate by pulling it up, and then exposed and developed through a photomask. After forming the etching resist layer of a resist pattern, a metal conductor layer is formed in a predetermined conductor pattern by performing an etching process to a board | substrate, The manufacturing method of the printed wiring board characterized by the above-mentioned.

The present invention is characterized by containing at least one type of photosensitive compound molecule having a viscosity of 2000 mPa · s or more and a resin having an ethylenically unsaturated group capable of photopolymerization at a side chain at 25 ° C. and 1 atm, and having no tack. An etching resist layer can be formed.

Best Mode for Carrying Out the Invention

 EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The photosensitive resin composition of this invention has resin which has a photopolymerizable ethylenically unsaturated group in a side chain, and 3 or more ethylenically unsaturated groups in a molecule | numerator, and contains the photosensitive compound whose viscosity is 2000 mPa * s or more at 25 degreeC and 1 atmosphere. to be. Preferably, it is the photosensitive resin composition which further contains resin which can melt | dissolve in aqueous alkali solution, a photoinitiator, and a solvent.

As a resin soluble in aqueous alkali solution, maleic anhydride copolymers, such as styrene maleic anhydride resin, or ester compounds which have ethylenically unsaturated groups, such as methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylic acid; Copolymers with ethylenically unsaturated monomers having carboxyl groups such as (meth) acrylic acid, ethylenically unsaturated monomers without carboxyl groups such as styrene, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylate And a copolymer of an ester compound having an ethylenically unsaturated group with an ethylenically unsaturated monomer having a carboxyl group such as (meth) acrylic acid. These copolymer resins can be used individually or in mixture.

The weight average molecular weight of the resin which is soluble in the aqueous alkali solution is usually 5000 to 200,000, preferably 10,000 to 100,000. When the weight average molecular weight is less than 5000, the developing solution resistance of the weak alkaline aqueous solution such as the aqueous sodium carbonate solution or the aqueous sodium metasilicate solution, such as the developing solution is poor, and the solubility of the exposed portion by the developing solution is also advanced. In some cases, dissolution and peeling are performed by a developing solution without distinction between the exposed portion and the unexposed portion, and drawing of the resist pattern may be difficult. On the other hand, when the weight average molecular weight exceeds 200,000, in the weak alkaline aqueous solution which becomes a developing solution, dissolution of an unexposed part may become difficult and image development may not be possible. When the weight average molecular weight is more than 200,000, the resist film is extremely slow in the step of peeling the resist from the exposed portion with a strong alkaline aqueous solution such as an aqueous sodium hydroxide solution after etching, and thus a conventionally used peeling line cannot be used. have.

In addition, the acid value of the resin soluble in these aqueous alkali solutions is usually suitably 20 to 300 mgKOH / g, and preferably 50 to 200 mgKOH / g. When the acid value is less than 20 mgKOH / g, dissolution of the unexposed portion may be difficult in developing a weak alkaline aqueous solution such as an aqueous sodium carbonate solution or an aqueous sodium metasilicate solution. In addition, in the peeling step, peeling of the resist film may be extremely late. On the other hand, when the acid value is more than 300 mgKOH / g, as in the case where the weight average molecular weight is low, the developing solution resistance of the weak alkaline aqueous solution is inferior, and the solubility of the exposed portion by the developing solution is also advanced. In some cases, dissolution and peeling are performed by a developing solution without distinction between the exposed portion and the unexposed portion, and drawing of the resist pattern may be difficult. The acid value can be measured by titrating a sample having a unit weight with 0.1 N KOH anhydrous methanol, for example, using an indicator such as phenolphthalein.

It is preferable to contain 10-80 weight% of resin soluble in the aqueous alkali solution which does not have a photopolymerizable ethylenically unsaturated group in a molecule, More preferably, it is 20-60 weight%.

As resin which has an ethylenically unsaturated group in a side chain, ethylenically unsaturated monocarbons, such as (meth) acrylic acid, in epoxy resins, such as a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, or a cresol novolak-type epoxy resin The resin which added acid and unsaturated polybasic anhydride, resin which added hydroxyethyl (meth) acrylate or glycidyl (meth) acrylate to maleic anhydride copolymer, such as styrene maleic anhydride resin, etc. are mentioned. . Alternatively, a hydroxyl group may be used in a copolymer of an ester compound having an ethylenically unsaturated group such as methyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth) acrylate and an ethylenically unsaturated monomer having a carboxyl group such as (meth) acrylic acid. Copolymer which added the compound which has ethylenically unsaturated group which has hydroxyl groups, such as hydroxyethyl (meth) acrylate which has, ethylenic unsaturation, such as methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate Ethylene unsaturated group which added hydroxyethyl (meth) acrylate or the compound which has carboxyl group to the copolymer resin of ester compound which has group, and glycidyl acrylate, or ethylene which has carboxyl groups, such as (meth) acrylic acid A unsaturated unsaturated monomer, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, etc. The copolymer etc. which have the ethylenically unsaturated group which added hydroxyethyl (meth) acrylate or the compound which has a carboxyl group to the copolymerization resin of the ester compound which has an ethylenically unsaturated group and glycidyl acrylate are mentioned.

Or the resin etc. which add the ethylenically unsaturated monomer containing glycidyl groups, such as glycidyl (meth) acrylate, with respect to the copolymer which has a carboxyl group are mentioned. These resins and copolymers can be used individually or in mixture.

As for the ethylenically unsaturated group equivalent of resin which has an ethylenically unsaturated group in a side chain, 100-1000 g / eq is suitable. When an ethylenically unsaturated group equivalent is larger than 1000 g / eq, exposure sensitivity may not improve. More preferably, it is 200-700 g / eq.

The amount of the resin having an ethylenically unsaturated group equivalent of 100 to 1000 g / eq is preferably 5 to 60% by weight in the solid component of the composition, more preferably 10 to 50% by weight.

Moreover, the photosensitive compound used for the photosensitive resin composition of this invention causes reaction, such as bridge | crosslinking, superposition | polymerization, or dimerization by exposure, and is insoluble with respect to a developing solution by exposing the dry film of the photosensitive resin composition formed from the photosensitive resin composition. It has a property of forming an etching resist layer as being. When the viscosity of the main component of the photosensitive compound is less than 2000 mPa · s at 1 atm and 25 ° C., when the produced etching resist layers are subjected to overlapping loads, the photosensitive compound migrates to the surface of the coating film and generates adhesion between the etching resist layers. There is. Preferably, it is 2000 mPa * s or more, More preferably, it is 4000 mPa * s or more, and solid may be sufficient.

Preferred photosensitive compounds having three or more ethylenically unsaturated groups include triallyl isocyanurate, isocyanuric acid EO-modified triacrylate, polyfunctional urethane adducts, polyfunctional polyester acrylates, pentaerythritol tetra (meth ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

The photosensitive compound which has two or less ethylenically unsaturated groups is unpreferable since there exists a possibility of reducing exposure sensitivity.

When using the photosensitive compound whose viscosity is less than 2000 mPa * s at 25 degreeC and 1 atmosphere, it is preferable to set it as 30 weight% or less, Preferably it is 20 weight% or less of the total amount of the photosensitive compound used. As the compound having an ethylenically unsaturated group, an unsaturated compound having one ethylenically unsaturated group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth ) Acrylate, N-vinylpyrrolidone, (meth) acryloyl morpholine, methoxy tetraethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, N, N-dimethyl (meth) acrylic Amide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acryl Elate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl acrylate, etc. are mentioned. Moreover, as an unsaturated compound which has two ethylenically unsaturated groups, it is a diethylene glycol di (meth) acrylate, a triethylene glycol di (meth) acrylate, a tripropylene glycol di (meth) acrylate, and a trimetholpropane di ( Meth) acrylate, EO addition product di (meth) acrylate of bisphenol A, etc. are mentioned. As an unsaturated compound which has three ethylenically unsaturated groups, a trimethol propane tri (meth) acrylate, a trimethol propane PO modified tri (meth) acrylate, a trimethol propane EO modified tri (meth) acrylate, penta Erythritol triacrylate, etc. are mentioned, These can have a 3 or more ethylenically unsaturated group and can be used in combination with the photosensitive compound whose viscosity is 2000 mPa * s or more at 25 degreeC and 1 atmosphere.

It is preferable that the ratio of the photosensitive compound with respect to the photosensitive resin composition of this invention shall be 5 to 60 weight% in solid content of the said composition, More preferably, it is 7 to 50 weight% solid content. If it is less than 5% by weight, curing at exposure becomes insufficient, and tends to dissolve during development. When it exceeds 60 weight%, sticking may occur when a resist film is superimposed.

As for solid content concentration of the photosensitive resin composition of this invention, less than 70 weight% is preferable. If it is 70 weight% or more, the viscosity of the photosensitive resist liquid will become high, and it may become impossible to form a uniform etching resist layer, and when it is less than 5 weight%, hardening will become inadequate by exposure and will melt | dissolve at the time of image development. There is a case. Preferably it is 7-50 weight%.

Examples of the organic solvent component used in the present invention include linear, branched, secondary or polyhydric alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, 2-butyl alcohol, hexanol, ethylene glycol, and acetone. , Ketones such as methyl ethyl ketone, cyclohexanone and isophorone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve, and carbitols such as carbitol and butyl carbitol And propylene glycol alkyl ethers such as propylene glycol methyl ether, and polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether, and ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, and butyl carbitol acetate Acetic acid esters such as propylene glycol monomethyl ether acetate, lactic acid esters such as ethyl lactate and butyl lactate Tere, pyrvinic acid esters, ethoxypropionates, dialkylglycol ethers, and the like; n-hexane, cyclohexane, tetrahydrofuran, and the like.

As a photoinitiator, any initiator can be used as long as it initiates polymerization of an unsaturated compound by irradiation of active rays such as ultraviolet rays and visible rays. For example, benzophenones such as benzophenone and Michler's ketone, benzoin alkyl ethers such as benzoin and benzoin isobutyl ether, 2,2-dimethoxy-2-phenylacetophenone and 2,2-die Acetophenones such as oxyacetophenone and 2,2-cyclo-4-phenoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone Anthraquinones such as propylphenones such as 2-ethyl anthraquinone and 2-t-butyl anthraquinone, thioxanthones such as diethyl thioxanthone, diisopropyl thiacanthone and chloro thioxanthone, and the like Other benzyl, 1-hydroxycyclohexylphenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, p-dimethylaminobenzoic acid ethyl ester, p-dimethylamino benzoic acid iso Amyl etc. are mentioned. These photoinitiators can be used individually or in mixture. As for the ratio of the photoinitiator with respect to the photosensitive resin composition of this invention, 0.2-20 weight% in solid content of the said composition is preferable, More preferably, it is 1-10 weight%.

Moreover, a leveling agent, an antifoamer, a thixotropic agent, a coloring agent, a dye, a pigment, an inorganic filler, an organic filler, etc. can be further added to the photosensitive resin composition of this invention as needed.

The etching resist layer coated with the photosensitive resist liquid of the present invention by a dipping method is used at the planar portion of the substrate in order to sufficiently maintain the strength against contact during conveyance and injection of the developer or etching solution in the developing step and the etching treatment step. It is preferable that the thickness of the resist layer of is 3 micrometers or more, and it is especially strong at 5 micrometers or more, and it becomes a resist layer excellent in the etching ability. In addition, in order to achieve particularly high resolution and etching accuracy, the thickness of the resist layer is preferably 30 µm or less, particularly preferably 20 µm or less in the planar portion of the substrate.

The photosensitive resin composition of this invention can form a uniform photosensitive resist film in a thin film by the roll method or the immersion method on the board | substrate with which the metal conductor layer was formed in the surface of a general hard (rigid) wiring board, a flexible wiring board, a metal board | substrate, etc. Can be. The resin composition of this invention is especially suitable for forming a photosensitive resist film by the immersion method. Usually, after treating the surface of the substrate conductor with an acid such as sulfuric acid or by polishing the metal surface with a brush or the like to clean the surface, the photosensitive resin composition of the present invention is applied to the conductor layer of the substrate by a roll method or an immersion method. After coating, the solvent is dried to form a uniform photosensitive resist film of a thin film having a thickness of 3 to 20 µm, preferably 8 to 15 µm, and then a predetermined circuit pattern is exposed to ultraviolet or visible light through a photomask. It exposes and hardens | cures and hardly removes an unexposed part with weak alkaline aqueous solution, such as about 0.5-3.0 weight% of sodium carbonate aqueous solution. Next, after removing the exposed conductor layer by etching, the target conductor circuit can be obtained by peeling off the cured photosensitive resist film on the surface of the remaining conductor layer with a strong alkaline aqueous solution such as about 1.0 to 5.0% by weight of sodium hydroxide solution. have.

When the photosensitive resin composition of this invention is used, the etching resist layer produced can be formed without sticking, exposure sensitivity is favorable, and the etching resist layer excellent in the developing solution resistance, etching resistance, and peelability of an exposure part can be formed.

EXAMPLE

Hereinafter, an Example demonstrates this invention. Unless stated otherwise, parts means parts by weight.

(Measurement and Evaluation Method)

Resin molecular weight: It measured by gPC and calculated | required the weight average molecular weight.

Resin acid value: 1g of samples was titrated with 0.1N of KOH anhydrous methanol, it measured using indicators, such as phenolphthalein, and it expressed by the number of milligrams of KOH.

Solvent amount: The solvent content in the photosensitive resin composition solution was displayed by weight%.

Film thickness: It measured using the eddy current type simple film thickness meter (isoscope MP30; manufactured by Fisher Instruments).

Developability: Spray development was carried out for 60 seconds at a pressure of 0.18 Pa using a 1.0% by weight aqueous solution of sodium carbonate at 30 ° C., and the following determination was performed on the unexposed part.

○ When there is no residue, if there is × residue.

Exposure sensitivity: It exposes by ultraviolet-ray of accumulated light quantity 100mJ by double-sided simultaneous exposure machine [HMW-532D] (made by Oak Seisakusho Co., Ltd.) for photoresist exposure, and sprays 2 kg of 1.0 weight% sodium carbonate aqueous solution of 30 degreeC after that spray pressure The step number of stages (the number of stoppers of the coating film of 21 steps of stages) when spraying for 60 second at / cm <^2> was confirmed.

Sensitivity 2 steps or less were made into (circle) and 3-4 steps | paragraphs (circle) and 5 or more steps | paragraphs were made into (circle).

Tackiness: Cut the coated substrate into 10cm × 10cm, overlap the coating surface, and leave it under a load of 20g / cm ² for 1 day, and there is no adhesion. I did it.

Coating property: When the board | substrate was immersed and pulled up in the photosensitive resist liquid, the thing with no deviation of the thickness of a coating film surface was made into (circle) and the thing with a deviation.

(Synthesis of Resin Solution A)

55.0 parts of methyl methacrylate, 10.0 parts of 2-hydroxyethyl acrylate, 18.1 parts of n-butyl acrylate, and 16.9 parts of methacrylic acid are dissolved in 150.0 parts of methyl ethyl ketone, stirring in a nitrogen atmosphere using a polymerization initiator, The polymerization was carried out under reflux conditions to obtain a resin solution A having a polystyrene equivalent weight average molecular weight of 28000, an acid value of 110 mgKOH / g, and a solid content concentration of 40.0% by weight.

(Synthesis of Resin Solution B)

55.0 parts of methyl methacrylate, 10.0 parts of 2-ethylhexyl acrylate, 15.0 parts of benzyl methacrylate, and 20.0 parts of methacrylic acid were dissolved in 150.0 parts of methyl ethyl ketone, and stirred and reflux conditions in a nitrogen atmosphere using a polymerization initiator. It superposed | polymerized under the obtained resin solution B of the polystyrene conversion weight average molecular weight 63000, the acid value 130 mgKOH / g, and solid content concentration 40.0 weight%.

(Synthesis of Resin Solution C)

58.0 parts of methyl methacrylate, 9.0 parts of 2-ethylhexyl acrylate, 10.0 parts of benzyl methacrylate, and 23.0 parts of methacrylic acid were dissolved in 150.0 parts of methyl ethyl ketone, and stirred and reflux conditions in a nitrogen atmosphere using a polymerization initiator. It superposed | polymerized under the obtained resin solution C of the weight average molecular weight 107000 of polystyrene conversion, 150 mgKOH / g of acid value, and 40.0 weight% of solid content concentration.

(Production of Photosensitive Resist Stock E)

Resin solution A 30.0 parts, isocyanuric acid EO modified triacrylate 3.0 parts (solid / 25 degreeC), dipentaerythritol hexaacrylate 4.0 parts (viscosity; 4200 mPa * s / 25 degreeC), resin which has an ethylenically unsaturated group in a side chain (Molecular weight: 15000, unsaturated group equivalent: 350 g / eq, solid content 60 wt%) 10 parts, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 1.5 parts, diethyl thi 0.5 part of oxaanthone and 0.1 part of UV-Blue 236 (made by Mitsui Chemicals) were mixed, and the photosensitive resist stock solution E of 55.2 weight% of solid content concentration was prepared.

(Production of Photosensitive Resist Stock Solution F)

Resin solution B 30.0 parts, dipentaerythritol hexaacrylate 4.0 parts (viscosity; 4200 mPa * s / 25 degreeC), pentaerythritol tetraacrylate 3.0 parts (solid / 25 degreeC), the compound which has an ethylenically unsaturated group in a side chain (molecular weight: 15000, ethylenically unsaturated group equivalent: 350 g / eq, solid content 60% by weight) 10 parts, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 1.5 parts, diethyl thi 0.5 part of oak-santh and 0.1 part of UV-Blue 236 (made by Mitsui Chemicals) were mixed, and the photosensitive resist stock solution F of 55.2 weight% of solid content concentration was manufactured.

(Preparation of photosensitive resist stock solution g)

Resin solution C 30.0 parts, dipentaerythritol hexaacrylate 3.0 parts (viscosity; 4200 mPa * s / 25 degreeC), pentaerythritol tetraacrylate 4.0 parts (solid / 25 degreeC), the compound which has an ethylenically unsaturated group in a side chain (molecular weight: 15000, ethylenically unsaturated group equivalent: 450 g / eq, solid content 60% by weight) 10 parts, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 1.5 parts, diethyl thi 0.5 part of oxaanthone and 0.1 part of UV-Blue 236 (made by Mitsui Chemicals) were mixed, and the photosensitive resist stock solution G of 55.2 weight% of solid content concentration was manufactured.

(Production of Photosensitive Resist Stock Solution H)

40.0 parts of resin solution B, 7.0 parts of dipentaerythritol hexaacrylate (viscosity; 4200 mPa · s / 25 ° C), 1.5 parts of 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one And 0.5 parts of diethyl thioxanthone and 0.1 part of UV-Blue 236 (manufactured by Mitsui Chemical Co., Ltd.) were mixed to prepare a photosensitive resist stock solution H having a solid content concentration of 51.1 wt%.

(Preparation of Photosensitive Resist Stock Solution I)

Resin solution B 30.0 parts, trimetholpropane triacrylate 7.0 parts (viscosity; 65 mPa * s / 25 degreeC), the compound which has an ethylenically unsaturated group in a side chain (molecular weight: 15000, ethylenically unsaturated group equivalent: 350 g / eq, solid content) 60 parts by weight) 10 parts, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one 1.5 parts, diethyl thioxanthone 0.5 part, UV-Blue 236 (manufactured by Mitsui Chemical Co., Ltd.) ) 0.1 part was mixed to prepare a photosensitive resist stock solution I having a solid concentration of 55.2% by weight.

(Production of Photosensitive Resist Stock Solution Z)

Resin solution A 30.0 parts, dipentaerythritol hexaacrylate 2.0 parts (viscosity; 4200 mPa * s / 25 degreeC), pentaerythritol tetraacrylate 5.0 parts (solid / 25 degreeC), The compound which has an ethylenically unsaturated group in a side chain (ethylenic Unsaturated group equivalent: 86 g / eq) 10 parts, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one 1.5 parts, diethyl thioxanthone 0.5 part, UV-Blue 236 ( 0.1 part of Mitsui Chemicals Co., Ltd. product) was mixed, and the photosensitive resist stock solution Z of 63.3 weight% of solid content concentration was manufactured.

(Production of Photosensitive Resist Stock Solution AA)

Resin solution B 30.0 parts, dipentaerythritol hexaacrylate 5.0 parts (viscosity; 4200 mPa * s / 25 degreeC), pentaerythritol tetraacrylate 2.0 parts (solid / 25 degreeC), the compound which has an ethylenically unsaturated group in a side chain (ethylenic Unsaturated group equivalent: 1260 g / eq) 10 parts, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one 1.5 parts, diethyl thioxanthone 0.5 part, UV-Blue 236 ( 0.1 part of Mitsui Chemicals Co., Ltd.) was mixed, and the photosensitive resist stock solution AA of 55.2 weight% of solid content concentration was manufactured.

(Example 1)

(Production of Photosensitive Resist Liquid K)

35.0 parts of MEK and 15.9 parts of propylene glycol monomethyl ether acetate were mixed and stirred in the photosensitive resist stock solution E, and the photosensitive resist liquid K was prepared.

(Example 2)

(Production of Photosensitive Resist Liquid L)

Photosensitive resist stock solution E was used as it was.

(Example 3)

(Production of Photosensitive Resist Liquid M)

35.0 parts of MEK and 15.9 parts of propylene glycol monomethyl ether acetate were mixed and stirred with the photosensitive resist stock solution F, and the photosensitive resist liquid M was produced.

(Example 4)

(Production of Photosensitive Resist Liquid N)

Photosensitive resist stock solution F was used as it was.

(Example 5)

(Production of Photosensitive Resist Liquid O)

35.0 parts of MEK and 15.9 parts of propylene glycol monomethyl ether acetate were mixed and stirred with the photosensitive resist stock solution g, and the photosensitive resist liquid O was prepared.

(Example 6)

(Production of Photosensitive Resist Liquid P)

The photosensitive resist stock solution g was used as it was.

(Comparative Example 1)

(Production of Photosensitive Resist Liquid Q)

35.0 parts of MEK and 15.9 parts of propylene glycol monomethyl ether acetate were mixed and stirred in the photosensitive resist stock solution H, and the photosensitive resist liquid Q was prepared.

(Comparative Example 2)

(Production of Photosensitive Resist Liquid R)

35.0 parts of MEK and 15.9 parts of propylene glycol monomethyl ether acetate were mixed and stirred in the photosensitive resist stock solution I, and the photosensitive resist liquid R was produced.

(Example 7)

(Production of Photosensitive Resist Liquid AE)

46.2 parts of MEK and 19.8 parts of propylene glycol monomethyl ether acetate were mixed and stirred with the photosensitive resist stock solution Z, and the photosensitive resist liquid AE was produced.

(Example 8)

(Production of Photosensitive Resist Liquid AF)

35.0 parts of MEK and 15.9 parts of propylene glycol monomethyl ether acetate were mixed and stirred in the photosensitive resist stock solution AA, and the photosensitive resist liquid AF was produced.

(Comparative Example 3)

(Production of Photosensitive Resist Liquid AG)

Instead of 3.0 parts of isocyanuric acid EO-modified triacrylate (solid / 25 ° C.) in the photosensitive resist stock solution F, 3.0 parts of polyethylene glycol diacrylate (50 mPa · s / 25 ° C.) was added, and 35.0 parts of MEK and propylene glycol mono 15.9 parts of methyl ether acetate was further mixed and stirred to prepare a photosensitive resist liquid AG.

(Manufacturing method of a printed wiring board)

The printed board of the glass epoxy double-sided copper clad laminated board (plate thickness 0.2mm, copper thickness 18 micrometers, board | substrate size 370mm x 260mm) was prepared.

Next, the photosensitive resist liquid and stock solution (G) were stored in the stainless steel container, and the immersion bath was produced. Then, the printed wiring board prepared as described above is immersed at a speed of 50 cm / min perpendicular to the liquid level, and the immersion is stopped once with the upper end 1 cm of the substrate rising above the liquid level, and then the entire substrate at a pulling speed of 50 cm / min. The photosensitive resist liquid was applied up from the liquid surface, dried at 80 ° C. for 10 minutes in a hot air dryer, and then allowed to cool to room temperature.

Using two mask films drawn with a pattern capable of forming a conductor pattern, the wiring patterns of the respective mask films are orthogonal to each other so that the mask films are placed on both sides of the substrate, and the double-sided simultaneous exposure machine for photoresist exposure [HMW-532D (Oak Seisakusho Co., Ltd.) was exposed to ultraviolet rays with an integrated light quantity of 100 to 500 mJ, and then developed by spraying a 1.0 wt% sodium carbonate aqueous solution at 30 ° C. with a spray pressure of 2 kg / cm ² to develop The etching resist layer of the resist pattern was formed.

Subsequently, the copper-exposed part was etched away by a 40 ° C cupric chloride etching solution, and after washing with water, 40 ° C and 3.0% by weight of a sodium hydroxide aqueous solution were sprayed at a spray pressure of 2 kg / cm ² to form an etching resist layer. Was removed, the metal conductor layer of the conductor pattern was formed, and the printed wiring board was produced.

Table 1 shows the test results of the printed wiring board obtained as described above.

TABLE 1

According to the present invention, an etching resist layer having good exposure sensitivity without a tack can be formed, which is a very important invention in industry.

Claims (5)

At least 1 type of resin which has an ethylenically unsaturated group which can be photopolymerizable in a molecule | numerator, and the said ethylenically unsaturated group equivalent is 100-1000 g / eq, and has 3 or more ethylenically unsaturated groups, and has a viscosity of 25 m and 2000 mPa * s under 1 atmosphere. A photosensitive resin composition comprising a photosensitive compound which is not less than 4200 mPa · s and a resin which is soluble in an alkaline aqueous solution having no ethylenically unsaturated group capable of photopolymerization in a molecule. The method of claim 1, The solvent contained in the said photosensitive resin composition is 30 weight%-95 weight%, The photosensitive resin composition characterized by the above-mentioned. The substrate on which the metal conductor layer is formed on the surface of the insulated substrate is immersed in the photosensitive resin composition according to claim 1, and the substrate is coated with the photosensitive resin composition on the surface of the substrate. The substrate is exposed and developed through a photomask to form a predetermined resist pattern. A metal conductor layer is formed in a predetermined conductor pattern by forming an etching process on the substrate after forming the etching resist layer of the printed wiring board. The method of claim 1, A photosensitive resin composition comprising a weight average molecular weight of 5000 to 200000 of a resin soluble in an alkaline aqueous solution having no photopolymerizable ethylenically unsaturated group in its molecule. The method of claim 1, The photosensitive resin composition characterized by the acid value of resin which can be used for the alkaline aqueous solution which does not have a photopolymerizable ethylenically unsaturated group in a molecule | numerator from 20 mgKOH / g-300 mgKOH / g.