JPH10161308A - Photopolymerizable resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable resin compsn. having satisfactory etching resistance, sensitivity and resolution, excellent in adhesion to a printed circuit board and a metallic foil substrate (42 alloy, 36 alloy, 'Kovar(R)', SUS, etc.) and developable with an alkaline aq. soln. SOLUTION: This photopolymerizable resin compsn. contains (a) 20-90 pts.wt. polymer having a carboxyl group content of 100-600 (expressed in terms of acid equiv.) and a wt. average mol.wt. of 20,000-500,000, (b) 5-60 pts.wt. photopolymerizable monomer having at least two terminal ethylenic unsatd. groups, (c) 0.01-20 pts.wt. photopolymn. initiator and (d) 0.1-50 pts.wt. compd. having one epoxy group and at least one terminal ethylenic unsatd. group in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable resin composition which can be developed with an aqueous alkaline solution and is suitable for use in making printed wiring boards and processing metal foil substrates, and uses thereof.

[0002]

2. Description of the Related Art In recent years, a so-called dry film resist (DFR) having a structure in which a photopolymerizable resin layer is sandwiched between support films has been widely used as a photoresist for producing a printed wiring board and for processing a metal base material. The DFR is generally produced by laminating a photopolymerizable layer composed of a photopolymerizable composition on a support film, and in many cases, further laminating a protective film on the composition. The photopolymerizable resin layer is generally of an alkali developing type using a weak alkaline aqueous solution as a developing solution.

[0003] In the process of processing a printed wiring board and a metal foil substrate, one of the particularly important characteristics required for the photoresist is that the photoresist is not affected by a chemical such as an etching solution, and the substrate coated with the photoresist is used. It can be sufficiently protected. For example, in the case of a base material such as a copper-clad laminate or a ferrous metal foil substrate (42 alloy, 36 alloy, Kovar material, etc.), peeling and floating of the cured resist generated during etching is caused by the distance between the cured resist and the metal surface. This causes problems such as disconnection between patterns, a decrease in the width of the wiring pattern, and a disorder in the shape of the wiring peripheral portion.

Further, the photoresist must be capable of forming stable circuit wiring without meandering or peeling due to a developing solution or washing water in a developing step. For example, if the liquid temperature and spray pressure of the developing solution and washing water in the developing process are high,
In some cases, meandering and peeling of the photoresist at the thin line portion of the circuit pattern occurred, causing serious defects in the circuit pattern. Further, when the development time is long and over-development occurs, the same problem may occur. These problems are due to insufficient adhesion between the cured resist and the metal surface of the substrate, and research and development of adhesion promoters have been actively conducted. It has been proposed to add a heterocyclic nitrogen-containing compound such as benzotriazole or benzimidazole to the photopolymerizable resin composition as described in U.S. Pat. No. 3,622,334.

However, when these compounds are used, the penetration of the etching solution into the metal surface of the copper clad laminate and the meandering of the resist line are improved,
Adhesion to an iron-based metal foil substrate such as an alloy, a 36-alloy, or a Kovar material was not sufficient, and meandering and peeling of the cured resist occurred after development. Furthermore, during high-temperature etching (70 ° C. or higher), not only the adhesion of the photoresist to the base material but also the chemical resistance were insufficient, so that peeling and floating of the cured resist occurred very easily. As a result, serious defects such as a short circuit between circuit wiring patterns and a decrease in wiring pattern width have been caused. In particular, among alkali-developable photopolymerizable resins or DFRs that can be developed with a chemical solution such as sodium carbonate, those that can withstand the infiltration of an etching solution generated during high-temperature etching using an iron-based metal foil base material have not been put to practical use. .

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned drawbacks and to provide a printed wiring board or a metal foil base material (42 alloy, 36 alloy, Kovar, SUS material, etc.) with an etching resistance or the like. An object of the present invention is to provide a photopolymerizable resin composition, a photopolymerizable resin laminate which can be developed with an alkaline aqueous solution having good sensitivity and resolution and excellent adhesion, and a method for processing and manufacturing a metal substrate using the same. is there.

[0007]

The present inventors have made intensive studies to solve the above-mentioned problems. As a result, surprisingly, the present inventors have found that the following photo-polymerizable compounds having the following essential components (a) to (d) are essential components. It has been found that the above object can be achieved by using a resin composition, and the present invention has been completed. That is, the present application provides the following inventions.

(1) (a) a polymer having a carboxyl group content of 100 to 600 in acid equivalent and a weight average molecular weight of 20,000 to 500,000, 20 to 90 parts by weight, and (b) at least two terminal ethylenically unsaturated compounds Photopolymerizable monomer having a group, 5-6
0 parts by weight, (c) a photopolymerization initiator, 0.01 to 20 parts by weight (d) a compound containing one epoxy group and at least one terminal ethylenically unsaturated group in a molecule, 0.5 to 30 parts by weight A photopolymerizable resin composition for a dry film, comprising:

(2) A photopolymerizable resin laminate in which a layer comprising the above photopolymerizable resin composition is provided on a support. (3) A lead for providing a photosensitive coating on a metal foil substrate, patterning the photosensitive coating by exposing and developing it through a mask, and etching the metal foil using the patterned photosensitive coating as an etching resist. In a method for manufacturing a frame, a lead is laminated on a metal foil substrate with a dry film comprising the photopolymerizable resin composition according to (1) or the photopolymerizable resin laminate according to (2). The method of manufacturing the frame.

(4) A photosensitive coating is provided on a metal foil substrate, and the photosensitive coating is patterned by exposing and developing through a mask, and the patterned photosensitive coating is used as an etching resist for the metal foil. In the method for producing a color selection mask of a cathode ray tube for etching a film, a dry film comprising the photopolymerizable resin composition according to the above (1) or the photopolymerizable resin laminate according to the above (2) is placed on a metal foil substrate. A method for producing a color selection mask for a cathode ray tube, comprising laminating.

The present application also provides the following applied invention. (5) The metal foil substrate with the photosensitive coating patterned
The manufacturing method according to the above (3) or (4), wherein a heating step is performed before the etching. (6) The method according to the above (3) or (4), wherein the lamination to the metal foil is performed by pressing with a two-stage laminator to laminate. Here, the parts by weight of each component indicate the ratio of each component contained in the composition.

Hereinafter, the present invention will be described in detail. The photopolymerizable resin composition for a dry film resist of the present invention can be obtained by mixing each component according to a conventional method. Examples of the compound containing one epoxy group and at least one terminal ethylenically unsaturated group in the molecule of the component (d) used in the present invention include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate,
1,2-epoxy-9-decene, 6,7-epoxy-
3,7-dimethyloctyl (meth) acrylate, 2,
3-epoxybutyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2,3-epoxy-2-ethylhexyl (meth) acrylate, 3 [4-
(2,3-epoxy proxy) butoxy] -2-hydroxypropyl (meth) acrylate,

1,2-epoxypropyl-α-cyano-
β-hydroxyphenyl (meth) acrylate, 2,3
-Epoxy-2-methylpropyl (meth) acrylate, 2- (glycidyloxy) ethyl (meth) acrylate, β-glycidyloxyethyl (meth) acrylate,
2-norbornyl-5 (or6)-(epoxyethyl)
-(Meth) acrylate, 1-undecanol-10,
11-epoxy (meth) acrylate, 2-propanol-1,3-epoxy (meth) acrylate, 1,2-
Cyclohexanediol-4,4-bis [(2,3-epoxypropoxy) methyl] -2- (meth) acrylate, 1-octadecanol-9,10-epoxy (meth) acrylate, 1-propanol-2,3 -Epoxy-2-furan (meth) acrylate, 3,4-epoxycyclohexylethylene, 3,4-epoxycyclohexyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 2,3-epoxycyclohexyl (Meth) acrylate and the like.

The amount of the compound containing one epoxy group and at least one terminal ethylenically unsaturated group in the molecule is 0.1.
When the amount is 1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, and more preferably 1 to 20 parts by weight, an unexpected effect of improving adhesion and etching resistance is exhibited.

The amount of the carboxyl group contained in the polymer of the component (a) used in the present invention is from 100 to 600 in terms of acid equivalent. The molecular weight is from 20,000 to 500,000. Here, the acid equivalent refers to the weight of a polymer having one equivalent of a carboxyl group therein. The carboxyl group in the polymer is necessary for having developability and releasability in an aqueous alkali solution.
When the acid equivalent is 100 or less, a coating solvent or other composition,
For example, the compatibility with the monomer is reduced, and if it is 600 or more, the developability and the peelability are reduced. Further, when the molecular weight is 500,000 or more, the developability decreases, and when the molecular weight is 20,000 or less, it becomes difficult to maintain a uniform thickness of the photopolymerizable resin layer when used in the photopolymerizable resin laminate, and The resistance to liquid deteriorates.

The measurement of the acid equivalent is carried out by potentiometric titration with 0.1 N sodium hydroxide using Hiranuma reporting titrator COMTITE-7. Also,
The molecular weight was determined by gel permeation chromatography manufactured by JASCO (pump: TRIROTAR-V, column: Sh
Odex A-80M 2 in series, mobile phase solvent; TH
F, using a calibration curve with a polystyrene standard sample).

As the polymer, a known polymer used in a conventional dry film resist for patterning a printed wiring board can be used. For example, an acrylic resin, an epoxy resin, a styrene resin, a phenol resin, a urethane resin, or the like can be used. As the polymerizable monomer component of the polymer, a known polymerizable monomer used in a conventional dry film resist for patterning a printed wiring board can be used. A dry film composition which can be alkali-developed is generally obtained by copolymerizing one or more of each of the following two types of monomers. The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. For example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester and the like.

The second monomer is non-acidic, has one polymerizable unsaturated group in the molecule, and has the developability of the photopolymerizable resin layer, the resistance in the etching and plating steps, and the flexibility of the cured film. Etc. are selected to maintain various characteristics. For example, methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-
There are butyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate, and 2-hydroxylpropyl (meth) acrylates. Also, esters of vinyl alcohol such as vinyl acetate and the like, (meth) acrylonitrile,
There is styrene or a polymerizable styrene derivative. It can also be obtained by polymerization of only a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule.

The amount of the polymer contained in the photopolymerizable resin composition must be in the range of 20 to 90 parts by weight. When the amount of the polymer is 90 parts by weight or more or less than 20 parts by weight,
The cured image formed by exposure does not have sufficient properties as a resist, for example, sufficient resistance in tenting, etching, and various plating steps.

The photopolymerizable resin composition of the present invention comprises (b)
It is essential to include a photopolymerizable monomer having at least two terminal ethylene groups of the component. Examples of the monomer include 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polyoxyethylene. Polyoxyalkylene glycol di (meth) acrylate such as polyoxypropylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) Acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate,
Polyoxyethyltrimethylolpropane triacrylate,

Dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, 2,2-
Examples include bis (4-methacryloxypentaethoxyphenyl) propane and a polyfunctional (meth) acrylate containing a urethane group. Also, JP-A-59-204837, page 7, upper right column, line 5 to page 12, upper right column, line 20;
No. 11446, page 3, lower left column, line 27 to lower right column, second
The compounds described in line 8 can also be used.

These monomers may be used alone or in combination of two or more. The use amount is preferably 5 to 60% by weight. If the amount is less than 5% by weight, sensitivity and film strength are not sufficient, and if it exceeds 60% by weight, the photosensitive layer protrudes during storage, which is not preferable.

The photopolymerizable resin composition of the present invention contains the photopolymerization initiator (c) as an essential component. The photopolymerization initiator used in the present invention is any known compound that is activated by various kinds of actinic rays, for example, ultraviolet rays, and starts polymerization. For example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-
Chloroanthraquinone, 2-chloroanthraquinone, 2
-Methylanthraquinone, 1,4-naphthoquinone, 9,
10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methyl Quinones such as anthraquinone, benzophenone Michler's ketone [4,4'-
Bis (dimethylamino) benzophenone], 4,4'-
Aromatic ketones such as bis (diethylamino) benzophenone,

Benzoin, benzoin ethyl ether,
Benzoin ethers such as benzoin phenyl ether, methyl benzoin and ethyl benzoin; dialkyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal; 2- (o-chlorophenyl) -4,
Biimidazole compounds such as 5-diphenylimidazolyl dimer, acridines such as 9-phenylacridine, thioxanthones such as diethylthioxanthone and chlorothioxanthone, dialkylaminobenzoates such as ethyl dimethylaminobenzoate, 1-phenyl- 1,
2-propanedione-2-o-benzoyl oxime, 1
Oxime esters such as -phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime. These photopolymerization initiators may be used alone or in combination.

Preferred examples of the photopolymerization initiator include thioxanthones such as diethylthioxanthone and chlorothioxanthone, dialkylaminobenzoic esters such as ethyl dimethylaminobenzoate, benzophenone, 4,4 and the like.
4'-bis (dimethylamino) benzophenone, 4,
4'-bis (diethylamino) benzophenone, 2-
(O-chlorophenyl) -4,5-diphenylimidazolyl dimer, and combinations thereof.

The amount of the photopolymerization initiator contained in the photopolymerizable resin composition of the present invention is 0.01 to 20 parts by weight. When the photopolymerization initiator is used in an amount of 20 parts by weight or more, the active absorbance of the photopolymerizable composition becomes high, and when used as a photopolymerization laminate, curing at the bottom portion of the photopolymerization layer becomes insufficient. If the amount is less than 0.01 parts by weight, sufficient sensitivity cannot be obtained.

The thermal stability of the photopolymerizable resin composition of the present invention,
It is preferable that the photopolymerizable resin composition contains a polymerization inhibitor in order to improve the storage stability. For example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-
Cresol, 2,2'-methylenebis (4-ethyl-6
-Tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.

The photopolymerizable resin composition of the present invention contains a dye,
A coloring substance such as a pigment may be contained. For example, fuchsin,
Phthalocyanine green, auramine base, chalcoxide green S, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond green and the like. Further, a coloring dye which develops color by light irradiation may be contained. Examples of the color-forming dye include a combination of a leuco dye or a fluoran dye and a halogen compound. For example, tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-
2-methylphenyl) methane [leucomalachite green] and the like.

On the other hand, examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, Tris (2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p
-Chlorophenyl) ethane, hexachloroethane, triazine compounds, and the like. Further, a combination of a biimidazole compound and a leuco dye or a combination of a triazine compound and a leuco dye is useful. Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

The photopolymerizable resin laminate of the present invention comprises a photopolymerizable resin layer containing the above photopolymerizable resin composition, and a support layer for supporting the photopolymerizable resin layer. The support layer is desirably a transparent layer that transmits active light. As a support layer that transmits active light, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film,
Examples include a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may be stretched if necessary. A thinner thickness is more advantageous in terms of image forming properties and economy, but generally has a thickness of 10 to 30 μm because of the need to maintain strength.

A protective layer is laminated on the surface opposite to the photopolymerizable resin layer laminated with the support layer, if necessary. The important property of this protective layer is that it has a good adhesion to the photopolymerizable resin layer.
The protective layer is sufficiently smaller than the support layer and can be easily peeled off. For example, there are a polyethylene film and a polypropylene film. Also, JP-A-59-20245
No. 7, a film having excellent releasability can be used. The thickness of the photopolymerizable resin layer varies depending on the application.
The thickness is from 10 to 100 μm, preferably from 10 to 80 μm. Also, the film thickness increases as the thickness increases.

Next, the metal foil processing step using the photopolymerizable resin laminate of the present invention will be briefly described. First, using a laminator, if there is a protective layer, the protective layer is peeled off, and then the photopolymerized layer is heat-pressed and laminated on the metal surface. The heating temperature at this time is generally 40 to 160 ° C. Further, by performing the pressure bonding twice or more, the adhesion and the etching resistance are improved. At this time, the press bonding may be performed by using a two-stage laminator provided with two rolls, or may be repeated several times and passed through the rolls and press-bonded (for a two-stage laminator, see Japanese Patent Application Laid-Open No. 63-7777). Gazette). Next, if necessary, the support layer is peeled off, and image exposure is performed with actinic light through a mask film. Next, if there is a support layer on the photopolymerized layer after exposure, the support layer is removed if necessary, and then the unexposed portion is developed and removed using a developing solution of an alkaline aqueous solution.

As the alkaline aqueous solution, an aqueous solution of sodium carbonate, potassium carbonate or the like is used. These are selected in accordance with the properties of the photopolymerizable resin layer, but are selected from 0.5% to 3%.
% Aqueous sodium carbonate solution is common. The substrate thus obtained may optionally be subjected to a heating step at 100 to 300 ° C. Next, a metal image pattern is formed on the metal surface exposed by development using a known method such as an etching method. Thereafter, the cured resist image is generally stripped off with an aqueous alkaline solution that is stronger than the aqueous alkaline solution used for development. There is no particular limitation on the alkaline aqueous solution for stripping, but aqueous solutions of sodium hydroxide and potassium hydroxide are generally used. Further, it is possible to add a small amount of a water-soluble solvent to a developer or a stripper.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the examples and comparative examples, (1) sensitivity, (2) resolution, (3) state of etching solution penetration, and (4) comprehensive evaluation were evaluated as follows. (1) Sensitivity A 27-step tablet with brightness changed from transparent to black in 27 steps [manufactured by Asahi Kasei Corporation: optical density D = 0.
50 to 1.80, ΔD = 0.05], the number of steps corresponding to the time when the metal foil substrate was exposed after development was determined. This numerical value is usually desirably 10 to 14 stages. If the number of steps is 15 or more, fog occurs and the resolution is reduced. On the other hand, if it is less than 9 steps, the photo-curing reaction becomes insufficient and a clear pattern cannot be obtained, or the adhesiveness of the resist line decreases.

(2) Resolution The resolution of the resolution mask (stripe) after development was measured. The smaller the value, the better the resolution. (3) State of Infiltration of Etching Solution The presence or absence of excessive infiltration of the etching solution was visually observed with a SEM photograph (500 times). (4) Comprehensive evaluation When all of the evaluation results of (1) to (3) above were satisfied, it was judged as ○. Others were evaluated as x.

[0036]

【Example】

Example 1 [Formulation of composition for dry film and evaluation on copper clad laminate] The following components (A) to (J) were mixed in accordance with the mixing ratio shown in Table 1 to prepare a composition for dry film resist. did. (A) 180% by weight of a 35% MEK solution of a copolymer of styrene / methyl acrylate / methyl methacrylate / methacrylic acid = 15/10/50/25 (weight ratio) (B) Trimethylolpropane triacrylate 20
Parts by weight

(C) 15 parts by weight of tetrapropylene glycol dimethacrylate (D) Epoxy group-containing unsaturated compound: 5 parts by weight of glycidyl methacrylate (E) 4 parts by weight of benzophenone (F) 4,4'-diethylaminobenzophenone
1 part by weight (G) 2- (O-chlorophenyl) -4,5-diphenylimidazolyl dimer 2 parts by weight (H) malachite green 0.1 part by weight (I) leuco crystal violet 1 part by weight (J) methyl ethyl ketone 20 Parts by weight

The above composition was uniformly dissolved to obtain a mixed solution. This mixed solution was uniformly applied to a 25 μm-thick polyethylene terephthalate film using a bar coater. This was dried in a dryer at 90 ° C. for 3 minutes to obtain a photopolymerizable resin laminate having a photopolymer layer having a thickness of 15 μm. Thereafter, a 35 μm polyethylene film was laminated on the surface of the photopolymerization layer on which the polyethylene terephthalate film was not laminated, to produce a laminated film-1.

The obtained laminated film-1 was coated with a thickness of 35 μm.
The laminate was laminated at 105 ° C. while peeling off the polyethylene film so that the photopolymerizable resin laminate faced the copper surface of the copper-clad laminate of m. Next, a resolution mask film (striped) was placed on the polyethylene terephthalate film side, and an ultra-high pressure mercury lamp (manufactured by Oak Works: HMW-2)
01 KB) at 60 mJ / cm ² . Subsequently, after removing the polyethylene terephthalate film, a 1% aqueous solution of sodium carbonate (30 ° C.) was added for about 3 hours.
The unexposed portion was dissolved and removed by spraying for 0 second, and the photopolymerizable resin was patterned. Then, the copper foil is etched with a ferric chloride solution (47 Baume, 70 ° C., 5 minutes) using the patterned photopolymerizable resin film as an etching resist,
Next, the photopolymerizable resin film was peeled off using a 3% aqueous solution of caustic soda (temperature: 50 ° C.), and a sample for evaluation was prepared and evaluated. Table 1 shows the results.

Examples 2 to 7, Comparative Examples 1 and 2 [Evaluation on iron-based metal foil base material: 42 alloy substrate] The procedure was carried out except that the types and the mixing ratios of the epoxy group-containing unsaturated compounds were as shown in Table 1. Example 1 was repeated to prepare a composition for a dry film resist to prepare a laminated film-1. Then, a sample for evaluation was produced by repeating Example 1 except that this was laminated on a 42-alloy substrate having a thickness of 150 μm (manufactured by Nippon Mining & Metals Co., Ltd .: DF-CP-1 / 2H [0.15t]). . Table 1 shows the results.

Example 8, Comparative Example 3 [Evaluation of Etching Solution Penetration After Heating Step] Samples patterned according to Example 2 and Comparative Example 1 were heated at 200 ° C. for 1 minute, Etching was performed in the same manner as in Example 1, and evaluation samples were prepared and evaluated. Table 1 shows the results.

Example 9 [Evaluation of etchant penetration by using a two-stage laminator] When laminating a photopolymerizable resin laminate to a substrate, a two-stage laminator [AL-, manufactured by Asahi Kasei Kogyo Co., Ltd.]
700], an evaluation sample was prepared and evaluated in accordance with Example 2. Table 1 shows the results.

[0043]

[Table 1]

From the results shown in Table 1, it can be seen that the photopolymerizable resin laminate of the present invention to which the epoxy group-containing unsaturated compound has been added shows the chemical resistance of the photopolymerizable resin and the metal surface of the substrate. Since the adhesiveness is high, the infiltration of the etching solution does not occur, and the sensitivity and the resolution are also good. On the other hand, Comparative Examples 1 and 3 in which the mixing ratio of the unsaturated compound having an epoxy group was not added.
The edge of the wiring pattern is unclear due to the infiltration of the etching solution due to insufficient chemical resistance of the photopolymerizable resin and adhesion to the 42 alloy substrate. Furthermore, as shown in Comparative Example 3, it can be seen that this sample cannot obtain sufficient etching resistance even after the heating step. Further, an epoxy group-containing unsaturated compound having two epoxy groups in one molecule.
In Comparative Example 2 using more than one compound, patterning could not be performed because the alkali developability of the photopolymerizable resin layer was reduced.

Example 10 [Production of a lead frame] A dry film resist (base film: PET + photopolymerizable resin layer) prepared in Example 2 was applied to a 150-μm-thick 42-alloy base material. Both sides were laminated at 105 ° C. so as to face the substrate. Next, a negative film mask having a lead frame pattern (208 pins) is overlaid on the base film of the photopolymerizable resin laminate so as to be vertically aligned from both sides, and both are brought into close contact with each other by applying a vacuum, and the exposure amount is 60 mJ / cm.
Exposure at ² . After that, peel off the base film,
1% aqueous sodium carbonate solution (liquid temperature 30 ° C) as a developer
To develop a lead frame pattern.

Next, a ferric chloride solution (solution temperature: 70 ° C., 47 Baume) was used as an etching solution, and etching was performed from both sides until the etching penetrated the substrate. Next, the photopolymerizable resin layer was removed using 3% caustic soda (solution temperature: 70 ° C.) as a stripping solution to obtain a desired lead frame. When the obtained lead frame was visually observed with an electron microscope, the adhesion between the photopolymerizable resin layer and the 42 alloy substrate was good, and the obtained lead frame pattern was very sharp without erosion of the etching solution. there were.

Comparative Example 4 A lead frame was produced by repeating Example 10 except that the dry film resist produced in Comparative Example 1 was used. In this case, excessive erosion of the etchant was observed from the interface between the light-weight synthetic resin layer and the 42 alloy base material.

Example 11 [Production of a color selection mask] A dry film resist (base film: PET + photopolymerizable resin layer) prepared in Example 2 was applied to a 150-μm-thick 36-alloy base material by using the photopolymerizable resin layer. Were laminated at 105 ° C. such that the surface of the substrate faced the substrate. Next, a color selection pattern (upper surface: 100 μm, lower surface: 1) was formed on the base film of the photopolymerizable resin laminate.
A negative film mask having a thickness of 50 nμm) was overlapped from both sides so as to be vertically aligned, and both were brought into close contact with each other by applying a vacuum, and exposed at an exposure amount of 60 mJ / cm ² . Thereafter, the base film was peeled off and developed using a 1% aqueous solution of sodium carbonate (solution temperature: 30 ° C.) as a developer to form a color identification pattern.

Next, a ferric chloride solution (solution temperature: 70 ° C., 47 Baume) was used as an etching solution, and etching was performed from both sides. When the etching has progressed to a predetermined depth, a narrow pattern of the opening of the photopolymerizable resin layer (upper surface:
A 100 μm side) is covered with a protective film and further etched to form a wide pattern (lower surface: 1) of the opening of the photopolymer resin layer.
The protective film was peeled off from the 50 μm side), and the photopolymerizable resin layer was removed using 3% sodium hydroxide (liquid temperature: 50 ° C.) as a peeling solution to obtain a target color selection mask. When the obtained color selection mask was visually observed with an electron microscope, the adhesion between the photopolymerizable resin layer and the 36 alloy base material was good, and the edge of the obtained color selection mask pattern was not corroded by the etching solution. It was very sharp without.

Comparative Example 5 A lead frame was produced by repeating Example 11 except that the dry film resist produced in Comparative Example 1 was used. In this case, excessive erosion of the etching solution was observed from the interface between the light-weight synthetic resin layer and the 36 alloy base material. In addition, a portion where the light-weight synthetic resin layer was floating was also observed.

[0051]

Since the photopolymerizable resin composition for a dry film resist of the present invention contains an unsaturated compound having an epoxy group, the photopolymerizable resin layer formed from the composition of the present invention is not suitable for printed wiring. It can be laminated with high adhesion not only to copper-based metal materials such as plates, but also to iron-based metal materials such as for metal processing. Furthermore, since the resistance to an alkaline developing solution or a strongly acidic etching solution is also good, it can be seen that it has extremely high chemical resistance.

Accordingly, a dry film resist having a photopolymerizable resin layer formed from the photopolymerizable resin composition of the present invention can be used not only for patterning a copper-based metal substrate but also for a lead frame using a ferrous metal substrate, a cathode wire. It is also useful for patterning a color selection mask (shadow mask) for a tube. That is, when a copper-based or iron-based metal material is etched using the patterned photopolymerizable resin layer as an etching resist, the photopolymerizable resin layer has not only high adhesion to the material to be etched but also contains an epoxy group. Since the unsaturated compound has good chemical resistance, even if the etching time is lengthened, it is possible to prevent the infiltration of the etching solution from the interface between the two. Therefore, a printed wiring board, a metal foil substrate, and the like can be processed with high accuracy.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01L 23/50 H01L 23/50 A H05K 3/06 H05K 3/06 H J

Claims (4)

[Claims] 1. A polymer having a carboxyl group content of 100 to 600 in acid equivalent and a weight average molecular weight of 20,000 to 500,000, 20 to 90 parts by weight, and (b) at least two terminal ethylenically unsaturated groups. (C) a photopolymerization initiator, 0.01 to 20 parts by weight; (d) a compound containing one epoxy group and at least one terminal ethylenically unsaturated group in the molecule; 0.1 to 50 parts by weight of a photopolymerizable resin composition for a dry film. 2. A photopolymerizable resin laminate comprising a support and a layer comprising the photopolymerizable resin composition according to claim 1 provided on a support. 3. A photosensitive film is provided on a metal foil substrate, and the photosensitive film is patterned by exposing and developing through a mask, and the patterned photosensitive film is used as an etching resist to form a metal foil. In a method for producing a lead frame to be etched, a dry film comprising the photopolymerizable resin composition according to claim 1 or the photopolymerizable resin laminate according to claim 2 is laminated on a metal foil substrate. Lead frame manufacturing method. 4. A photosensitive film is provided on a metal foil base material, and the photosensitive film is patterned by exposing and developing through a mask, and the patterned photosensitive film is used as an etching resist to form a metal foil. In the method for producing a color selection mask for a cathode ray tube to be etched, a dry film comprising the photopolymerizable resin composition according to claim 1 or the photopolymerizable resin laminate according to claim 2 is laminated on a metal foil substrate. A method for manufacturing a color selection mask for a cathode ray tube, comprising the steps of: