JPH1124258A - Dry film resist for tenting - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the dry film resist to be used for tenting excellent in sensitivity, tent film strength, adhesion, contrast, and stability after lamination. SOLUTION: This dry film resist is obtained by forming a photosensitive resin composition into a support film, and this composition comprises (a) a polymer containing carboxylic groups (b) an ethylenically unsaturated compound, (c) 0.01-1.0 pts.wt. of an acridine derivative, (d) 0.01-3.0 pts.wt. of a halogen compound, (e) 0.01-6.0 pts.wt. of a lophine dimer, and (f) 0.01-3.0 pts.wt. of a leuco dye when (a)+(b) is 100 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry film resist for tenting used in the manufacture of printed wiring boards, and more particularly, to excellent sensitivity, fine wire adhesion, and tent film strength, and also excellent stability after lamination. And a dry film resist for tenting.

[0002]

2. Description of the Related Art A photoresist method using a photosensitive resin composition is used for manufacturing a printed wiring board and the like. In this photoresist method, for example, a photosensitive material is first exposed on a support such as a transparent film. After applying the photosensitive resin composition to form a photosensitive resin composition layer, the photosensitive resin composition layer is laminated on the surface of a substrate on which a desired pattern is to be formed, and then the photosensitive resin composition layer is formed. After exposing the original image through a pattern mask, the unexposed portions are removed by a developing process using a solvent or an aqueous alkali solution to form a resist image, and the formed resist image is used as a protective mask,
A method of manufacturing a printed circuit board by performing a well-known etching process or pattern plating process and then stripping the resist is generally performed.

[0003] In such a manufacturing process, it is required to have high sensitivity in order to improve productivity and shorten time, and for the purpose of having such high sensitivity, Japanese Patent Application Laid-Open No. Hei. Japanese Patent Application Laid-Open No. 4-170546 proposes that a photosensitive resin composition contains an acridine derivative. JP-A-1-203413
The publication describes that a halogen compound (trihalomethyl compound) is further contained.

[0004]

However, although the photosensitive resin compositions described in the above publications are excellent in sensitivity, they do not consider the fine wire adhesion and the strength of the tent film. After careful consideration,
With the fineness of printed wiring boards and metal microfabrication, especially when used for tenting, fine wire adhesion and tent films are not yet satisfactory, and further improvements are needed. . In addition, the contrast after exposure is low in the above technique, and there remains a problem in workability. Under such circumstances, the present invention provides a tenting dry film resist having high sensitivity, having excellent fine wire adhesion and tent film strength, and also having excellent stability after lamination. The purpose is to provide.

[0005]

Means for Solving the Problems However, as a result of intensive studies to solve such problems, the present inventor has found that a photosensitive resin composition layer comprising the following (a) to (f) is provided on a support film. The present inventors have found that a dry film resist for tenting formed according to the present invention meets the above object, and have completed the present invention. (A) Carboxyl group-containing polymer (b) Ethylenically unsaturated compound (c) Acridine derivative 0.01 to 1.0 part by weight based on 100 parts by weight of the total of (a) and (b) (d) Halogen compound 0.01 to 3.0 parts by weight (e) Rofin dimer 0.01 to 6.0 parts by weight (f) Leuco dye 0.01 to 3.0 parts by weight

In the present invention, when the (c) acridine derivative is a compound represented by the following formula (1) or (d) the halogen compound is tribromomethylphenylsulfone, the effect of the present invention is particularly remarkable. Demonstrate.

Embedded image (In the formula, R is any of hydrogen, a phenyl group, an alkyl group, and an alkoxy group.)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. As the (a) carboxyl group-containing polymer used in the present invention, an acrylic copolymer containing (meth) acrylic acid ester as a main component and copolymerized with an ethylenically unsaturated carboxylic acid is preferably used. If necessary, an acrylic copolymer obtained by copolymerizing another copolymerizable monomer can be used. In this case, the content of each component is (meth) acrylate component 70 to 8
5% by weight, preferably 75 to 82% by weight, and 15 to 30% by weight, preferably 1 to 30% by weight of an ethylenically unsaturated carboxylic acid component.
8 to 25% by weight, other copolymerizable monomer components are 0 to
It is often 15% by weight.

Here, the (meth) acrylic acid ester includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate,
-Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl ( (Meth) acrylate and the like.

As the ethylenically unsaturated carboxylic acid, for example, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid are preferably used.
Dicarboxylic acids such as fumaric acid and itaconic acid, or anhydrides and half esters thereof can also be used. Of these, acrylic acid and methacrylic acid are particularly preferred.

Other copolymerizable monomers include, for example, tetrahydrofurfuryl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, (meth) acrylamide, 2,2,3,3 -Tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, alkyl vinyl ether, (meth) acrylonitrile and the like.

The carboxyl group-containing polymer (a) thus obtained may be used in combination with a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin, and the like. The weight average molecular weight of (a) the carboxyl group-containing polymer is 10,000 to 300,000, preferably 10,000 to 150,000, and more preferably 3 to 350,000.
When the molecular weight is less than 10,000, cold flow is liable to occur. Conversely, when the molecular weight is more than 300,000, development is difficult, resulting in a decrease in resolution or poor releasability at the time of resist peeling. .

(B) The ethylenically unsaturated monomers include tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate,
2,2-bis (4-acryloxydiethoxyphenyl)
Propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3-
(Meth) acryloyloxypropyl acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, 1,6-hexamethyldiglycidyl ether di (meth) acrylate, trimethylolpropane triglycidyl ether Examples include polyfunctional monomers such as tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, and glycerin polyglycidyl ether poly (meth) acrylate.

An appropriate amount of a monofunctional monomer may be used together with these polyfunctional monomers. Examples of such a monofunctional monomer include 2-phenoxy-2-hydroxypropyl (meth) acrylate and 2- (meth) acrylate. Acryloyloxy-2-hydroxypropyl phthalate, 3-
Chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate,
Half (meth) acrylate of a phthalic acid derivative, N-methylol (meth) acrylamide, etc. are mentioned.

The mixing ratio of (b) the ethylenically unsaturated monomer is 5 to 5% based on the total weight of (a) the carboxyl group-containing polymer and (b) the ethylenically unsaturated monomer.
It is desirable to select from the range of 90% by weight, preferably 20 to 80% by weight, particularly preferably 40 to 60% by weight.
(B) Insufficient ethylenically unsaturated monomer indicates poor curing,
(B) Excessive amount of the ethylenically unsaturated monomer is not preferable because it causes an increase in tackiness, a cold flow, and a decrease in the peeling rate of the cured resist.

The (c) acridine derivative is not particularly limited, but is preferably a compound represented by the above formula (I). Specific examples include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p
-Ethylphenyl) acridine, 9- (pn-propylphenyl) acridine, 9- (p-iso-propylphenyl) acridine, 9- (pn-butylphenyl) acridine, 9- (p-tert-butyl) Phenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9-
(P-acetylphenyl) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9 −
(M-methylphenyl) acridine, 9- (mn-propylphenyl) acridine, 9- (m-iso-propylphenyl) acridine, 9- (mn-butylphenyl) acridine, 9- (m-tert) -Butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9- (m-ethoxyphenyl) acridine, 9-
(M-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (m-cyanophenyl) acridine, 9- (m-chlorophenyl) acridine, 9 -(M-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-iso-propylacridine, 9-
Cyanoethyl acridine, 9-hydroxyethyl acridine, 9-chloroethyl acridine, 9-methoxy acridine, 9-ethoxy acridine, 9-n-propoxy acridine, 9-iso-propoxy acridine, 9-
Chloroethoxy acridine and the like. Among them, 9
-Phenylacridine is preferred.

(D) Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, and tetrabromide. Carbon, tris (2,3-dibromopropyl) phosphate, trischloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethanehexachloroethane and the like. However, among them, tribromomethylphenylsulfone is particularly preferably used.

(E) Examples of the lophin dimer include triphenyl biimidals, particularly 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer,
(O-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2-
(O-methoxyphenyl) 4,5-diphenylimidazole dimer, 2,4- (p-methoxyphenyl) -5-
Phenylimidazole dimer, 2- (o-ethoxyphenyl) -4,5-diphenylimidazole dimer, 2,
4-di (p-ethoxyphenyl) -5-phenylimidazole dimer and the like, and preferably 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is used.

(F) Examples of the leuco dye include leuco crystal violet [tris (4-dimethylaminophenyl) methane], leucomalachite green, leucoaniline, leucomethyl violet, leuco diamond green, and benzoyl leucomethylene blue. Among them, leuco crystal violet, leuco diamond green and benzoyl leucomethylene blue are preferably used.

The content of the above (c) to (f) in the present invention is as follows: (c) acridine derivative with respect to 100 parts by weight of the total of (a) a carboxyl group-containing polymer and (b) an ethylenically unsaturated monomer. 0.01 to 1.0 part by weight, preferably 0.02 to 0.7 part by weight, more preferably 0.05 to 0.5 part by weight, (d) halogen compound 0.1.
01 to 3.0 parts by weight, preferably 0.05 to 2.0 parts by weight, more preferably 0.1 to 1.5 parts by weight, (e) 0.01 to 6.0 parts by weight of a fin dimer, Preferably 0.1
To 6.0 parts by weight, more preferably 0.5 to 4.0 parts by weight, (f) 0.01 to 3.0 parts by weight of leuco dye, preferably 0.05 to 2.0 parts by weight, more preferably 0.1 ~
It must be 1.5 parts by weight.

When each component is out of the above range, the effect of the present invention is not remarkably exhibited. That is, when the (c) acridine derivative is less than 0.01 part by weight, sensitivity is low and workability is poor.
If it exceeds 0 parts by weight, on the contrary, the sensitivity becomes too high, the stability is poor and the strength of the tent film is reduced. (D) If the amount of the halogen compound is less than 0.01 parts by weight, sufficient curing cannot be obtained, and the strength of the tent film is reduced and the adhesiveness of the fine wire is insufficient.
When the amount exceeds the weight part, the color tone changes greatly, and there is a problem in stability after lamination. (E) The rofin dimer is 0.0
If it is less than 1, sufficient curing cannot be obtained, resulting in a decrease in adhesion. If it exceeds 6.0 parts by weight, color tone stability becomes insufficient and tent film strength decreases. (F) If the leuco dye is less than 0.01, sufficient contrast at the time of exposure cannot be obtained,
The fine wire adhesion decreases, and if it exceeds 3.0 parts by weight, the color tone stability when left after lamination is also impaired.

In the present invention, additives other than the above (c) to (f) may be appropriately employed, if necessary. Examples of the additives include an initiator, a thermal polymerization inhibitor, a plasticizer,
(F) Dyes (pigments, discoloring agents) other than leuco dyes, adhesion promoters, antioxidants, solvents, surface tension modifiers, stabilizers, chain transfer agents, defoamers, flame retardants, and the like.

Examples of the initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, and 3,3'-dimethyl- 4-methoxybenzophenone, benzophenone, p, p'-bis (dimethylamino) benzophenone, p, p'-bis (diethylamino) benzophenone, pivaloin ethyl ether, 1,1-dichloroacetophenone, pt-butyldichloroacetophenone , 2-chlorothioxanthone,
2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-
Dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibezosparone, 1- (4-isopropylphenyl) -2
-Hydroxy-2-methyl-1-propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, and the like.
Used in combination of more than one species.

The thermal polymerization inhibitor is added to prevent thermal polymerization or polymerization with time of the photosensitive resin composition, and includes p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, Hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-
p-cresol, nitrobenzene, picric acid, p-toluidine and the like.

The plasticizer is added to control the physical properties of the film. Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate and diallyl phthalate; triethylene glycol diacetate, tetraethylene glycol diacetate and the like. Glycol esters; phosphate esters such as tricresyl phosphate and triphenyl phosphate;
Amides such as p-toluenesulfonamide, benzenesulfonamide, Nn-butylacetamide; aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dioctyl azelate, dibutyl malate; citric acid Triethyl, tributyl citrate, glycerin triacetyl ester,
Glycols such as butyl laurate, dioctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate, polyethylene glycol and polypropylene glycol are exemplified.

Examples of the dye include tris (4-diethylamino-2-methylphenyl) methane, brilliant green, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3- Diphenyltriazine, alizarin red S, thymolphthalein, methyl violet 2B, quinaldine red, rose bengal, methanil yellow, thymol sulfophthalein, xylenol blue, methyl orange,
Orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl red, congo red, benzopurpurine 4B, α-naphthyl red, nile blue A, phenacetaline, methyl violet, malachite green, parafuchsin, oil blue # 60
3 [manufactured by Orient Chemical Industry Co., Ltd.], Victoria Pure Blue BOH, Spiron Blue GN [manufactured by Hodogaya Chemical Industry Co., Ltd.], rhodamine 6G and the like.
It is preferable to contain 0.5% by weight, preferably 0.01 to 0.2% by weight.

The color-changing agent is added to the photosensitive resin composition so that a visible image can be given by exposure, and specific examples thereof include diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, Diphenyl-p-phenylenediamine, p-toluidine,
4,4'-biphenyldiamine, o-chloroaniline,
And the like.

Examples of the adhesion promoter include benzimidazole, benzthiazole, benzoxozole, benztriazole, 2-mercaptobenzthiazole,
-Mercaptobenzimidazole and the like.

As described above, the photosensitive resin composition layer composed of at least the compositions (a) to (f) is formed on a support film, and a protective film is laminated on the composition layer if necessary. , Support film / photosensitive resin composition layer (/
Thus, the dry film resist for tenting of the present invention, which is excellent in sensitivity, adhesion, tent film strength, contrast, and the like, can be obtained.

The support film used in the present invention has heat resistance and solvent resistance when forming the photosensitive resin composition layer. Specific examples of the support film include, for example, a polyester film, a polyimide film, a polystyrene film, an aluminum foil, and the like, but the present invention is not limited to only these examples. The thickness of the support film varies depending on the material of the film, and thus cannot be determined unconditionally. Usually, the thickness is appropriately adjusted depending on the mechanical strength of the film. It is about.

If the thickness of the photosensitive resin composition layer is too small, the coating becomes non-uniform or pinholes are liable to be formed during coating and drying, and if the thickness is too large, Is usually 5 to 300 μm, especially 10 to 1 μm, because the exposure sensitivity decreases and the developing speed decreases.
It is preferably 00 μm.

In the protective film used in the present invention, when the photoresist film is used in the form of a roll, the photosensitive resin composition layer having adhesiveness may be transferred to a support film or the photosensitive resin composition layer may be used. It is used by being laminated on a photosensitive resin composition layer for the purpose of preventing a wall or the like from adhering to the layer. Examples of such a protective film include a polyester film, a polyethylene film, a polypropylene film, a Teflon film, a polyvinyl alcohol film, and the like, but the present invention is not limited to only these examples. The thickness of the protective film is not particularly limited, and may be usually 10 to 50 μm, especially 10 to 30 μm.

A dry film resist using a photosensitive resin composition comprising at least the above-mentioned compositions (a) to (f) is prepared by adding the above-mentioned photosensitive resin composition to a support such as a polyester film, a polypropylene film or a polystyrene film. After coating on the film surface, it is manufactured by coating a protective film such as a polyethylene film or a polyvinyl alcohol-based film on the coated surface as necessary.

Next, the production of a printed wiring board using the dry film resist for tenting of the present invention will be described. To form an image with a dry film resist, compare the adhesive strength between the support film and the photosensitive resin composition layer and the adhesive strength between the protective film and the photosensitive resin composition layer, and determine the film with the lower adhesive strength. After peeling, the side of the photosensitive resin composition layer was attached to both surfaces of a metal surface such as a copper surface of a copper-clad substrate (a substrate having holes of 0.1 to 6 mm in diameter of 1 to 4 holes / cm ² ). Thereafter, exposure is performed by bringing a pattern mask into close contact with the other film. When the photosensitive resin composition does not have adhesiveness, the other film may be peeled off, and then the pattern mask may be brought into direct contact with the photosensitive resin composition layer for exposure. Exposure is usually performed by ultraviolet irradiation, and as a light source at that time, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, or the like is used. After irradiation with ultraviolet rays, heating can be performed as necessary to complete the curing.

After exposure, the film on the resist is peeled off and developed. Since the photosensitive resin composition of the present invention is a dilute alkali developing type, development after exposure is performed using a dilute aqueous solution of about 0.3 to 2% by weight of an alkali such as sodium carbonate or potassium carbonate. In the alkaline aqueous solution,
A surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.

After the development, etching is usually performed by an ordinary method using an acidic etching solution such as an aqueous cupric chloride-hydrochloric acid solution or an aqueous ferric chloride-hydrochloric acid solution. Rarely, an ammonia-based alkali etching solution is also used. After the etching process,
The remaining hardened resist is removed. Stripping and removal of the cured resist is performed using an alkali stripping solution composed of an aqueous alkali solution having a concentration of about 0.5 to 5% by weight such as sodium hydroxide or potassium hydroxide.

The dry film resist for tenting using the photosensitive resin composition of the present invention can be used for producing printed wiring boards,
Very useful as an etching resist used for precision metal processing, lead frame manufacturing, etc., (a) carboxyl group-containing polymer, (b) ethylenically unsaturated compound, (c) acridine derivative, (d) halogen compound , (E) a rofin dimer, and (f) a leuco dye in specific amounts, thereby exhibiting excellent effects in sensitivity, adhesion, tent film strength, and contrast.

[0037]

The present invention will be described in more detail with reference to the following examples. Unless otherwise specified, “%” and “parts” are based on weight. Examples 1 to 3 and Comparative Examples 1 to 8 (a) a carboxyl group-containing polymer, and (b) the following ethylenically unsaturated monomers, (c)
As for (d), (e), (f) and other additives, dopes of the photosensitive resin compositions having the compositions shown in Table 1 were prepared. (A) 40% methyl ethyl ketone / isobutylene copolymer having a composition of methyl methacrylate / butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid (weight ratio: 54/10/15/21) and a weight average molecular weight of 80,000 Propyl alcohol (weight ratio: 90/10) 150 parts Solution (solids 60 parts) (b) Trimethylolpropane triacrylate 28 parts 2-acryloyloxyethyl-2-hydrido 12 parts Roxyethyl phthalic acid

[0038]

(Table 1) (c) (d) (e) (f) Other 9PA TBMPS HABI LCV MG (parts) (parts) (parts) (parts) (parts) Example 1 0.1 1.5 2.0 0.3 0.05 〃 2 0.2 1.0 1.0 0.6 0.05 ３ 3 0.3 0.8 1.0 0.6 0.05 Comparative Example 1 0 1.5 3.0 0.6 0.05 〃 2 1.2 0.8 2.0 0.3 0.05 〃 3 0.3 0 3.0 0.6 0.05 〃 4 0.3 3.5 2.0 0.6 0.05 ５ 5 0.3 1.5 0 0.6 0.05 〃 6 0.3 1.5 7.0 0.6 0.05 〃 7 0.3 1.5 3.0 0 0.05 ８ 8 0.3 1.5 3.0 4.0 0.05

Note) 9PA: 9-phenylacridine TBMPS: tribromomethylphenylsulfone HABI: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer LCV: leuco crystal violet MG: malachite green (Parts) is an amount based on 100 parts of the total amount of (a) and (b).

Next, each of the dopes was coated on a polyester film having a thickness of 20 μm using an applicator having a gap of 10 mils and left at room temperature for 1 minute and 30 seconds.
The resultant was dried in an oven at 60 ° C., 90 ° C., and 110 ° C. for 3 minutes each to have a resist thickness of 50 μm, and a polyethylene film was further laminated to obtain a dry film resist. After peeling off the polyethylene film from the dry film resist, the photosensitive resin composition surface was laminated on both sides of the copper-clad substrate preheated to 60 ° C. in an oven at a laminating roll temperature of 100 ° C., a roll pressure of 3 kg / cm ² , and a laminating speed. Lamination was performed at 1.5 m / sec. The copper-clad substrate used here was 1.6 mm thick, and had a width of 2 μm in which 35 μm copper foil was attached to both surfaces of a glass fiber epoxy base material.
00mm, 250mm long substrate, 4.5m diameter
100 holes were drilled.

Thereafter, the following items were evaluated as follows. (Sensitivity) After laminating the above-mentioned dry film resist on a copper-clad substrate, a negative film (Stoffer 21-step tablet) made so that the amount of light transmission decreases stepwise was manufactured by Oak Manufacturing Co., Ltd. Exposure machine HMW
Exposure was performed at -532D with a 5 kW ultra-high pressure mercury lamp every 20 mj. After 15 minutes from the exposure, the polyester film was peeled off, and a 1% aqueous solution of sodium carbonate at 30 ° C. was used as a break point (time for completely dissolving unexposed portions) at 2 °.
The unexposed portion was dissolved and removed by spraying for twice the developing time to obtain a cured resin image. Based on each development amount and the number of steps remaining after the development, an exposure amount (mj / cm ² ) sufficient to give 8 steps with a Stoffer 21 step tablet was examined.

(Tent film strength) After laminating the dry film resist on a copper-clad substrate, exposure and development are performed in the same manner as described above, and then the substrate is immersed in water adjusted to 20 ° C. and left for 5 minutes. And then the diameter 4.5 on the substrate
The rheometer (made by FUDOH) was used to measure the strength of the film formed on the hole of mm by using a cylinder having an insertion diameter of 2.0 mm.
Was measured to determine the strength (g) up to breaking.

(Fine Wire Adhesion) After laminating the dry film resist on a copper-clad substrate, the line width was 10
Using a pattern mask of 5, 20, 25, 30, 35, 40, 45, 50 μm (space width: 400 μm),
Similarly, the minimum line width (μ
m) was examined.

(Contrast) After laminating the above-mentioned dry film resist on a copper-clad substrate, exposing it with an exposure amount until the number of steps of the step tablet becomes eight, and then, after one minute, a color difference between an unexposed part and an exposed part ( ΔE) was measured with a color difference meter (Z-Σ80, manufactured by JASCO Corporation). The larger the ΔE, the higher the contrast.

(Stability after lamination) After laminating the above dry film resist on a copper-clad substrate, and leaving it under an ultraviolet cut lamp (2000 lux) for 3 days, a change in color tone was measured by a color difference meter (Nihon Bunko Co., Ltd.) Company; Z- $ 8
0) and evaluated according to the following criteria. ○: Difference before and after leaving less than 5 ×: Difference between before and after leaving is 5 or more

After the exposure and development, etching was performed with a cupric chloride etchant for 90 seconds, and then spraying with a 3% aqueous sodium hydroxide solution at 50 ° C. for 120 seconds to remove the cured resin film used as the resist. You.

Table 2 shows the evaluation results of the examples and the comparative examples.

[Table 2] Sensitivity Tent film strength Fine wire adhesion Contrast After lamination (mj / cm ² ) (g) (μm) Stability of ΔE Example 1 48> 500 3020 ○ 〃 240> 500 3022 ○ 〃3 34> 500 3022 ○ Comparative Example 1 160 340 3021 ○ 〃2 <5 280 4510 〃 340 420 40 24 〃 ４ 428 300 3022 × ５540> 500 406 〃 640> 500 30 24 × ７ 740> 500 40 <1 ○ 〃840> 500 30 23 ×

[0048]

The dry film resist of the present invention is excellent as a dry film resist for tenting because it has excellent sensitivity, tent film strength, fine line adhesion, contrast, and stability after lamination. It can be used for manufacturing printed wiring boards, manufacturing lead frames, precision metal processing, and the like.

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[Procedure amendment]

[Submission date] September 8, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

The (c) acridine derivative is not particularly limited, but is preferably a compound represented by the above formula (I). Specific examples include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p
-Ethylphenyl) acridine, 9- (pn-propylphenyl) acridine, 9- (p-iso-propylphenyl) acridine, 9- (pn-butylphenyl) acridine, 9- (p-tert-butyl) Phenyl) acridine, 9- (p - methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9-
(P-acetylphenyl) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9 −
(M-methylphenyl) acridine, 9- (mn-propylphenyl) acridine, 9- (m-iso-propylphenyl) acridine, 9- (mn-butylphenyl) acridine, 9- (m-tert) -Butylphenyl) acridine, 9- (m - methoxyphenyl) acridine, 9- (m-ethoxyphenyl) acridine, 9-
(M-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine, 9- (m-diethylaminophenyl) acridine, 9- (m-cyanophenyl) acridine, 9- (m-chlorophenyl) acridine, 9 -(M-bromophenyl) acridine, 9-methylacridine, 9-ethylacridine, 9-n-propylacridine, 9-iso-propylacridine, 9-
Cyanoethyl acridine, 9-hydroxyethyl acridine, 9-chloroethyl acridine, 9-methoxy acridine, 9-ethoxy acridine, 9-n-propoxy acridine, 9-iso-propoxy acridine, 9-
Chloroethoxy acridine and the like. Among them, 9
-Phenylacridine is preferred.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

Thereafter, the following items were evaluated as follows. (Sensitivity) After laminating the above-mentioned dry film resist on a copper-clad substrate, a negative film (Stoffer 21-step tablet) made so that the amount of light transmission decreases stepwise was manufactured by Oak Manufacturing Co., Ltd. Exposure machine HMW
Exposure was performed at -532D with a 5 kW ultra-high pressure mercury lamp every 20 mj. After 15 minutes from the exposure, the polyester film was peeled off, and a 1% aqueous solution of sodium carbonate at 30 ° C. was used as a break point (time for completely dissolving unexposed portions) at 2 °.
The unexposed portion was dissolved and removed by spraying for twice the developing time to obtain a cured resin image. Based on the number of steps remaining after the development, the exposure amount (mj / cm ² ) sufficient to give 8 steps with a 21-step stofer tablet was examined.

Claims (3)

[Claims] 1. A dry film resist for tenting, wherein a photosensitive resin composition layer comprising the following (a) to (f) is formed on a support film. (A) Carboxyl group-containing polymer (b) Ethylenically unsaturated compound (c) Acridine derivative 0.01 to 1.0 part by weight based on 100 parts by weight of the total of (a) and (b) (d) Halogen compound 0.01 to 3.0 parts by weight (e) Rofin dimer 0.01 to 6.0 parts by weight (f) Leuco dye 0.01 to 3.0 parts by weight 2. The dry film resist for tenting according to claim 1, wherein (c) the acridine derivative is a compound represented by the following formula (1). Embedded image (In the formula, R is any of hydrogen, a phenyl group, an alkyl group, and an alkoxy group.) 3. The tenting dry film resist according to claim 1, wherein (d) the halogen compound is tribromomethylphenylsulfone.