JP2635353B2 - Image forming method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an image forming method in the fields of a printed circuit board using a photoresist film, precision metal processing, and the like.

[Prior art] Conventionally, in order to form a printed circuit board, especially a fine wiring circuit usually called an industrial board, a photoresist film is laminated on a copper-clad laminate having a copper foil adhered to the surface. However, a method of performing exposure and development and plating or etching through a pattern mask has been implemented. The photoresist film has a three-layer structure of a light-transmitting support film, a photosensitive resin layer, and a protective film. To form an image using the film, first, peel off the protective film,
The photosensitive resin layer is pressed onto the copper-clad laminate, the pattern mask is adhered to the light-transmitting support film, irradiated with active light (usually ultraviolet light) (exposure), and then sprayed with an alkaline aqueous solution or an organic solvent. Alternatively, a resist pattern is formed by immersion (development), and the exposed copper foil is plated with metal, and then the cured resist is peeled off with an aqueous alkali solution or an organic solvent (resist peeling). A method of removing (etching) a copper foil portion exposed with a solution of copper, hydrogen peroxide / sulfuric acid, alkaline ammonia or the like, or a method of etching and peeling a resist after development with a reverse pattern has been adopted.

[Problems to be Solved by the Present Invention] However, in recent years, as electronic devices have become lighter and thinner and smaller, and high-density (high-resolution) circuits have become strictly required, conventional photoresist films have become increasingly demanded. Can't be satisfied. In other words, in order to achieve high resolution, the thickness is preferably as small as possible in order to expose through a light-transmitting support film, but on the other hand, in order to serve as a support when a photosensitive resin layer is applied. Some self-holding properties are required, and a thickness of 15 to 25 μm is generally required. In addition, if the light-transmitting support film can be peeled off and the pattern mask can be exposed directly to the photosensitive resin layer for exposure, the resolution will be greatly improved, but the ordinary photosensitive resin layer will have considerable adhesion. When the pattern mask is brought into close contact with the pattern mask, it is difficult to be peeled off due to its adhesiveness, and there is a problem that the pattern mask is contaminated.

There has been proposed a method of solving these disadvantages and obtaining a high resolution. One is a method in which a photosensitive resin having no tackiness is used alone (JP-A-61-201237). However, when a photosensitive resin having no tackiness is used alone, due to its properties, a) poor adhesion to a copper-clad laminate, etc., b) low exposure sensitivity, c) low development speed, D) Insufficient tenting performance such as lack of flexibility after exposure and e) Lack of toughness of the tent film causes disadvantageous results in the manufacture of printed circuit boards and precision metal processing. Another method is to provide a transparent resin layer having no stickiness to a pattern mask between the support film and the photosensitive resin layer (Japanese Patent Laid-Open No. 59-97138). Before the developed photosensitive resin layer is developed, the transparent resin layer must be mechanically or chemically removed. This is not rational in the manufacturing process, and when chemically removed with a developer or the like, the management of the solution is troublesome and not preferable. Further, the resolution may be deteriorated due to the interposition of the transparent resin layer, which is not preferable.

[Means for Solving the Problems] The present inventors have conducted intensive studies to solve such problems, and found that the polyester film (a), the photosensitive resin layer (b) having tackiness, and the non-stickiness (A) of a photoresist film formed by sequentially laminating a photosensitive resin layer (c) and a vinyl alcohol-based resin film (d) is peeled off, and polymerized and adhered so that (b) comes into contact with the substrate;
After exfoliating (d), it is exposed through a pattern mask,
Next, in the case of development, or by peeling (e) of the photoresist film [I] obtained by sequentially laminating the polyester film (a), the photosensitive resin layer (b) having adhesiveness, and the polyethylene film (e). And (b) are polymerized and brought into contact with the substrate, and then (a) is peeled off, and then a polyester film (a '), a photosensitive resin layer (c) having no tackiness, and a vinyl alcohol-based resin film (D) are sequentially laminated on a photoresist film [I
When (a ') of (I) is peeled off and polymerized and adhered so that (b) and (c) come into contact with each other, and after (d) is peeled off and exposed through a pattern mask and then developed, extremely high resolution is obtained. The present inventors have found that an image having excellent image quality can be formed and completed the present invention.

The feature of the photoresist film of the present invention is that the conventional photoresist film has a three-layer structure of a support film / a photosensitive resin layer having ordinary tackiness / a protective film, whereas the conventional photoresist film has a three-layer structure. A non-adhesive photosensitive resin layer is provided between the adhesive resin and the photosensitive resin layer. In manufacturing a photoresist film, the support film and the material of each photosensitive resin are made of conventional photo resist. The resist film can be selected from those used for the resist film, and a conventional method can be used for the film forming step as it is.

According to the method of the present invention, it is possible to place a pattern mask directly on a photosensitive resin layer having no tackiness and to perform exposure, so that there is no problem that the pattern mask is hardly peeled off or contaminated. As a result, the resolution can be improved without deteriorating the resist performance required for the conventional photoresist film, and a high-density printed circuit board or metal processing board can be obtained.

As the photoresist film used in the method of the present invention, one having a four-layer structure of (a) / (b) / (c) / (d) is used, and (a) / (b) / (e);
In some cases, two kinds of films having a three-layer structure of (a ') / (c) / (d) are used. (A) or (a ')
Is a polyester film which functions as a support film and has heat resistance and solvent resistance necessary for coating and drying a photosensitive resin solution to obtain a uniform photosensitive layer. The practical thickness of the film is about 15 to 25 μm.

The adhesive photosensitive resin layer (b) of the present invention contains a known polymer compound and a photopolymerizable vinyl monomer as essential components.

Examples of the polymer compound include a vinyl copolymer, a polyester resin, an epoxy resin, and the like, and these are used alone or in combination of two or more. Components used in the vinyl copolymer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl ( Examples thereof include (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, styrene, (meth) acrylamide, (meth) acrylonitrile, and vinyl acetate. Polyester resins include di- or higher-valent carboxylic acids such as (phthalic anhydride), isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, (maleic anhydride), fumaric acid, adipic acid, trimellitic anhydride, and pyromellitic anhydride. Ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, dipropylene glycol,
It is obtained by an esterification reaction with a divalent or higher valent alcohol such as triethylene glycol, neopentyl glycol, hydrogenated bisphenol A, glycerin, and trimethylolpropane. Examples of the epoxy resin include bisphenol epoxy resin, novolak epoxy resin, and the like, and those obtained by adding a monovalent carboxylic acid such as acetic acid, oxalic acid, (meth) acrylic acid, and the like.

Photopolymerizable vinyl monomers include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate.
Acrylate, 1,6-hexanediol di (meth) acrylate, 2,2-bis [4- (meth) acryloxydiethoxyphenyl] propane, 2,2-bis [4- (meth)
[Acryloxypolyethoxyphenyl] propane, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth)
Acryloxyethyl phosphate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, glycerin triglycidyl ether tri (meth) acrylate, etc. These are used alone or in combination of two or more. The polymer compound and the vinyl monomer are mixed at a ratio of 70/30 to 30/70 (weight ratio).
If the ratio is 70/30 or more, the film has poor flexibility and poor adhesion, and the developing speed is low. If the ratio is 30/70 or less, the film is too soft or has high fluidity, resulting in a cold flow, which is not practical. In the photosensitive resin layer (b) having tackiness, a usual sensitizer, dye, coloring pigment, adhesion improver, polymerization inhibitor, coating surface improver,
A plasticizer or the like can be contained.

The thickness of the photosensitive resin layer (b) having adhesiveness is 5 to 100.
μm, preferably 10 to 50 μm. 5μ thickness
m or less, practical chemical resistance, adhesion, and developability are difficult to obtain, and when the thickness is 100 μm or more, defects such as low exposure sensitivity, low development speed, and poor resolution appear. Not preferred.

The non-sticky photosensitive resin layer (c) of the present invention comprises, as an essential component, a known polymer compound and a photopolymerizable vinyl monomer used in the above-mentioned sticky photosensitive resin layer (b). Containing, furthermore ordinary sensitizers, dyes, coloring pigments,
An adhesion improver, a polymerization inhibitor, a coating surface improver, a plasticizer and the like can be contained. In order to produce (c), the mixing ratio of the polymer compound and the vinyl monomer is from 95/5 on a weight basis.
70/30. When the ratio is 95/5 or more, the exposure sensitivity, the developing speed, and the crosslinkability are reduced. The difference between the photosensitive resin layers (b) and (c) is that in the adhesive strength to a normal polyester film (adhesive tape, 180 ° peel strength in accordance with the adhesive sheet test method JISZ 0287-1980), the (c) layer 5g / inch or less in the case, 5g / inch in the (b) layer
It is preferably the above, and can be obtained by limiting the components and the mixing ratio of the polymer compound and the polymerizable vinyl monomer as described above.

The thickness of the photosensitive resin layer (c) having no tackiness is 1 to 10
μm, and preferably 3 to 8 μm. 1μ thick
m or less, coating on the support film, when drying, the film thickness unevenness and the occurrence of pinball, etc. are likely to occur,
Further, the photopolymerizable vinyl monomer contained in the adhesive photosensitive resin layer (b) laminated thereon penetrates into the non-adhesive photosensitive resin layer (c) with time. do it,
There is a risk of giving the surface stickiness. The thickness is 10μ
Above m, defects such as a decrease in development speed and a decrease in flexibility become remarkable.

The vinyl alcohol resin film (d) used in the present invention is not only a polyvinyl alcohol obtained by homopolymerizing vinyl acetate but also saponified, and a copolymer of an ethylenically unsaturated monomer copolymerizable with vinyl acetate. It may be saponified. The thickness of the film is suitably from 10 to 30 μm.

To give specific examples of the polyvinyl alcohol-based resin, the average degree of polymerization of 500 to 3000, preferably 1000 to 2500, saponification degree 9
A film of polyvinyl alcohol of 4 mol% or more, preferably 96 mol% or more, preferably a heat-treated film is used. The heat treatment condition is a temperature of 80 to 240 ° C, preferably 90 to 200 ° C.
The temperature is selected from the range of 0.5 seconds to 60 minutes, preferably 1 second to 10 minutes at ° C. Further, a film obtained by uniaxially or biaxially stretching such a film can also be used. Further, other vinyl alcohol resins can also be used, and 1 to 70 mol% of vinyl acetate and ethylene, propylene to various α-olefins having about 20 carbon atoms are copolymerized and saponified, formaldehyde, acetaldehyde, Acetalized product reacted with aldehydes such as butyraldehyde, copolymerizable unsaturated acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid or copolymer thereof, and saponified product of ester thereof and vinyl acetate Any of saponified copolymers of vinyl ethers and vinyl acetate can be used, and these include those heat-treated and stretched. Since these vinyl alcohol resins vary in a complicated manner depending on the combination of the type of knitting, the degree of modification, the degree of saponification, etc., conditions are selected so as to meet the purpose of the present invention according to each case. These vinyl alcohol-based resins may be used not only in a single variety but also in a plurality of types. Further, a small amount of starch, cellulose derivative, casein, etc. may be used in combination.

Further, a plasticizer, a surfactant, a lubricant and the like can be blended.

The photoresist film used in the present invention is prepared as follows.

Four-layer structure (a) / (b) / (c) / (d) (a) A polyester resin (a) is provided with an adhesive photosensitive resin layer (b), and further an adhesive is provided thereon. A method of laminating a photosensitive resin layer (c) having no vinyl resin film and further laminating a vinyl alcohol film (d).

(B) a two-layer film in which a photosensitive resin (b) having tackiness is provided on a polyester film (a), and a photosensitive resin layer (c) having no tackiness on a vinyl alcohol-based resin film (d). A method of laminating the provided two-layer film so that the layer (b) and the layer (c) adhere to each other.

(C) A two-layer film is prepared by providing a photosensitive resin layer (b) having tackiness on a polyester film (a), while a photosensitive resin layer (c) having no tackiness on the polyester film (a ') And a method in which (a ') of a three-layer film in which a vinyl alcohol-based resin film (d) is sequentially laminated is peeled off, and lamination is performed so that (b) and (c) come into contact with each other.

(D) The three-layer film (e) obtained by sequentially laminating the polyester film (a), the photosensitive resin layer (b) having tackiness, and the polyester film (e) is peeled off, and one of the above-mentioned (c) is used. (a ') / (c) / (d) A method of peeling off (a') of a three-layer film and laminating so that (b) and (c) are in contact with each other.

Three-layer structure (a) / (b) / (e), (a ') / (c)
In the case of / (d), in this case, the production mode is not so large. Usually, the polyester film (a) or (a ′) is used as a support film, and the (b) or (c) layer is provided. The layer (e) or (d) may be laminated.

Next, the method for forming an image of the present invention will be described in detail.

(A) When a four-layer film is used a) First, the polyester film (a) is peeled off, and the photosensitive resin layer (b) having adhesiveness is laminated so as to be in contact with the base material. Crimp. As the base material, there are a copper plate, an iron plate, an aluminum plate, a stainless steel plate and the like, and well-known materials such as a laminate of a copper foil and an aluminum foil on the surface of an inorganic or organic substrate having electrical insulation properties can be used.

B) The vinyl alcohol resin film (d) is peeled off by a known method such as mechanical treatment, water treatment, and solvent treatment.

C) Further, a pattern mask is brought into close contact with the photosensitive resin layer (c) having no tackiness by vacuum, and exposed to active light such as ultraviolet rays through the pattern mask.

D) Next, a developing solution is sprayed or immersed in the photoresist film on the exposed substrate, so that the photosensitive resin layer (c) having no tackiness and the photosensitive resin layer (b) having tackiness are provided.
Are simultaneously developed to form an image. Examples of the developer used include an aqueous alkali solution such as sodium carbonate and caustic soda, and 1,1,1-trichloroethane. Further, organic solvents such as triethanolamine and butyl cellosolve can be added.

E) When using the developed photoresist film for plating, first perform the necessary pretreatment, and then perform the desired plating process such as copper sulfate plating, copper pyrophosphate plating, solder plating, tin plating, and nickel plating. Do.
Next, the photoresist is removed with an aqueous alkaline solution such as caustic soda or caustic potassium or methylene chloride, and the exposed metal plate or metal foil portion is further exposed to a solution of ferrous chloride, cupric chloride, hydrogen peroxide / sulfuric acid, alkaline ammonia or the like. And remove by etching.

F) When the developed photoresist is used for tenting or etching, the exposed metal plate or metal foil portion is removed with the same etching solution as described above, and then an aqueous alkali solution such as caustic soda or caustic potassium or chloride is used. The resist is removed with methylene or the like.

(B) When a three-layer film is used a) A resist film consisting of a polyester film (a) / (b) / polyethylene film (e) is peeled off, and the base film is brought into contact with (b). And heat pressed with a hot roll.

B) Peel off (a).

C) The resist film composed of the polyester film (a ') / (c) / (d) is stripped of (a') and polymerized so that (b) and (c) come into contact.

The following are (b), (c), and (c) for a four-layer film.
Steps (d), (e) and (f) are sequentially performed.

EXAMPLES Hereinafter, the method of the present invention will be described in more detail by way of examples. “Parts” indicates parts by weight.

Example 1 (Preparation of photosensitive resin having no tackiness) Acrylic resin (methyl methacrylate / methacrylic acid =
98/2 weight ratio, molecular weight about 100,000) 75 parts, trimethylolpropane trimethacrylate 10 parts, 1,6-hexanediol acrylate 8 parts, 2-ethylanthraquinone 1.8 parts,
0.2 part of malachite green was uniformly mixed with methyl ethyl ketone / isopropyl alcohol (95/5) so that the solid content became 50%.

(Preparation of Photosensitive Resin Having Adhesion) Acrylic resin (methyl methacrylate / n-butyl acrylate / methacrylic acid = 75/22/3 weight ratio, molecular weight of about 9)
10,000) 60 parts, trimethylolpropane triacrylate 18
Parts, tetraethylene glycol diacrylate 15 parts, 2
-3.3 parts of ethyl anthraquinone, 0.2 of malachite green
The mixture was uniformly mixed with methyl ethyl ketone / toluene / methyl cellosolve (85/10/5) so that the solid content was 40%.

(Preparation of Photoresist Film) A photosensitive resin layer (b) having an adhesive property is coated on a polyester film (a) having a film thickness of 23 μm, and dried at 60 ° C. for 3 minutes and then at 105 ° C. for 3 minutes to obtain a film thickness of 40 μm. (B) was obtained. Next, a photosensitive resin layer (c) having no tackiness was applied thereon and dried at 90 ° C. for 3 minutes to obtain a coating film (c) having a thickness of 5 μm. Further from this on average polymerization degree 1700,
A polyvinyl alcohol resin film (average saponification degree: 98 mol%) (film thickness: 24 μm, heat treatment at 150 ° C., 10 minutes) was laminated and thermocompression-bonded with a roll to produce a four-layer photoresist film.

(Manufacture of Printed Circuit Board) On a 50 μm thick copper-clad laminate heated to 60 to 70 ° C., while peeling (a) of the photoresist film obtained above, a photosensitive resin layer having an adhesive property ( Roll pressing was performed at 100 to 110 ° C so that b) was in contact with the copper part. Next, the polyvinyl alcohol-based resin film was peeled off, and Stouffer 21
Step tablet and resolution test pattern length
100mm, line width / line interval = 20/20 (μm), 30/30 (μ
m), 40/40 (μm), 50/50 (μm), 60/60 (μm)
m), 70/70 (μm), 80/80 (μm), 90/90 (μm)
m) and 100/100 (μm) were provided in close contact with a negative film (5), and exposed under vacuum using a 3 kw ultrahigh pressure mercury lamp. The exposed substrate was spray-developed with 1,1,1-trichloroethane at 20 ° C. to form an image. The exposure amount and the development time were adjusted so that the step sensitivity became 9 steps. Then, etching is performed with a cupric chloride solution, the photosensitive resin layer is peeled off with methylene chloride, and the resolution is 40 μm.
Was obtained. The obtained results are shown in (Table-
All are described in 1).

Example 2 (Preparation of photosensitive resin having no tackiness) Polyester resin (maleic anhydride / sorbic acid / terephthalic acid / propylene glycol = 30/11/13/46 weight ratio, molecular weight about 1200, acid value 145) 50 Part, trimethylolpropane trimethacrylate 7.5 parts, neopentyl glycol diacrylate 4 parts, benzophenone 2 parts, ethyl Michler ketone 0.15 parts, malachite green 0.05 parts methyl ethyl ketone / isopropyl alcohol (90/10) 4
One part was mixed uniformly.

(Preparation of Photosensitive Resin Having Adhesion) Acrylic resin (methacrylic acid / acrylic acid / methyl methacrylate / 2-ethylhexyl acrylate = 20/2/65 /
13 weight ratio, molecular weight about 100,000, acid value 145) 30 parts, trimethylolpropane triacrylate 10 parts, propylene glycol dimethacrylate 10 parts, 1,6-hexanediol diacrylate 4.5 parts, benzophenone 2.8 parts, ethylmichler 0.2 parts of ketone and 0.1 parts of malachite green were mixed with methyl ethyl ketone / toluene / methyl cellosolve (70/15/1
5) Mix uniformly into 42 parts.

(Preparation of Photoresist Film) A photosensitive resin having tackiness was applied on a polyester film having a thickness of 25 μm, and dried at 60 ° C. for 3 minutes and then at 105 ° C. for 3 minutes to obtain a coating film having a thickness of 40 μm. 23μ thickness
m is coated with a non-tacky photosensitive resin and dried at 90 ° C. for 3 minutes to obtain a 5 μm-thick coating film, on which a saponified ethylene-vinyl acetate copolymer film (ethylene content (40 mol%, saponification degree: 99 mol%, thickness: 13 μm) were thermocompressed to obtain a three-layer laminate. Then, the polyester film of the laminate is peeled off, and the two laminated films are superimposed on each other so that the photosensitive resin layers are in contact with each other using the previously prepared film, and pressed with a hot roll at 60 ° C. to obtain a photoresist film. Was.

(Manufacture of Printed Circuit Board) The polyester film of the obtained photoresist film was peeled off, laminated on a copper-clad laminate in the same manner as in Example 1, and exposed similarly. Exposed substrate at 30 ° C 1.
An image was formed by spray development with a 3% aqueous sodium carbonate solution. The exposure amount and the development time were adjusted so that the step sensitivity became 9 steps. Then, etching was performed with a cupric chloride solution, and the photosensitive resin layer was further stripped with a 5% aqueous sodium hydroxide solution to obtain a printed circuit board having a resolution of 40 μm.
The obtained results are all described in (Table 1).

Example 3 (Preparation of Photosensitive Resin Having No Adhesion) Epoxy Ester Resin ｛EOCN-104S (Nippon Kayaku Co., Ltd., Cresol Novolak Epoxy Resin) / phthalic acid / benzoic acid = 55/38/7 weight ratio, Molecular weight about 3500, acid value 130｝
50 parts, trimethylolpropane trimethacrylate 7.5
Parts, 4 parts of neopentyl glycol diacrylate, 2 parts of benzophenone, 0.15 part of Michler's ketone, and 0.1 part of malachite green were uniformly mixed with 46 parts of methyl ethyl ketone / isopropyl alcohol (90/10).

(Preparation of Photosensitive Resin Having Adhesiveness) The same photosensitive resin as in Example 2 was prepared.

(Preparation of Photoresist Film) In the same manner as in Example 2, a photosensitive resin layer having a thickness of 5 μm and having no stickiness without pinholes and a photosensitive resin layer having an adhesiveness of 40 μm were laminated. A photoresist film was obtained.

(Manufacture of Printed Circuit Board) Example 2 was performed using the obtained photoresist film.
A printed circuit board having a resolution of 40 μm was obtained in the same manner as described above. The obtained results are all described in (Table 1).

Example 4 (Preparation of Photoresist Film) The photosensitive resin solution having tackiness used in Example 1 was applied to a 25 μm-thick polyester film, dried at 60 ° C. for 3 minutes and then at 105 ° C. for 3 minutes. A photosensitive layer having a thickness of 30 μm was formed. A 30 μm-thick polyethylene film was thermocompression-bonded thereon to obtain a resist film [I] having an acid layer structure.

Similarly, the non-tacky photosensitive resin solution used in Example 1 was applied to a polyester film having a thickness of 23 μm and dried at 90 ° C. for 3 minutes to form a photosensitive layer having a thickness of 3 μm. A 25 μm thick vinyl alcohol resin film (average degree of polymerization 1800, average degree of saponification 99 mol%,
This was heat-treated at 0 ° C. for 10 minutes) to obtain a three-layer resist film [II].

(Manufacture of Printed Circuit Board) 100 to 110 ° C. so that the photosensitive layer is in contact with the copper part on a copper-clad laminate having a copper thickness of 50 μm heated to 60 to 70 ° C. while peeling off the polyethylene film of the resist film [I]. And roll-pressed. Then, after the polyester film is peeled off, the resist film [II] is peeled off on the polyester film at 90 ° C. so that the photosensitive layers come into contact with each other while the polyester film is peeled off.
Was crimped.

Thereafter, the vinyl alcohol-based resin film was peeled off in the same manner as in Example 1, a pattern mask was brought into direct contact with the non-adhesive photosensitive resin layer (c), and the film was brought into vacuum contact with the photosensitive resin layer (c), and exposure was performed to form an image. .

 The results are all described in (Table 1).

Comparative Example 1 (Preparation of Photoresist Film) On a polyester film having a thickness of 25 μm, the photosensitive resin having the adhesive property described in Example 1 was applied, dried at 60 ° C. for 3 minutes and then at 100 ° C. for 5 minutes, and dried. A sticky coating film of 45 μm was obtained.

(Manufacture of a printed circuit board) The photoresist film is pressure-bonded on a 50-mm thick copper-clad laminate heated to 60-70 ° C with a hot roll at 100-110 ° C so that the photosensitive resin layer contacts the copper portion. did. Next, the step tablet and the resolution test pattern were brought into close contact with the polyester film, and a printed circuit board was obtained in the same procedure as in Example 1. All the results obtained (Table-
It was described in 1).

Comparative Example 2 The layer configuration in Example 1 was (a) / (c) / (b) /
A resist film was prepared in the same manner as in (d). (D) was peeled off and tried to be laminated on the substrate.
(C) The peeling was observed and the operation was impossible. Further, when (a) was peeled off and laminated with a substrate, the adhesive strength was poor and it was not practical.

Adhesion to copper plate: The entire surface of the photosensitive resin layer, which has been thermocompression bonded at 90-100 ° C, is exposed to a 100 × 100 (mm) square copper-clad laminate at a predetermined exposure level, and a base metal test (based on JIS K5400) ). That is, using a cutter knife to the test piece, with a cut to allow 100 squares in a 100 mm ^2, the number of the top subjected to peeling test with Sellotape from no deficiency in 100 squares Described.

Resolution: After the photosensitive resin layer was peeled off, the copper portion on which a clear image was formed by the resolution test pattern was observed under a microscope, and the line spacing was described.

[Effects] According to the present invention, a printed circuit board having an image with excellent resolution can be manufactured.

Claims (2)

(57) [Claims] 1. A polyester film (a), a photosensitive resin layer (b) having tackiness, a photosensitive resin layer (c) having no tackiness, and a vinyl alcohol resin film (d) are sequentially laminated. (A) of the photoresist film is peeled off, and polymerized and adhered so that (b) comes into contact with the substrate;
After exfoliating (d), it is exposed through a pattern mask,
Then, an image forming method is developed. 2. A polyester film (a), a photosensitive resin layer (b) having tackiness, and a polyethylene film (e).
(E) of the photoresist film [I] obtained by sequentially laminating the polymer film, polymerizing and bonding so that (b) comes into contact with the substrate, and then removing (a), and then removing the polyester film (a ′). ), A photosensitive resin layer (c) having no tackiness, and a vinyl alcohol-based resin film (d) sequentially laminated on the photoresist film [II] (a ').
(B) and (c) are polymerized and brought into contact with each other, and after exfoliating (d), exposure is performed through a pattern mask, and then development is performed.