JP2000227657A - Photosensitive resin laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin laminated body having good adhesion and accordance to a substrate and good developability after laminating by incorporating a vinyl copolymer having a specified weight average molecular weight obtained by copolymerizing specified plural monomers, an aliphatic carboxylic acid having plural carboxy groups in one molecule, etc. SOLUTION: The photosensitive resin laminated body has a photosensitive resin layer containing a vinyl copolymer having a weight average molecular weight of 20,000-300,000 obtained by copolymerizing a 1st monomer selected from α,β-unsaturated carboxylic acids, a 2nd monomer selected from compounds of the formula and a 3rd monomer selected from the group consisting of alkyl (meth)acrylates having a 1-6C alkyl group, etc., an ethylenically unsaturated addition-polymerizable monomer, a photopolymerization initiator and an aliphatic carboxylic acid having two or more carboxy groups in one molecule. In the formula, R1 is H or 1-3C alkyl, X is halogen or 1-3C alkyl and (n) is 0 or an integer of 1-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin laminate, and more particularly to a photosensitive resin laminate which is suitable for manufacturing a printed wiring board and which can be alkali-developed, and a method for manufacturing a printed wiring board using the same.

[0002]

2. Description of the Related Art Conventionally, a so-called dry film resist (hereinafter abbreviated as DFR) comprising a support and a photosensitive resin layer has been used as a resist for manufacturing a printed wiring board. The DFR is generally produced by laminating a photosensitive resin composition on a support, and in many cases, further laminating a protective film on the composition.

In order to manufacture a printed wiring board using a DFR, first, a protective film is peeled off, and then the DFR is laminated on a substrate such as a copper-clad laminate. Next, the support is peeled off if necessary, and exposure is performed through a wiring pattern mask film or the like. If there is a support after exposure, the support is peeled off, and the unexposed portion of the photosensitive resin layer is dissolved or dispersed and removed with a developer to form a cured resist pattern on the substrate.

The process of forming a circuit after development is roughly divided into two methods. The first method is to further remove the resist after etching and removing the copper surface not covered by the cured resist pattern, and the second method is to perform a plating treatment of copper and solder on the copper surface. After that, the resist is removed, and the exposed copper surface is etched.

As a substrate for manufacturing a printed wiring board, paper-phenol resin, paper-epoxy resin, glass-
A rigid substrate in which a copper foil is stretched on a plate of an epoxy resin, a glass-polyester resin, or the like, or a flexible substrate in which a copper foil is stretched on a polymer film such as a polyimide film or a polyester film is used. Among them, a printed wiring board manufactured from a flexible substrate (hereinafter abbreviated as a flexible wiring board) can be used in a narrow space, and therefore is important as a material for reducing the weight and thickness of the device and is produced in large quantities.

[0006] Manufacturing of this flexible wiring board involves three process problems that are not present in rigid wiring boards. One is that since the substrate is a film, the substrate itself is likely to break or wrinkle before and after lamination or when passing through a developing, etching, or peeling device. In such a state where the smoothness of the base material is impaired, the conventional DFR cannot provide sufficient adhesion or follow-up, or the formed cured resist floats from the substrate during manufacturing. As a result, chipping of the wiring pattern and disconnection were likely to occur.

[0007] The second problem is the developability of DFR laminated on a flexible substrate. Since the flexible substrate is in the form of a film, the surface cannot be adjusted by mechanical polishing, and it is desired to laminate the DFR on an irregular surface.
In that case, the conventional DFR was not completely developed by normal development, and a defect such as a short circuit occurred. In particular, when the substrate is stored for a long period of time from lamination to development, the above-described phenomenon becomes conspicuous and causes a problem.

[0008] As a final problem, there is a problem in manufacturing a flexible substrate. In the manufacture of flexible wiring boards, a flexible substrate is often supplied in a roll form, continuously laminated, exposed, developed, wound up again in a roll form before proceeding to the next step, and stored. The stored substrate is a roll-shaped substrate in which the cured resist pattern after development is in contact with the surface of the flexible substrate not covered with copper, that is, the polymer film surface. When the substrate was pulled out from the roll to perform the next step, a part of the cured resist pattern was missing or disappeared from the copper surface because the cured resist pattern was attached to the polymer film that had been overlapped in the conventional DFR. Such a phenomenon of the loss at the time of peeling the cured resist pattern from the roll is called blocking, and a DFR that does not cause blocking has been desired in the art.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to have good adhesion and follow-up properties to a substrate during lamination and after curing, and to provide a long-term storage after lamination. An object of the present invention is to provide a DFR that has good developability and does not cause blocking of a cured resist pattern.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a copolymer containing a styrene derivative as a monomer as a vinyl copolymer and 2
A photosensitive resin using an aliphatic carboxylic acid having two or more carboxyl groups has an adhesive property to a flexible substrate.
The present invention has been found to have good followability, good developability even when stored for a long time after lamination, and no blocking of the cured resist pattern.

That is, the first invention of the present application includes a support (A) and a photosensitive resin layer (B), and the photosensitive resin layer (B)
Is (i) (a) at least one first monomer selected from α, β-unsaturated carboxylic acids, and (b) at least one first compound selected from compounds represented by formula (1) Second
Monomer,

[0012]

Embedded image (Wherein R1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X is a halogen atom or an alkyl group having 1 to 3 carbon atoms, n is an integer of 0 or 1 to 3, and n is 2 or more) And (c) alkyl (meth) acrylate having an alkyl group having 1 to 6 carbon atoms, hydroxy having a hydroxyalkyl group having 2 to 6 carbon atoms. Alkyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide and a compound in which hydrogen bonded to nitrogen is substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and (meth) acrylic A vinyl copolymer having a weight average molecular weight of 20,000 to 300,000 obtained by vinyl copolymerizing at least one third monomer selected from the group consisting of glycidyl acid, A photosensitive resin laminate comprising: (i) an ethylenically unsaturated addition-polymerizable monomer, (iii) a photopolymerization initiator, and (iv) an aliphatic carboxylic acid having two or more carboxyl groups in a molecule. Body.

According to a second aspect of the present invention, a photosensitive resin layer is laminated on a substrate using the photosensitive resin laminate according to claim 1, a resist pattern is formed by an exposure step and a development step, and then an etching step is performed. This is a method for manufacturing a printed wiring board, in which a peeling step is performed to form a wiring pattern. Hereinafter, the present invention will be described in detail.

The photosensitive resin laminate of the present invention comprises a support (A)
And the photosensitive resin layer (B). The support (A) of the present invention is a film for supporting the photosensitive resin layer (B), and is preferably made of a transparent material that transmits active light. 10 to 100 μm for such a material
Although there is a synthetic resin film of polyethylene, polypropylene, polycarbonate, polyethylene terephthalate and the like having a thickness of about, polyethylene terephthalate having appropriate flexibility and strength is usually preferably used.

The photosensitive resin layer (B) of the present invention comprises (i) a vinyl copolymer, (ii) an ethylenically unsaturated addition-polymerizable monomer, (iii) a photopolymerization initiator, and The iv) component is an aliphatic carboxylic acid as an essential component, and may contain a dye, a pigment, a color former, a plasticizer, and a radical polymerization inhibitor as necessary. The vinyl copolymer of the component (i) of the present invention can be obtained by copolymerizing one or more of the following three types of monomers.

(A) The first monomer is an α, β-unsaturated carboxylic acid, and the proportion of the first monomer in the component (i) is preferably 15 to 40% by weight. More preferably 20
３０30% by weight. If the proportion is less than 15% by weight, development with an alkaline aqueous solution becomes difficult. If the proportion is more than 40% by weight, it becomes insoluble in the solvent during the polymerization, so that the synthesis becomes difficult.

Specific examples of such α, β-unsaturated carboxylic acids include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid and maleic acid half ester, each of which is used alone. Or two or more of them may be combined. For use in the present invention,
Particularly, (meth) acrylic acid is preferred. (B) The second monomer is a compound represented by the following formula (1), and the proportion of the second monomer in the copolymer of the component (i) is preferably from 5 to 35% by weight. More preferably 15
３０30% by weight. If the proportion is less than 5% by weight, sufficient adhesion cannot be obtained. 35% by weight
If the amount is larger, the solubility in a solvent decreases during the copolymerization, so that the polymerization is hardly completed, and the development time of the photosensitive resin layer becomes extremely long.

[0018]

Embedded image (Wherein R1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X is a halogen atom or an alkyl group having 1 to 3 carbon atoms, n is an integer of 0 or 1 to 3, and n is 2 or more) , A plurality of Xs may be the same or different.) Specific examples of such compounds include styrene,
Examples thereof include α-methylstyrene, p-methylstyrene, p-chlorostyrene, and the like, and each may be used alone or in combination of two or more. Styrene is particularly preferred for use in the present invention.

(C) The third monomer is an alkyl (meth) acrylate having an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 to 6 carbon atoms, (meth) ) Selected from the group consisting of acrylonitrile, (meth) acrylamide, a compound in which hydrogen bonded to nitrogen is substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and glycidyl (meth) acrylate It is at least one compound, and the proportion of the component (i) in the vinyl copolymer is preferably from 20 to 75% by weight. More preferably 45 to
65% by weight. If the proportion is less than 20% by weight, the flexibility of the photosensitive resin layer decreases. The ratio is 7
If the content is more than 5% by weight, the storage stability as a roll-shaped product is reduced.

Specific examples of such a compound include methyl (meth) acrylate, ethyl (meth) acrylate,
N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Propyl,
(Meth) acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, (meth) acrylonitrile, glycidyl (meth) acrylate and the like may be used alone or in combination of two or more. As the material used in the present invention, particularly (meth)
Methyl acrylate is preferred.

The weight average molecular weight of the vinyl copolymer (i) of the present invention is in the range of 20,000 to 300,000, preferably 30,000 to 150,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. When the weight average molecular weight is less than 20,000, the strength of the cured film is reduced and the cured film is easily chipped. If the weight average molecular weight exceeds 300,000, the viscosity of the photosensitive resin composition becomes too high, and the adhesion to the substrate is reduced.

The amount of the vinyl copolymer (i) contained in the photosensitive resin layer (B) is from 30 to 30% by weight based on the total weight.
A range of 80% by weight is preferred. More preferably, 40 to
65% by weight. If this amount is less than 30% by weight,
The dispersibility in an alkali developing solution is reduced, and the developing time is significantly increased. If the amount exceeds 80% by weight, photo-curing of the photosensitive resin layer becomes insufficient, and the resistance as a resist decreases.

In the present invention, it is essential to include a vinyl copolymer using a styrene derivative as a monomer. If necessary, a vinyl copolymer not using a styrene derivative may be used in combination. As the vinyl copolymer used in combination with the vinyl copolymer (i), one or more of the following two types of monomers are used, and the acid equivalent is adjusted to 100 to 600. A copolymerized product is used.

The first monomer used in the vinyl copolymer used in combination with the vinyl copolymer (i) is an α, β-unsaturated carboxylic acid, and specifically, (meth) acrylic acid , Fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid half ester and the like. The second component used for the vinyl copolymer used in combination with the component (i) vinyl copolymer
Are alkyl (meth) acrylates having an alkyl group having 1 to 6 carbon atoms, hydroxyalkyl (meth) acrylates having a hydroxyalkyl group having 2 to 6 carbon atoms, (meth) acrylonitrile, and (meth) acrylamide. Compounds in which the hydrogen bonded to the nitrogen is substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, glycidyl (meth) acrylate, and the like.

The vinyl copolymer used in the present invention is prepared by adding a monomer mixture to a solution diluted with a solvent such as acetone, methyl ethyl ketone or isopropanol, and then starting radical polymerization of benzoyl peroxide, azobisisobutyronitrile or the like. It is preferable to synthesize by adding an appropriate amount of an agent and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. In some cases, after the reaction is completed, a solvent is further added to adjust the concentration to a desired concentration. As a synthesis means, bulk polymerization, suspension polymerization, and emulsion polymerization are used in addition to solution polymerization.

As the ethylenically unsaturated addition polymerizable monomer which is the component (ii) of the present invention, a conventionally known compound can be used. Specific examples of such unsaturated addition-polymerizable monomers include 1-hydroxy-3-phenoxypropyl acrylate, phenoxytetraethylene glycol acrylate, β-hydroxypropyl-β′-
(Acryloyloxy) propyl phthalate, 1,4-
Tetramethylene glycol (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, 1,4
-Cyclohexanediol di (meth) acrylate,
1,4-cyclohexanediol di (meth) acrylate, octapropylene glycol di (meth) acrylate, glycerol (meth) acrylate, 2-di (p-
(Hydroxyphenyl) propanedi (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropanetri (meth) acrylate, polyoxypropyltrimethylolpropanetri (meth) acrylate, polyoxyethyltrimethylolpropanetri (meth) acrylate, Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether, tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, diallyl phthalate, polyethylene glycol di (meth) Acrylate, polypropylene glycol di (meth) acrylate, 4-normal octylphenoxypentapropylene glycol Acrylate, bis (triethylene glycol methacrylate) nonapropylene glycol, bis (tetraethylene glycol methacrylate) polypropylene glycol, bis (triethylene glycol methacrylate) polypropylene glycol, bis (diethylene glycol acrylate) polypropylene glycol, 4-normal octylphenoxypentaethylene glycol Examples include tripropylene glycol acrylate, phenoxytetrapropylene glycol tetraethylene glycol acrylate, and compounds containing both an ethylene oxide chain and a propylene oxide chain in the molecule of a bisphenol A (meth) acrylate monomer. Further, a urethane compound of a polyvalent isocyanate compound such as hexamethylene diisocyanate and tolylene diisocyanate and a hydroxy acrylate compound such as 2-hydroxypropyl (meth) acrylate can also be used. These ethylenically unsaturated addition-polymerizable monomers of component (ii) may be used alone or in combination of two or more.

The amount of the ethylenically unsaturated addition polymerizable monomer (ii) contained in the photosensitive resin layer (B) is preferably from 20 to 70% by weight based on the total weight. More preferably, it is 30 to 60% by weight. When the amount is less than 20% by weight, the curing of the photosensitive resin is insufficient, and the strength as a resist is insufficient. On the other hand, when the amount exceeds 70% by weight, the storage stability as a photosensitive resin laminate is obtained. Decrease.

The photopolymerization initiator as the component (iii) of the present invention is preferably contained in the photosensitive resin layer (B) of the present invention in an amount of 0.01 to 20% by weight based on the total weight. More preferably, it is 1 to 10% by weight. If the amount of the component (iii) is less than 0.01% by weight, the sensitivity is not sufficient. On the other hand, when the amount of the component (iii) is more than 20% by weight, the ultraviolet ray absorption rate increases, and the curing of the bottom portion of the photosensitive resin layer becomes insufficient.

Specific examples of the component (iii) include benzyl dimethyl ketal, benzyl diethyl ketal, benzyl dipropyl ketal, benzyl diphenyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin phenyl ether, and thioxanthone. 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,
2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone, 4,4 '-Bis (dimethylamino) benzophenone [Michler's ketone] 4.4'-
Aromatic ketones such as bis (diethylamino) benzophenone; biimidazole compounds such as 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer;
Acridines such as -phenylacridine, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylglycine, and further 1-phenyl-1,2-propanedione-2- Oxime esters such as o-benzoyl oxime, ethyl 2,3-dioxo-3-phenylpropionate-2- (o-benzoylcarbonyl) -oxime, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and p-diisopropyl Examples thereof include aminobenzoic acid and esters thereof with alcohols, p-hydroxybenzoic acid esters, and the like. Among them, 2- (o-chlorophenyl) -4,
Preferred is a combination of 5-diphenylimidazolyl dimer and Michler's ketone.

The aliphatic carboxylic acid having two or more carboxyl groups in the molecule of the component (iv) of the present invention includes:
Specifically, oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethyl Glutaric acid, maleic acid,
Fumaric acid, itaconic acid, 1-butene-2,4-dicarboxylic acid, dibromosuccinic acid, aspartic acid, diaminopimelic acid, glutamic acid, malic acid, tartaric acid, oxaloacetic acid, acetone dicarboxylic acid, α-ketoglutaric acid, butane-1, 2,3-tricarboxylic acid, 3-butene-1,
2,3-tricarboxylic acid, 1-hexene-2,4,6-
Tricarboxylic acid, citric acid, aconitic acid, butanetetracarboxylic acid and the like.

In order to further enhance the effects of the present invention, an aliphatic carboxylic acid having three or more carboxyl groups in the molecule is more preferable. Specifically, butane-1,2,3-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, 1-hexene-2,4,6-tricarboxylic acid, citric acid, aconitic acid, butanetetra And carboxylic acids. Among them, particularly preferred is citric acid.

The amount of the component (iv) contained in the photosensitive resin layer (B) of the present invention is 0.005 to 0.5 based on the total weight.
% Is preferable, and 0.01% to 0.3% is more preferable.
If this amount is less than 0.005%, good developability cannot be obtained when stored for a long time after lamination. If the amount is more than 0.5%, the sensitivity as a photosensitive resin decreases, or the adhesion of a resist pattern decreases when exposed and developed after storage after lamination.

Thermal stability of the photosensitive resin layer (B) of the present invention,
In order to improve storage stability, it is preferable to include a radical polymerization inhibitor. Examples of such a radical polymerization inhibitor include 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) and the like.

The photosensitive resin layer (B) of the present invention comprises a dye,
A coloring substance such as a pigment may be contained. Such coloring substances include, 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.

The photosensitive resin layer (B) of the present invention may contain a coloring dye which develops a color upon irradiation with light. As such a coloring dye, a combination of a leuco dye and a halogen compound is well known. As leuco dyes,
For example, tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-3-methylphenyl) methane [leucomalachite green] and the like can be mentioned. On the other hand, as the halogen compound, 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 and the like can be mentioned.

Further, in the photosensitive resin layer (B) of the present invention,
If necessary, additives such as a plasticizer may be contained. Examples of such additives include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and acetyl tri-citrate. Examples include n-propyl, tri-n-butyl acetylcitrate, and polypropylene glycol.

A protective layer (C) is laminated on the photosensitive resin laminate of the present invention, if necessary. In the adhesive strength between the photosensitive resin layer (B) and the support (A), the adhesive strength between the photosensitive resin layer (B) and the protective layer (C) is sufficiently smaller than the adhesive strength between the photosensitive resin layer (B) and the support (A). This is a characteristic required for the protective layer, and the protective layer can be easily peeled off. Examples of such a film include a polyethylene film and a polypropylene film.

A method of preparing a photosensitive resin laminate by sequentially laminating the support (A), the photosensitive resin layer (B), and the protective layer (C) can be performed by a conventionally known method. .
As such a method, for example, a photosensitive resin layer (B)
The photosensitive resin composition used in the above is mixed with a solvent that dissolves them to form a uniform solution, and the solution is applied to the support (A) using a bar coater or a roll coater and dried to obtain a support. The photosensitive resin layer (B) is laminated on the body. Next, a photosensitive resin laminate can be produced by laminating the protective layer (C) on the photosensitive resin layer.

Next, a method for manufacturing a printed wiring board using the photosensitive resin laminate of the present invention will be described. The printed wiring board is manufactured through the following steps. (1) A laminating step of using a hot roll laminator to adhere to a substrate such as a copper-clad laminate while peeling off the protective layer of the photosensitive resin laminate. (2) Adhering a mask film having a desired wiring pattern to a support. Exposure step of exposing using an actinic light source (3) After peeling off the support, an unexposed portion of the photosensitive resin layer is dissolved and removed using an alkaline developer to form a resist pattern on the substrate ( 4) An etching step in which an etching solution is sprayed on the formed resist pattern to etch a copper surface not covered with the resist pattern. (5) A stripping step in which the resist pattern is removed from the substrate using an alkali stripping solution. Pass through a transparent high-transmittance mask film and cover the portions to be left as wiring and the openings of the conductive through holes. Although active ray is irradiated to a portion to be left as, as the active light used herein, ultraviolet rays such as ultra-high pressure mercury lamp is used.

As the alkaline aqueous solution used in the developing step, an aqueous solution of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or the like is used. Most commonly, a 0.5-3% aqueous sodium carbonate solution is used. The etching step is performed by a method suitable for the DFR to be used, such as acidic etching or alkali etching.

The removal of the photocurable resist after etching is as follows:
Peeling is performed by using an aqueous solution of an alkali that is stronger than the aqueous alkali solution used in the development. For example, 1
An aqueous solution of ５5% sodium hydroxide or potassium hydroxide is used.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples. Examples and comparative examples were performed by the following methods.

[0043]

Examples 1 to 5 and Comparative Examples 1 and 2 1) Basic evaluation (Preparation of photosensitive resin laminate) A photosensitive resin composition having the composition shown in Table 1 was mixed, and a 20 μm-thick polyethylene terephthalate film was mixed with a bar. It was applied uniformly using a coater and dried in a dryer at 90 ° C. for 2 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 25 μm.

A 30 μm thick polyethylene film was laminated on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate. (Lamination) While peeling off the polyethylene film of the photosensitive resin laminate, apply a hot roll laminator ("AL-70" manufactured by Asahi Kasei Kogyo Co., Ltd.) to the polyimide flexible copper-clad laminate without any surface treatment of the photosensitive resin layer.
Laminated at 05 ° C. Air pressure is 3.5kg / cm
^The lamination speed was 1.5 m / min.

(Exposure) The photosensitive resin layer has no mask film or a mask film required for evaluation.
60 steps using a 7-step tablet (Asahi Kasei Kogyo) and an ultra-high pressure mercury lamp (HMW-801 manufactured by Oak Manufacturing Co., Ltd.)
Exposure was performed at mJ / cm ² . (Development) After peeling off the polyethylene terephthalate film, a 1% aqueous solution of sodium carbonate at 30 ° C. was sprayed for a predetermined time to dissolve and remove unexposed portions of the photosensitive resin layer.
At this time, the minimum development time required to completely dissolve the photosensitive resin in the unexposed portion was defined as the minimum development time.

2) Independent Line Adhesion The flexible substrate 15 minutes after the lamination was exposed through a line pattern having a width of the exposed portion and the unexposed portion of 1: 100. The development was performed for a development time twice as long as the minimum development time, and the minimum mask width at which the cured resist line was normally formed was defined as the adhesion value of the independent line.

The independent line adhesion was evaluated according to the following criteria based on the results so far. 30 µm or less ······· ◎ Over 30 µm and 40 µm or less ··· Over 40 µm and 50 µm or less · △ Over 50 µm ······ 3) Adhesion of independent lines Except that the flexible substrate after lamination was stored for 7 days at a temperature of 23 ° C. and a humidity of 50% RH, exposure and development were performed in the same manner as in 2) above to evaluate the adhesion of the independent lines. did. 30 µm or less ········· Over 30 µm and 40 µm or less ··· Over 40 µm and 50 µm or less ··· Over 50 µm ········ × 4) Developability (after lamination) Developability of Storage Sample) The laminated flexible substrate was stored for 7 days at a temperature of 23 ° C. and a humidity of 50% RH. Minimum development time 2
After the development for twice the developing time, the development residue of the photosensitive resin layer was observed and ranked as follows. No development residue ・ ・ ・ ・ ・ ・ ・ ・ ・ ○ Some development residue ・ ・ ・ ・ ・ ・ ・ △ Full development residue ・ ・ ・ ・ ・ ・ ・ × 5) Bending property 2.5cm width Exposure using a mask film with a strip-shaped exposure part, after developing with a development time twice the minimum development time,
A strip-shaped flexible substrate including a strip-shaped exposed portion and cut into a width of 3 cm was bent along a metal bar, and was reciprocated 10 times while being kept in contact with the metal bar. The following ranking was carried out according to the minimum thickness of the metal rod which did not peel off the cured resist film from the substrate even after being squeezed. The thickness of the metal rod was indicated by the diameter in mm. 2 mmφ or less ········ 3 to 5 mmφ ······· 6 mmφ or more ··················· 6) Followability A photosensitive resin laminate was laminated on the attached product, and both exposed and unexposed portions were exposed through a line pattern having a width of 100 μm.
After development for twice the minimum development time, the adhesion of the cured resist at the fold was examined. The ranking was made as follows according to the number of lines that did not follow out of the 100 cured resist lines. 0 ····· 5 or less ··· 6 to 50 ········· 51 X 100) ... 7) Blocking property Laminate the photosensitive resin laminate on a 25 x 15 cm flexible substrate, and expose both exposed and unexposed parts through a mask film with a width of 50 m, After the development, the substrates are stacked with a development time twice as long as the minimum development time, and sandwiched between glass plates equivalent to a load of 1 kg.
Stored under H conditions for 2 days. Thereafter, when the overlapping substrate was peeled off, the state of the resist line peeled off from the substrate due to the adhesion to the polyimide film surface was observed and ranked as follows. No line peeling ············· Partial line peeling ······· The entire line peeling ······ × × The composition and results of the examples and comparative examples are shown in Table 1. Show.

The composition abbreviations shown in Table 1 are as follows. P-1: methyl methacrylate / methacrylic acid / styrene / n-butyl acrylate (weight ratio 40/25/25 /
35% methyl ethyl ketone solution of a copolymer having the composition of 10) and having a weight average molecular weight of 60,000 P-2: having a composition of methyl methacrylate / methacrylic acid / styrene (weight ratio: 62/23/15) 35% methyl ethyl ketone solution of a copolymer having a weight average molecular weight of 80,000 P-3: having a composition of methyl methacrylate / methacrylic acid / styrene (weight ratio: 50/25/25) and having a weight average molecular weight of 50,000 35% methyl ethyl ketone solution of a certain copolymer P-4: a copolymer having a composition of methyl methacrylate / methacrylic acid / n-butyl acrylate (weight ratio 65/25/10) and a weight average molecular weight of 120,000 M-1: bis (triethylene glycol methacrylate) nonapropylene glycol M-2: 4-normal octyl Enoxypentaethylene glycol tripropylene glycol acrylate M-3: bis (triethylene glycol methacrylate) dodecapropylene glycol M-4: urethane compound of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate M-5: phthalic anhydride and 2 -Reacted product of half-esterified product with hydroxypropyl acrylate and propylene oxide (OEA-200 manufactured by Nippon Shokubai Kagaku Co., Ltd.) M-6: Nonaethylene glycol diacrylate M-7: 8 mol of propylene oxide and ethylene oxide 8 in bisphenol A A monomer in which methacrylic acid is ester-bonded after reacting with M. M-8: trioxyethyltrimethylolpropane triacrylate M-9: tetraethylene glycol dimethacrylate M-10: Heptapropylene glycol dimethacrylate (APG-400 manufactured by Shin-Nakamura Chemical Co., Ltd.) I-1: Benzophenone I-2: Michler's ketone I-3: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl di I-4: benzyl dimethyl ketal I-5: 2,4-diethylthioxanthone I-6: ethyl p-dimethylaminobenzoate C-1: tartaric acid C-2: malic acid C-3: aconitic acid C-4 : Succinic acid C-5: Citric acid D-1: Malachite green D-2: Leuco crystal violet D-3: Tribromophenyl sulfone

[0049]

[Table 1]

[0050]

As described above, the photosensitive resin laminate of the present invention has good adhesion and followability to a flexible copper-clad laminate, and has good developability even when stored for a long time after lamination. Since it is present and does not cause blocking of the cured resist pattern, it can be used very advantageously in the production of printed wiring boards.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA11 AA14 AB11 AB15 AC01 AD01 BC13 BC31 CB13 CB14 CB16 CB41 CB43 CB45 CB55 CC20 FA17 FA41 FA44 5E339 BE11 CC01 CC10 CD01 CE16 CF16 CF17 CG01 DD02

Claims (2)

[Claims] 1. A photosensitive resin layer comprising a support (A) and a photosensitive resin layer (B), wherein the photosensitive resin layer (B) comprises (i) (a) α, β-
At least one first monomer selected from unsaturated carboxylic acids, (b) at least one second monomer selected from compounds represented by the formula (1), (Wherein R1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X is a halogen atom or an alkyl group having 1 to 3 carbon atoms, n is an integer of 0 or 1 to 3, and n is 2 or more) And (c) alkyl (meth) acrylate having an alkyl group having 1 to 6 carbon atoms, hydroxy having a hydroxyalkyl group having 2 to 6 carbon atoms. Alkyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide and a compound in which hydrogen bonded to nitrogen is substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and (meth) acrylic A vinyl copolymer having a weight average molecular weight of 20,000 to 300,000 obtained by vinyl copolymerizing at least one third monomer selected from the group consisting of glycidyl acid, A photosensitive resin laminate comprising: (i) an ethylenically unsaturated addition-polymerizable monomer, (iii) a photopolymerization initiator, and (iv) an aliphatic carboxylic acid having two or more carboxyl groups in a molecule. body. 2. After laminating a photosensitive resin layer on the substrate by using the photosensitive resin laminate according to claim 1, forming a resist pattern by an exposure step and a development step, and performing an etching step and a peeling step to perform wiring. A method for manufacturing a printed wiring board for forming a pattern.