JP3267703B2 - New photopolymerizable resin laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali-developable photopolymerizable resin laminate suitable for producing a printed wiring board.

[0002]

2. Description of the Related Art Conventionally, a so-called dry film photoresist (hereinafter abbreviated as DFR) comprising a support layer and a photopolymerizable layer has been used as a resist for producing a printed wiring board. DFR is generally prepared by laminating a photopolymerizable layer composed of a photopolymerizable composition on a support layer, and often further laminating a protective film on the composition.

In order to prepare a printed wiring board using a DFR, a protective film is first peeled off, and then a DF is formed on a substrate for forming a permanent circuit such as a copper-clad laminate using a laminator or the like.
R is laminated. Next, if necessary, the support layer is peeled off, and exposure is performed through a wiring pattern mask film or the like. If there is a support layer after exposure, the support layer is peeled off as necessary, and the unpolymerized layer of the photopolymerizable layer is dissolved or dispersed and removed with a developer to form a cured resist image on the substrate. As the photopolymerizable layer, an alkali developing type using a weakly alkaline aqueous solution as a developing solution and a solvent developing type using an organic solvent are known. In recent years, however, demand for the alkali developing type has increased due to environmental problems or costs. I have.

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

[0005] In a printed wiring board manufactured using DFR, a conductive circuit forming material layer, for example, a copper thin film layer, provided on the inner peripheral surface of a through hole, is used to form one side of a permanent circuit forming substrate. There is a type in which the other surface is electrically connected. As a method of manufacturing this type of printed circuit board, a copper through-hole method and a solder through-hole method are generally used, and a tenting method has been widely used in the copper through-hole method.

In the solder through hole method, the inner peripheral surface of the through hole is coated with a conductive circuit constituent material, for example, an etching resistant metal for protecting a copper thin film layer, for example, solder plating, and then unnecessary portions on the substrate surface are etched. . In various plating steps such as copper plating and solder plating in the above-described method, if the adhesion between the resist and the base material is insufficient, a plating solution enters between the lower part of the resist and the substrate to form plating, A so-called plating hole occurs.
If the plating gets loose, it causes a short circuit between the circuits and rattling of the circuits. Therefore, a DFR having excellent plating resistance is required.

On the other hand, the cured resist is developed, plated,
It may come into contact with the ring roll during transportation during etching, etc., or may touch the equipment when attaching to a plating jig.In the case of a flexible substrate, it may bend or bend during operation, If it is hard and brittle, it will chip or crack, causing serious problems. Further, from the viewpoint of productivity, there is a need for a DFR that can be rapidly developed and peeled.

The photopolymerizable layer of DFR widely used at present has (1) at least one etching group,
(2) a thermoplastic organic polymer binder, (3) a photopolymerization initiator, and (4) other additives. No. 9177, Japanese Patent Publication No. 57-2169
No. 7).

As the unsaturated compound, acrylic acid and methacrylic acid esters of aliphatic polyhydric alcohols are most common, and at least two unsaturated compounds such as trimethylolpropane triacrylate, pentaerythritol triacrylate and polyethylene glycol diacrylate are used. Those having an unsaturated group are known. However, when the above-mentioned monomer having at least two unsaturated groups is used, there is a problem that the flexibility of the cured resist is not sufficient, and the peeling is slow and the productivity is poor. It has been known that the use of a monomer having one unsaturated group in combination is effective for softening and improving the releasability of a cured resist (for example, JP-A-60-11840). In addition, there is a problem that plating resistance is remarkably deteriorated.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photopolymerizable resin laminate in which the cured resist has good flexibility and excellent peelability and plating resistance.

[0011]

As a result of intensive studies to solve the above-mentioned problems, when a compound of the following general formula [I] is used as a monomer, the cured resist has good flexibility and peelability. Without impairing the plating resistance, and found to have excellent properties in terms of plating resistance, etching resistance and tenting resistance, and completed the present invention.

That is, the present invention relates to the following: (1) The carboxyl group content is 100 to 60 in acid equivalent.
0, a polymer having a weight average molecular weight of 20,000 to 500,000
90% by weight, (2) 2 to 30% by weight of a photopolymerizable monomer represented by the following chemical formula [I],

[0013]

Embedded image

(3) 5 to 40% by weight of a photopolymerizable monomer having at least two terminal ethylene groups, (4) 0.01 to 20% by weight of a photopolymerization initiator, and the photopolymerization of (2) The sum of the photo-polymerizable monomer and the photo-polymerizable monomer of (3) is 7 to 60% by weight, for making a printed wiring board comprising a photo-polymerizable layer composed of a photo-polymerizable composition and a support layer . there is provided a photopolymerizable resin laminate.

Further, according to the present invention, the above photopolymerizable resin laminate is laminated on a metal surface of a substrate for a printed circuit board by heating and pressing, using a laminator, and is image-exposed to active light through a mask film. The support layer is peeled off as necessary, and if there is a support layer on the photopolymerizable resin layer after exposure, if necessary, remove the support layer, and then remove an unexposed portion using a developing solution of an alkaline aqueous solution, A metal image pattern is formed by performing an etching method or a plating method on a metal surface exposed by development, and thereafter, the cured resist image is peeled off with an alkaline aqueous solution stronger than the alkaline aqueous solution used in the development. A method for producing a printed wiring board is provided. It is essential that A of the photopolymerizable monomer represented by the formula [I] contains both repeating units represented by the following formula 3, and the total of repeating units is 2 to 15, and may be random or block. Absent.

[0016]

Embedded image

The above compound [I] can be obtained by an esterification reaction of a modified monool obtained by adding ethylene oxide and propylene oxide to an alkyl-substituted or unsubstituted phenol by a known method, and acrylic acid or methacrylic acid. Can be. This modified monol is known as a nonionic surfactant, and for example, Dispanol LS-100 (trade name, manufactured by NOF Corporation) is commercially available.

The photopolymerizable composition of the present invention must contain 2 to 30% by weight of the monomer represented by the formula [I], and more preferably 5 to 15% by weight. If it is less than 2% by weight, the effect of improving flexibility and peelability is not sufficient, and if it exceeds 30% by weight, plating resistance and storage stability deteriorate. It is essential that the photopolymerizable composition contains a photopolymerizable monomer having at least two terminal ethylene groups. Examples of the monomer include 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 2-di ( (p-hydroxyphenyl) propanedi (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropanetri (meth) acrylate, polyoxypropyltrimethylolpropanetri (meth) acrylate, polyoxyethyltrimethylolpropanetriacrylate, dipenta Erythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, 2,2-bi (4
-Methacryloxypentaethoxyphenyl) propane,
Polyoxyethylene polyoxypropylene glycol di
(Meth) acrylate, urethane acrylate, for example, a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate, and a compound having a hydroxyl group and a (meth) acryl group in one molecule (for example, , 2-hydroxypropyl acrylate, oligopropylene glycol monomethacrylate, etc.).

Of these, preferred examples are polyethylene glycol di (meth) acrylate, 2,2-
Examples thereof include bis (4-methacryloxypentaethoxyphenyl) propane, polyoxyethylene polyoxypropylene glycol di (meth) acrylate, and a urethane compound of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate.

These monomers can be used alone or in combination of two or more. The use amount is more preferably 5 to 40% by weight, and the total amount with the compound [I] is 7 to 60% by weight.
It is necessary to be. If the amount is less than 7% by weight, the sensitivity and the film strength are not sufficient. If the amount exceeds 60% by weight, the photopolymerizable layer protrudes significantly during storage, which is not preferable.

The amount of the carboxyl group contained in the polymer used in the present invention must be 100 to 600 in terms of acid equivalent, and preferably 300 to 400. The molecular weight is 20,000-5
It is necessary to be 100,000, more preferably 40,000 to 200,000. Here, the acid equivalent refers to the weight of a polymer having one equivalent of a carboxyl group therein. The carboxyl group in the polymer is necessary for having developability and releasability in an aqueous alkali solution. If the acid equivalent is 100 or less, the compatibility with the coating solvent or another composition, for example, a monomer is reduced, and if the acid equivalent is 600 or more, the developability and the releasability are reduced. Also,
When the molecular weight is 500,000 or more, the developability decreases, and when the molecular weight is 20,000 or less, it becomes difficult to maintain a uniform thickness of the photopolymerizable layer when used in a photopolymerizable resin laminate, and the resistance to a developer is increased. Worsens.

The acid equivalent was measured using a Hiranuma reporting titrator COMMITE-7 at 0.1 N
It is performed by potentiometric titration with sodium hydroxide. The molecular weight was determined by gel permeation chromatography (Pump: TRIROTAR-V, column;
Shodex A-80M 2 in series, mobile phase solvent; T
HF, using a calibration curve with a polystyrene standard sample) as the weight average molecular weight.

The polymer is obtained by copolymerizing one or more of the following two types of monomers. The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. For example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester and the like. The second monomer is non-acidic, has one polymerizable unsaturated group in the molecule, and has various properties such as developability of the photopolymerizable layer, resistance in the etching and plating steps, and flexibility of the cured film. Is selected to maintain the characteristics of For example, methyl
There are alkyl (meth) acrylates such as (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Further, there are esters of vinyl alcohol such as vinyl acetate, and styrene or a polymerizable styrene derivative. It can also be obtained by polymerization of only a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule.

The amount of the polymer contained in the photopolymerizable composition must be in the range of 20 to 90% by weight, preferably 30 to 70% by weight. 90% by weight of polymer
When the content is above or less than 20% by weight, a cured image formed by exposure does not have sufficient properties as a resist, for example, sufficient resistance in tenting, etching, and various plating steps.

The photopolymerizable composition of the present invention contains a photopolymerization initiator as an essential component. The photopolymerization initiator used in the present invention is any known compound that is activated by various kinds of actinic rays, for example, ultraviolet rays, and starts polymerization. For example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,2
3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9.1
Quinones such as 0-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, benzophenone, Michler's ketone [4,4'-bis (dimethylamino) A) benzophenone], aromatic ketones such as 4,4'-bis (diethylamino) benzophenone, benzoin ethers such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin and ethyl benzoin, benzyl dimethyl ketal, benzyl diethyl ketal, 2- (o-chlorophenyl)
Biimidazole compounds such as -4,5-diphenylimidazolyl dimer, combinations of thioxanthones and alkylaminobenzoic acid, for example, ethylthioxanthone and ethyl dimethylaminobenzoate, 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and isopropylthioxanthone A combination with ethyl dimethylaminobenzoate, a combination of 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and Michler's ketone, and a further combination of 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer Of isomers, benzyldimethyl ketal and Michler's ketone, acridines such as 9-phenylacridine, 1-phenyl-1,2-propanedione-2-o-benzoyloxime, 1-phenyl-1,2-propene There are Panjion-2-(o-ethoxycarbonyl) oxime esters such as oxime.
These initiators may be used alone or in combination.

Preferred examples of the initiator include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazolyl. And dimers, and combinations thereof. The amount of the photopolymerization initiator contained in the photopolymerizable composition of the present invention is 0.01 to 20% by weight, preferably 0.05 to 10% by weight. When the amount of the photopolymerization initiator is 20% by weight or more, the active absorbance of the photopolymerizable composition becomes high, and when used as a photopolymerized laminate, the curing of the bottom portion of the photopolymerizable layer by polymerization becomes insufficient. If it is less than 0.01% by weight, sufficient sensitivity cannot be obtained.

In order to improve the thermal stability and storage stability of the photopolymerizable composition of the present invention, it is preferable that the photopolymerizable composition contains a polymerization inhibitor. For example, p-
Methoxyphenol, hydroquinone, pyrogallol,
Naphthylamine, tert. -Butylcatechol, cuprous chloride, 2,6-di-tert. -Butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6-te
rt. Butylphenol), 2,2'-methylenebis (4-methyl-6-tert.butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.

The photopolymerizable composition of the present invention may contain coloring substances such as dyes and pigments. For example, fuchsin, phthalocyanine green, auramine base, chalcoxide green S, paramagenta, crystal violet,
Methyl Orange, Nile Blue 2B, Victoria Blue, Malachite Green, Basic Blue 20, Diamond Green and the like.

Further, a coloring dye which develops a color upon irradiation with light may be contained. Examples of the color-forming dye include a combination of a leuco dye or a fluoran dye and a halogen compound. For example, tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet],
Tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green] and the like. On the other hand, examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris (2 , 3
-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1
-Trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane and the like. Further, a combination of a biimidazole compound and a leuco dye is also useful.

Further, the photopolymerizable composition may contain additives such as a plasticizer, if necessary. Examples thereof include phthalic esters such as diethyl phthalate, p-toluenesulfonamide, and triethylene glycol diacetates. The present invention comprises a photopolymerizable layer comprising the above photopolymerizable composition, and a support layer for supporting the photopolymerizable layer. The support layer is desirably a transparent layer that transmits active light.

Examples of the support layer that transmits active light include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, and polymethyl methacrylate copolymer. Examples include a coalesced film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film.
These films may be stretched if necessary. A thinner thickness is advantageous in terms of image formability and economy, but it is 10 to 30 μm in order to maintain strength.
Is common.

A protective layer is laminated on the surface opposite to the photopolymerizable layer laminated with the support layer, if necessary. An important property of this protective layer is that the protective layer is sufficiently smaller than the support layer in terms of adhesion to the photopolymerizable layer and can be easily peeled off. For example, there are a polyethylene film and a polypropylene film. Further, a film having excellent releasability as disclosed in JP-A-59-202457 can be used. Although the thickness of the photopolymerizable layer varies depending on the application, it is 5 to 100 μm, preferably 5 to 90 μm for producing a printed circuit board.
m, and the thinner, the higher the resolution. Also, the film thickness increases as the thickness increases.

Next, the process for producing a printed circuit board using the photopolymerizable resin laminate of the present invention is based on the prior art, but will be briefly described. First, using a laminator, if there is a protective layer, after peeling off the protective layer, the photopolymerizable layer is laminated on the metal surface of the printed circuit board substrate by heating and pressing. The heating temperature at this time is generally 40 to 160 ° C. Next, if necessary, the support layer is peeled off, and image exposure is performed with actinic light through a mask film. Next, if there is a support layer on the photopolymerized layer after exposure, the support layer is removed if necessary, and then the unexposed portion is developed and removed using a developing solution of an alkaline aqueous solution. As the alkaline aqueous solution, sodium carbonate, potassium carbonate,
An aqueous solution of sodium hydroxide, potassium hydroxide or the like is used.

These are selected in accordance with the characteristics of the photopolymerizable layer, and a 0.5% to 3% aqueous sodium carbonate solution is generally used. Next, a metal image pattern is formed on the metal surface exposed by the development by using a known method such as an etching method or a plating method. Thereafter, the cured resist image is generally stripped off with an aqueous alkaline solution that is stronger than the aqueous alkaline solution used for development. The aqueous alkali solution for peeling is not particularly limited, but an aqueous solution of 1 to 5% sodium hydroxide or potassium hydroxide is generally used. Further, it is possible to add a small amount of a water-soluble solvent to a developer or a stripper.

[0035]

Examples are shown below.

[0036]

Example 1 The compounds described in Example 1 of Table 1 were uniformly dissolved. Next, this mixed solution is uniformly applied to a 25 μm-thick polyethylene terephthalate film using a bar coater, and dried in a drier at 90 ° C. for 5 minutes to laminate a 50 μm-thick photopolymerizable resin layer. I got a body. Thereafter, a 35 μm polyethylene film was laminated on the surface of the photopolymerizable layer on which the polyethylene terephthalate film was not laminated to obtain a laminated film. On the other hand, 35
A copper-clad laminate obtained by laminating a μm rolled copper foil is wet-buffered (trade name: Scotch Bright # 6002, manufactured by 3M).
Continuously) The photopolymerized layer was laminated at 105 ° C. with a hot roll laminator while peeling off the polyethylene film of the laminated film on the polished surface to obtain a laminated body.

An ultra-high pressure mercury lamp (Oak Seisakusho, HMW-201KB) is passed through a mask film through this laminate.
To expose the photopolymerizable layer at 80 mj / cm ² . Then, after peeling off the polyethylene terephthalate film,
A 1% by weight aqueous solution of sodium carbonate at 60 ° C. was sprayed for about 70 seconds to dissolve and remove the unexposed portions, thereby obtaining a good cured image. Evaluation was made by the following method. Table 1 shows the evaluation results. The result of the peelability evaluation test was that peeling was possible in 48 seconds.

(1) Sensitivity test After laminating a photopolymerizable layer on a copper-clad laminated substrate by the above method,
After passing through a step tablet (21-step step tablet manufactured by Stouffer), 1
Exposure was performed at 00 mj / cm ² . Next, after peeling off the polyethylene terephthalate film, development was carried out in the same manner as described above. At this time, read the maximum number of steps on the step tablet where the film remains completely. (2) Flexibility test Flexible copper-clad laminate (Nicaflex F-30T,
After laminating the photopolymerization layer on Nikkan Kogyo Co., Ltd., it is exposed and developed by the same method as described above to form a cured resist pattern having a width of 20 cm and a length of 20 cm, and has a diameter of 2 mm to 10 mm.
, And bend it several times, and iron it several times to observe the resist pattern. In the case of a composition having good flexibility, even a metal rod of 2 mm does not crack or float, and is evaluated as 2 mm at this time. That is, the smaller the numerical value, the better the flexibility. (3) Plating property test A laminate was laminated in the same manner as described above, and passed through a positive mask through an ultra-high pressure mercury lamp at 60 mj / cm.
Exposure at ² . After developing by the same method, the following plating step was further performed. After peeling off the cured resist, observe with an optical microscope. Degreasing step; Acid cleaner FR (trademark, Schering) 20
%, Sulfuric acid 10% immersion for 4 minutes at 40 ° C. water washing process room temperature, immersion and spray soft etching process; ammonium persulfate aqueous solution 200 g / l, normal temperature for 60 seconds water washing process; normal temperature, immersion and spray sulfuric acid treatment process; sulfuric acid 10% room temperature 2 Minute Copper sulfate plating process; Plating solution composition Copper sulfate 70 g / l Sulfuric acid (98%) 190 g / l Hydrochloric acid (36%) 0.12 g / l Copper glyme PCM (trademark of Japan Ronal Company) 10 cc / l Total amount with pure water 1 To liters.

Current density 1.2 A / dm ² Room temperature 30 minutes Rinse step; Room temperature, immersion and spray Solder plating step; Plating composition Hoofuka stannous (45%) 64 cc / l Hoofuka lead (45%) 22 cc / L Houfukka Hydroic Acid 200cc / l Plutin LA Conductivity Salt (trademark of Japan Lee Ronal Co.) 20g / l Plutin LA Starter 40cc / l (trademark of Japan Lei Ronal) Make up to 1 liter with pure water.

Current density: 1.0 A / dm ² 10 minutes (4) Peelability evaluation test The cured resist pattern obtained by the same method as above
It is immersed in a 3% aqueous sodium hydroxide solution at 50 ° C., and the minimum time until the cured resist pattern is peeled from the substrate is measured.

○: Peelable in less than 50 seconds Δ: Peelable in 50 seconds or more and less than 65 seconds ×: Peelable in 65 seconds or more

[0042]

Examples 2 to 4 and Comparative Examples 1 to 4 Photopolymerizable resin laminates having the compositions shown in Table 1 were obtained in the same manner as in Example 1. A sensitivity test, a flexibility test, a plating property test, and a peelability test were performed. The results are shown in Tables 1 and 2. Table 1 and Table 2
The symbols used in are as follows. B-1: Methyl methacrylate 57% by weight, methacrylic acid 23% by weight, butyl acrylate 10% by weight of a terpolymer in methyl ethyl ketone (solid content 3
2%, weight average molecular weight 85,000) M-1; reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate M-2 to M-8;

[0043]

Embedded image

M-9; 2,2-bis (4-methacryloxypentaethoxyphenyl) propane A-1; benzophenone A-2; 4,4'-diethylaminobenzophenone A-3; malachite green A-4; leuco crystal Violet A-5; Tribromomethylphenylsulfone A-6; 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

Industrial Applicability The photopolymerizable resin laminate of the present invention exhibits particularly excellent performance in plating resistance, flexibility and peelability, and is very useful as a dry film resist for producing an alkali-developed circuit board.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-202740 (JP, A) JP-A-4-195050 (JP, A) JP-A-61-98716 (JP, A) JP-A-63-98716 197939 (JP, A) JP-A-62-208042 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/027 501

Claims (2)

(57) [Claims] (1) 20 to 90% by weight of a polymer having a carboxyl group content of 100 to 600 as an acid equivalent and a weight average molecular weight of 20,000 to 500,000, and (2) a light represented by the following chemical formula [I]. Heavy synthetic monomer
2 to 30% by weight, (3) 5 to 40% by weight of a photopolymerizable monomer having at least two terminal ethylene groups, (4) 0.01 to 20% by weight of a photopolymerization initiator, and (2) a photopolymerizable monomer. Wherein the total of the photopolymerizable monomers of (3) and (3) is 7 to 60% by weight, wherein the photopolymerization for preparing a printed wiring board comprises a photopolymerizable layer comprising a photopolymerizable composition and a support layer. Resin laminate. 2. A laminator is used to laminate the photopolymerizable resin laminate according to claim 1 on a metal surface of a substrate for a printed circuit board by thermocompression bonding. Through an image exposure with active light through, if the support layer on the photopolymerizable resin layer after exposure, if necessary, remove this, then remove the unexposed parts using a developing solution of an alkaline aqueous solution, and develop Forming a metal image pattern by subjecting the exposed metal surface to an etching method or a plating method, and then peeling off the cured resist image with an alkaline aqueous solution stronger than the alkaline aqueous solution used in the development. How to make a wiring board.