JPH09236916A - Resin composition curable by crosslinking laminated body and curing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the roughening of the surface of a resist by acid or alkali solvent treatment after curing. SOLUTION: This resin composition is prepd. by blending 30-60 pts.wt. at least one kind of ethylenic unsatd. compd. having two or more (meth)acryloyloxy groups in one molecule with 30-60 pts.wt. polymer for a binder contg. 15-30wt.% at least one kind of α,β-unsatd. carboxyl group-contg. monomer and 5-30wt.% at least one kind of hydroxyl group-contg. monomer, 10-30 pts.wt. water-soluble polymer for a binder contg. 10-40wt.% hydroxyl group-contg. monomer and 1-20 pts.wt. block polyisocyanate compd., and 100 pts.wt. of the composition is further blended with 0.001-10 pts.wt. photopolymn. initiator to obtain the objective resin compsn. In order to ensure a sufficiently large film thickness on a pattern, the resin compsn. is used in the form of a dry film resist using a substrate film having a roughened surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable curable resin composition useful as a protective film, a structural material, particularly a solder resist used as an interlayer insulating film of a build-up type multilayer wiring printed circuit board, and a laminate using the same. Regarding the body

[0002]

2. Description of the Related Art Conventionally, when a multilayer wiring printed circuit board is formed by stacking wiring layers in a multilayer structure by a build-up method, in order to improve the adhesion between the interlayer insulating film and the conductive circuit and the insulating film, the surface of the insulating layer is improved. There is known a method of roughening the surface to give an anchor effect. As one example, an organic solvent solution of a photosensitive resin mixed with an inorganic filler such as hydroxide, carbonate, or sulfate, which is soluble in acid or alkali, or heat-resistant resin powder, is applied on a substrate. Then, a method of roughening the surface of the insulating layer by dissolving the filler or the resin powder with an acid or alkali solution after curing the insulating layer formed by drying the solvent by heat is known. .

[0003]

However, according to this method, it is not possible to perform tenting on a small-diameter through hole in which parts are not soldered, and it is not possible to secure a sufficient film thickness on the pattern. The problem is that the process is complicated due to the coating and drying of the solvent solution.

Therefore, in order to secure a sufficient film thickness on the pattern, a method of thermocompression bonding a dry film resist (hereinafter referred to as "DFR") under reduced pressure is conceivable. Was difficult to roughen. Further, when the above-mentioned inorganic filler or resin powder was mixed into the conventional DFR composition component, a smooth DFR could not be manufactured.

An object of the present invention is to provide a crosslinkable curable resin / fat composition capable of roughening the resist surface by curing with a solvent such as acid or alkali after curing, and also an interlayer insulating film having good adhesion. It is to provide a laminate capable of forming.

[0006]

The gist of the present invention is to provide at least one ethylenically unsaturated compound (A) having two or more (meth) acryloyloxy groups in one molecule.
60 parts by weight, at least one kind of α, β-unsaturated carboxyl group-containing monomer (b-1) 15 to 30% by weight, at least one kind of hydroxyl group-containing monomer (b-2) 5 to 3
0% by weight and other copolymerizable monomer (b-3) 40-
30 to 6 polymer (B) for binder comprising 80% by weight
0 to 40 parts by weight of the hydroxyl group-containing monomer unit
Water-soluble binder polymer (C) containing 10 to 3% by weight
0 parts by weight, block type polyisocyanate compound (D)
1 to 20 parts by weight, and (A), (B), (C),
The cross-linking curable resin composition comprises 0.001 to 10 parts by weight of the photopolymerization initiator (E) based on 100 parts by weight of the component (D). Further, the gist of the present invention is a laminate obtained by sequentially laminating a support film having a roughened surface by sand mat or chemical mat processing, the above-mentioned cross-linking curable resin composition and a protective film. Further, the gist of the present invention resides in a method of crosslinking and curing these resin compositions by using light irradiation and heat treatment in combination.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The crosslinkable curable resin composition of the present invention is conveniently used in the form of DFR. DFR
Is prepared by dissolving a cross-linking curable resin composition in an appropriate solvent to prepare a dope, coating the dope on a supporting film such as a polyester film, and drying the dope to form a resin layer. A protective film such as a polyethylene film may be laminated on the resin layer.

The ethylenically unsaturated compound (A) having two or more (meth) acryloyloxy groups in one molecule used in the crosslinkable curable resin composition of the present invention is a polyhydric alcohol (meth) acryl. An acid ester is mentioned.
For example, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2-bis [ 4- (meth) acryloyloxypolypropyleneoxyphenyl] propane,
Hydroxypivalic acid neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tris [ethoxy (meth) acrylate], trimethylolpropane tris [diethoxy (meth) acrylate],
Trimethylolpropane tris [triethoxy (meth)
Acrylate], isocyanuric acid triethylol di (meth) acrylate, isocyanuric acid triethylol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate
Examples thereof include acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, (meth) acrylamides, etc. can be used, and these can be used 1 type or in mixture of 2 or more types.

The ethylenically unsaturated compound (A) is contained in an amount of 30 to 60 parts by weight based on 100 parts by weight of the resin component. 3
When the amount is less than 0 parts by weight, the crosslink density of the obtained crosslinked cured resin becomes too low, and chemical resistance, solder heat resistance, and electrical insulation under high humidity are significantly reduced. On the other hand, when the content of the ethylenically unsaturated compound (A) exceeds 60 parts by weight, cold flow is likely to occur in a dry film resist, and the crosslinking density of the obtained crosslinked cured resin becomes high. Too much, the polymerization shrinkage strain becomes large,
Adhesion to the substrate may decrease.

When the cross-linking cured resin obtained by the present invention is a protective film for a solder resist such as a flexible substrate or a base material made of glass, plastic, metal, or a composite material thereof, where flexibility is particularly required. The total (meth) acryloyl group concentration of the ethylenically unsaturated compound (A) contained in the crosslinkable curable resin composition is 0.0.
It is preferably in the range of about 01 to 0.003 mol / g. If the concentration of the (meth) acryloyl group is too low, the sensitivity of the resulting cross-linkable curable resin composition to light is lowered, which is industrially undesirable. Further, the crosslink density of the crosslinked cured resin obtained by curing this resin composition may be too low, and the solder heat resistance, solvent resistance, and electrical insulation may be reduced. On the other hand, if the concentration is too high, the resulting crosslinked cured resin becomes hard and brittle, and is not suitable as a protective film for a flexible substrate or a base material requiring flexibility.

The binder polymer (B) constituting the cross-linking curable resin composition of the present invention comprises an α, β-unsaturated carboxyl group-containing monomer (b) so that it can be developed with a dilute aqueous alkali solution such as sodium carbonate. It is necessary to copolymerize at least one of -1) as a copolymer component in an amount of 15 to 30% by weight.

Specific examples of the monomer include (meth) acrylic acid, cinnamic acid, crotonic acid, sorbic acid,
Examples thereof include itaconic acid, propionic acid, maleic acid, and fumaric acid, and their half-esters or anhydrides can also be used. The most preferred of these are acrylic acid and methacrylic acid.

The content of the monomer (b-1) in the polymer (B) for binder needs to be in the range of 15 to 30% by weight. If it is less than 15% by weight, the development cannot be performed with an alkaline aqueous solution, or the development time becomes too long and the resolution is lowered. On the other hand, when it exceeds 30% by weight, the water absorption of the cross-linked cured resin after curing becomes large, and not only it cannot withstand alkali degreasing, but also the electrical insulation property under high humidity conditions is significantly reduced.

Since the polymer (B) for binder uses the block type polyisocyanate compound (D) as a thermal crosslinking agent, at least one of the hydroxyl group-containing monomer (b-2) is used as a copolymer component. To use.

Specific examples of the monomer (b-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2-hydroxypropyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate and 6-hydroxyhexyl (meth) acrylate can be used.

The content of the monomer (b-2) in the binder polymer (B) is required to be in the range of 5 to 30% by weight. If it is less than 5% by weight, thermal cross-linking by the block-type polyisocyanate compound (D) becomes insufficient and the alkali resistance of the cured product decreases, which is not preferable. On the other hand, when it exceeds 30% by weight, the amount of unreacted hydroxyl groups remaining after the reaction with the compound (D) is increased, and the hydrophilicity of the crosslinked cured resin may be excessively increased. It is not preferable because it may adversely affect various electrical characteristics such as volume resistance.

Copolymerizable monomers (b-) other than the above-mentioned two kinds of monomers which are constituent components of the polymer (B) for binder.
3) is not particularly limited and may be arbitrarily selected according to the purpose. Specific examples include alkyl acrylate or alkyl methacrylate in which the alkyl group has 1 to 8 carbon atoms. One or more polymerizable compounds selected may be mentioned. These may be used alone or in combination of two or more. The content of the monomer (b-3) in the binder polymer (B) is in the range of 40 to 80% by weight.

Specific examples of the alkyl acrylate useful as the monomer (b-3) include methyl acrylate, ethyl acrylate, n-propyl acrylate and iso.
-Propyl acrylate, n-butyl acrylate, s
ec-butyl acrylate, t-butyl acrylate,
2-ethylhexyl acrylate etc. are mentioned.

Examples of alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n
-Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate and the like can be mentioned.

The binder polymer (B) preferably has a weight average molecular weight in the range of 50,000 to 200,000. If the weight average molecular weight is too small, it tends to cause a cold flow phenomenon in the case of a dry film resist, and if the weight average molecular weight is too large, the unexposed portion has insufficient solubility in an alkaline developer, and its developability is poor, It takes a long time to develop and tends to cause a reduction in resolution.

The binder polymer (B) used in the present invention is contained in an amount of 30 to 60 parts by weight per 100 parts by weight of the resin component. The content of the polymer (B) for binder is 3
When the amount is less than 0 parts by weight, the film forming property of the photosensitive layer of the obtained dry film resist is impaired, sufficient film strength cannot be obtained, and cold flow is likely to occur. Conversely, 60
If the amount is more than parts by weight, the solvent resistance of the cured product decreases.

The cross-linking curable resin composition of the present invention contains at least one hydroxyl group-containing monomer component so that the surface of the cross-linked curable resin after curing can be roughened with an acid or an alkali. The polymer (C) for a water-soluble binder is contained in an amount of 10 to 40% by weight. Examples of the water-soluble binder polymer (C) include polyvinyl alcohol resin,
Examples thereof include polyvinyl acetal resins obtained by acetalizing polyvinyl alcohol with an acid catalyst.

The water-soluble binder polymer (C) preferably has a weight average molecular weight of 10,000 to 70,000. If the weight average molecular weight is too small, the adhesiveness between the photosensitive layer and the protective film of the obtained dry film resist becomes too high, and the handling property of the dry film resist in the use process is deteriorated, which is not preferable. If the weight average molecular weight is too large, roughening becomes difficult even if the surface of the crosslinked cured resin after curing is treated with acid or alkali.

When the water-soluble binder polymer is a polyvinyl acetal resin, the monomer component thereof is composed of three units of vinyl alcohol unit, vinyl acetal unit, and vinyl acetate unit, and when the proportion of vinyl acetate increases, the resin becomes Since it becomes softer and the heat distortion temperature decreases, DF
When R is thermocompression-bonded, the film becomes too soft and the workability deteriorates, which is not preferable. Further, when the polyvinyl acetal resin has the same molecular weight, the viscosity increases as the proportion of vinyl alcohol units increases, that is, as the concentration of hydroxyl groups increases, which is not preferable because it becomes difficult to handle when processed into DFR. Therefore, when increasing the concentration of hydroxyl groups, it is necessary to control the molecular weight in consideration of handling.

The water-soluble binder polymer (C) used in the present invention is 10 to 3 in 100 parts by weight of the resin component.
0 parts by weight are contained. Polymer for water-soluble binder (C)
Is less than 10 parts by weight, it is not preferable because sufficient roughening cannot be achieved and sufficient adhesion strength cannot be obtained even after treatment with acid or alkali after curing. On the other hand, if it exceeds 30 parts by weight, the alkali resistance, solvent resistance, heat resistance, etc. after curing will be significantly reduced.

The crosslinkable curable resin composition of the present invention contains a block type polyisocyanate compound (D).
The block type polyisocyanate compound is generally called a block isocyanate or a blocked polyisocyanate, and is a compound stable at room temperature obtained by reacting a polyisocyanate compound with a compound (blocking agent) having a certain active hydrogen. is there.

Examples of the block type polyisocyanate compound used in the present invention include tolylene diisocyanate, xylylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate) and trimethyl. Hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate and their adducts, biurets, isocyanurates and the like pre-polymer stabilized with a blocking agent, for safety and hygiene,
It is preferable to use a prepolymer having a low vapor pressure,
Particularly preferred are isocyanurate compounds that are chemically and thermally stable.

In the resin composition of the present invention, the isocyanate group regenerated by heat reacts with the hydroxyl group or the carboxyl group contained in the binder polymer (B) to crosslink the binder polymers (B) with each other, Makes the cured resin crosslinked by light stronger.

The block type polyisocyanate compound (D) is contained in an amount of 1 to 20 in 100 parts by weight of the resin component of the present invention.
It is contained in parts by weight. If the amount is less than 1 part by weight, a high degree of alkali resistance of the cured product cannot be sufficiently obtained. If the amount exceeds 20 parts by weight, the dissociated isocyanate groups remain in the resin in an unreacted state, which may lead to deterioration of the electrical insulating property of the cured product, which is not preferable.

As the photopolymerization initiator (E) for photopolymerizing the resin component of the present invention, conventionally known ones can be used depending on the light source such as ultraviolet rays and visible rays. Specific examples of the UV initiator include benzophenone, Michler's ketone, 4,4-bis (diethylamino) benzophenone,
Known materials such as t-butyl anthraquinone, 2-ethyl anthraquinone, thioxanthones, benzoin alkyl ethers and benzyl dimethyl ketals can be used, and two or more kinds thereof may be used in combination.

The photopolymerization initiator (E) is contained in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the resin component of the present invention. If the content of the photoinitiator is less than 0.01 parts by weight, the composition will not be sufficiently photocured, while if it exceeds 10 parts by weight, the composition will be thermally unstable.

In the crosslinkable curable resin composition of the present invention, an adhesion promoter may be added as an additional component to the crosslinkable curable resin composition, particularly when adhesion to a metal such as copper is required. it can.

Specific examples of the adhesion promoter include benzotriazole, tolyltriazole, carboxybenzotriazole, benzimidazole, benzothiazole, rhodanine, 5-phenyl-1H-tetrazole, 1-phenyl-5-mercaptotetrazole and 1-methyl. -5
-Mercaptotetrazole, 5-mercaptotetrazole, 5-aminotetrazole and the like can be mentioned, but an adhesion promoter containing 5-aminotetrazole as a main component is preferable from the viewpoint of improving the adhesion to the substrate. Examples of the compound that can be used in combination with 5-aminotetrazole include 5-
A heterocyclic compound containing an element that easily forms a coordinate bond with a metal, such as a tetrazole derivative other than aminotetrazole, a triazole derivative, an imidazole derivative, a thiazole derivative, and a thiadiazole derivative can be used.

The amount of the adhesion promoter added is preferably 0.005 parts by weight or more from the viewpoint of adhesion to metal. From the viewpoint of solubility and cost, it is preferably 5 parts by weight or less.

When the cross-linking curable resin composition of the present invention is used as a protective film for plastic molded products, glass substrates, etc., or as a structural material for spacers of optical parts, the above adhesion promoter is unnecessary. Is.

If desired, various additives such as a thermal polymerization inhibitor, a dye, a flame retardant, an isocyanate reaction catalyst, a plasticizer and a filler may be added to the crosslinkable curable resin composition of the present invention.

In the present invention, in order to obtain the desired crosslinked curable resin, it is preferable to use the above specific crosslinkable curable resin composition and to proceed the curing sufficiently.

As a method for sufficiently promoting the curing,
Various methods conventionally known in the field of paints and the like can be used. Examples of the method that can be used include ultraviolet irradiation by a high-pressure mercury lamp or the like, visible light irradiation by an argon laser or the like, since the crosslinkable curable resin composition of the present invention is composed of a photocrosslinking component and a thermal crosslinking component, It is preferable to combine heat curing with these methods.

[0039] As the ultraviolet radiation energy in the case of ultraviolet irradiation, 0.5 J / cm ² is preferably used in a range of to 10 J / cm ^2, the temperature of the substrate and the solder resist by irradiation with ultraviolet rays is excessively If you go up,
It is preferable to irradiate several times.

Further, the heat treatment used in combination with the ultraviolet irradiation treatment dissociates the blocking agent of the block type polyisocyanate compound and promotes the reaction of the produced isocyanate group,
It is effective in forming a crosslinked structure. As a heating method, for example, far-infrared heating, a heating furnace, or the like can be used.
It is preferable to carry out the treatment within the range of not more than the time.

Using the cross-linking curable resin composition of the present invention, D
When manufacturing FR, a well-known thing can be used for a support film and a protective film. However, in order to further enhance the anchor effect of the multilayer wiring printed circuit board, it is preferable to use a support film having a surface roughened by sand mat or chemical mat processing. As a material of such a film, a plastic material can be mentioned, but when the active film such as ultraviolet rays is irradiated and cured, the support film preferably has a high light transmittance. Furthermore, since a hot roll laminator is used when laminating this DFR on a substrate, it is preferable to use one having a small heat shrinkage. Therefore, specific examples of the support film include a polyester film and a polyethylene naphthalate film. The thickness of the support film is preferably 10 to 40 μm. If it is too thin, heat shrinkage tends to occur during lamination, and if it is too thick, it is disadvantageous in terms of cost and the resolution decreases. In the present invention, by forming a cross-linking curable resin composition on the roughened surface of this support film, one kind of unevenness necessary for improving the adhesion strength with plated copper, which will be described in detail later, can be easily formed. It becomes possible to do.

[0042]

The present invention will be described below in more detail with reference to examples. Examples 1 to 3 and Comparative Example 1 An alkali development type DFR was manufactured under the following conditions. First, an ethylenically unsaturated compound (A), a polymer for a binder (B), a water-soluble binder polymer (C) a blocked isocyanate compound (D), benzyl dimethyl ketal and other components are blended and crosslinked as shown in Table 1. A curable resin composition solution was obtained. 30 parts by weight of the polymer (C) for water-soluble binder is a mixed solution of 70% by weight of methyl ethyl ketone and 30% by weight of isopropyl alcohol.
What was dissolved in 0 parts by weight was used.

Next, this cross-linking curable resin composition solution was applied on a polyester film having a thickness of 20 μm so that the thickness after drying would be 75 μm, and then the solvent was dried by heating, and further, a polyethylene having a thickness of 30 μm was applied thereon. After stacking the films, slit both ends, width 300 mm and length 50
m was wound on a roll to prepare a DFR. A crosslinked cured resin was formed by the following method using each of the alkali developable DFRs produced by the above method, and the performance thereof was evaluated as follows.

In Examples 1 to 3, the DFR surface was roughened, but in Comparative Example 1, it was not roughened.

[Printed Wiring Board for Test] The following printed wiring board was used for performance evaluation as a solder resist. -Substrate; glass epoxy double-sided copper-clad laminated substrate having a solid copper portion of 5 cm x 5 cm or more [Method of forming cross-linking cured resin] (1) Laminate Using a vacuum laminator HLM-V570 (manufactured by Hitachi Capacitor Co., Ltd.) A dry film resist was laminated on a printed wiring board under the following laminating conditions. Substrate preheating roller temperature 120 ° C. Heat shoe temperature 100 ° C. Laminating pressure (cylinder pressure) 5 kgf / cm ² Pressure in vacuum chamber 10 mmHg Laminating speed 0.8 m / min (2) Exposure Solder on both sides of substrate laminated with dry film resist Photo resist masks are overlaid, and a DFR exposure machine HTE-106 (manufactured by Hitec Co., Ltd.) is used.
25-step step tablet (manufactured by Mitsubishi Rayon Co., Ltd.)
Then, the exposure was performed so that the remaining 15 steps would be left.

(3) Development The supporting film was peeled off from the exposed substrate, and spray development was carried out with a 1% sodium carbonate aqueous solution at 30 ° C. using a conveyor type developing machine. The time during which the unexposed portion can be completely removed by development was defined as the "minimum development time", and the subsequent processing and evaluation used the product developed for twice the minimum development time.

(4) Washing with water and drying The substrate after development was sprayed with tap water at room temperature for 1 minute, water on the substrate was removed with an air knife, and further dried at 70 ° C for 5 minutes.

(5) Post-curing After irradiation with ultraviolet rays from a high-pressure mercury lamp at 1 J / cm ² × 3 times, heat treatment was carried out at 180 ° C. for 1 hour.

[Evaluation Method] The sample prepared by the above-mentioned forming method was roughened by the following procedure, and the surface of the sample was observed to evaluate the degree of roughening of the surface.

(1) Mackyudizer 9 heated to 70 ° C.
After immersing in 204JH (hole conditioner solution made by MacDermid Japan) for 5 to 10 minutes, it was washed with water and drained for 3 minutes.

(2) Immersion in a 7% potassium permanganate aqueous solution heated to 80 ° C. for 5 minutes, followed by washing with water for 6 minutes and draining.

Examples 4 to 6 and Comparative Example 2 In Examples 1 to 3 and Comparative Example 1, instead of the 20 μm thick polyester film, a 38 μm thick sand-matted polyester film (Dia foil Hoechst # 38W-) was used. 1 mat product), and a laminate was manufactured in the same manner as in Examples 1 to 3 and Comparative Example 1 except that the crosslinked curable resin composition solution was applied onto the roughened surface. evaluated. In addition, Examples 4, 5, 6 and Comparative Example 2 correspond to Examples 1, 2, 3 and Comparative Example 1, respectively. In Examples 4 to 6, the surface of the cured resin layer was roughened, and two types of irregularities having different shapes and sizes were formed. One of the irregularities was due to the support film. In Comparative Example 2, the surface of the cured resin layer was not roughened.

[0053]

[Table 1]

[0054]

EFFECTS OF THE INVENTION The cross-linking curable resin composition of the present invention can be used as an interlayer insulating film of a multi-layer printed circuit board by a build-up method because the resist surface can be roughened by treatment with a solvent such as acid or alkali after curing. can do. Further, according to the laminate of the present invention, it is possible to form an interlayer insulating film having good adhesion.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03F 7/004 512 G03F 7/004 512 7/033 7/033 (72) Inventor Seiichi Nomi Hiroshima Prefecture 20-1 Miyukicho, Otake-shi Central Research Laboratory, Mitsubishi Rayon Co., Ltd.

Claims (6)

[Claims] 1. At least one 30 to 60 parts by weight of an ethylenically unsaturated compound (A) having two or more (meth) acryloyloxy groups in one molecule, and an α, β-unsaturated carboxyl group-containing unit amount. At least one kind of body (b-1) 15
To 30% by weight, at least one kind of the hydroxyl group-containing monomer (b-2) 5 to 30% by weight, and another copolymerizable monomer (b-3) 40 to 80% by weight. 30 to 60 parts by weight of polymer (B), 10 to 30 parts by weight of a water-soluble binder polymer (C) containing 10 to 40% by weight of a hydroxyl group-containing monomer unit, and block type polyisocyanate compound (D) 1 to 20 parts by weight, and 0.001 to 10 parts by weight of the photopolymerization initiator (E) is mixed with 100 parts by weight of the components (A), (B), (C) and (D) in total. Crosslinking curable resin composition. 2. The crosslinkable curable resin composition according to claim 1, wherein the water-soluble binder polymer (C) is a polyvinyl acetal obtained by acetalizing polyvinyl alcohol. 3. A method of cross-linking and curing the cross-linking curable resin composition according to claim 1 or 2, using light irradiation and heat treatment in combination. 4. A laminate comprising a support film having a roughened surface formed by sand mat or chemical mat processing, the cross-linking curable resin composition according to claim 1 and a protective film, which are sequentially laminated. 5. The laminate according to claim 4, wherein the water-soluble binder polymer (C) is a polyvinyl acetal obtained by acetalizing polyvinyl alcohol. 6. A method of cross-linking and curing the cross-linking curable resin composition according to claim 4 or 5 by using light irradiation and heat treatment in combination.