JPH07256832A - Crosslink curable resin composition laminate - Google Patents

Abstract

PURPOSE:To obtain a thin crosslink curable resin composition laminate which can be used as metal working resist and high resolution by laminating a support film, a crosslink curable resin layer made of specific crosslink curable resin composition having a specific thickness value and a protective film. CONSTITUTION:A crosslink curable resin composition laminate is formed of a support film, a crosslink curable resin layer and a protective film. Crosslink curable resin composition for forming the layer is formed of thermoplastic polymer for binder in which one type of alpha,beta-unsaturated carboxyl group- containing monomer having 3-15 carbons atoms of a range of 15-35wt.% is copolymerized with other copolymerizable monomer of 85-65wt.%, one type of crosslinkable monomer having two or more ethylene unsaturated groups in one molecule, photopolymerization initiator and ultraviolet absorber, wherein 0.01-10 pts.wt. of the absorbent is contained in total 100 pts.wt. of the thermoplastic polymer and the crosslinkable monomer. A thickness of the layer is 1-30mum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having a photopolymerizable resin composition developable with an alkaline aqueous solution.

[0002]

2. Description of the Related Art In recent years, a so-called dry film resist having a structure in which a cross-linking curable resin layer is sandwiched between a protective film and a support film has been widely used as a photoresist for producing a printed wiring board.

As the cross-linking curable resin layer, there are known a solvent developing type which develops and removes an unexposed portion with a chlorine-based organic solvent and an alkaline developing type which develops and removes an unexposed portion with an alkaline aqueous solution. Alkali-developing dry film resists have become the mainstream because of their effects on production cost and manufacturing cost.

The method of using an alkali-developing dry film resist having a protective film and a supporting film is as follows. First, while the protective film is peeled from the dry film resist, the cross-linking curable resin surface is laminated on a copper clad laminate by heat. Then, a photo tool is brought into close contact with the support film surface of the resist film, and the portion to be cured is exposed and cured with ultraviolet rays or the like. Then, after removing the supporting film, the unexposed portion is developed and removed with a weak alkaline aqueous solution such as sodium carbonate to obtain a resist circuit pattern. Then, in the case of the copper through-hole method, after etching the copper surface, the hardened resist is peeled off with a strong alkaline aqueous solution such as sodium hydroxide to obtain a printed wiring board. In the case of the solder through-hole method, after the copper plating and the solder plating are performed, the cured resist is peeled off with a strong alkaline aqueous solution, and the exposed copper is etched to obtain a printed wiring board.

In recent years, attempts have been made to use this dry film resist for metal processing such as manufacturing of lead frames. That is, in metal processing by etching or plating, a dry film resist that has been conventionally used for manufacturing a printed wiring board is used as a resist for the etching or plating.

Up to now, there have been two resists in metal processing.
Liquid type liquid resists were the mainstream, but in this case, there were problems such as short pot life after mixing the two liquids, difficult uniform coating, poor working environment, and difficult waste liquid treatment. . However, there have been problems that the dry film resist that has been conventionally used for manufacturing a printed wiring board is too thick even if it is used as it is, or that the required resolution cannot be achieved even if the thickness is reduced.

[0007]

DISCLOSURE OF THE INVENTION An object of the present invention is to overcome the above-mentioned drawbacks and to use as a resist for metal processing, which has a high resolution and a thin cross-linking curable resin composition laminate (dry film resist). ) Is to provide.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, by incorporating an ultraviolet absorber in the resin composition of a cross-linking curable resin composition laminate, The inventors have found that the object of (1) is achieved and completed the present invention. That is, the present invention includes a support film (A), a crosslinkable curable resin layer (B), and a protective film (C).
In the cross-linked curable resin composition laminate, the cross-linked curable resin layer (B) has an α, β-unsaturated carboxyl group-containing monomer having 3 to 15 carbon atoms. Thermoplastic polymer (b-1) for a binder, which is obtained by copolymerizing at least one of the above with 85 to 65% by weight of another copolymerizable monomer in the range of 15 to 35% by weight, and 2 or more in one molecule. Of at least one crosslinkable monomer (b-2) having an ethylenically unsaturated group, a photopolymerization initiator (b-3) and an ultraviolet absorber (b-4), and an ultraviolet absorber ( b-
4) is 0.0 with respect to the total 100 parts by weight of the thermoplastic polymer for binder (b-1) and the crosslinkable monomer (b-2).
1 to 10 parts by weight is contained, and the cross-linking curable resin layer (B) has a thickness of 1 to 30 μm.

As the support film (A) used in the present invention, any commercially available transparent plastic film can basically be used, but when the resin composition is cured by irradiation with ultraviolet rays, Since irradiation is performed through this support film, the support film (A) preferably has a high light transmittance, and preferably does not scatter transmitted light.

Furthermore, since a hot roll laminator is used when laminating this cross-linking curable resin composition laminate on a substrate, it is preferable that the shrinkage due to heat is small.

Specific examples of the support film (A) include PET film (polyethylene terephthalate film) and PEN film (polyethylene naphthalate film).

The thickness of the support film (A) is 10 to 40 μm.
m is preferred. If it is too thin, heat shrinkage tends to occur at the time of lamination, and if it is too thick, it is disadvantageous in terms of cost and the resolution tends to decrease.

The thermoplastic polymer for binder (b- which constitutes the crosslinking curable resin composition (B) in the present invention.
1) is a copolymer component containing one or more α, β-unsaturated carboxyl group-containing monomers having 3 to 15 carbon atoms so that it can be developed with a dilute aqueous alkali solution such as sodium carbonate. It is necessary to copolymerize at a ratio of 35% by weight.

Examples of carboxylic acid type monomers that can be used include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, itaconic acid, propiolic acid, maleic acid and fumaric acid. , These half-esters or anhydrides can also be used. The most preferred compounds among these are acrylic acid and methacrylic acid.

It is necessary to use these carboxylic acid type components so that the content in the copolymer is in the range of 15 to 35% by weight. If the content of the carboxylic acid type component in the copolymer is less than 15% by weight, it cannot be developed by an alkaline aqueous solution, or the development time is too long and the resolution is lowered. On the other hand, when the copolymerization amount of the carboxylic acid type component exceeds 35% by weight, the photo-cured part to be left as a pattern is easily swollen and removed by the alkaline developing solution, and therefore a high resolution pattern is obtained by developing. It becomes difficult to control, and the water resistance of the cured part also decreases.

The thermoplastic polymer for binder (b- which constitutes the cross-linking curable resin composition (B) in the present invention.
As other copolymerizable component constituting 1), a compound represented by the general formula [I]

[0017]

[Chemical 2]

(Wherein R is H, an alkyl group having 1 to 6 carbon atoms or a halogen atom), and one or more compounds selected from the group consisting of ring-substituted derivatives thereof. 2 to 25% by weight of the second polymerizable compound consisting of, and further, an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and a hydroxyalkyl group having 2 to 8 carbon atoms. Third polymerizable substance 10 comprising one or more compounds selected from the group consisting of hydroxyalkyl acrylates
-40% by weight, and one or more compounds selected from the group consisting of alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms and hydroxyalkyl methacrylate having a hydroxyalkyl group having 2 to 8 carbon atoms. It is preferable that the fourth polymerizable substance consisting of 30 to 70% by weight.

The second polymerizable substance which can be copolymerized with the thermoplastic polymer (b-1) for binder is represented by the general formula [I].

[0020]

[Chemical 3]

(Wherein R is H, an alkyl group having 1 to 6 carbon atoms or a halogen atom) and a ring-substituted derivative thereof.

As a substituent of the benzene ring, a nitro group,
Examples thereof include an alkyl group, an alkoxy group, an acyl group, a carboxyl group, a sulfone group, a hydroxyl group and halogen, and the substitution residue of the benzene ring may be in the range of 1 to 5. Preferred substituents are single alkyl groups such as methyl or t-butyl groups. The most preferred of these compounds is styrene.

These second polymerizable components are preferably copolymerized in the thermoplastic polymer for binder (b-1) in an amount of 2 to 25% by weight, more preferably 3 to 20. % By weight. When the copolymerization amount of the component is less than 2% by weight, excellent chemical resistance, particularly plating resistance, tends not to be sufficiently exhibited, and conversely, when the component exceeds 25% by weight, it is obtained. There is a tendency that the development time and the peeling time of the dry film resist become too long and the resolution of the dry film resist decreases.

The third polymerizable substance which can be contained in the thermoplastic polymer (b-1) for binder is an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and a hydroxyalkyl group having 2 to 8 carbon atoms. Is at least one kind of hydroxyalkyl acrylate having Examples of these compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate. , 2-ethylhexyl acrylate and the like. Most preferred of these compounds are
Methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate.

These acrylate-type components impart appropriate flexibility to the photopolymerizable or radiation-curable resin composition of the present invention, so that the thermoplastic polymer (b) for a binder is used.
It is desirable to copolymerize -1) so as to be in the range of 10 to 40% by weight, and a more preferable range is 15 to 35% by weight. Acrylate type component content is 10% by weight
If the amount is less than that, a sufficiently flexible dry film resist cannot be obtained, the adhesion to the substrate is insufficient, and the plating resistance and etching resistance of the resist tend to decrease.
On the other hand, when the copolymerization amount of the third polymerizable substance exceeds 40% by weight, on the contrary, the resist resin is too soft, and when the resulting dry film resist is rolled and stored, It tends to cause a so-called cold flow phenomenon, which exudes with time from between the support films.

The fourth polymerizable substance which can be copolymerized in the binder thermoplastic polymer (b-1) is combined with an alkyl acrylate or a hydroxyalkyl acrylate, and has a Tg suitable for the binder thermoplastic polymer (b-1). At least one of alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms and hydroxyalkyl methacrylate having a hydroxyalkyl group having 2 to 8 carbon atoms, which is copolymerized to give (glass transition temperature). is there. Examples of these compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate,
Examples thereof include n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 2-ethylhexyl methacrylate. The most preferred of these compounds is methyl methacrylate.

These methacrylate components are preferably copolymerized in the thermoplastic copolymer (b-1) for binder so as to be in the range of 30 to 70% by weight, more preferably 35 to 65% by weight. is there.

The thermoplastic polymer (b-1) for binder used in the present invention is a cross-linking curable resin composition 100.
It is preferable that the amount is 45 to 75 parts by weight, preferably 50 to 70 parts by weight. When the content of the thermoplastic polymer for binder (b-1) is less than 45 parts by weight, the film-forming property of the cross-linking curable resin layer of the obtained dry film resist is easily impaired, and it is difficult to obtain sufficient film strength. However, cold flow is likely to occur and the peeling time tends to be long. On the other hand, when the content of the thermoplastic polymer (b-1) exceeds 75 parts by weight, the flexibility of the resin composition is low and the adhesive force with the surface of the base material is likely to be impaired. Further, the cured film after exposure of such a resin composition is likely to lose the gloss of the surface when developed, or to be unable to obtain sufficient chemical resistance, particularly plating resistance and etching resistance.

Next, at least one crosslinkable monomer (b-2) having two or more ethylenically unsaturated groups in one molecule, which constitutes the crosslinkable curable resin composition of the present invention, will be described. To do.

Specific examples of the crosslinkable monomer include 1,3
-Butanediol di (meth) acrylate, 1,6-hexanediol 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 [polyethoxy (meth) acrylate], trimethylolpropane tris [polypropyleneoxy (meth) acrylate], isocyanuric acid triethyloldi (meth) ) Acrylate,
Isocyanuric acid triethylol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate Poly (meth) acrylates of polyhydric alcohols such as acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylates and urethane (meth) acrylates, and the like, These can be used alone or in combination of two or more.

The crosslinkable monomer (b-) having two or more ethylenically unsaturated groups in one molecule used in the present invention.
2) is preferably contained in an amount of 25 to 55 parts by weight in 100 parts by weight of the crosslinkable resin composition of the present invention. When the content of the crosslinkable monomer (b-2) is less than 25 parts by weight, the gloss of the surface is likely to be lost when developed with an alkaline aqueous solution. On the other hand, when a dry film resist having a content of the crosslinkable monomer (b-2) of more than 55 parts by weight is used, the unexposed resin composition becomes too soft and cold flow or the like may occur. Inconvenient problems are likely to occur.

An ultraviolet polymerization initiator is used as the photopolymerization initiator (b-3) used for photopolymerizing the crosslinking curable resin composition in the present invention. Examples thereof include benzophenone, Michler's ketone and 4,4'-bis. (Diethylamino) benzophenone, t-butylanthraquinone,
Known compounds such as 2-ethylanthraquinone, thioxanthones, benzoin alkyl ethers, and benzyl ketals can be used, or two or more kinds may be used in combination.

The photopolymerization initiator (b) used in the present invention
-3) is usually a thermoplastic polymer for binder (b-
0.1 to 10 parts by weight based on 100 parts by weight of the total of 1) and the crosslinkable monomer (b-2). If the amount is less than 0.1 part by weight, photo-curing is difficult to occur sufficiently, while if the amount exceeds 10 parts by weight, thermal instability tends to occur.

The cross-linking curable resin composition laminate of the present invention is used for metal working, and the base material used for metal working is usually a copper alloy, a stainless plate, a 42 alloy material or the like. Usually, only degreasing treatment is performed on these metal base materials, and it is rare to polish the surface like a copper clad laminate which is a printed wiring board material.

The surface of the metal substrate as described above is very smooth, and when the crosslinkable resin composition is cured, the reflection of ultraviolet rays on the surface of the metal substrate is very large. Furthermore, as a resist for metal processing, a resist having a smaller thickness is required as compared with a conventional cross-linking curable resin composition used for producing a printed wiring board. The reflection (halation) of ultraviolet rays on the surface of the material greatly affects the resolution of the material.

As a method for preventing the influence of reflection (halation) of ultraviolet rays on the surface of a metal substrate, Japanese Patent Publication No. 51-3
7562, JP-A-59-2114847 and JP-A-62.
The method of adding a light-absorbing substance, a so-called dye, is described in each publication of No. -30241. However,
In this method, the heat stability of the light-absorbing substance is low, unnecessary coloring occurs in the cross-linking curable resin composition containing the light-absorbing substance, the sensitivity is lowered, and the adhesiveness to the metal substrate is lowered. There was a problem to do.

Considering this point, as a result of earnest study,
An ultraviolet absorber (b- as an active energy ray absorber for preventing the influence of halation in the crosslinkable curable resin composition).
It was found that the addition of 4) is very effective in preventing the deterioration of resolution.

As the compound to be used, a commonly used ultraviolet absorber can be used. Specifically, salicylic acid-based compounds,
At least one selected from benzophenone compounds, benzotriazole compounds, and cyanoacrylate compounds can be used.

More specific compounds include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-. Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-
Dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2
-(2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3
′, 5′-Di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-
Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy) -3 ', 5'-The-
tert-amylphenyl) benzotriazole, 2-
{2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ′
′, 6 ″ -Tetrahydrphthalimidomethyl) -5′-
Methylphenyl} benzotriazole, 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate and the like can be mentioned.

The ultraviolet absorber used in the present invention is
0.01 to 10 relative to 100 parts by weight of the total amount of the thermoplastic polymer for binder (b-1) and the crosslinkable monomer (b-2).
It is contained in parts by weight. If the amount is less than 0.01 parts by weight, the antihalation effect is not sufficiently exhibited, while if it exceeds 10 parts by weight, it is disadvantageous in terms of cost and the sensitivity tends to be lowered.

The cross-linking curable resin composition of the present invention comprises a polymerization having one ethylenically unsaturated group in one molecule for the purpose of adjusting the cross-linking density of the cured product and obtaining appropriate flexibility. A polymerizable monomer may be added. Examples of compounds include phenoxydiethoxy (meth) acrylate, methoxypolyethylene glycol (meth) acrylate,
Examples thereof include n-butoxymethyl acrylamide and iso-butoxymethyl acrylamide, which may be used alone or in combination.

The amount of the polymerizable monomer having one ethylenically unsaturated group in one molecule is such that two or more ethylenically unsaturated groups are contained in one molecule constituting the resin composition of the present invention. It is preferable to use the crosslinking monomer (b-2) in an amount that does not exceed the amount used. If the usage exceeds
Although the flexibility of the obtained resin composition is improved, the crosslink density becomes too low, and the chemical resistance of the cured product tends to decrease.

The crosslinkable curable resin composition of the present invention may contain an adhesion promoter such as tetrazole or its derivative in order to further improve the adhesion to the metal surface of the substrate. Tetrazole or a derivative thereof can improve adhesion to a metal surface with a small amount of addition, and examples thereof include 1-phenyltetrazole, 5-phenyltetrazole, 5-aminotetrazole and 5-amino-.
1-methyltetrazole, 5-amino-2-phenyltetrazole, 5-mercapto-1-phenyltetrazole, 5-mercapto-1-methyltetrazole and the like can be mentioned, and these can be used alone or in combination.

The amount of tetrazole or its derivative used is
0.005 to 5 per 100 parts by weight of the total of the thermoplastic polymer for binder (b-1) and the crosslinkable monomer (b-2).
It is preferably in the range of parts by weight. If it is less than 0.005 part by weight, the adhesion to the metal surface of the base material tends to be insufficient, while if it exceeds 5 parts by weight, it takes a long time to dissolve in the crosslinkable resin composition, and crosslinking cure The sensitivity of the mold resin composition also tends to decrease.

The crosslinkable curable resin composition of the present invention comprises
If necessary, components such as a thermal polymerization inhibitor, a dye, a plasticizer and a filler can be added.

The crosslinkable curable resin composition of the present invention comprises
Dissolving and mixing each of the above components in a solvent having a not too high boiling point, for example, one or more of acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, dichloromethane, chloroform, methyl alcohol, ethyl alcohol, isopropyl alcohol, etc. It can be used as a simple solution. The amount of these solvents used is 200 parts by weight or less, preferably 50 to 150 parts by weight, based on 100 parts by weight of the total amount of the thermoplastic polymer for binder (b-1) and the crosslinkable monomer (b-2). .

The thickness of the crosslinking curable resin composition in the present invention is preferably 1 to 30 μm. If it is less than 1 μm, there is a problem in the strength of the cured film, and if it exceeds 30 μm, the resolution is low and it cannot be used. More preferably, it is 5 to 25 μm.

As the protective film (C) used in the present invention, basically any commercially available transparent plastic film can be used, and specific examples include PE film (polyethylene film) and PP film ( Polypropylene film). The thickness of the support film (C) is preferably 10 to 40 μm.

Next, the method of using the crosslinkable curable resin composition of the present invention will be described.

First, as a first step, a cross-linking curable resin layer made of the above-mentioned cross-linking curable resin composition is formed on the metal surface of the target substrate.

The crosslinking curable resin composition of the present invention comprises
The solution-like resin composition is applied onto a support film such as polyethylene terephthalate and dried to form a dry film resist, which is laminated on a substrate to form a crosslinkable curable resin layer. To form a dry film resist using the crosslinking curable resin composition of the present invention,
Blade coater, rod coater, knife coater,
It can be applied using a roll doctor coater, comma coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, curtain coater, etc., but it is necessary to vaporize the solvent. When using a flammable organic solvent as the dryer, use one equipped with an air heating type heat source by steam from the viewpoint of safety, a method of countercurrent contact with hot air in the dryer and a nozzle to support A spraying method or the like is used. The shape of the dryer is selected according to the purpose, such as an arch type or a flat type, and used.

The dried dry film resist is preferably laminated with a protective film such as polyethylene or polypropylene.

As the method for laminating the dry film resist on the substrate, various methods known in the art can be used. After peeling off the protective film of the crosslinkable resin composition laminate of the present invention, the substrate is The resin composition surface is laminated on the surface by, for example, a normal pressure heat roll pressure bonding method, a vacuum heat roll pressure bonding method, a vacuum heat press pressure bonding method, or the like.

When this dry film resist is laminated on a substrate, in order to improve the filling of the resist with scratches on the surface of the substrate, the temperature is usually about 120 ° C. for lamination. Next, the cross-linking curable resin layer is exposed to ultraviolet light through a photomask to form a pattern.

Next, after peeling the supporting film (A),
The uncured portion (unexposed portion) is removed using an alkaline developer. As the alkaline developer, for example, an aqueous solution of sodium carbonate, an aqueous solution of sodium phosphate, an aqueous solution of potassium carbonate can be used, and a small amount of a defoaming agent or a surfactant can be added to these aqueous solutions. Further, a spray method is most commonly used as a removing method, but a part thereof can be replaced by a dipping method.

[0056]

EXAMPLES The present invention will be specifically described below based on examples.

Synthesis Example 1 (thermoplastic polymer A for binder
Ingredients) The following ingredients were prepared.

(Polymerizable monomer) Methacrylic acid 50 g Styrene 20 g Methyl acrylate 50 g Methyl methacrylate 80 g (Solvent) Methyl ethyl ketone 100 g Isopropyl alcohol 220 g (Polymerization initiator) Azobisisobutyronitrile 2 g Nitrogen inlet, stirrer, condenser and temperature In a 1000 ml four-necked flask equipped with a meter, put all of methacrylic acid, styrene, methyl acrylate, methyl methacrylate and methyl ethyl ketone, 140 g of isopropyl alcohol and 0.4 g of azobisisobutyronitrile under a nitrogen atmosphere and stir. While raising the temperature of the hot water bath to 80 ° C., polymerization was carried out at that temperature for 2 hours. Then, the remaining amount of azobisisobutyronitrile was added in 5 batches every 1 hour, the temperature inside the flask was raised to the boiling point of the solvent, and the polymerization was continued at that temperature for 2 hours. After that, when the temperature inside the flask became 50 ° C. or lower, the remaining amount of isopropyl alcohol was added and the polymerization reaction product was taken out from the flask to obtain a solution of the thermoplastic polymer A. The polymerization rate of the monomer mixture in the thermoplastic polymer A is 99.5% or more,
The solid content in the thermoplastic polymer solution was 38.7% by weight.

Examples 1 to 7 and Comparative Examples 1 to 2 Using the synthesized thermoplastic polymer A, a cross-linking curable resin composition solution having the composition shown in Table 1 was prepared.

[0060]

[Table 1]

1)

[Chemical 4]

2)

[Chemical 5]

3)

[Chemical 6]

4) Compound A: p-tert-butylphenyl salicylate 5) Compound B: 2-hydroxy-4-methoxybenzophenone 6) Compound C: 2-hydroxy-4-octoxybenzophenone 7) Compound D: 2- ( 2'-hydroxy-5'-methylphenyl) benzotriazole 8) Compound E: 2- (2'-hydroxy-3'-ter
t-Butyl-5'-methylphenyl) -5-chlorobenzotriazole 9) Compound F: 2-ethylhexyl-2-cyano-3,
3′-diphenyl acrylate This adjusted composition solution was stirred with a propeller-type mixer to give a coating width of 3 on a polyester film having a thickness of 20 μm.
It was applied to a thickness of 00 mm and then dried using a hot air drier so that the thickness of the crosslinkable curable resin composition was 15 μm. Subsequently, a polyethylene protective film having a thickness of 30 μm was laminated on the dried coating film, slit into a width of 250 mm and wound on a roll to a length of 120 m.

Evaluation methods -Lamination on substrate The obtained dry film resist was laminated on a copper alloy substrate whose coating film surface was degreased while peeling off the protective film.

Laminating conditions: Laminating temperature = 120 ° C. Laminating pressure = 1.6 kg / cm ² Laminating speed = 1.5 m / min Minimum development time 1% by weight carbonic acid after peeling the supporting film from the above laminated product The time (minimum development time) required to wash off the cross-linking curable resin layer with a sodium aqueous solution until the surface of the substrate was exposed was measured.

The developing conditions were as follows. The results are shown in Table 2.
It was shown to.

Development conditions: developer temperature = 30 ° C. spray pressure = 1.6 kg / cm ² · sensitivity A 25-step step tablet manufactured by Mitsubishi Rayon Co., Ltd. was brought into close contact with the support film of the above laminate.
Ultra high pressure mercury lamp (USH-102D manufactured by USHIO INC.)
Change the exposure time with and expose, peel the support film,
Development was carried out for twice the minimum development time measured above. The exposure time of the remaining 11 steps of the step tablet was taken as the sensitivity. The results are shown in Table 2.

Resolution: A resolution chart manufactured by Mitsubishi Rayon Co., Ltd. is adhered to the support film of the above laminated product, and the remaining 11 steps of the step tablet is exposed by an ultra-high pressure mercury lamp (USH-102D manufactured by USHIO INC.). It was exposed for a few seconds, the support film was peeled off, and development was performed for a time twice the minimum development time measured above. The state of line and space = 30/30 μm was observed. The results are shown in Table 2.

[0070]

[Table 2]

[0071]

As is apparent from the above, the cross-linking curable resin composition laminate according to the present invention effectively prevents reflection (halation) on the metal surface of the substrate, and provides high resolution required for metal processing. Has a great contribution to the metal processing industry.

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[Procedure amendment]

[Submission date] April 12, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

Examples 1 to 6 and Comparative Examples 1 to 2 Using the synthesized thermoplastic polymer A, crosslinkable curable resin composition solutions having the compositions shown in Table 1 were prepared.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

[0060]

[Table 1]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0070

[Correction method] Change

[Correction content]

[0070]

[Table 2]

Claims (2)

[Claims] 1. A cross-linking curable resin composition laminate comprising a support film (A), a cross-linking curable resin layer (B) and a protective film (C), which are laminated in this order. B) contains at least one α, β-unsaturated carboxyl group-containing monomer having 3 to 15 carbon atoms in an amount of 15 to
35% by weight of other copolymerizable monomers 85 to 6
Thermoplastic polymer for binder (b) copolymerized with 5% by weight
-1) At least one crosslinkable monomer (b-2) having two or more ethylenically unsaturated groups in one molecule, a photopolymerization initiator (b-3) and an ultraviolet absorber (b-). 4) and the ultraviolet absorber (b-4) is 0.01 per 100 parts by weight of the total of the thermoplastic polymer for binder (b-1) and the crosslinkable monomer (b-2). -10 parts by weight are contained,
A cross-linking curable resin composition laminate, wherein the cross-linking curable resin layer (B) has a thickness of 1 to 30 μm. 2. The thermoplastic polymer (b-for binder according to claim 1, which constitutes the cross-linking curable resin composition (B).
The other copolymerizable monomer constituting 1) is represented by the general formula [I] (Wherein, R is H, an alkyl group having 1 to 6 carbon atoms or a halogen atom), and one or more compounds selected from the group consisting of ring-substituted derivatives thereof. 2 to 25% by weight of the polymerizable compounds, and an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 8 carbon atoms. 10-40% by weight of a third polymerizable substance consisting of one or more compounds selected from the group consisting of
And a one or more compounds selected from the group consisting of an alkylmethacrylate whose alkyl group has 1 to 8 carbon atoms and a hydroxyalkylmethacrylate whose hydroxyalkyl group has 2 to 8 carbon atoms. A cross-linkable curable resin composition laminate, comprising 30 to 70% by weight of a polymerizable substance.