JPH09324097A - Resin composition for metal surface protection, laminate made therefrom, and production of printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. for metal surface protection which is insoluble in an aq. weak alkali soln. and can be peeled off with an aq. strong alkali soln. when applied to the surface of a copper foil of a copper-clad laminate by compounding specified amts. of a specific copolymer, a specific ethylenically unsatd. compd., and a specific compd. SOLUTION: This compsn. is prepd. by compounding the following ingredients in a specified ratio: a copolymer having a specified wt.-average mol.wt. and obtd. from specified amts. of at least one polymerizable vinyl monomer having a COOH group, at least one (3-8C)-alkyl (meth)acrylate, and at lest one hydroxy-(1-2C)-alkyl (meth)acrylate; at least one ethylenically unsatd. compd. having a b.p. of 100 deg.C or higher and selected from among compds. represented by formulas I [wherein R<1> is H or a 1-3C alkyl; X is CH2 CH2 O; Y is CH2 CH (CH3 )O, CH2 CH2 CH2 CH2 O, etc.; Z is a 2-16C hydrocarbon group; and (n), (m), (p), and (q) are each 1-14], II, and III; and a compd. represented by formula IV (wherein R<2> and R<3> are each H or CH3 ; R<4> and R<5> are each a 1-3C alkyl; and (n) is 3-9).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metal surface protective resin composition, a laminate using the same, and a method for producing a printed circuit board.

[0002]

2. Description of the Related Art As a copper clad laminate used for manufacturing a printed circuit board, one having a structure in which copper foil is laminated on both surfaces of a glass cloth-epoxy resin sheet is widely used. Further, the resist used for manufacturing the printed circuit board is described in Japanese Patent Publication No. 1-3.
A photosensitive resin composition represented by the photosensitive resin composition described in Japanese Patent No. 6924 is widely used, and a photosensitive layer comprising the photosensitive resin composition is coated on a support and dried. Laminates (hereinafter referred to as photosensitive films) are also widely used. The mainstream of these photosensitive films is the alkaline type, in which the uncured portion is soluble in a weak alkaline aqueous solution and thus developable, and the cured portion can be peeled off by a strong alkaline aqueous solution.

A printed circuit board is prepared by laminating a photosensitive layer of a photosensitive film on a copper clad laminate which has been polished or treated with chemicals, and then curing the photosensitive layer into a circuit pattern by exposure through a photo tool, and then a support. Is removed and the uncured portion is developed using a weak alkaline aqueous solution such as a 0.5 to 2.0 wt% sodium carbonate aqueous solution to form a resist image (cured portion) on the copper clad laminate. Then, after the exposed copper surface outside the resist image area is removed by etching with an etching solution, 1.0 to
It is manufactured by peeling the resist image with a 5.0% by weight aqueous solution of a strong alkali such as sodium hydroxide.

The conventional printed circuit board is mainly a printed circuit board in which a circuit is formed on both sides of a copper clad laminate or a circuit is formed on only one side of the copper clad laminate. In the process of manufacturing multilayer printed wiring boards,
There is a demand for manufacturing a printed circuit board for manufacturing a multilayer printed wiring board in which a circuit is formed on one surface of a copper-clad laminate and the other surface is left with a copper foil.

In response to this demand, in the conventional method, photosensitive layers of a photosensitive film are laminated on both sides of a copper clad laminate, and then one side (hereinafter referred to as A side) is exposed through a photo tool to form a photosensitive layer into a circuit pattern. After curing, the other surface (hereinafter referred to as "B side") is entirely exposed to completely cure the photosensitive layer, and then developed, etched and peeled to produce a printed circuit board for manufacturing a multilayer printed wiring board. Was there.

In the above manufacturing process, when a foreign substance or the like is present on the Β surface during exposure, the existing portion of the foreign substance or the like is not exposed and becomes uncured, and the uncured portion is developed to remove the resist. The copper in that portion is etched during the etching process, resulting in a fatal defect.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metal which is insoluble in a weak alkaline aqueous solution and can be peeled off by a strong alkaline aqueous solution when laminated on a metal surface such as a copper foil of a copper clad laminate. It is to provide a surface protection resin composition.

Another object of the present invention is to provide a copper clad laminate suitable for use in manufacturing a printed circuit board for manufacturing a multilayer printed wiring board.
It is an object of the present invention to provide a laminate in which a layer of the above metal protective resin composition is laminated on a support which can omit the exposure of the surface and can eliminate defects due to the inclusion of foreign matters.

Another object of the present invention is to provide a method for manufacturing a printed circuit board using the above laminate.

[0010]

The present invention provides (A) and (a)
At least one vinyl-polymerizable first monomer selected from vinyl-polymerizable monomers having a carboxyl group, (b) selected from the group consisting of alkyl acrylates and alkyl methacrylates having an alkyl group having 3 to 8 carbon atoms. At least one vinyl-polymerizable second monomer and (c)
A copolymer of at least one vinyl-polymerizable third monomer selected from the group consisting of an alkyl acrylate having an alkyl group having 1 to 2 carbon atoms, an alkyl methacrylate, a hydroxyalkyl acrylate and a hydroxyalkyl methacrylate, The content of the vinyl-polymerizable first monomer unit in the polymer is [(4-12) / t] mol%
(T represents the number of carboxyl groups per unit of the vinyl-polymerizable first monomer), and the weight average molecular weight is 30,000.
A copolymer (A) of 0 to 400,000, and (B) a general formula (I)

[0011]

[Chemical 7] (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents

[0012]

Embedded image And Y is

[0013]

Embedded image And Z represents a hydrocarbon group having 2 to 16 carbon atoms;
m, p and q are each independently an integer of 1 to 14)
A compound represented by the general formula (II)

[0014]

Embedded image (Wherein R ¹ , X, Y, Z, n, m, p, and q have the same meanings as in formula (I)) and the formula (III)

[0015]

Embedded image (In the formula, R ¹ , X, Y, Z, n, m, p and q have the same meanings as in the general formula (I)), and the boiling point of at least one selected from the group consisting of compounds is 100. An ethylenically unsaturated compound (B) having a temperature of ℃ or more, (C) the general formula (IV)

[0016]

[Chemical 12] (In the formula, R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ and R ⁵ each independently have 1 to 3 carbon atoms.
An alkyl group of n is an integer of 3 to 9) and a compound (C) represented by the formula (1) is added to the copolymer (A) and the ethylenically unsaturated compound (B) based on the total amount. The blending ratio of the polymer (A) is 50 to 80% by weight, the blending ratio of the ethylenically unsaturated compound (B) is 20 to 50% by weight,
The compounding ratio of the compound (C) is 1 to 100 parts by weight of the total amount of the copolymer (A) and the ethylenically unsaturated compound (B).
The metal surface protection resin composition is provided in an amount of 20 parts by weight.

The present invention also provides a layered product obtained by applying a solution of the metal surface protection resin composition onto a support and drying the solution.

The present invention also relates to one side (A side) of the copper clad laminate.
Laminate a photosensitive film on the other side (one side B)
After laminating the above-mentioned laminated body on, the photosensitive layer on the Α-side is exposed in a circuit pattern to remove the support of the photosensitive film and the support of the laminated body. A printed circuit board manufacturing method characterized in that the exposed part is developed, the copper foil of the copper-clad laminate is etched, and then the resin layer on the Α surface and the Β surface is peeled off with a strong alkaline aqueous solution. After laminating a photosensitive film on one surface (A surface) of the plate and laminating the laminate on the other surface (B surface), the Α surface is exposed in a pattern, and the unexposed portion of the Α surface is exposed with a weak alkaline aqueous solution. Is developed and the copper foil of the copper clad laminate is etched, and then a
The present invention provides a method for manufacturing a printed circuit board, characterized in that the resin on the surface and on the Β surface is peeled off.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the components contained in the metal surface protective resin composition of the present invention will be described in detail.

The vinyl-polymerizable first monomer (a) used in the copolymer (A) in the present invention is the copolymer (A).
A carboxylic acid having one ethylenically unsaturated group (for example, acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid,
Maleic acid or the like) or an acid anhydride thereof (for example, maleic anhydride or the like) or a half ester (for example, maleic acid half ester or the like), and among them, methacrylic acid is preferable.

The content of the vinyl-polymerizable first monomer unit in the copolymer (A) is [(4-12) / t] mol%,
[(5-10) / t] mol% is more preferable, and [(5-8) / t] mol% is particularly preferable. If this content is less than (4 / t) mol%, it will be difficult to peel off with a strong alkaline aqueous solution, and if it exceeds (12 / t) mol%, it will be easily dissolved in a weak alkaline aqueous solution.

The vinyl-polymerizable second monomer (b) used in the copolymer (A) in the present invention is the copolymer (A).
To provide releasability, flexibility, and chemical resistance to an etching treatment liquid, etc., and alkyl acrylates and alkyl methacrylates having an alkyl group having 3 to 8 carbon atoms (for example, propyl (meth) acrylate ((meth ) Acrylate means acrylate and methacrylate, the same shall apply hereinafter), butyl (meth) acrylate,
Octyl (meth) acrylate and the like). The Tg of the homopolymer having a weight average molecular weight of the second monomer (measured by GPC and converted to standard polystyrene) of 100,000 is 70.
It is preferable that the temperature is not higher than ° C.

The content of the vinyl-polymerizable second monomer unit in the copolymer (A) is preferably 10 to 30 mol%. The vinyl-polymerizable second monomer unit is the vinyl-polymerizable first monomer unit.
When the amount of the vinyl-polymerizable second monomer unit exceeds 30 mol%, the vinyl-polymerizable first monomer unit of the copolymer (A) has a close relationship with the monomer unit in terms of releasability. Even if the amount of the monomer unit is in the range of [(4 to 12) / t] mol%, the releasability tends to be poor. Further, if it is less than 10 mol%, the above-mentioned chemical resistance and peeling property tend to be poor.

The reason why the vinyl-polymerizable second monomer having a Tg of the homopolymer of 70 ° C. or lower is used is to lower the Tg of the copolymer (A) to be in a preferable range.

The vinyl-polymerizable third monomer (c) used in the copolymer (A) in the present invention imparts adhesiveness to the metal plate of the resist and has 1 to 2 carbon atoms.
Alkyl (meth) acrylates having an alkyl group of (for example, methyl (meth) acrylate, ethyl (meth) acrylate, etc.) and hydroxylalkyl (meth) acrylates (for example, hydroxylmethyl (meth) acrylate, hydroxylethyl (meth) acrylate, etc.) ) Are mentioned, and among them, methyl methacrylate is preferable.

The molecular weight of the copolymer (A) is a factor which imparts film-forming property to the resin composition of the present invention and further determines resistance to a developing solution, a processing solution and a stripping solution.

The weight average molecular weight of the copolymer (A) is 30,000 to 400,000,
It is more preferably from 00 to 300,000, and 5
Particularly preferably, it is from 20,000 to 200,000. When the weight average molecular weight is less than 30,000, the film-forming property is impaired and the resistance to the weak alkaline aqueous solution is lowered, and when it exceeds 400,000, the film-forming property and the resistance are very good, Peeling becomes difficult. From the viewpoint of film flexibility, the Tg of the copolymer (A) is preferably in the range of 60 to 100 ° C.

The copolymer (A) is obtained by radical-polymerizing a predetermined amount of a vinyl-polymerizable first monomer, a vinyl-polymerizable second monomer and a vinyl-polymerizable third monomer with azobisisobutyronitrile or the like. It is obtained by heat polymerization in the presence of a catalyst.

In the present invention, the ethylenically unsaturated compound (B) has the general formula (I)

[0030]

Embedded image (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents

[0031]

Embedded image And Y is

[0032]

Embedded image And Z represents a hydrocarbon group having 2 to 16 carbon atoms;
m, p and q are each independently an integer of 1 to 14)
A compound represented by the general formula (II)

[0033]

Embedded image (Wherein R ¹ , X, Y, Z, n, m, p, and q have the same meanings as in formula (I)) and the formula (III)

[0034]

Embedded image (Wherein R ¹ , X, Y, Z, n, m, p and q have the same meanings as in formula (I)), and at least one compound selected from the group consisting of compounds The boiling point is 1
It is more than 00 ° C.

Specific examples of the ethylenically unsaturated compound (B) and
In the general formula (I), R ¹Is CH_Three-, X is-
CH_TwoCH_TwoO-, Y is -CH_TwoCH (CH_Three) O- and Z are
-(CH_Two)₆-, N is 1, m is 1, p is 9, and q is 9
Is commercially available and is preferably used.

The boiling point of the ethylenically unsaturated compound (B) is 1
When the temperature is lower than 00 ° C., when the photosensitive film is produced, it is volatilized during drying and the photocurability is lowered.

The content of the copolymer (A) contained in the metal surface protective resin composition of the present invention is 50 to 50 with respect to the total amount of the copolymer (A) and the ethylenically unsaturated compound (B). 80
%, More preferably 55 to 75% by weight, particularly preferably 60 to 70% by weight.
When the content of (A) is less than 50% by weight, the resin layer is softened and cold flow occurs during storage, and when it exceeds 80 parts by weight, the resin layer becomes brittle and easily peels off before laminating. The content of the ethylenically unsaturated compound (B) is the same as that of the copolymer (A) and the ethylenically unsaturated compound (B).
20 to 50% by weight based on the total amount of
More preferably, it is 30% by weight, and particularly preferably 30-40% by weight. When the content of (B) is less than 20% by weight, the resin layer becomes brittle and easily peels off before lamination, and when it exceeds 50% by weight, the resin layer is softened and cold flow occurs during storage.

Examples of the compound (C) represented by the general formula (IV) in the present invention include polyethylene glycol diacetate (having 3 to 9 ethylene groups), polyethylene glycol dipropionate (having ethylene group number). 3-9), polyethylene glycol dibutyrate (having 3-9 ethylene groups), polypropylene glycol diacetate (having 3-9 propylene groups), polypropylene glycol dipropionate (having propylene groups) The number is 3 to 9), polypropylene glycol dibutyrate (the number of propylene groups is 3 to 9), polyethylene glycol di (meth) acrylate (the number of ethylene groups is 3 to 9), polypropylene glycol di ( (Meth) acrylate (having 3 to 9 propylene groups), etc. That.

The content of the compound (C) contained in the metal surface protective resin composition of the present invention is 1 with respect to 100 parts by weight of the total amount of the copolymer (A) and the ethylenically unsaturated compound (B). To 20 parts by weight, more preferably 2 to 15 parts by weight, and particularly preferably 3 to 10 parts by weight. When the content of the compound (C) is less than 1 part by weight,
The adhesion between the resin layer and the metal surface deteriorates, making it easier to peel off.
When it exceeds the weight part, the resin layer is softened and cold flow occurs.

Generally, in order to prevent thermal polymerization during the heating step and during storage, it is preferable to include a radical polymerization inhibitor in the resin composition. Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, etc., but low volatility at 200 ° C. or lower is preferable. As such, for example, hydroquinone substituted with an alkyl group such as a methyl group, an ethyl group, a propyl group, t-butylcatechol, and a first chloride
Copper, 2,6-di-t-butyl-p-cresol, 2,2
-Methylenebis (4-ethyl-6-t-butylphenol), 2,2-methylenebis (2-methyl-6-t-butylphenol) and the like. The preferred blending amount of these is the copolymer (A) and the ethylenically unsaturated compound (B).
The total amount is 0.01 to 0.5 parts by weight based on 100 parts by weight.

Further, in order to improve the stability of the resist after being laminated on copper, a copper antioxidant such as benzotriazole, benzotriazole hydrochloride, benzotriazole organic acid salt or aminobenzothiazole may be added. The preferable mixing ratio of these is 0.01 to 100 parts by weight of the total amount of the copolymer (A) and the ethylenically unsaturated compound (B).
0.5 parts by weight.

The metal surface protective resin composition of the present invention may contain coloring substances such as dyes and pigments. The coloring substance is
Those that do not affect the characteristics as a resist and do not decompose or volatilize at a temperature of 200 ° C. or less are preferable. Examples of such a colorant include fuchsin, auramine base,
Chalcoside Green S, Paramagenta, Crystal Violet, Methyl Orange, Nile Blue 2B, Victoria Blue, Malachite Green, Basic Blue 20, Iodine Green, Night Green B, Trivalosan, New Magenta, Acid Violet R
RH, red violet 5RS, new methylene blue GG and the like can be mentioned. Moreover, you may add additives, such as an adhesion promoter, to the metal surface protection resin composition of this invention.

The laminate of the present invention can be manufactured as follows.

First, the metal surface protection resin composition is uniformly dissolved in a solvent to obtain a solution. The solvent is not particularly limited as long as it dissolves the metal surface protection resin composition, and one or several kinds of solvents may be used. The solvent is preferably used in an amount of 10 to 50 parts by weight with respect to 100 parts by weight of the metal surface protection resin composition.

Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, dichloromethane, chloroform, methyl alcohol and ethyl alcohol.

Then, a solution of the metal surface protection resin composition is uniformly applied onto the support, and then dried by heating and / or blowing with hot air, and the solvent is removed to remove the resin layer (dry film).
And The thickness of the resin layer is not particularly limited and is 10 to 10
The thickness is preferably 0 μm, more preferably 15 to 60 μm. The laminate comprising the two layers of the resin layer and the support can be stored as it is or on the surface of the resin layer opposite to the surface on which the support is provided, by further laminating a protective film and winding in a roll shape.

Examples of the support include films made of polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polyvinylidene chloride and the like, and polyethylene terephthalate film is preferable. Since these must be removable from the resin layer later, they are materials that cannot be removed,
It must not be surface-treated so that it cannot be removed. The thickness of these films is 5-100 μm
Is preferable, and 10-30 μm is more preferable. These films can also be used as a protective film.

A printed circuit board for producing a multilayer printed wiring board in which a circuit is formed on the Α side and a copper foil is entirely left on the Β side can be manufactured as follows.

If the protective film, if any, is removed, the laminate of the present invention is laminated by pressing the resin layer against the copper clad laminate B surface while heating.

Since it is necessary to form a circuit on the Α plane,
A photosensitive film conventionally used for manufacturing a printed circuit board is laminated by the same method as the above-mentioned laminating method. Then, the Α plane is exposed through a photo tool in a circuit pattern, and the Β plane is not exposed. Then, if a support is present on the surface of the photosensitive film or the laminate, after removing it, a weak alkaline aqueous solution such as 0.5 to 3.0% by weight of sodium carbonate is used, and a known method is used. For example, the unexposed portion of the A surface is developed by spraying, rocking dipping, scraping, or the like. At this time, the resin layer on the Β surface remains without being developed. Then, after etching the copper foil on the A-side, the residual resin layer on the Α-side and the Β-side is peeled off using a strong alkaline aqueous solution such as 1.0 to 5.0% by weight of sodium hydroxide. A printed circuit board for a multilayer printed wiring board is obtained.

[0051]

The present invention will be described below with reference to examples.

A metal surface protective resin composition was prepared by blending the materials shown in Table 1, and was evenly applied onto a polyethylene terephthalate film having a thickness of 20 μm, dried for 3 minutes by a hot air convection dryer at 100 ° C., and laminated. I made it a body. The thickness of the resin layer after drying was 25 μm.

Next, the copper clad laminate having a clean surface was heated and pressed with a rubber roll so that the resin layer was in contact with the copper surface, and was bonded. After that, the polyethylene terephthalate film was removed, and the mixture was washed with 1.0% by weight sodium carbonate aqueous solution.
Spray development for 00 seconds, with cupric chloride etchant,
After spray-etching for 500 seconds, spray-peeling was performed for 50 seconds with a 3.0 wt% sodium hydroxide aqueous solution.
As a result, the resin composition was not attacked by the developing solution and the etching solution and could be peeled off by the peeling solution. Further, as a result of examining the occurrence of cold flow by winding the laminated body 200 m in a roll shape, no bleeding of the resin layer from the edge of the laminated body was observed even after standing for 5 months.

Example 1

[0055]

[Table 1] Comparative Example 1

[0056]

[Table 2] A metal surface protective resin composition was prepared in the same manner as in Example 1 except that the copolymer Α in Table 1 was changed to the copolymer Β shown in Table 2 and evaluated in the same manner as in Example 1. did. As a result, the composition was not attacked by the developing solution or the etching solution, but could not be removed by the removing solution.

Comparative Example 2

[0058]

[Table 3] A metal surface protective resin composition was prepared in the same manner as in Example 1 except that the copolymer A in Table 1 was changed to the copolymer C shown in Table 3, and the evaluation was performed in the same manner as in Example 1. did. As a result, the composition was attacked by the developer.

Comparative Example 3

[0060]

[Table 4] A metal surface protective resin composition was prepared in the same manner as in Example 1 except that the copolymer A in Table 1 was changed to the copolymer D shown in Table 4, and the evaluation was performed in the same manner as in Example 1. did. As a result, the composition was not attacked by the developing solution or the etching solution, but could not be removed by the removing solution.

Comparative Example 4 A metal surface protecting resin composition was prepared in the same manner as in Example 1 except that triethylene glycol diacetate was not added, and the same method as in Example 1 was evaluated. . As a result, the composition was not attacked by the developing solution and the etching solution, but the infiltration of the developing solution and the etching solution was observed, which was considered to be caused by the insufficient adhesion of the composition to copper.

Comparative Example 5 A metal surface protecting resin composition was prepared in the same manner as in Example 1 except that the blending amount of triethylene glycol diacetate was changed to 30 parts by weight.
Evaluation was performed in the same manner as in. As a result, the composition is not attacked by the phenomenon liquid and the etching liquid, and
It could be peeled off by the peeling liquid. However, as a result of examining the occurrence of cold flow by winding the laminated body 200m in a roll shape, the resin layer leached from the end portion of the laminated body when left for one month.

Comparative Example 6 In Example 1, NK oligo UA-13 was added to tetraethylene glycol diacrylate (Shin-Nakamura Chemical Co., Ltd.).
A metal surface protecting resin composition was prepared in the same manner as in Example 1 except that the product was changed to trade name, A-4G), and evaluated in the same manner as in Example 1. As a result, the composition was attacked by the developer.

Comparative Example 7 In Example 1, NK oligo UA-13 was mixed with polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.,
A metal surface protective resin composition was prepared in the same manner as in Example 1 except that the trade name was changed to A-14G), and evaluated in the same manner as in Example 1. As a result, the composition was attacked by the developer.

Comparative Example 8 In Example 1, NK oligo UA-13 was added to trimethylolpropane triacrylate (Shin-Nakamura Chemical Co., Ltd.).
Example 1, except that the product name is changed to A-TMPT)
A metal surface protection resin composition was prepared in the same manner as in Example 1
Evaluation was performed in the same manner as in. As a result, the composition was attacked by the developer.

[0066]

By using a laminate using the metal surface protection resin composition of the present invention, a double-sided copper clad laminate is
The exposure of the surface can be omitted, defects can be eliminated by the inclusion of foreign matters, etc., and it is possible to easily manufacture a highly accurate printed circuit board for manufacturing a multilayer printed wiring board.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08F 222/22 MMW C08F 222/22 MMW C08J 7/04 C08J 7/04 C08K 5/11 C08K 5 / 11 C08L 35/02 C08L 35/02 C09D 133/06 PGC C09D 133/06 PGC PGF PGF H05K 3/06 H05K 3/06 C // (C08F 220/12 220: 26 220: 04) (72) Inventor Kaku Hajime Maru 4-13-1, Higashi-cho, Hitachi-shi, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki factory

Claims (3)

[Claims] 1. (A) (a) at least one vinyl-polymerizable first monomer selected from a vinyl-polymerizable monomer having a carboxyl group, and (b) an alkyl group having 3 to 8 carbon atoms At least one vinyl-polymerizable second monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, and (c) alkyl acrylates, alkyl methacrylates, hydroxyalkyl acrylates and hydroxyalkyls having an alkyl group of 1 to 2 carbon atoms. A copolymer of at least one vinyl-polymerizable third monomer selected from the group consisting of methacrylate,
The content of the vinyl-polymerizable first monomer unit in the copolymer is [(4-12) / t] mol% (t represents the number of carboxyl groups per unit of the vinyl-polymerizable first monomer). .)so,
A copolymer (A) having a weight average molecular weight of 30,000 to 400,000, and (B) a general formula (I): (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents And Y is And Z represents a hydrocarbon group having 2 to 16 carbon atoms;
m, p and q are each independently an integer of 1 to 14)
A compound represented by the general formula (II): (Wherein R ¹ , X, Y, Z, n, m, p and q have the same meanings as in formula (I)) and a compound represented by formula (III): (In the formula, R ¹ , X, Y, Z, n, m, p and q have the same meanings as in the general formula (I)), and the boiling point of at least one selected from the group consisting of compounds is 100. An ethylenically unsaturated compound (B) having a temperature of not less than 0 ° C, and (C) a general formula (IV) (In the formula, R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ and R ⁵ each independently have 1 to 3 carbon atoms.
An alkyl group of n is an integer of 3 to 9) and a compound (C) represented by the formula (1) is added to the copolymer (A) and the ethylenically unsaturated compound (B) based on the total amount. The blending ratio of the polymer (A) is 50 to 80% by weight, the blending ratio of the ethylenically unsaturated compound (B) is 20 to 50% by weight,
The compounding ratio of the compound (C) is 1 to 100 parts by weight of the total amount of the copolymer (A) and the ethylenically unsaturated compound (B).
20 parts by weight of a metal surface protective resin composition. 2. A laminate obtained by applying a solution of the metal surface protection resin composition according to claim 1 on a support and drying the solution. 3. A photosensitive film is laminated on one side (A side) of the copper clad laminate, and the laminate according to claim 2 is laminated on the other side (B side), and then a photosensitive layer on the A side is formed into a circuit. After pattern-wise exposure to remove the support of the photosensitive film and the support of the laminate, the unexposed part of the photosensitive layer on the Α surface is developed with a weak alkaline aqueous solution, and the copper foil of the copper-clad laminate is etched. Then, on the Α plane and Β with a strong alkaline aqueous solution.
A method for manufacturing a printed circuit board, characterized in that the resin layer on the surface is peeled off.