JPS63124046A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To easily remove a resin after forming an electroless copper plating pattern by incorporating a binder component composed of a photosensitive component and a polymer having a tertiary or the secondary amine to the titled composition. CONSTITUTION:The photosensitive component comprises a compd. having vinyl, aryl or methacryl group, etc. The binder component comprises the polymer having the tertiary amine or the secondary amine, such as the polymer of vinyl pyridine, vinyl imidazole, vinyl pyrolidone, or N,N-dimethyl acrylamide, etc. The titled composition is produced by mixing the photosensitive material and the binder component, and the photosensitive material is formed by said material. The copper pattern is formed on a substrate by forming the electroless copper plating pattern to the photosensitive material, followed by dipping it in an acidic solution to remove the resin. Accordingly, as said binder component is used as the binder, the binder has an excellent durability for the electroless copper plating bath and is easily removed, and enables to make the fine copper wiring pattern.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention involves coating a substrate, irradiating it with light through a negative mask, and developing it with an organic solvent, acidic aqueous solution, or water to form a pattern. The present invention relates to a photosensitive resin composition that has excellent resistance to alkali aqueous solutions and can be peeled off with organic solvents or acidic aqueous solutions.

[Conventional technology]

Conventional printed wiring board manufacturing methods include 1, for example, ``Electronic Technology J, published in 1982, Vol. 23, No. 14, 108-l.
As described on page 11, the substructive method has mainly been used to remove unnecessary copper foil portions of copper-clad laminates by etching, but this method eliminates the waste caused by etching the copper foil and can be done at a low cost.

Additive methods have been developed that allow high-density patterning.

This additive method involves printing or photoengraving a resist on a board that has been fully activated after drilling a hole, or a catalyst-containing board, and then adding the necessary conductor pattern only by electroless plating. After plating, printing a resist or photolithography, and forming the necessary conductor pattern by electrolytic plating, the wiring pattern can be formed using the semi-additive method, which removes the metal resist and the electroless steel plating other than the conductor pattern, and the conventional substructive method. There is a part-additive method in which only the through holes are formed using electroless plating.

The resists used in these additive methods have a thick electroless plating bath that has a pH of 12 or higher and is maintained at a temperature of around 80°C. Therefore, a resist with excellent alkali resistance is required.

In addition, there are two patterning methods: screen printing and photoengraving, but while screen printing is easy, the minimum pattern width is about 200 μm, and misalignment is more likely to occur. The following patterning is also possible, and the positional accuracy of the pattern is very good, but since the resist itself must have photosensitivity, material development is difficult, and it is inferior to the former in terms of heat resistance and adhesion.

[Problem that the invention seeks to solve]

The above-mentioned additive resists have conventionally been used as permanent resists because they cannot be easily removed from the substrate once they have been cured. However, there are no photolithographic resists that are sufficient as permanent resists in terms of adhesion and heat resistance, and in particular, one that can be used as an inner layer of a multilayer substrate has not yet been developed.

On the other hand, if the resist can be easily removed after forming the electroless steel pattern, the adhesion and heat resistance of the resist itself can be ignored by using a conventional solder resist or prepreg. However, a resist that can be easily removed after forming an electroless steel pattern has not yet been developed.

This invention was made to solve the above-mentioned problems, and an object thereof is to provide a photosensitive resin composition that can be easily removed even after forming an electroless steel plating pattern by patterning.

[Means for solving problems]

The photosensitive resin composition of the present invention uses a polymer having a tertiary amine or a secondary amine as a binder component.

The binder component in this invention is a polymer having a tertiary amine or a secondary amine in the molecule, and its molecular weight is preferably z, ooo to soo, ooo, and specifically vinylimidazole, vinylpyridine, vinylpyrrolidone, N, N-dimethylacrylamide.

N,N-dimethylaminoethyl acrylate, N,N
- Using a homopolymer such as dimethylaminopropylacrylamide, a copolymer of at least two of these, a copolymer containing at least 10% or more of the above heptad units, or at least one of aminoacetal, pyridine aldehyde, and dimethylaminobenzaldehyde. Polyvinyl alcohol or polyethyleneimine having a degree of polymerization of 500 to 4,000 is preferable.

As the photosensitive component, a photosensitive component having a vinyl group, an allyl group, an acrylic group, or a methacrylic group and at least one of a tertiary amine or a secondary amine is preferable, and specifically, vinyl pyrrolidone, vinyl pyridine,
Vinylimidazole, N,N-dimethylacrylamide, N,N-dimethylaminoethyl acrylate, N,N
-dimethylaminopropylacrylamide, tetraglycidylaminodiphenylmethanetetraacrylate, triglycidyl-para-aminophenol triacrylate, triglycidyl-methaminophenol triacrylate, diglycidylaniline diacrylate.

Diglycidyl toluidine diacrylate, tetraglycidyl metaxylylene diamine, tetraacrylate, diglycidyl tribromoaniline diacrylate, tetraglycidyl bisaminomethyl cyclohexane tetraacrylate, dimethyl-1°3-glycidylhydantoin diacrylate, methyl ethyl-1,3 -Glycidylhydantoin diacrylate, pentamethylene-1,3-
Glycidylhydantoin diacrylate, acrylate-modified or methacrylate-modified polyglycidylamine, etc. are preferred.

In addition to these components, the photosensitive resin composition of the present invention may further include a photopolymerization initiator, a coloring agent, a solvent, a pigment,
It may contain a leveling agent, an antifoaming agent, etc., and these are used by mixing or kneading.

The photosensitive resin composition of the present invention includes, for example, 5 to 30% by weight of the binder component, 10 to 80% by weight of the photosensitive component,
There is one containing 0.1 to 10% by weight of photopolymerization initiator and the remainder being solvent.

Examples of the photopolymerization initiator include 2.2-jethoxyacetophenone, anthraquinone, 2-methylanthraquinone, 2-t-butylanthraquinone, benzyl methyl ketal, benzyl-β-methoxyethyl acetal, 1
-Phenyl 1,2-propanedione-2-(0-ethoxycarbonyl)oxime, benzophenone, 0-benzoin methyl benzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, benzyl, 2 -Phenyl-2-hydroxyacetophenone, benzoin methyl ether, benzoin isopropyl ether, P-dimethylaminobenzoic acid, ethyl p-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, isoamyl p-dimethylbenzoate, benzoin -n-butyl ether, benzoin isobutyl ether, benzoin alkyl ether, 4'-isopropyl-2-hydroxy-2-
Methyl-propiophenone, p-dimethylaminoacetophenone, p-t-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, chlorothioxanthone, 2-isopropylthioxanthone, dibenzosuberone, 2,5 -bis-(4'-diethylaminobenzal)
Cyclopentanone, 1-acetylamino-4-nitronaphthalene, 5-nitroacenaphthene, 1-nitropylene, α,α-dichloro-4-phenoxyacetophenone,
Examples include 1-hydroxycyclohexylphenyl ketone, and one type or a mixture of two or more of these can be used.

The above-mentioned photosensitive resin composition has a polymer having at least one of tertiary amine or secondary amine in the molecule, a vinyl group, allyl group, acrylic group, or methacrylic group in the molecule, and a tertiary amine. It is obtained by adding a compound having at least one type of amine or secondary amine and dissolving it in an organic solvent.

The photosensitive resin composition of the present invention is applied to a substrate used for manufacturing printed circuit boards, such as a glass epoxy laminate or a glass polyimide laminate, and exposed to ultraviolet light by applying a negative mask or placing it a little apart from the coating agent. After irradiation, development with an organic solvent aqueous solution or water, and then sufficient exposure, immersion in an electroless plating bath to deposit a wiring pattern.

The patterned photosensitive resin is removed using an organic solvent or acidic aqueous solution to form an electroless steel pattern on the substrate.

That is, the photosensitive resin composition obtained as described above is coated on various substrates such as glass epoxy laminates and glass polyimide laminates by methods such as spin cording, dip coating, roller coating, and screen printing. Alternatively, a dry film is formed in advance and attached to the substrate by thermocompression bonding. In order to improve the adhesion between the substrate and the resist film, it is desirable to roughen the substrate surface using a solvent or mechanical polishing.

The substrate coated with the above photosensitive resin composition is prebaked at a predetermined temperature for 1 hour to vapor-deposit most of the solvent.
After the surface is made tack-free, a mask is applied and exposed to ultraviolet light. on the other hand.

In the case of dry film, leave it at room temperature for about 30 minutes after pressure bonding, and then fit the mask tightly over the base film.

After exposure to UV light, peel off the base film.

After this, in order to promote polymerization, both are left for 10 to 30 minutes at room temperature to 80°C, and then a solvent such as methanol, ethanol, water, acetone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or a mixture thereof is used. Development is performed using a solvent to which a salt such as ammonium chloride or ammonium sulfate is added as necessary.

After this, it was washed with water and dried, and then post-exposed at a dose of about 2 J/c+e'', and then exposed to light at a temperature of about 130°C for 3 hours.
Complete curing is performed by leaving it for 0 minutes to 1 hour. The formed resist pattern has a resolution of up to 50 μm, and no change was observed even if it was left in an electroless steel plating tank at pH 12, 5, and 70 to 80°C for more than 18 hours, and it has sufficient resistance to corrosion. It has electrolytic plating bath properties.

Further 10% H2SO, methanol solution, 15% II,
After immersing the substrate in an acidic solution such as an aqueous So4 solution, the resist pattern can be easily removed from the substrate by lightly rubbing the surface with a brush or the like, and a copper pattern can be obtained on the substrate.

The photosensitive resin composition of the present invention contains a tertiary amine or a secondary amine in the system, so it is resistant to alkaline solutions, easily swells in acidic solutions, and contains a photocurable component. Therefore, patterning can be done by photolithography. As a result, a fine resist pattern can be obtained which has excellent resistance to electroless plating baths exhibiting strong alkalinity of ρ<2> and which can be easily removed with an acidic solution.

As mentioned above, since the photosensitive resin composition of the present invention contains a polymer having a tertiary amine or a secondary amine,
After being applied to a substrate and cured with light, it exhibits excellent resistance to alkaline aqueous solutions and can be easily removed from the substrate with acidic solutions.

〔Example〕

Examples of the present invention will be described below.

Example 1 50 g of polyvinylpyridine (Molecular capsule 1 manufactured by Tokonshu Kagaku Co., Ltd.)
0000) was dissolved in 100 g of dimethylformamide.

To this were added 100 g of methacrylated polyglycidylamine (molecular weight approximately 1000) and 50 g of diglycidyl tribromoaniline dimethacrylate and dissolved by heating. Next, 5 g of Michler's ketone and 10 g of benzophenone were added and dissolved to obtain photosensitive resin composition 1.

Example 2 Polyvinylpyrrolidone (Molecular capsule 100 manufactured by Tokyo Kasei Co., Ltd.)
00) Dissolve 50g in 100g of dimethylformamide and add methacrylated polyglycidylamine 1
Next, 5 g of Michler's ketone and benzophenone TOG were added and dissolved to obtain a photosensitive resin composition 2.

Example 3 Polyvinyl alcohol acetalized 60% using pyridine-4-aldehyde (degree of polymerization 2000) sog
was dissolved in 100 g of dimethylformamide, 100 g of methacrylated polyglycidylamine and 70 g of diglycidyl tribromoaniline dimethacrylate were added thereto and dissolved by heating. Next, 5 g of Michler's ketone and 10 g of benzophenone were added and dissolved to form a photosensitive resin composition. Thing 3
I got it.

Example 4 30 g of polydimethylacrylamide (molecular weight 5 x 10') radically polymerized by a conventional method, 70 g of dimethyl 1,3 glycidylhydantoin diacrylate, and vinylpyrrolidone Log were dissolved in 100 g of dimethylformamide, and further, Michler's ketone 5K, benzophenone t
og was added and dissolved to obtain a photosensitive resin composition 4.

Example 5 20 g of poly-4-vinylimidazole (molecular weight 2 x 10'), 5 g of 4-vinylimidazole, and 20 g of polyglycidylamine acrylate, which were radically polymerized by a conventional method.
, 5 g of vinyl pyrrolidone was dissolved in 100 g of dimethylformamide, and 5 g of Michler's ketone and benzophenone Log were further added and dissolved to obtain photosensitive resin composition 5.

Comparative Example 1 Bisphenol A epoxy diacrylate (VR-60
, manufactured by Showa Kobunshi Co., Ltd.) 50 g, trimethylolpropane triacrylate 5 g, tetrabisphenol A ethylene oxide adduct acrylate (GX6094 No.
Comparative sample 1 was obtained by dissolving 10 g of Kogyo Seiyaku C Co., Ltd. il) in 50 g of cellosolve acetate, and further adding and dissolving 5 g of Michler's ketone and 10 g of benzophenone.

Comparative Example 2 50 g of polyacrylic acid 60% acrylated using glycidyl acrylate, 10 g of polyethylene glycol dimethacrylate (NK Ester 23G, manufactured by Shin-Nakamura Chemical Co., Ltd.), EO-modified phenoxylated phosphoric acid acrylate (AR-260, (manufactured by Otona Kagaku Co., Ltd.) was dissolved in 50 g of toluene, and then 5 g of Michler's ketone was added.
, benzophenone Log was added and dissolved to obtain Comparative Sample 2.

Test example 200m+e x 250mm
Coat the resist sample using a μm bar coater, and
Dry at 5℃ for 30 to 60 minutes Next, place a mask tightly on the coated surface and irradiate the substrate with a certain amount of light using a high-pressure mercury lamp (5001), then leave the substrate at 60℃ for 30 minutes. After developing with 4 constant developer and washing with water, use a high pressure mercury lamp (
1.5k11) with a light intensity of 2 J/co" and after-baking at 130°C for 30 minutes. After cooling the board, it was immersed in the following electroless copper plating solution and heated to 72°C with air agitation. Plating was carried out for 18 hours to form a conductor circuit with a thickness of approximately 32 μm.

[Electroless steel plating solution composition]

CuSO4・5H2Q l
Og ethylenediaminetetraacetic acid 30g formalin (37%) 3g polyethylene glycol (molecular weight 600) 20g
2.2'-dipyridyl 0.03
gNa01l
l1g water total amount 1000I
After washing the substrate with water and drying it, immersing it in a specified acidic stripping solution, rub the surface with a nylon brush to remove the swollen resist, wash it with water, and remove 5% ammonium carbonate.
After washing with an aqueous solution, the copper pattern was washed again with water and dried, and the copper pattern was observed with the naked eye or using an optical microscope.

Table 1 shows the evaluation results according to the above evaluation method.

As is clear from Table 1, photosensitive resin compositions
, Comparative Samples 1 and 2 were all able to pattern the lines and spaces of the 50μ grave, but Comparative Sample 2
has poor alkali resistance and undergoes hydrolysis during electroless plating, making it impossible to obtain fine copper wiring patterns. Furthermore, although it was possible to form a copper wiring pattern in Comparative Sample 1, the patterned resist could not be removed from the substrate.

On the other hand, photosensitive resin compositions Nos. 1 to 5 all had excellent electroless plating bath resistance, and fine copper wiring patterns were obtained. 10%) 12sO4 methanol solution
By dipping for ~2 minutes, the resist pattern swelled significantly and could be easily removed by rubbing with a nylon brush.

〔Effect of the invention〕

As explained above, according to the present invention, since it contains a binder component made of a polymer having at least one type of tertiary amine or secondary amine in its molecule, it has excellent properties against electroless steel plating baths after photocuring. It has durability, is easily removable, functions as a photoresist, and has the effect of providing a fine copper wiring pattern on a substrate.

Claims (5)

[Claims] (1) A photosensitive resin composition containing a photosensitive component and a binder component made of a polymer having at least one type of tertiary amine or secondary amine in the molecule. (2) The photosensitive component includes a compound having a vinyl group, allyl group, acrylic group, or methacrylic group in the molecule and at least one type of tertiary amine or secondary amine. The photosensitive resin composition according to item 1. (3) The photosensitive resin composition according to claim 1, wherein the photosensitive component is vinylpyrrolidone, vinylpyridine, vinylimidazole, polyglycidylamine acrylate, or glycidylhydantoin acrylate. (4) Homopolymer or copolymer of two or more binder components of vinylpyridine, vinylimidazole, vinylpyrrolidone, N,N-dimethylacrylamide, N,N-dimethylaminoethyl acrylate, or N,N-dimethylaminopropylacrylamide The photosensitive resin composition according to any one of claims 1 to 3, characterized in that: (5) Polymerization degree of 500 when the binder component is acetalized with an aldehyde containing a tertiary amine or a secondary amine
The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition is polyvinyl alcohol having a molecular weight of 4,000 to 4,000.