JPS61177449A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition capable of enduring to conditions of an electroless copper plating by incorporating a reaction product of a carboxylic acid having an ethylenically unsaturated bond and an epoxy resin, a thermoplastic resin, a compd. contg. an ethylenically unsaturated bond or an epoxy group, a photopolymerization initiator, a thermocuring catalyst, a solvent and a coloring to the titled composition. CONSTITUTION:The titled composition comprises the reaction product of the carboxylic acid contg. the ethylenically unsaturated bond and the epoxy resin, the thermoplastic resin, the compd. contg. the ethylenically unsaturated bond or the epoxy group, the photopolymerization initiator, the thermocuring catalyst, the solvent and the coloring matter to the titled composition. The preferable carboxylic acid contg. the ethylenically unsaturated bond is an acrylic acid, a methacrylic acid etc. By applying the titled composition, the plating resist pattern having the fine pattern can be formed by a photographic method. As said plating resist has the resistance for the heated electro copper plating solution, the printed board having the fine pattern can be cheaply prepared by a full-additive process.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is capable of forming a complete polymerized film by coating a substrate, irradiating it with light through a negative mask, forming a pattern with an organic solvent, and then baking it. The present invention relates to a photosensitive resin composition capable of forming.

[Conventional technology]

Conventionally, the main method for producing printed wiring boards has been the subtractive method, in which unnecessary copper foil parts of copper-clad laminates are removed by etching. In order to manufacture printed wiring boards at low cost and to increase the reliability of through-holes, an additive method has been developed in which only the necessary conductor pattern parts are added by electroless copper plating.

This additive method includes a fully additive method in which a hole is drilled in the board and then the entire surface is activated, or a catalyst-containing board is printed with a metal resist, and the necessary conductor pattern is added only by electroless steel plating. After plating steel, printing a metal resist, and forming the necessary conductor pattern by electroplating, we use a semi-additive method to remove the electroless steel plating other than the conductor pattern portion of the metal resist, and a through-plating method using a copper-clad laminate. The Bartley additive method is used to form the hole using electroless steel plating.

[The pause that the invention attempts to solve]

In this additive method, the formation of the resist pattern is generally done by screen printing resist ink, but the minimum pattern width that can be formed using the screen printing method is about 200 μm, and Fine pattern formation must be performed by a photographic method using a photoresist. However, most of the photoresists currently on the market for manufacturing printed circuit boards are acrylic-based, so they are susceptible to hydrolysis reactions.
It does not withstand electroless copper plating under high temperature, highly basic conditions.

The present invention was made in order to solve the above-mentioned problems, and aims to provide a photosensitive resin composition that can form fine patterns by photographic methods and that can withstand electroless copper plating conditions. A photosensitive resin composition comprising a reaction product of an acid and an epoxy resin, a thermoplastic resin, a compound having an ethylenically unsaturated bond or an epoxy group, a photopolymerization initiator, a thermosetting catalyst, a solvent, and a colorant.

[For production]

In order to form a pattern using the photosensitive resin composition according to the present invention, the photosensitive resin composition is completely polymerized on a substrate.

That is, the photosensitive resin composition of the present invention is
It is applied onto substrates used for manufacturing printed circuit boards such as epoxy laminates and glass/polyimide laminates, and after drying to a state suitable for irradiation with ultraviolet light by adhering a negative mask, the light is irradiated through a designated negative mask. After irradiation, the remaining solvent is completely removed by heating, development is performed using an organic heating medium, and then baking is performed to form a metskire resist pattern that is resistant to electroless copper plating liquid. It is.

The preferred carboxylic acid having an ethylenically unsaturated bond used in the present invention is acrylic acid.

Examples include methacrylic acid.

Epoxy resins include bisphenol A epoxy resins, glycidyl ether type epoxy resins such as cresol novolac type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, Examples include epoxy resins having 0 or more epoxy groups in the molecule, such as monocyclic epoxy resins and halogenated epoxy resins. These epoxy resins may be used alone or in a mixed system of more than one type. Especially as desirable.

Examples include cresol novolac type epoxy resin and phenol novolac type epoxy resin. Therefore, in the present invention, the reaction product of a carboxylic acid having an ethylenically unsaturated bond and an epoxy resin is preferably an acrylic (methacrylated) epoxy resin (hereinafter simply referred to as an acrylated epoxy resin).

Since the above epoxy resin has a relatively low molecular weight, a thermoplastic resin with a large molecular weight is added to obtain good pattern resolution, smoothness of the final film, and properties of the heat-resistant electrolytic steel plating solution. .

Thermoplastic resins with high molecular weight and excellent chemical resistance include polysulfone, polyethersulfone, phenoxy, polyphenylene oxide, polycarbonate, etc. Among these, particularly desirable ones are those with relatively high molecular weight and excellent chemical resistance. Examples include phenoxy or polysulfone resins that have excellent chemical resistance and a glass transition point of 100°C or higher.

The compound having an unsaturated bond or an epoxy functional group used in the photosensitive resin composition of the present invention is preferably a liquid or semi-liquid compound containing at least one ethylenically unsaturated bond in seven molecules. be. These compounds include polyethylene glycol diacrylate, trimethylolpropane triacrylate and tris(co-acryloxy)isocyanurate. Liquid bisphenol Am epoxy resin is an example of a liquid or semi-liquid compound containing at least three epoxy groups in one molecule.

Photopolymerization initiators used in the present invention include anthraquinone and comethylanthraquinone.

Anthraquinone derivatives such as coethylanthraquinone and coated t-butylanthraquinone, ketones such as benzophenone, acetophenone, and benzoin, and mixtures of Michler's ketone and benzophenone, and thioxanthone and aromatic amines are used.

The solvent used is one that has suitable flowability and is capable of dissolving the solid components of the composition. The boiling point of the solvent is selected so that it has appropriate fluidity and an appropriate volatilization rate to suppress the formation of bubbles in the formed film. Suitable solvents include ethylene glycol monoethyl ether (cellosolve), ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether acetate (cellosolve acetate), ethylene glycol monomethyl ether acetate (methyl cellosolve acetate), xylene, Examples include toluene, methyl ethyl ketone, trichlene, acetone, which are solvents with a fast volatilization rate, and butylcarpitol, which is a solvent with a slow volatilization rate, and one or more of these solvents may be used as a mixture, if necessary.

Coloring agents include green to blue dyes or pigments such as ethyl violet, crystal violet, Victoria blue, and phthalocyanine green.

Catalysts for thermal curing include coechyl-gmethyl-imidazole, /, lf-diazo-bicyclo [5, Hiroshi,
O] Undesenuk (DBU), Hiroshi, l-methylene dianiline, N, N,! (, hr -tetramethyl-t, 3
-Amines such as butanediamine can be mentioned.

The composition ratio of the photosensitive resin composition according to the present invention is as follows.

It is determined by the viscosity required for the application, the rate of UV curing, and the desired thickness and hardness of the coating formed.

Desirable component proportions of the composition are as follows: Niacrylated epoxy resin (tO~100% desirably 30~i
oo% of epoxy functional groups are acrylated) 10
-20% by weight, thermoplastic resin 10 to -0% by weight, liquid or semi-liquid compound θ to /6% by weight having an ethylenically unsaturated bond or epoxy group, photopolymerization initiator 0.03 to 7
．． 5% by weight, curing catalyst 0.03-0015% by weight, colorant 0. /~0. rwt%, wt% old residual solve acetate, trichlene, and other solvents. The best results are 16% by weight of acrylated epoxy resin (0% of the epoxy groups are acrylated), 16% by weight of thermoplastic resin,
Contains IQ compound having ethylenically unsaturated bonds, 0.7% by weight of photopolymerization initiator, 403% by weight of curing catalyst, 0.3% by weight of colorant, 16% by weight of trichloride, 0% by weight of cellosolve acetate. obtained in a composition containing.

The acrylated epoxy resin used in the present invention is
It is synthesized by the method described below. That is, an epoxy resin is completely dissolved in a solvent such as tricrene, methyl ethyl ketone, cellosolve, cellosolve acetate, etc., and ethyl-ethyl-methylimidazole or the above DBU is added to the epoxy resin as a catalyst.
%, and a carboxylic acid having an ethylenically unsaturated bond is added to the obtained solution, and the mixture is reacted at toA-ioo°C for an hour.

The relative proportion of the carboxylic acid having ethylenically unsaturated bonds to the epoxy resin is 10-100%.

Desirably, the amount is sufficient to stoichiometrically react with go-ioo% of the epoxy groups in the epoxy resin.

This reaction product is combined with a thermoplastic resin, a liquid or semi-liquid compound containing at least one ethylenically unsaturated bond or an epoxy functional group in one molecule, a photopolymerization initiator, a curing catalyst, a colorant, and a solvent. Stir and mix to obtain a photosensitive resin composition.

The obtained composition is applied onto various substrates such as glass-epoxy laminates and glass-polyimide laminates by methods such as spin cording, dip coating, and roller coating. In order to improve the adhesion between the substrate and the coating film, it is desirable to roughen the substrate using a solvent or mechanical polishing.

The substrate coated with the above composition is prebaked at a predetermined temperature and time to volatilize most of the solvent and create a negative image.
After the mask is brought into close contact and conditions are favorable for exposure, exposure is performed through a negative mask. Next, the composition is heated at a temperature corresponding to the boiling point of the solvent contained in the composition for 1 hour to completely remove the solvent remaining in the coating film, and then treated with tricrene, methyl ethyl ketone, toluene, and cyclohexanone m.
'sl, 2. Development is carried out using a solvent such as coachtrachlorethylene or a mixed solvent thereof. After this, wash with water and dry, about 1 liter! Complete curing is achieved by exposure to temperatures of 30 minutes to 30 degrees Celsius.

The formed mesh resist pattern has a resolution of up to 50 μm (% pH 12), and no change was observed even after being left in an electroless steel plating bath at 0 to 10°C for more than 41 hours. It has excellent electroless plating solution resistance.

〔Example〕

Preferred embodiments of the present invention will be shown below, but the present invention is not particularly limited thereto.

Example I Cresol novolac type epoxy resin KSCN-tqz
XL (Sumitomo Chemical Exhibition product name, epoxy equivalent tqr) iqz
Ti is dissolved in cellosolve acetate, and this solution is reacted with methacrylic acid ttg at 95° C. for 3 hours using coethyl-Hiro-methyl-imidazole as a catalyst to obtain an acrylated epoxy resin solution as a reaction product. In this acrylated epoxy resin solution, phenoxy resin (
Union Carbide product name UCARPKHC)
J 00 Ii, ! -ethyl anthraquinone z0,
9. DBU Ko17 Talocyanine Green! 1. p-methoxyphenol o, rg, and methyl ethyl ketone 3 as thermal polymerization inhibitors! A photosensitive resin composition was obtained by mixing rO/i. Glass was activated after drilling holes in the obtained composition.
Approximately 6 using a roller corp on an epoxy laminate
It is coated to a thickness of 0 μm and prebaked for 30 minutes in an SO°C oven. Next, through a predetermined negative mask, an ultra-high pressure mercury lamp having an intensity of approximately IIEW per cd of the coating surface is irradiated for 19 to 10 seconds to perform exposure. Thereafter, it is dried at 90° C. for 30 minutes and developed with a mixed solvent of methyl ethyl ketone and toluene. After washing with water and drying, 1
Curing is carried out by heating at 10° C. for 1 hour.

The above-described d pattern exhibits strong adhesion to the substrate and does not change even under electroless copper plating conditions.

Example Cophenol novolac type epoxy resin DT! ,N'1J
t (trade name, manufactured by Tau Chemical Co., Ltd., epoxy equivalent: 176N)
1) Add θop to Trichloride 2 o o g, and add methacrylic to this solution. Polysulfone 200 dissolved in t,t,2,2'-tetrachloroethane was added to the reaction product obtained by reacting 26AII with DBU coy as a catalyst at 90°C for 3 hours! , methyl cellosolve acetate roy, benzophenone 9g and Michlerkent/f
mixture of i, tris-(-monoacryloxy)-isocyanurate (Hitachi Chemical Mm product name, FA-ri 3/-A) 1
00! , Crystal Violet 31. p-methoxy-
Phenol Q,/i was mixed to obtain a photosensitive resin composition.

The resulting composition was coated using a dip coating method.
Coated on activated glass/polyimide laminate,
Prebaking is performed at 60°C for 30 minutes. Exposure, development, and curing are then performed as described in Example 1. The substrate coated with the resulting plating resist pattern was immersed in an electroless copper plating bath for 16 hours to reduce the thickness, y
An oμ-like copper wiring pattern was formed, and no deterioration of the plating resist or precipitation of plating on the resist was observed.

Example 3 Cresol novolac type epoxy resin E8CN-/9
! XL/9! I was dissolved in 7 clohexanone λoog,
To this solution, 3 gg of acrylic acid and Koechyl-Hiro-Methylimidazole tig were added and reacted at 90°C for 2 hours.
001. Coated t-butyl-anthraquinone 109. )
Limethylolpropane triacrylate 30g, Ethyl Violet 3I, Coethyl-Hiro-Methylimidazole Co I.

p-Methoxyphenol o, tg, Serotsuru 7tl.

i was added to obtain a photosensitive resin composition.

The resulting composition was applied onto a glass-epoxy laminate using a spinner, and Example 1. - Pattern width in the same way as ! A mesh resist pattern of θ μm was obtained. This metal resist pattern showed good adhesion to the substrate, and no change was observed even after electroless steel plating was performed for a long time.

Example Gphenol novolac type epoxy resin DEN (431
(Product name manufactured by Dow Chemical Company, epoxy equivalent weight /74~/
El')/gel was dissolved in methyl ethyl ketone troy, acrylic acid sty and DBU 9 were added to this solution, and the resulting product was reacted at 90°C for 3 hours.
Phenol A type epoxy resin DERjJ (trade name manufactured by Dow Chemical Company), polyol, polysulfone/10! ! , co-methylanthraquinone 1077, co-methyl-goo-methylimidazole 2g, phthalocyanine green! rf
l, p-methoxyphenol 0. /l and butylcarbitolg θOg were added to obtain a photosensitive resin composition.

The resulting composition was coated with a coating of about 15 μm using a dip coater.
The coating was applied once to each door to a thickness of about 30 μm on an activated glass polyimide substrate, and dried at 60° C. for 2θ minutes. Then t, about 5 Or per l! Exposure was carried out by irradiating both sides through a negative mask for 20 seconds with a high-pressure mercury lamp having an intensity of LW. After being left at 90°C for 1 hour, it was developed with cellosolve acetate, washed with water, dried, and post-cured at 130°C for 1 hour.

The substrate on which the photoresist pattern was formed as described above was immersed in an electroless copper plating solution at 70° C. for 2 hours to obtain a copper wiring pattern with a thickness of 20 μm and a width of 10 μm. No deterioration of the short-circuit JP photoresist pattern due to the precipitation of copper plating on the resist due to the plating solution or contamination of the plating solution was observed.

Example ! Cresol novolac type epoxy resin E8CN-/? j
XL /9jTii to cellosolve acetateoo
g, and in this solution, methacrylic r! IRtbi was reacted at 100° C. for 3 hours to obtain an acrylated epoxy resin. To this, phenoxy tree 1i (UCARRKHC) 2
0011.2-tert-butyl-anthraquinone iog.

DBU Ko I, phthalocyanine green! rfi, p-methoxyphenol o, zti, methyl ethyl ketone 3j
.

1. A photosensitive resin composition was obtained by mixing DERJJ27θI.

The resulting composition was patterned in the same manner as in Example 3, and electroless copper plating was performed to obtain a desired copper wiring pattern. In order to compare plating liquid resistance and plating characteristics, the following comparative example 1. Raise the ko.

Comparative Example l Cresol novolac type epoxy resin E8CN-/9!
rXL /9! ;11 and methacrylic acid u,? 9. An acrylated epoxy resin liquid in which 5% of the epoxy equivalent groups are acrylated was obtained from tricrene-〇0I% coethyl anthraquinone 109, A photosensitive resin composition was obtained by adding 2 g of ethyl violet, DBU CoI, and cellosolve acetate 〇θy. This composition was patterned and plated in the same manner as in Example 1, but although it had plating solution resistance, the surface was rough during development and a large amount of copper plating was deposited on the resist.

Comparative example Acrylated ebony synthesized in the same manner as in Example 1 Coethyl anthra to oxyresin! Non-toy.

DBU Co I, Phthalocyanine Green SI, Methyl Ethyl Ketone J! A photosensitive resin composition was obtained by mixing Ofl.

Although the above-mentioned composition was applied by the method shown in Example fR/-j, it was not possible to obtain a uniform coating film.

Although pattern formation and plating were performed in the same manner as in Example 1, good plating liquid resistance and plating properties were not obtained.

In addition, in the above examples, pattern formation by a photographic method was described, but if finely powdered silica or the like is added to give chicken tropism to the photosensitive resin composition, a resist ink can be used to form a pattern by screen printing. It is also possible to use it as an example, and it has the same effect as the above embodiment.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to form a metskiresist pattern having a fine pattern using a photographic method, and since this metskiresist has heat-resistant electrolytic copper plating liquid properties, it can be formed at low cost by the full φ additive method. This has the effect of making it possible to manufacture printed circuit boards with fine patterns.

Claims (4)

[Claims] (1) Reaction product of carboxylic acid having an ethylenically unsaturated bond and epoxy resin, thermoplastic resin, compound having an ethylenically unsaturated bond or epoxy group, photopolymerization initiator, thermosetting catalyst, solvent, and coloring A photosensitive resin composition consisting of an agent. (2) The reaction product of a carboxylic acid having an ethylenically unsaturated bond and an epoxy resin is such that 10 to 100% of the epoxy groups of the epoxy resin are acrylated by the carboxylic acid having an ethylenically unsaturated bond. The photosensitive resin composition according to claim 1. (3) The photosensitive resin composition according to claim 1, wherein the thermoplastic resin is a high molecular weight phenoxy resin or polysulfone resin. (4) Claims in which the compound having an ethylenically unsaturated bond or an epoxy group has at least two or more ethylenically unsaturated bonds or epoxy groups in one molecule and is a liquid or semi-liquid compound at room temperature. 2. The photosensitive resin composition according to item 1.