JPS61272228A - Photo-setting resin composition - Google Patents

Abstract

PURPOSE:The titled composition, containing a specific epoxy compound, monomer and/or prepolymer of diallyl phthalate, photopolymerization initiator and epoxy hardener and useful for forming protective films having improved solvent, chemical, heat and weather resistance and mechanical strength. CONSTITUTION:A photo-setting resin composition containing (A) an epoxy compound containing at least one acryloyl group and/or methacryloyl group, (B) monomer and/or prepolymer of diallyl phthalate, (C) a photopolymerization initiator, benzophenone, (D) an epoxy hardener, e.g. triethylenetetramine and, as necessary, (E) an adhesion improver, e.g. myristic acid chromium complex.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a photocurable resin composition. More specifically, the present invention relates to a resin composition for forming a protective film that has excellent properties that can be used in printed circuit board production, metal precision processing, and the like.

(Prior art) In the precision processing industry, such as nameplate and printed circuit board manufacturing,
It is well known that a photocurable resin composition is used to form a protective film for plating or etching.

Conventionally, these types of photocurable resins have been used: (1) casein, polyvinyl alcohol and dichromate system, G2) polycinnamate vinyl ester system, (3)
It is a photopolymerizable resin based on acrylic copolymer mixed with divinyl monomer, oligomer, etc.

In addition to the low cost of the system (1), the system (3) has the following advantages:
It has the stability and high resolution of the system 2), and is also characterized by a large allowable range of film thickness and ease of processing.

In addition, since it is possible to create photopolymerizable resins that can be developed with water, alkaline, or solvent by combining the ingredients, it is also possible to manufacture photosensitive resin letterpress or print circuit boards in the form of a film in advance. used in However, the photosensitive resins known to date, including this photopolymerizable resin system, have some points that are greatly desired to be improved. That is, the protective coatings obtained from these systems have insufficient spreading resistance, chemical resistance, heat resistance, and mechanical strength, and their range of use as protective coatings is limited.

For example, these coatings can withstand neutral and weakly acidic solutions, but not strongly acidic and alkaline solutions.

Therefore, etching solutions, plating solutions, etc. are limited. In addition, it is susceptible to chlorinated hydrocarbons such as tricrene and ketone solvents such as methyl ethyl ketone, and has poor mechanical properties, strength, heat resistance,
Due to insufficient weather resistance, it cannot be used as a permanent protective film. It is for these reasons that this method has not been adopted in fields that used screen printing methods using epoxy resin, such as non-electrolytic copper plating resists and permanent protective films.0 (Problems to be solved by the invention) The present invention The object of the present invention is to provide a photocurable resin composition for forming a protective film having excellent solvent resistance, chemical resistance, heat resistance, weather resistance, and mechanical strength.

(Means for Solving the Problems) As a result of intensive studies to solve these problems, the present inventors have found that the present inventors have found that the present inventors have found that the present inventors have found that the present inventors have found that the present inventors have found that the present inventors have found that the present inventors have found that the present inventors have found that the present inventors have developed a method that contains at least one 7-acryloyl group and (t) or methacryloyl group. A photocurable resin composition containing as main components an epoxy compound, (a) diallyl phthalate diammonium and/or prepolymer, C) a photopolymerization initiator, and (i) an epoxy curing agent achieves the above objectives. They discovered what could be done and completed the present invention.

(Function) Each of the components constituting the photocurable resin composition proposed by the present invention will be explained below.

The photocurable resin composition of the present invention must contain an epoxy compound containing at least one 7-acryloyl group and/or methacryloyl group. The resol-type or novolac-type epoxy acrylate or methacrylate resin used in the present invention is a resol-type phenol having two or more epoxy groups, an epoxy compound from a resol-type resol or a phenol novolak or a cresol novolac, dicyclopentadiene, a phenolic It is obtained by reacting a polymer epoxy resin or the like with acrylic acid or methacrylic acid. Furthermore, it is obtained by reacting a flame-retardant epoxy compound such as brominated bisphenol or brominated phenolphthalein with acrylic acid or methacrylic acid. The esterification rate of these compounds is determined by considering the imparting of photocurability through the introduction of ethylenic double bonds and the adhesion of epoxy groups. and/or the amount of acrylic acid or methacrylic acid used must be determined so as to introduce a methacryloyl group and to obtain a reaction product having at least one epoxy group per molecule. Direct esterification of one or more epoxy compounds with acrylic acid or methacrylic acid is generally carried out in an aromatic organic solvent such as toluene or xylene at a temperature in the range of 60°C to 140°C with stirring while passing nitrogen gas. conduct. Included in the reaction mixture is an esterification catalyst and an inhibitor to prevent premature polymerization of one or more ethylenically unsaturated components. Examples of catalysts include triethylamine, benzyltrimethylammonium methoxide, dimethylbenzylamine, zirconium octoate, and the like. Examples of suitable polymerization inhibitors include hydroquinone and t-butylvitroquinone.

The second essential component of the photocurable resin composition of the present invention is a diallyl phthalate monomer and/or prepolymer. Diallyl phthalate used in the present invention is a generic name that also includes diallyl phthalate and diallyl terephthalate. The diallyl phthalate monomer is a polymerizable monomer that is liquid at room temperature, and the diallyl 7-thalate brevolimer is semi-solid. Diallyl phthalate is relatively stable, but when polymerized with a polymerization initiator, it becomes a cured product with excellent heat resistance, chemical resistance, electrical properties, etc.

Examples of the photopolymerization initiator as the third essential component include benzophenones, benzoin, benzoin alkali ethers such as benzoin ethyl ether, alkyl anthraquinones such as ethyl anthraquinone and butyl anthraquinone, acetophenones, benzyl ketals, etc. can. These photopolymerization initiators may be used alone or as a mixture of two or more. Further, the amount added is 0.01 to 15% by weight based on the resin, preferably 0ff5
The epoxy curing agent, which is the fourth essential component, can be used in the range of ~10% by weight. When heated above 80°C, the epoxy curing agent reacts with the epoxy group to promote curing, increase adhesion to the substrate, and improve chemical resistance. and increases the hardness of the coating itself. Examples of epoxy curing agents include amines such as triethylenetetramine, P,P'-diaminodiphenylmethane metaxylene diamine, and phenyldimethylmethane;
Acid anhydrides such as 7-tar acid anhydride, dodecyl succinic anhydride, 2-ethyl-4-methylimidazole, 2-methyl-imidazole, 2-methylimidazole isocyanuric acid adduct, 2-7z dilimidazole isocyanuric acid Examples include imidazole and imidacillin derivatives such as adducts, 1-7dine ethyl-2-ethyl-4-methylimidazole, and 2-ethyl-4-methylimidacillin. It is also possible to use a mixture of 2a or more of these.

Furthermore, an adhesion improver can be mentioned as a fifth essential component for improving quality. Adhesion improvers are compounds added to improve adhesion to metal surfaces such as stainless steel, Kovar, copper, nickel, aluminum, etc. Examples include chromium myristate complexes, chromium methacrylate complexes, etc. carboxylic acid chromium complex, 2-mercaptothiazoline, 2-methylthiazoline, 2-mercapto-1-
Sulfur-containing organic compounds such as methylimidazole, 2-mercaptobenzimidazole, 2-mercaptoimidazole, 2-mercaptopropionic acid, thiourea, thiosemicarnocin, thioglycolic acid, thioglycerin, etc.1.
Triazoles such as 1,2.3-benzotriazole, 1-(N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, tetra-methyl-titanate, tetra-ethyl-titanate, tetra-propyl-titanate, Tetra-stearyl titanate, tetra-
Titanium-containing organic compounds such as 2-ethylhexyl titanate, phosphorus-containing organic compounds such as 2-ethylhexylamide phosphate, triphenyl phosphite, hydrogenated hisphenol A phosphite, and γ-mercaptoglobil trimethoxysilane, r- Examples include silicon-containing organic compounds such as aminopropyltriethoxysilane, r-glycidoxyglobyltrimethoxysilane, and r-methacryloxytrimethoxysilane. These may be used alone or in combination.

The resin component of the present invention is a mixture of a partially esterified epoxy resin and a diallyl phthalate monomer and/or prepolymer, the mixing ratio of which is 25 to 90% by weight,
A range of 75 to 10% by weight is preferred.

A thermal polymerization inhibitor, a plasticizer, a filler, a dye, a pigment, and an antifoaming agent may be added to the composition of the present invention in order to improve storage stability and handling properties.

Examples of thermal polymerization inhibitors include radical polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and methylhydroquinone, and the appropriate amount of the additive is in the range of 0.001 to 0.2% by weight based on the resin. It is.

As the plasticizer, dimethyl 7-talate, diptyl 7-talate, etc. can be used. Addition of plasticizer imparts flexibility to light and heat cured films.

As the filler, fine powders such as silicon dioxide, titanium dioxide, alumina, Merck, antimony trioxide, and calcium carbonate can be used. These fillers can be successfully dispersed in the resin by treatment with a silane-based, titanium-based, or other coupling agent.

Examples of dyes and pigments include phthalocyanine blue,
7. Can open talocyanine green etc.

These examples are just examples, and the invention is not limited to these.゛The photocurable resin composition of the present invention can be applied by any known method, such as a brush coating method, a roller coater method, a spray method, a tipping method, a flow coach ink method, a bar coater method, a screen printing method, etc. It can be applied to films, plastics, metals, etc. Furthermore, it can be applied directly to furniture, plywood, and other supports as a furniture coating. Furthermore, a film obtained by applying the photocurable resin composition to a film of polyester or the like and drying it can also be laminated onto a support using a hot roll.

Next, active light such as ultraviolet rays is irradiated through a suitable pattern to cure the exposed areas, and then development is performed using a solvent such as 1.1.1-trichloroethane to dissolve the unexposed areas. The film thus obtained becomes a corrosion-resistant film for ordinary etching, but it also becomes an excellent protective film when subjected to a heat treatment process at 80°C to 300°C, usually 80°C to 170°C. That is, it is not attacked by aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as trichlene, and ketone hydrocarbons such as methyl ethyl ketone, and is sufficiently resistant to strongly acidic and strongly alkaline aqueous solutions. Because it has excellent heat resistance, mechanical strength, and weather resistance, it can be used as an etching resist such as name plates, as well as plating resist and solder resist, and can be used as a permanent protective film. .

Furthermore, it can be used as an adhesive, a plastic relief material, and a material for printing plates.

According to the present invention, the curing of the photocurable resin composition is substantially performed in two stages. That is, in the first step, after coating the composition on a specific support, the composition is exposed to actinic light such as an ultraviolet lamp or an ultra-high pressure mercury lamp through an appropriate pattern, and then trichlorethylene, 1.1 .1
- Develop with an organic solvent such as trichloroethane, xylene, methyl ethyl ditone, etc. to form a desired pattern. This first stage is a curing reaction based on unsaturated double bonds in the composition. The second step is the reaction of the epoxy group with the epoxy curing agent and is carried out by exposure to a temperature in the range of 80°C to 170°C for a period of time. Furthermore, by performing KUV irradiation after the second heat treatment, it is possible to improve the chemical resistance and heat resistance. This UV irradiation may be performed before the heat treatment in the second stage.

The present invention will be explained in more detail below with reference to examples, but these examples do not limit the scope of the present invention.

Example 1 100 g of diallyl ortho 7 talate momer and 1 g of K dicyanocyanamide are added and dispersed using three rolls. To this, 100% of a partial esterified product of a phenol novolak type epoxy resin and acrylic acid was preliminarily added.
A photocurable resin composition was prepared by adding a solution of 4 g of benzoin ethyl ether and 4 g of benzoin ethyl ether.

This photocurable resin composition was applied twice over the entire surface of an alumite plate by screen printing. Then, at 70°C for 20
Dry with air for minutes. The film thickness after drying was 25 μm.

A pattern was adhered thereon and exposed for 50 seconds using an ultra-high pressure mercury lamp, and the unexposed and uncured portions were developed with 1.1.1-)lichloroethane to form a pattern. This coating is 16
After heat treatment at 0℃ for 40 minutes, 15% of 70℃
Etching was performed by immersing it in an aqueous sodium hydroxide solution.

This photocurable resin sufficiently withstood strong alkaline aqueous solution at high temperature.

Example 2 In 40.5 g of the photocurable resin composition of Example 1, 0.1
g of chromium myristate complex was added to prepare a photosensitive solution.

This photosensitive solution was applied to the entire surface of a stainless steel plate by screen printing and dried. The film thickness was 10 μm. Thereafter, the pattern was adhered and exposed for 50 seconds using an ultra-high pressure mercury lamp. 1.1.1- )! A pattern was formed by developing with dichlorothane. After heating with air at 160° C. for 40 minutes, the resist film was etched with a 40% ferric chloride aqueous solution containing a small amount of nitric acid, and the resist film withstood sufficiently and remained in the same state as the initial state.

On the other hand, the photosensitive solution of Example 1 to which no chromium complex was added was applied to a similar stainless steel plate and subjected to the same treatment as above, followed by etching with the same ferric chloride aqueous solution as the photo. the result,
The resist film withstood etching well, but some areas were slightly raised.

The addition of chromium myristate complex was effective in improving the adhesion of photocurable resin.Example 3 100g of diallyl isophthalate prepolymer (product name: Daiso Isodap, manufactured by Osaka Ichita) was added to diallyl isophthalate. After dissolving 100 g of the monomer and 100 g of methyl isobutyl ketone, 5 g of 1-benzimidazole guanidine was added and kneaded using a triple roll.

To this, 100 g of a partially methacrylated epoxy resin (approximately 50% esterified) and 10 g of benzophenone were added by reacting methacrylic acid with a phenol novolak type epoxy resin (trade name: Ebicoat 152, manufactured by Shell Chemical ■). A photocurable resin composition was prepared.

This photocurable resin composition is applied to a copper-clad laminate using a roll coater.
The film was coated using
A protective coating of m was obtained. It was exposed for 60 seconds to an ultra-high pressure mercury lamp through an appropriate pattern.

A pattern was then obtained by developing with 1.1.1-trichloroethane. This plate was cut into two pieces and heat treated at 160°C for 30 minutes and at 170°C for 20 minutes. The resulting protective coating is 24% containing a small amount of sulfuric acid (1,6%)
It was etched with an aqueous ammonium persulfate solution and plated with the following electroless copper plating, but it was sufficiently usable.

Furthermore, it was found that it could be sufficiently used as a permanent mask. Example 4 100 g of the diallyl isophthalate prepolymer shown in Example 3 was dissolved in a mixed solvent of 100 g of ethyl cellosolve acetate and 100 g of methyl isobutyl ketone.
5 g of an epoxy curing agent Chiea Sol 2MA (manufactured by Shikoku Kasei Kogyo ■) was added and kneaded, and the mixture was kneaded using a three-roll mill.

To this, 100 g of an epoxy resin (approximately 75% esterified), which was partially acrylated by reacting acrylic acid with a phenol novolak type epoxy resin, 10 g of benzophenone, and 3 g of Michler's ketone were added to prepare a photocurable resin composition. did.

This photocurable resin composition was applied to a copper-clad glass epoxy substrate using a roll coater and dried at 65° C. for 30 minutes to obtain a protective film with a thickness of 27 μm.

It was exposed for 60 seconds to an ultra-high pressure mercury lamp through an appropriate pattern. A pattern was then obtained by developing with 1.1.1-) dichloroethane. Divide this board into two parts and heat both to 160℃3.
Heat treatment was performed for 0 minutes. One sheet has a deposition rate of 3.5μm
/H solution for 10 hours, no abnormalities were observed in the protective film. When one of the remaining sheets was plated with the same plating solution for 15 hours, a slight black stain was observed in the copper under the protective film.

1 as an adhesion improver to the photocurable resin composition having the above composition.
．． 2.2 g of 3-benzotriazole was added. This composition was coated, developed and exposed in the same manner as the additive-free product, and then heat treated. As a result of plating for 10 and 15 hours using the same plating solution, no abnormality was observed in the protective coatings of both sheets. Moreover, there were no abnormalities such as cracks on the copper under the protective coating. Addition of adhesion enhancer clearly contributed to the improvement of adhesion.

Example 5 The diallyliso7talate prepo lJ? shown in Example 3
-100gt-ethyl cellosolve acetate 100g,
After dissolving 20g of butyl cellosolve, use imidazole curing agent 2E4MZ (Shikoku Kasei ■) as an epoxy curing agent.
10 g of silicon oxide fine powder Aerosilna 380 (manufactured by Nippon Aerosil ■) treated with 2-mercaptopropion powder and a silane coupling agent as an adhesion improver,
Phthalocyanine blue 3g as a coloring agent, benzophenone 12g1 Michler's ketone 3gs as a polymerization initiator
Furthermore, 082 g of hydroquinone was kneaded and kneaded using three rolls. To this was added 100 g of an epoxy resin (approximately 50% esterified), which was partially acrylated by reacting a phenol novolak type epoxy resin with acrylic acid, to obtain a photocurable resin composition.

This composition was applied to a patterned glass epoxy substrate using a roll coater and dried at 60°C for 20 minutes to obtain a protective film with a thickness of 20 μm. This plate was exposed for 60 seconds to an ultra-high pressure mercury lamp through an appropriate pattern. then 1
．． 1.1-) Developed with dichloroethane. This board is 16
It was heat-treated at 0° C. for 30 minutes and further UV irradiated for 10 seconds. When this plate was plated for 10 hours with the plating solution shown in Example 4, no abnormality was observed in the protective coating.

Further, no abnormality was observed in the copper under the protective film.

Example 6 100 g of diallyl phthalate prepolymer (trade name: Daisodatsubu A1 manufactured by Osaka Ichita) was kneaded with 50 g of methyl isobutyl ketone, 50 g of butyl cellosolve, 5 g of tetrapropyl titanate, and 10 g of calcium carbonate.
I trained it with three rolls.

To this, 50 g of partially acrylated epoxy resin (approximately 35% esterification) by reacting cresol novolak type epoxy resin with acrylic acid, 12 g of benzine engineered ethyl ether, and 2 g of Michler's ketone were added to prepare a photocurable resin composition. .

This was applied to a copper-clad laminate by screen printing to a uniform thickness, and dried at 65° C. for 30 minutes to obtain a protective wave film with a thickness of 20 μm. The pattern was exposed to ultra-high pressure mercury lamp for 60 seconds.

A pattern was then obtained by developing with 1.1.1-trichloroethane. This plate was heat treated at 160° C. for 30 minutes and then plated for 13 hours using the plating solution shown in Example 3. As a result, no abnormalities were observed on the protective coating or the copper surface beneath the coating.

On the other hand, a photocurable resin composition was prepared using the components of the above composition except for tetrapropyl titanate. When this was plated through a similar process, no abnormality was observed in the protective coating, but partial discoloration was observed on the copper surface under the coating.

Example 7 30 g of diallylisophthalate prepolymer shown in Example 3 1 30 g of methyl isobutyl ketone.

Butyl cellosolve 30g,) diphenyl phosphite 1
g1 5 g of calcium carbonate was kneaded and kneaded using three rolls.

To this were added 100 g of an epoxy resin (approximately 45% esterified), which was partially methacrylated by reacting a 7-enol novolac type epoxy resin with methacrylic acid, 7 g of benzene ethyl ether, and 1 g of Michler's ketone, to form a photocurable composition. I got it.

As a result of plating through the same operations as in Example 6, no abnormality was observed not only on the coating but also on the copper surface underneath.

Example 8 In the composition shown in Example 7, a photocurable resin composition was prepared by using r-mercaptoglobil trimethoxysilane (trade name: KBM803 manufactured by Shin-Etsu Silicone) in the tri-7enyl phosphite glue. As a result of performing plating using similar operations, no abnormalities were observed not only on the protective coating but also on the copper surface underneath.

Example 9 Diallyl phthalate prepolymer 65 shown in Example 3
g1 30 g of methyl isobutyl ketone, 30 g of butyl cellosolve, 1 g of r-glycidoxyglobiltrimethoxysilone, 13 g of silicon oxide, and 2 g of 7-talocyanine glycol.
The mixture was kneaded and kneaded using three rolls.

100g of epoxy resin (approximately 60X esterification), which is partially acrylated by reacting dicyclopentadiene and phenolic polymer epoxy resin with acrylic acid.
, benzoin ethyl ether 5g 1 Michler's ketone 1
g was added to prepare a photocurable resin.

As a result of milling through the same operations as in Example 6, no abnormality was observed not only on the coating but also on the copper surface under the coating.

Claims (1)

[Scope of Claims] 1 (A) an epoxy compound containing at least one acryloyl group and/or methacryloyl group (B) a monomer of diallyl phthalate and/or
Photocurable resin composition 2 characterized by containing a prepolymer (C) a photopolymerization initiator (D) an epoxy curing agent as a main component (A) Containing at least one acryloyl group and/or methacryloyl group Epoxy compound (B) diallyl phthalate monomer and/or
A photocurable resin composition containing as main components a prepolymer (C) a photopolymerization initiator (D) an epoxy curing agent (E) an adhesion improver.