JPH0339746A - Alkali developable photosensitive resin composition - Google Patents

Abstract

PURPOSE:To enable alkali development and to form a soldering resist, to electroless gold plating or a soldering mask by using a specified photopolymerizable compd. together with an epoxy compd. CONSTITUTION:A photosensitive resin compsn. is composed of 100pts.wt. photopolymerizable unsatd. compd., 5-100pts.wt. compd. having at least one epoxy group and 0.1-30pts.wt. photopolymn. initiator or sensitizer. The photopolymerizable unsatd. compd. is obtd. by allowing a compd. having at least two epoxy groups to react with acrylic acid or methacrylic acid and satd. aliphat. monocarboxylic acid or arom. monocarboxylic acid and by allowing the resulting product to react with polybasic acid anhydride. Alkali development is enabled and a part hardened by exposure can form a superior soldering resist, a resist to electroless gold plating or a soldering mask.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an alkali-developable photosensitive resin composition, and more specifically, it relates to an alkali-developable photosensitive resin composition that is formed on a printed wiring board. Once a film is formed, alkaline development is possible after exposure, and the exposed and hardened portion is an alkali-developable, photosensitive resin composition that can be suitably used as a solder resist, electroless gold plating resist, and further as a solder mask. It is about things.

(Prior art) In recent years, as ICs and LSIs have become more dense, the printed wiring boards on which they are mounted have also become more dense, leading to miniaturization of lead wires or the elimination of lead wires. There is a shift to the surface mount method, in which components are mounted directly on the surface of the board.

By the way, when forming a solder resist on a printed wiring board, conventionally, a thermosetting type resist ink is printed by a screen printing method, and the transferred portion is thermoset. However, the reality is that this method cannot meet the demands for higher density, so a method of obtaining solder resist using the principles of photography has been developed, and along with this, the development of photoresist ink is being considered. has been done. The working environment also applies to photoresist inks.

In terms of processing costs, instead of the type that is developed with an organic solvent, a type that can be developed with a weak alkaline aqueous solution such as an aqueous sodium carbonate solution has been proposed.

For example, JP-A-61-243,869, JP-A-63
JP-278,052 discloses a resist ink composition or a photosensitive film composition that contains a resin component having a novolac type or bisphenol A type epoxy resin skeleton and can be developed with a slightly weak alkali aqueous solution. Also, JP-A-62-158.710, JP-A-62-285
．． No. 903 and JP-A No. 63-11.930 disclose an alkaline development type resin whose base polymer is a ring-opening addition of hydroxyalkylene acrylate or hydroxyalkylene methacrylate to a copolymer of maleic anhydride and styrene. Compositions are disclosed.

In addition, as the circuit density of printed wiring boards continues to increase, if it is difficult to take the lead wires due to the design, it is recommended that the lead wires be removed from the terminals instead of from the terminals.
A method of connecting from a part of the circuit is adopted, and in this case, electroless gold plating is performed to obtain a contact and to prevent corrosion of the copper that makes up the circuit.

However, since gold is expensive, it is desirable to apply an electroless gold plating resist before plating to avoid unnecessary adhesion of gold to copper circuits and lands. This electroless gold plating resist can be used as a solder resist, and furthermore, it is desirable for the process to also serve as a solder mask).

However, when the composition disclosed in the above-mentioned publication is used as a solder mask and as an electroless gold plating resist, it cannot sufficiently withstand the conditions of gold plating at high temperatures and under acidic conditions, and may cause whitening after processing. .

When used also as a solder mask, there was a problem in that the adhesion between the mask and the substrate deteriorated. Therefore, it was necessary to perform electroless gold plating before forming the solder mask.

(Problems to be Solved by the Invention) In view of the above circumstances, two objects of the present invention are to provide an alkaline development method which is capable of alkaline development and which can be suitably used as a solder resist, an electroless gold plating resist, and furthermore as a solder mask. An object of the present invention is to provide a type photosensitive resin composition.

(Means for Solving the Problems) As a result of intensive studies to solve these problems, the inventors of the present invention have found that using a specific photopolymerizable compound together with an epoxy compound can solve the problems described above. The invention has been achieved.

That is, the gist of the present invention is as follows.

Consisting of the following components (A), (B) and (C), (
The ratio of (B) tj, min to 100 parts by weight of component A) is 5 to 100 parts by weight, and the ratio of component (C) is 0.1 to 100 parts by weight.
30 parts by weight of an alkali-developable photosensitive resin composition.

(A) Component: (a) a compound having at least two epoxy groups, (b) acrylic acid or methacrylic acid and (
C) A photopolymerizable unsaturated compound obtained by reacting a reaction product obtained by reacting a monovalent saturated aliphatic carboxylic acid or a monovalent aromatic carboxylic acid with (d) a polybasic acid anhydride. .

Component (B): A compound having at least one epoxy group.

Component (C): photopolymerization initiator or sensitizer.

The present invention will be explained in detail below.

First, each component constituting the alkali-developable photosensitive resin composition of the present invention will be described.

(A) Component: (a) a compound having at least two epoxy groups, (b) acrylic acid or methacrylic acid [hereinafter referred to as (meth)acrylate], and (C) a monovalent saturated aliphatic carboxylic acid or a monovalent (a) in the photopolymerizable unsaturated compound obtained by reacting the polybasic acid anhydride (d) with the reaction product obtained by reacting the aromatic carboxylic acid of
) Compounds having at least two epoxy groups include bisphenol A epoxy resin, bisphenol F
Epoxy resins such as type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, diglycidyl isocyanurate, triglycidyl isocyanurate, biphenyl-4゜4'-diglycidyl ether, 3.3' , 5,5'-tetramethylbiphenyl-4,4'-diglycidyl ether, and other compounds having epoxy groups; and glycidyl methacrylate homopolymers, and glycidyl methacrylate-containing polymers such as glycidyl methacrylate/styrene copolymers.

Preferred among these are compounds having an epoxy group represented by the following general formulas [1] and [2].

・　・　・　[1] In the formula, R1 and R2 are hydrogen atoms or methyl groups.

Y is a hydrogen atom or a bromine atom. n indicates the degree of polymerization and is an integer of 1 to 30, preferably 5 to 10.

Examples of the compound having an epoxy group represented by the formula [1] include bisphenol A epoxy resin, bisphenol F epoxy resin, and the like.

In the formula, Ra, R, and R5 are groups selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a halogen atom, and 1m indicates the degree of polymerization, and is 2 to 30, preferably 5 to 1.
It is an integer of 0. Examples of the compound having an epoxy group represented by the formula [2] include novolac type epoxy resins.

Furthermore, as (A) monovalent saturated aliphatic carboxylic acid or monovalent aromatic carboxylic acid constituting J component, formic acid, acetic acid, propionic acid, n-butyric acid isobutyric acid, valeric acid, trimethylacetic acid , caproic acid, n-hebutanoic acid, caprylic acid, pelargonic acid, methoxyacetic acid, palmitic acid, monovalent saturated aliphatic carboxylic acids such as stearic acid, and benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, chlorogenated Benzoic acid, phenylacetic acid, anisic acid,
Examples include monovalent aromatic carboxylic acids such as benzoylbenzoic acid and naphthoic acid.

In addition, (d) polybasic acid anhydrides constituting component (A) include maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, tetrapropenylsuccinic anhydride, phthalic anhydride, hexahydrophthalic anhydride. Acid anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, 3-
Propyl hexahydrophthalic anhydride, 3-isopropyl hexahydrophthalic anhydride, 4-propyl hexahydrophthalic anhydride, 4-isopropyl hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride , 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, 4-ethyltetrahydrophthalic anhydride, 3-propyltetrahydrophthalic anhydride.

3-isopropyltetrahydrophthalic anhydride.

Examples include 4-propyltetrahydrophthalic anhydride and 4-isopropyltetrahydrophthalic anhydride.

The photopolymerizable unsaturated compound which is component (A) in the present invention can be produced, for example, as follows. That is, (a) a compound having at least two epoxy groups is dissolved in an ethylene oxide solvent such as cellosolve acetate, and (b) (meth)acrylic acid and (C) are dissolved in an ethylene oxide solvent such as cellosolve acetate.
A monovalent saturated aliphatic carboxylic acid or a monovalent aromatic carboxylic acid, optionally with the addition of 0.2 to 2% by weight of a reaction accelerator between the acid and the epoxy group, at 80 to 120°C for 2 to 8 hours. Allow time to react. Next, the desired product can be obtained by adding (d) polybasic acid anhydride to this reaction product and reacting at 80 to 120°C for 2 to 4 hours.

In this case, these raw materials.

It is preferable to carry out the reaction within the following range. When this value exceeds 1, the acid becomes excessive and may cause corrosion of the wiring. In addition, if this value is less than 0.8, the adhesion and photosensitivity of the coating may become insufficient, and the storage stability of the photopolymerizable unsaturated compound obtained by reacting the polybasic acid anhydride There is a tendency for sexual performance to decline. Also, the reaction ratio between (b) and (C) is the number of moles of (b): the number of moles of (C>) = 19:1
It is preferable to select within the range of 1:1. If the reaction is carried out outside this range, the adhesion or photosensitivity of the coating film tends to decrease.

What is the amount of (d) polybasic acid anhydride to be added?

It is preferable to carry out the reaction within the following range. When this value exceeds 1, the acid anhydride becomes excessive, which may cause corrosion of wiring, and the stability of the product also tends to decrease.

Moreover, when this value is less than 0.5, the content of carboxyl groups per unit weight becomes low, and therefore the developability in an alkaline aqueous solution tends to be reduced.

(B) tj constituting the resin composition in the present invention.

Compounds having at least one epoxy group with 9
It is blended for the purpose of heat curing the resin composition of the present invention. Such component (B) is 0. For example,
In addition to the epoxy resins represented by the general formula [1] or [2], epoxy resins such as bisphenol S-type epoxy resins and alicyclic epoxy resins, phenyl glycidyl ether, p
Examples include compounds having an epoxy group such as -butylphenyl glycidyl ether, talesyl glycidyl ether, diglycidyl isocyanurate, triglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate.

The photopolymerization initiator or sensitizer, which is component (C) constituting the resin composition of the present invention, acts on component (A) described above and the photopolymerizable monomers and oligomers blended as necessary. It initiates photopolymerization. Like this (C)
For example, 1 is equivalent to llE.

Acetophenone, 2,2-jethoxyacetophenone,
Acetophenones such as p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tart-butyltrichloroacetophenone, benzophenone, and 2-chlorobenzophenone.

p,p'-dichlorobenzophenone, p,p'-bisdimethylaminobenzophenone (also known as Michler's ketone), I),1)'-bisdiethylaminobenzophenone, 3,3°4,4"-tetra (tert-butylperoxy) Carbonyl> Benzophenones such as benzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyl dimethyl ketal.

Tetramethylthiuram monosulfide, tetramethylthiuram disulfide, thioxanthone.

Sulfur compounds such as 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone,
2-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1.2
- anthraquinones such as benzanthraquinone and 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutyronitrile, pensoyl peroxide, di-tert-butyl peroxide, and cumene peroxide;
2.4.5-) Thiol compounds such as aryl imidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole 2.4.6
-) lis(trichloromethyl) -s -) riazine,
Examples include organic halogen compounds such as 2.2.2-tribromoethanol and tribromomethylphenylsulfone. These compounds can also be used in combination of two or more. It is also possible to add compounds that do not act as photopolymerization initiators by themselves, but can increase the ability of the photopolymerization initiators when used in combination with the above compounds. Examples of such compounds include tertiary amines such as triethanolamine,
The alkali-developable photosensitive resin composition of the present invention is effective when these are used in combination with benzophenone.

It consists of component (A), component (B), and (C), and the blending ratio of each component in this resin composition is (
(B) Jilt content is 5 to 100 parts by weight of component Δ)
The amount of component (C) is 100 parts by weight, preferably 10 to 80 parts by weight, and 0.1 to 30 parts by weight, preferably 1 to 30 parts by weight, per 100 parts by weight of component (A).

When the blending ratio of component (B) to 100 parts by weight of component (A) is less than 5 parts by weight, the curability of the resin composition of the present invention by heating decreases. On the other hand, if it exceeds 100 parts by weight, the photopolymerization rate slows down, resulting in a decrease in sensitivity and making it difficult to develop with a weakly alkaline aqueous solution.

Furthermore, if the blending ratio of component (C) to 100 parts by weight of component (A) is less than 0.1 part by weight, the photopolymerization rate becomes slow and the sensitivity decreases. If it exceeds 30 parts by weight, it is difficult for light to reach the substrate, resulting in poor adhesion between the substrate and the resin.

The alkali-developable photosensitive resin composition of the present invention is.

It can be suitably used as a solder resist for printed wiring boards, an electroless gold plating resist, and a solder mask ε as described below. for example.

Is the alkali-developable photosensitive resin composition of the present invention dissolved in a solvent and applied to the surface of a printed wiring board?

Alternatively, a film is formed by a method such as attaching a dry film made of the alkali-developable photosensitive resin composition of the present invention to the surface of a printed wiring board.

Next, a negative film is placed on the film thus obtained, and after irradiating with actinic rays to harden the exposed areas, the unexposed areas are further eluted using a weak alkaline aqueous solution and developed.

Examples of solvents suitable for dissolving the alkali-developable photosensitive resin composition of the present invention include methyl ethyl ketone,
Examples include ketones such as methyl isobutyl ketone, and cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and cellosolve acetate.

Methods for applying a solution containing the alkali-developable photosensitive resin composition of the present invention to a printed wiring board include a solution dipping method, a spray method, and a method using a roller coater machine or a spinner coater. Yes 7 Either method can be adopted. By these methods 2
For example, if the solvent is removed after coating to a thickness of 20 to 30 μm, a film will be formed on the printed wiring board.

Further, a dry film can be prepared by coating a solution containing the alkali-developable photosensitive resin composition of the present invention on a flexible support such as a polyethylene terephthalate film and drying it. Note that the dry film may be covered with a polyethylene film or the like for protection.

Light suitable for curing the alkali-developable photosensitive resin composition of the present invention includes light from a light source such as an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, or a metal halide lamp. Note that the resin composition of the present invention can be cured not only by light but also by heat.

Examples of developing solutions suitable for alkali development after exposure include aqueous solutions of alkali metal or alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, and the like. Fine images can be precisely developed using a weakly alkaline aqueous solution containing 1 to 3% by weight of carbonates such as carbonate, potassium carbonate, and lithium carbonate.

Alkaline development is carried out at 10 to 50°C, preferably 20 to 40°C.
It can be carried out using a commercially available developer or ultrasonic cleaner at a temperature of .degree.

After alkaline development, in order to improve the corrosion resistance of the exposed and hardened area, it is desirable to further harden it by heat treatment.
Heat treatment significantly improves durability against strong alkaline water, adhesion to metals such as copper, heat resistance durability 9 surface hardness, etc., making it suitable for use as a protective mask for printed wiring boards such as electroless gold plating resistance and soldering heat resistance. The required properties are further improved. The heat treatment conditions are preferably 80 to 200°C for 10 minutes to 2 hours.

In the alkali-developable photosensitive resin composition of the present invention.

In addition to components (A), (B) and (C), a photopolymerizable monomer or oligomer, a curing accelerator having an epoxy group,
Compounding agents and additives such as thermal polymerization inhibitors, fillers, dyes, pigments, plasticizers, leveling agents, adhesion improvers, antifoaming agents, flame retardants, and organic solvents can be added to this product. The types and amounts of such compounding agents and additives can be appropriately selected within a range that does not impair the properties of the alkali-developable photosensitive resin composition of the present invention.

Photopolymerizable monomers and oligomers include 9, for example, 2
- Monomers having hydroxyl groups such as hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
Ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate.

Tetraethylene glycol diacrylate, tetramethylene glycol diacrylate, trimethylolethane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexa Acrylates, acrylic acid esters such as glycerol acrylate, and ethylene glycol dimethacrylate.

Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, di By reacting esters of unsaturated carboxylic acids such as esters of methacrylic acid such as pentaerythritol hexamethacrylate and glycerol methacrylate with aliphatic polyol compounds, diisocyanates and monohydric alcohols having at least one acrylate group or methacrylate group. Examples include the urethane acrylate compounds obtained. Moreover, these compounds can also be used in combination of 2 or more types. These compounds act as viscosity modifiers or photocrosslinking agents.

Epoxy group curing accelerators include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary
Examples include class ammonium salts and methylol group-containing compounds. When a film obtained by using a small amount of these together is heated afterward, properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical properties, and hardness are improved. Therefore, a product suitable for use as a solder resist or an electroless gold plating resist can be obtained.

Thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, and pyrogallol.

Examples include tert-butylcatechol and phenothiazine.

Fillers include white alumina, clay, talc, finely powdered silica, barium sulfate, and barium carbonate.

Examples include magnesium oxide and titanium oxide.

Phthalocyanine green is used as a dye and pigment.

Examples include phthalocyanine blue, phthalocyanine yellow benzidine yellow, permanent red R, and brilliant carmine 6B.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl, and the like.

Antifoaming agents and leveling agents include 9, for example, silicone-based,
Examples include fluorine-based and acrylic-based compounds.

! For example, 9 is an example of a refueling agent. Aluminum hydroxide.

Examples include inorganic flame retardants such as zinc borate, and organic flame retardants such as halogen-containing phosphates such as tris-(β-chloroethyl)-phosphate and pentachlorophenol methacrylate.

(Example) The present invention will be specifically explained below by referring to an example. Note that "parts" indicate "parts by weight."

Reference Examples 1 to 10 A photopolymerizable compound (A) It was synthesized using the formulation composition (Reference Examples 1 to 10) described later by the method described below.

(a)'J) A compound having at least two epoxy groups and a solvent were placed in a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, and the mixture was humidified at 50-60°C. to make a homogeneous solution. Then, (b) (meth)acrylic acid and (
C) Monovalent saturated aliphatic carboxylic acid or monovalent aromatic carboxylic acid, p-methoxyphenol (0.1% by weight of total solids) as a thermal polymerization inhibitor, 2-hydroxyethylimidazole (total solids) as a catalyst 0.1% by weight) was added, the temperature was raised to 80 to 90°C, and the reaction was allowed to proceed for 2 to 8 hours. At this time, a part of the contents of 1 reaction was taken out into an Erlenmeyer flask, and phenolphthalein was used as an indicator. Measure the acid value with IN alcoholic potassium hydroxide solution (2, the point when the value becomes 1 or less is considered the end point of the reaction (also.

Then, (d) polybasic acid anhydride is added to this solution.

Photopolymerizable unsaturated compounds (Reference Examples 1 to 10, containing an organic solvent) were obtained by reacting at 80 to 90°C for 2 to 8 hours. Furthermore, the acid value of the end point of the reaction was determined in the same manner as described above.

Reference Example 1 of Compounding Composition (a): Bisphenol A epoxy resin (Epicote 1,001. Epoxy equivalent: 450) 225 g Solvent: 200 g of ethyl cellosolve acetate (b) 43 g of nialic acid (c) 22 g of nibrobionic acid (0.30 mol) 〉
(d): Hexahydrophthalic anhydride reference example 2 (a): Bisphenol A type epoxy resin (Araldite 6071. Epoxy equivalent: 450) 225 g Solvent:
Methyl cellosolve acetate 230 g (b): methacrylic acid 60 g (0.70 mol) (C): isoacetic acid 18
g (0.20 mol) (d): 133 g of phthalic anhydride (
0.90 mol) Reference Example 3 (a> Nibrominated bisphenol A type epoxy resin (Epicote 1045. Epoxy equivalent 500) 25
g Solvent: 230 g of ethyl cellosolve acetate (b) 40 g of nialic acid (0,55 mol) (c): 26 g of n-butyric acid (0,30 mol) (d): 106 g of tetrahydrophthalic anhydride (0,70 (mol) Reference Example 4 (a): O-talesol novolak type epoxy resin (E
SCN-195HH, epoxy equivalent 200) 00g Solvent: Ethyl cellosolve acetate) 205g (b) Niacrylic acid 43g (0.60 mol) (C> Nistearic acid 57 g (0.20 mol) (d): Succinic anhydride 80
g (0.80 mol) Reference Example 5 (a) Nibrominated phenol novolac type epoxy resin (BRE N -S, epoxy equivalent 280) 28
0 g Solvent: 230 g of ethyl cellosolve acetate (b
) Niacrylic acid 36 g (0.50 mol) (C): Propionic acid 30 g (0.40 mol) (d): Succinic anhydride 80 g (0.80 mol) Reference example 6 (a): Bisphenol S type epoxy resin ( Epicote 807. Epoxy equivalent 500) 250 g Solvent: methyl cellosolve acetate) 275 g (b): Methacrylic acid 60 g (0.70 mol) (c): n-caproic acid 3
4g (0.20 mol) (d): 69g of anhydrous maleic R
(0.70 mol) Reference Example 7 (a) Nigericidyl methacrylate/styrene copolymer (epoxy equivalent: 250) 250 g Solvent Nibutyl Cellosolve Ace f-) 250 g (b): Methacrylic acid 52 g
(0.60 mol) (c): 26 g of n-butyric acid (OJO mol) (d): 133 g of phthalic anhydride (0.90 mol) Reference Example 8 (a): Bisphenol A epoxy resin (Epicote 1001.Epoxy Equivalent weight 450) 225 g Solvent: ethyl cellosolve acetate) 220 g (b) Niacrylic acid 65 g (0.90 mol) (C): Not used (d): Hexahydrophthalic anhydride 123 g <(
1,80 mol) Reference Example 9 (a): Bisphenol A epoxy resin (Epicote 1001. Epoxy equivalent: 450) 225 g Solvent: ethyl cellosolve acetate 230 g (b) Niacrylic acid 14 g (o, 20 mol) (C): Propion acid 52
g (0.70 mol) (d): 139 g (0.90 mol) of hexahydrophthalic anhydride Reference Example 10 (a): O-cresol novolac type epoxy resin (E
SCN-195HH, t! Oxy equivalent 200)00
g Solvent: ethyl cellosolve acetate 180 g (b) Niacrylic acid 58 g (0,80 mol) (C): Not used (d): Succinic anhydride 80 g (0,80 mol) Examples 1 to 7. Comparative Examples 1 to 3 Reference Examples 1 to 10t'The obtained component (A), component (B), (
C) component and photopolymerizable monomer, inorganic filler pigment and organic solvent are blended in the proportions (parts by weight) shown in Table 1,
Knead using a three-roll mill for testing.

A resist ink was prepared. Then, the thickness 1 was degreased and cleaned.
．． After applying these resist inks to a thickness of 17 to 25 μm on a 6non copper-clad laminate and drying them.

The negative film was adhered and exposed using a 3K11 ultra-high pressure mercury lamp C@Oak Seisakusho, HMII-6~N] for 100 seconds with ultraviolet light around a wavelength of 365 nm at an illuminance of 5 mw/cm. After exposure. Developing machine [manufactured by Yoshitani Shokai ■.

YCB-85], 30°C, 1% by weight carbonic acid)
The unexposed portion of the coating film was removed by immersion in an IJum aqueous solution for 80 seconds and developed. After that, use a hot air dryer to
Heat treatment was performed at ℃ for 50 minutes.

Regarding the samples obtained in the above process, the drying properties of the coating film, exposure sensitivity, developability to alkaline solutions, coating film hardness, adhesion to the substrate, soldering heat resistance, electroless gold plating resistance of the coating film,
Chemical resistance and insulation resistance were evaluated. The results are shown in Table 2.

Of these performance evaluations, the drying properties of the coating film.

Regarding the developability to alkaline aqueous solution and IL light sensitivity, the coating film obtained by applying resist ink to a thickness of 17 to 25 μm on a copper-clad laminate and drying it for 30 minutes at 70°C using a hot air dryer. evaluated.

Also, hardness, adhesion to the board, and soldering heat resistance.

Regarding electroless gold plating resistance, chemical resistance, solvent resistance, and insulation resistance, 500n+J/cm2@light, after development.

For edge resistance, 500 mJ/cm" N light, after development.

Heating was performed at 145° C. for 50 minutes, and the coating film as a solder resist after completely curing was evaluated.

In addition, each evaluation was performed as follows.

(1) Drying properties of coating films The drying properties of coating films were evaluated according to JIS K-5400.

The evaluation ranks are as follows.

○: No tack observed at all △: Slight tack observed ×: Significant tack observed (2) Exposure sensitivity Shidatsu Step Tablet Nα2 (manufactured by Eastman Kodak Company, optical density step 0.15) A negative film with 21 steps was closely attached to the coating film, and 3 was irradiated with a light intensity of 500 mJ/cm'' using a W ultra-high pressure mercury lamp.

This coating film was subjected to a developability test using a weak alkaline aqueous solution as described below, and the number of step tablets remaining on the copper foil was determined. In this method, the higher the sensitivity, the more steps remain.

(3) Developability in alkaline aqueous solution Using a 1% by weight aqueous solution of IJ carbonate.

8 at 30℃ under a pressure of 2゜1kg/cut using a developing machine.
Development was performed for 0 seconds. After development, observe at 30x magnification.

The remaining resin was visually evaluated.

The evaluation ranks are as follows.

○: Good developability (no resist remains on the copper surface) ×: Poor developability (some resist remains on the copper surface) (4) Coating film hardness JIS -5400 According to the test method, the highest hardness that does not cause scratches on the film when a load of 1 kg is applied using a pencil hardness tester is indicated. The pencil used was ``Mitsubishi Hi-Uni'' (manufactured by Mitsubishi Pencil Co., Ltd.).

(5) Adhesion to the substrate Cross-cuts are made on the coating film to create at least 100 squares.Next, a peeling test is performed using adhesive tape, and the state of peeling at the squares is visually checked. evaluated. The evaluation ranks are as follows.

○: No peeling was observed at all measurement points △: Peeling was observed at 1 to 20 of 100 measurement points X: Peeling was observed at 21 or more points out of 100 measurement points Item (6) Solder heat resistance According to JIS D-0202, the sample was immersed in a 260°C solder bath for 20 seconds, and the state of the coating film after immersion was evaluated. The evaluation ranks are as follows.

○: No abnormality in the appearance of the coating film ×: Blistering, melting, and peeling in the appearance of the coating film (7) Resistance to electroless gold plating The patterned substrate obtained by the above method was degreased and cleaned.
Then, a catalyst activation treatment was performed using a commercially available electroless nickel plating solution (pH = 6') at 90°C for 15 minutes. Furthermore, an electroless gold plating solution [pH=6.

Gold with a thickness of 2 μm was deposited by treatment with KAu (CN) 3 g/l] at 90° C. for 90 minutes. Next, a peeling test was conducted using an adhesive tape, and the state of peeling on the copper circuit was visually evaluated. The evaluation ranks are as follows.

○: No peeling was observed on the copper circuit △: l~2
Peeling was observed in some places.X: Peeling was observed in 3 or more places. did.

■Acid resistance 10% by weight HCI aqueous solution ■Alkali resistance 10% by weight NaOH aqueous solution ■Solvent resistance trichloroethane methylene chloride Isopropyl alcohol The evaluation ranks are as follows.

○: No abnormality ×: Dissolution or swelling (9) Insulation resistance A circular electrode was created on the film according to JIS Z-3197.

Insulation properties under normal conditions and after 100 hours at 55°C and 95%RH were measured using 5uper Megohmeter manufactured by Toa Denpa ■.
Measured using Model SM-5h.

As is clear from Tables 1 and 2, the film made of the alkali-developable photosensitive resin composition of the present invention is also excellent in electroless gold plating resistance and other properties.

(Effects of the Invention) Since the present invention is configured as described above, when a film made of the alkali-developable photosensitive resin composition of the present invention is formed on a printed wiring board, alkali development becomes possible after nine exposures. Moreover, the exposed and hardened portion forms an excellent solder resist and electroless gold plating resist, as well as a solder mask.

Therefore, according to the alkali-developable photosensitive resin composition of the present invention, electroless gold plating can be performed after forming a solder mask, and waste in electroless gold plating can be eliminated.

Moreover, the alkali-developable photosensitive resin composition of the present invention is
It has excellent acid resistance, alkali resistance, solvent resistance, soldering heat resistance, electrical insulation, mechanical strength, surface hardness, etc., so it is suitable for use as a permanent protective mask for plating resists, etc. in full additive methods. can do. In addition, we also supply etching resists, interlayer insulation materials, photosensitive adhesives, paints, and plastic reliefs for printed wiring boards.

It can be used as a hard coating agent for plastics, a PS plate as an offset printing plate, a photosensitive liquid for screen printing, a resist ink, etc. 9 It can be used in a wide range of fields.

Claims (3)

[Claims] (1) Consisting of the following components (A), (B), and (C), the ratio of component (B) to 100 parts by weight of component (A) is 5 to 100 parts by weight, and the ratio of component (C) is 0.1~
30 parts by weight of an alkali-developable photosensitive resin composition. (A) Component: (a) a compound having at least two epoxy groups, (b) acrylic acid or methacrylic acid, and (c
) A photopolymerizable unsaturated compound obtained by reacting a reaction product obtained by reacting a monovalent saturated aliphatic carboxylic acid or a monovalent aromatic carboxylic acid with (d) a polybasic acid anhydride. Component (B): A compound having at least one epoxy group. Component (C): photopolymerization initiator or sensitizer. (2) The alkaline developable photosensitive resin composition according to claim 1, wherein the compound having at least two epoxy groups is a compound represented by the following general formula [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ... [1] (However, in the formula, R_1 and R_2 are hydrogen atoms or methyl groups, Y is a hydrogen atom or bromine atom, and n indicates the degree of polymerization.) (3) The alkali-developable photosensitive resin composition according to claim (1), wherein the compound having at least two epoxy groups is a compound represented by the following general formula [2]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[2] (However, in the formula, R_3, R_4 and R_5 are hydrogen atoms,
It is a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and a halogen atom, and m is an integer of 2 or more and indicates the degree of polymerization. )