JPH1138621A - Photosensitive resin composition and circuit board obtained using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin compsn. forming a resist film excellent in adhesion to a copper substrate at the time of etching by using an unsatd. compd. having a sulfide bond. SOLUTION: The photosensitive resin compsn. contains an ionic group-contg. resin, a sulfide type unsatd. compd. having a sulfide bond in the molecular skeleton and contg. two or more photopolymerizable unsatd. groups in molecular terminals and a photopolymn. initiator. The average mol.wt. of the ionic group- contg. resin is preferably 1,000-20,000. A substrate is coated with the photosensitive resin compsn., the resultant resin film is cured by direct exposure with laser light or exposure through a negative mask so as to obtain a desired resist film (image) and the uncured part is removed by development with an aq. alkali or acid soln. to form the resist film on the substrate. The part of a metallic layer of copper, etc., not protected with the resist film is removed and then the resist film is removed to obtain the objective circuit board.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel photosensitive resin composition and a circuit board obtained by using the same.

[0002]

2. Description of the Related Art Conventionally, as a circuit board, a photosensitive resin solution was coated on a copper layer such as a surface copper foil or a copper plating layer of a copper-clad laminate, and then dried to form a photosensitive resin film. rear,
This is exposed to laser light directly or through a negative mask, the unexposed portion of the coating is removed with an aqueous alkali solution, and then the exposed copper layer is sprayed with an aqueous solution of cupric chloride or ferric chloride to eliminate the need for circuits. A circuit board obtained by removing a copper layer and then removing an exposed portion of the resist film using an alkaline aqueous solution is used.

As a photosensitive resin solution used for this circuit board, a solution obtained by dissolving a polycarboxylic acid resin as a main component as a resin component in an organic solvent is generally used. In recent years, with the increase in the density of circuit wiring patterns and the like, high-resolution copper circuits have been required. However, even if a conventional resist film is formed on a circuit board requiring such a high resolution, the adhesion between the resist film and copper is not good, so that cupric chloride or secondary chloride is required during etching. There has been a problem that an aqueous solution of iron penetrates into the interface between the resist film and copper, and unnecessary portions of copper are etched to increase the defective rate of the product.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to develop a photosensitive resin composition which forms a resist film having excellent adhesion to a copper substrate during etching.

[0005]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the use of unsaturated compounds having a sulfide bond has led to the problems of the prior art. And found that the present invention was completed.

That is, the present invention provides: (1) an ionic group-containing resin, (B) a sulfide bond in a molecular skeleton, and two or more photopolymerizable unsaturated groups at a molecular terminal. A photosensitive resin composition comprising a sulfide-based unsaturated compound and (C) a photopolymerization initiator, 2. on an insulating substrate having a metal layer such as copper on the surface, the following (1) (A) An ionic group-containing resin, (B) a sulfide-based unsaturated compound having a sulfide bond in a molecular skeleton and containing at least one photopolymerizable unsaturated group at a molecular terminal, and (C) a photopolymerization initiator. A step of coating the photosensitive resin composition to be contained, (2) a step of curing by directly exposing with a laser beam or through a negative mask so as to obtain a desired resist film (image) on the coated photosensitive resin film, 3) Alkali or Step of forming a resist film on a substrate by developing the uncured part of the aqueous solution,
The present invention relates to a circuit board obtained by (4) a step of removing a metal layer such as copper which is not protected by a resist film, and (5) a step of removing a resist film.

Hereinafter, the photosensitive resin composition of the present invention will be described.

The ionic group-containing resin (A) used in the present invention is obtained by neutralizing the uncured portion of the photosensitive film with a developer (aqueous solution of alkali or acid) and dissolving or dispersing in water. This is to make it possible to remove the coating on the hardened portion. Examples of the ionic group include an anionic group such as a carboxyl group and a cationic group such as a tertiary amino group. A photosensitive resin composition using a resin (A) containing an anionic group as an ionic group uses an aqueous alkali solution as a developer, and a photosensitive resin composition using a resin (A) containing a cationic group. The product is an aqueous acid solution as a developer.

The photosensitive resin composition containing the ionic group-containing resin (A) is usually used as an organic solvent-based resin composition dissolved or dispersed in an organic solvent. It can also be used as an aqueous resin composition (anionic electrodeposition paint, cationic electrodeposition paint, etc.) in which water is dissolved or dispersed in water by neutralizing ionic groups.

In the ionic group-containing resin (A) described above, the carboxyl group has an acid value of about 20 to 200 KO based on the acid value of the resin.
H / mg, especially those in the range of about 30-100 KOH / mg are preferred. When the acid value is less than about 20, there is a disadvantage that copper cannot be sufficiently removed in the next etching step due to poor film removal of the uncured film due to the treatment with the developing solution. Part (cured film part)
However, there is a disadvantage that a satisfactory copper circuit is not formed because the film is easily removed, which is not preferable. The tertiary amino group has an amine value of about 15 to 150, particularly about 30 to 8
Those in the range of 0 are preferred. If the amine value is less than about 15, there is a disadvantage that copper cannot be sufficiently removed in the etching step as described above, while if the amine value is more than about 150, there is a disadvantage that the resist film is apt to be removed, which is not preferable. .

The ionic group-containing resin (A) preferably has an average molecular weight of about 500 to 30,000, more preferably 1,000 to 20,000, in view of the balance of properties such as film-removing properties, fine wire adhesion, and film strength.

The ionic group-containing resin (A) can contain, if necessary, a photopolymerizable unsaturated group in addition to the ionic group. Since the resist film formed from the composition containing the photopolymerizable unsaturated group is a tough film, there is an advantage that the resist film is hardly peeled off by an external force such as friction and can exhibit stable performance. Examples of the photopolymerizable unsaturated group include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and a propenyl group. When a photopolymerizable unsaturated group is contained, the amount of the unsaturated group is about 1 to 5
The range of mol / Kg (resin) is preferable.

Next, the anionic polymerizable unsaturated resin (a) containing a carboxyl group will be described as the ionic group-containing resin (A). The resin (a) has an acid value of about 20 to
300, preferably about 40 to 110, and the amount of unsaturated group is about 1
５5 mol / Kg (resin) and number average molecular weight is about 300
As described above, the resin is preferably in the range of about 1,000 to 30,000.

As the base resin constituting the basic skeleton of the anionic polymerizable unsaturated resin (a), for example, acrylic resin, urethane resin, epoxy resin, polyester resin, polyether resin, alkyd resin, Examples thereof include a polyvinyl chloride resin, a fluorine resin, a silicon resin, a vinyl acetate resin, a novolak resin, and a modified resin of two or more of these resins.

As the anionic polymerizable unsaturated resin (a), for example, the following are typical examples.

(1) A polymerizable compound obtained by adding a reaction product of a compound having a polymerizable unsaturated bond and a hydroxyl group in one molecule and a diisocyanate compound to a high acid value acrylic resin having a hydroxyl group in a skeleton. A component mainly composed of an unsaturated resin or a combination of these and an ethylenically unsaturated compound having one or more polymerizable unsaturated bonds in one molecule.

(2) A polymerizable unsaturated resin obtained by adding an epoxy resin having an epoxy group to an α, β ethylenically unsaturated dibasic acid or an anhydride thereof, or a polymerizable unsaturated resin and a polymerizable unsaturated resin in one molecule A component mainly composed of a mixture with an ethylenically unsaturated compound having one or more bonds. (3) A polymerizable unsaturated resin composed of an unsaturated fatty acid-modified high acid value alkyd resin or a mixture of these with an ethylenically unsaturated compound having at least one polymerizable unsaturated bond in one molecule. component.

(4) A polymerizable unsaturated resin comprising a maleated oil, or a polymerizable unsaturated resin having one polymerizable unsaturated bond in one molecule.
A component mainly composed of a mixture with at least one ethylenically unsaturated compound.

(5) A polymerizable unsaturated resin obtained by adding a compound having a polymerizable unsaturated bond and a glycidyl group in one molecule to an acrylic resin having a high acid value, or a polymerizable unsaturated bond in one molecule and a polymerizable unsaturated resin A component mainly composed of a combination of an ethylenically unsaturated compound having at least one compound.

Among the above-mentioned polymerizable unsaturated resins, a preferable one is the unsaturated resin (5). The other cationically polymerizable unsaturated resin (b) is a resin containing an ethylenically unsaturated group such as an acryloyl group and a methacryloyl group and an amino group in a resin skeleton.

The following resins can be mentioned as the resin containing an ethylenically unsaturated group and an amino group.

(1) A resin obtained by adding a primary or secondary amine to an epoxy compound and then adding an isocyanate compound containing an ethylenically unsaturated group to a hydroxyl group.

(2) A resin obtained by adding a compound containing an ethylenically unsaturated group and a carboxyl group to an epoxy group of a resin containing an epoxy group and a tertiary amino group.

(3) After adding a primary amine to the monoepoxy compound and secondary aminating, the diepoxy compound or the polyepoxy compound is converted to a secondary amine having an equivalent number of epoxy groups of 1
After adding so as to be 2 or more, the above-mentioned ethylenically unsaturated group-containing compound containing a carboxyl group was added to the remaining epoxy group, or the above-mentioned ethylenically unsaturated group-containing isocyanate compound was added to the hydroxyl group. resin.

The sulfide-based unsaturated compound (B) used in the present invention hardens the film by exposure and improves the adhesion to copper to enable a high-resolution circuit. This sulfide unsaturated compound (B)
Is a compound having a sulfide bond in the molecular skeleton and containing at least one photopolymerizable unsaturated group at a molecular terminal.

The sulfide-based unsaturated compound (B) has, for example, a sulfide bond in the molecular skeleton, and has a functional group that reacts complementarily with a functional group of the following unsaturated compound in the molecule. 40000, especially about 10
Sulfide compound (a) in the range of 00 to 25000
And a reaction product of the unsaturated compound (b). Examples of functional groups that react complementarily include an epoxy group and a carboxyl group, a thiol group and an epoxy group, and a hydroxyl group and an isocyanate group.

As the sulfide compound (a), for example, an epoxy group-terminated polysulfide compound described in JP-A-6-116387 and a polysulfide polymer having a thiol group at a molecular terminal described in JP-A-4-7831 are used. can do. Since the detailed description of these is described in the official gazette, the preferred former one will be briefly described here.

The epoxy group-terminated polysulfide compound has the following general formula:

[0029]

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Wherein R1 and R3 are organic groups containing one or more carbon atoms, and R2 is

[0031]

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(Wherein R4 and R5 are organic groups containing at least 2 carbon atoms, m is 1-3 and represents the average content of sulfur atoms in the organic group R2, and n is 1-50 Represents the average content of the organic group R2 in one molecule.) Examples of R1 and R3 include bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, and halogenated compound. Bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, those having the same molecular structure as alicyclic epoxy resin, or those having a similar molecular structure to these, and having the following molecular structure thing.

[0033]

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The above R4 and R5 have the following molecular structures.

[0035]

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The trade names of epoxy group-terminated polysulfide compounds include, for example, FLEP-50 (epoxy equivalent 320), FLEP-60 (epoxy equivalent 280), FEP
LEP-65 (epoxy equivalent 315), FLEP-12
5X (epoxy equivalent: 850), FLEP-410C (all trade names, manufactured by Toray Thiokol Co., Ltd., epoxy equivalent: 1200), and the like.

As the unsaturated compound (b), those containing a carboxyl group include those containing an α, β-ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid and maleic acid, and those containing an epoxy group. Glycidyl acrylate, epoxy group-containing unsaturated monomer such as glycidyl methacrylate, hydroxyethyl acrylate,
Examples include a hydroxyl group-containing unsaturated monomer such as hydroxyethyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate, and an isocyanate group-containing unsaturated monomer such as isocyanate ethyl acrylate. In the unsaturated compound (b), acrylic acid and methacrylic acid are particularly preferable as the unsaturated compound (b) to be combined with the above-mentioned epoxy group-terminated polysulfide compound (a).

The compounding ratio of the polysulfide compound (a) and the unsaturated compound (b) is such that the ratio (a) :( b) of the number of functional groups that react complementarily is preferably 1: 0.8 to 2.0. Is preferably in the range of 1: 0.9 to 1.5.

The reaction between the polysulfide compound (a) and the unsaturated compound (b) can be carried out by a conventionally known production method according to the reaction between the functional groups of these compounds. Epoxy-terminated polysulfide compound (a) and α, β-ethylenically unsaturated carboxylic acid (b)
Is reacted with, for example, a mixture of the compound (a) and the compound (b) with an epoxy group and a carboxyl group as needed (for example, triethylammonium bromide).
To about 0.01 to 5 parts by weight, preferably about 0.1 part by weight, based on 100 parts by weight of the total of compound (a) and compound (b).
３3 parts by weight are dissolved or dispersed in an organic solvent inert to these compounds to give a reaction temperature of about 10
At 0 ° C., it can be produced by performing the reaction for about 3 to 8 hours.

The above-mentioned organic solvent is substantially inactive with the functional groups and unsaturated groups of the compounds (a) and (b), and has a boiling point of about 200 ° C. or less at which these compounds are dissolved or dispersed. Can be suitably used. In particular,
For example, ether solvents such as propylene glycol monomethyl ether, methyl cellosolve, and diethylene glycol monomethyl ether; ketone solvents such as methyl isobutyl ketone, isophorone and cyclohexanone; propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, and pentyl acetate;
Ester solvents such as ethylhexyl acetate, cyclohexyl acetate, and cellosolve acetate; and aromatic solvents such as xylene and toluene. The blending amount of the organic solvent is not particularly limited, but the solid concentration of the reaction product is 10 to 10.
It is considered that the range of 90% by weight is sufficient.

The mixing ratio of the ionic group-containing resin (A) and the unsaturated compound (B) is about 50 to 99% by weight, particularly about 48 to 80% by weight, based on the total weight of the two. About 1 to 50% by weight of the unsaturated compound (B),
A range of 20% by weight is preferred. If the content of the resin (A) is less than about 50% by weight and the content of the unsaturated compound (B) exceeds about 50% by weight, the curability and the like deteriorate, whereas the content of the resin (A) exceeds about 99% by weight and the content of the unsaturated compound (B) increases. ) Is less than about 1% by weight.

The photopolymerization initiator (C) used in the present invention
A conventionally known one can be used. This includes, for example, acetophenone, benzyl ketal, hydroxyacetophenone, benzoin ether, thioxanthone, phosphine oxide,
Benzoyl formate type and the like can be mentioned. Examples of the product name include Irgacure 651 (trade name, manufactured by Ciba Geigy, acetophenone-based photopolymerization initiator),
Irgacure 184 (trade name, manufactured by Ciba-Geigy, acetophenone-based photopolymerization initiator), Irgacure 1850
(Ciba-Geigy, trade name, acetophenone-based photopolymerization initiator), Irgacure 907 (Ciba-Geigy, trade name, aminoalkylphenone-based photopolymerization initiator), Irgacure 369 (Ciba-Geigy, trade name, aminoalkylphenone-based Photopolymerization initiator), Lucirin TPO (B
ASF, trade name, 2,4,6-trimethylbenzoyldiphenylphosphine oxide), Kayacure DE
TXS (manufactured by Nippon Kayaku Co., Ltd., trade name), CGI-78
4 (manufactured by Ciba-Geigy Corporation, trade name, titanium complex compound) and the like. These can be used alone or in combination of two or more.

The mixing ratio of the photopolymerization initiator (C) is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the components (A) and (B). .

The photosensitive resin composition of the present invention may further contain, if necessary, a photopolymerizable unsaturated compound (resin) (D) other than the above-mentioned components (A) and (B). . This includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate.
Acrylate, 2-ethylhexyl (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol Examples thereof include tetra (meth) acrylate and pentaerythritol tri (meth) acrylate.
As the trade name, for example, Aronix M-110 (manufactured by Toagosei Co., Ltd., trade name, weight average molecular weight 310), Aronix M-305 (manufactured by Toagosei Co., Ltd., trade name,
Weight average molecular weight 298), Aronix M-101 (manufactured by Toagosei Co., Ltd., trade name, weight average molecular weight 236),
Viscote well 215 (manufactured by Osaka Organic Synthetic Chemical Industry Co., Ltd., trade name, weight average molecular weight 212, neopentyl glycol diacrylate), Kayamer PM2 (manufactured by Nippon Kayaku Co., Ltd., trade name, acrylic phosphate monomer) NK Ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, epoxy acrylate, weight average molecular weight of about 512, degree of unsaturation "number of polymerizable unsaturated bonding groups per 1,000 molecular weight, and the same hereinafter) Meaning "about 2),
Viscote Well 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name, polyether acrylate, weight average molecular weight of about 5)
10, unsaturation degree 4), Actilane 210TP30 (manufactured by Nippon Sebel Hegner Co., Ltd., trade name, urethane acrylate, weight average molecular weight about 1900, unsaturation degree about 1), Shikko UV7510B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) Trade name, urethane acrylate, weight average molecular weight about 400
0, degree of unsaturation 0.75), violet UV7550 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name, urethane acrylate,
Weight average molecular weight of about 2400, and an unsaturation degree of 1.2). Among these, it is preferable to use those containing three or more photopolymerizable unsaturated groups on average in the molecule.

The above-mentioned other photopolymerizable unsaturated compound (D) has a total amount of about 0 to 40% by weight, particularly about 5 to 50% by weight, based on the total weight of the above (A), (B) and (C). preferable.

The photosensitive resin composition of the present invention may further comprise a photopolymerization sensitizer, a photopolymerization accelerator, a sensitizing dye, a filler, a colorant, a pigment, a fluidity regulator, Inhibitors and the like can be added.

The photosensitive resin composition of the present invention comprises an ionic group-containing resin (A), a sulfide unsaturated compound (B),
What dissolves or disperses the photopolymerization initiator (C) and, if necessary, another photopolymerizable unsaturated compound (D) in an organic solvent can be used. As the organic solvent, the same inert organic solvent as described above can be used.
The resin solid content is usually about 10 to 90% by weight, particularly about 20 to 90% by weight.
A range of 80% by weight is preferred.

The photosensitive resin composition of the present invention comprises an ionic group-containing resin (A), a sulfide unsaturated compound (B),
An aqueous dispersion obtained by dispersing the photopolymerization initiator (C) and, if necessary, another photopolymerizable unsaturated compound (D) in neutralized water can be used as a photosensitive electrodeposition coating material. When a resin having an anionic group such as a carboxyl group is used as the ionic group in the resin (A), the resin is used as a photosensitive anion type electrodeposition coating material, and the ionic group is a tertiary amino group such as a tertiary amino group. When a resin having a suitable cationic group is used, it is used as a photosensitive cationic electrodeposition coating.

The neutralizing agent used in the photosensitive anionic electrodeposition coating material neutralizes a carboxyl group contained in the skeleton of the resin (a) and includes, for example, monoethanolamine,
Diethanolamine, triethylamine, diethylamine, dimethylaminoethanol, cyclohexylamine, ammonia and the like can be used. The pH of the anionic electrodeposition paint can be used in the range of about 6 to 9.

The neutralizing agent used in the photosensitive cationic electrodeposition paint neutralizes the amino group contained in the skeleton of the resin (a), and is, for example, acetic acid, propionic acid, lactic acid, hydrochloric acid, sulfuric acid. , Phosphoric acid, formic acid, crotonic acid and the like can be used. The pH of the cationic electrodeposition paint is used in the range of 5 to 7.

The circuit board of the present invention comprises (1) (A) an ionic group-containing resin and (B) a sulfide bond on a surface copper foil or a copper layer such as a copper plating layer of a copper-clad laminate. Have
And a step of coating a sulfide-based unsaturated compound containing two or more photopolymerizable unsaturated groups at the molecular terminals and a photosensitive resin composition containing (C) a photopolymerization initiator, and (2) the coated photosensitive composition. Curing by directly exposing with a laser beam or through a negative mask so that a desired resist film (image) is obtained on the reactive resin film; It is obtained by a step of forming a resist film, (4) a step of removing a copper layer in a portion not protected by the resist film, and (5) a step of removing the resist film.

In the step (1), the photosensitive resin composition is
In the case of an organic solvent system, spray on the surface of the copper-clad laminate,
The photosensitive resin film can be formed by painting by means of immersion, a roller, silk printing, or the like, performing setting, etc., and drying at a temperature in the range of about 50 to 130 ° C. The coating thus formed is then exposed in step (2).

In the case where the photosensitive resin composition is an electrodeposition coating, after the electrodeposition coating, the photosensitive resin composition is dried at a temperature in the range of about 50 to 130 ° C. by draining, air blowing, or the like. The conductive resin film can be formed.

The thickness of the above photosensitive resin film is about 5 to 1
It is preferably in the range of 00 μm, especially about 10 to 60 μm.

The active energy rays used in the exposure in step (2) include, for example, ultraviolet rays, laser beams, X-rays, electron beams and ion beam rays.

Examples of the device for generating ultraviolet light include a mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide, a gallium lamp, and a chemical lamp.

Examples of the laser include a carbon dioxide gas laser, a YAG laser, an argon laser, an excimer laser, a mercury halide excimer laser, and a rare gas excimer laser.

The irradiation amount of the ultraviolet ray is not particularly limited.
Usually, it is preferably in the range of about 10 to 2,000 mj / cm2. In the case of an electron beam, it is preferable to irradiate an electron beam of 50 to 300 Kev usually for 1 to 20 Mrad.

In the developing step (3), when the anionic group-containing resin (a) is used as the photosensitive resin composition, the uncured coating is usually washed out with caustic soda, sodium carbonate, caustic potash, and ammonia. A weak alkaline aqueous solution obtained by diluting an amine or the like in water is used. When a cationic group-containing resin (b) is used as the photosensitive resin composition, the uncured film is usually washed out by diluting hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, silicic acid, formic acid, lactic acid and the like in water. A weakly acidic aqueous solution is used.

Exposed copper layer (non-circuit portion) in step (4)
Is removed by etching with an aqueous solution of ferric chloride or cupric chloride.

In step (5), the resist film is removed by using a strong alkali such as sodium hydroxide or a solvent such as methylene chloride.

[0062]

EXAMPLES The resin composition of the present invention will be described in detail with reference to examples. In the examples and comparative examples, “parts” indicates “parts by weight”.

Production Example of Unsaturated Resin (A) Solution A mixture of 40 parts by weight of methyl methacrylate, 40 parts by weight of butyl acrylate, 20 parts by weight of acrylic acid, and 2 parts by weight of azobisisobutyronitrile was placed in a nitrogen gas atmosphere. The mixture was dropped into 90 parts by weight of propylene glycol monomethyl ether monomethyl ether maintained at 110 ° C. over 3 hours.

After the dropping, the mixture was aged for 1 hour, and a mixed solution comprising 1 part by weight of azobisdimethyl valeronitrile and 10 parts by weight of propylene glycol monomethyl ether was added dropwise for 1 hour. A resin (acid value 155) solution was obtained. Next, 24 parts by weight of glycidyl methacrylate and 0.1 part of hydroquinone were added to this solution.
2 parts by weight and 0.1% of tetraethylammonium bromide.
Add 6 parts by weight, and blow at 5
After reacting for hours, the unsaturated resin (acid value 50, unsaturated degree 1.
35 mol / kg number average molecular weight about 20,000) solution was obtained.

Preparation Example of Sulfide-Based Unsaturated Compound (B) Compound 1: 100 parts by weight of FLEP-50 (trade name, epoxy equivalent: 320, manufactured by Toray Thiokol Co., Ltd.), 22.5 parts by weight of acrylic acid, and triethylammonium bromide 0 0.5 parts by weight dissolved in 53 parts by weight of propylene glycol monomethyl ether and reacted at 110 ° C. for 5 hours.

Compound 2: 100 parts by weight of FLEP-60 (trade name, epoxy equivalent: 280, manufactured by Toray Thiokol Co., Ltd.), 25.7 parts by weight of acrylic acid and 0.5 parts by weight of triethylammonium bromide were added to 54 parts by weight of propylene glycol monomethyl ether. 5 hours 11
What was made to react at 0 degreeC.

Compound 3: 100 parts by weight of FLEP-65 (trade name, epoxy equivalent: 315, manufactured by Toray Thiokol Co., Ltd.), 22.9 parts by weight of acrylic acid and 0.5 part by weight of triethylammonium bromide were added to 53 parts by weight of propylene glycol monomethyl ether. 5 hours 11
The reaction was maintained at 0 ° C. Compound 4: FLEP-125X (manufactured by Toray Thiokol Co., Ltd.
A product obtained by dissolving 0.6 parts by weight of acrylic acid and 0.5 parts by weight of triethylammonium bromide in 100 parts by weight of a trade name, epoxy equivalent 850) and reacting the mixture at 110 ° C. for 5 hours.

Compound 5: FLEP-410C (trade name, epoxy equivalent 1200, manufactured by Toray Thiokol Co., Ltd.)
A solution obtained by dissolving 0.3 parts by weight of acrylic acid and 0.5 parts by weight of triethylammonium bromide in 00 parts by weight and maintaining the temperature at 110 ° C. for 5 hours.

Examples 1 to 5 and Comparative Example 1 Organic solvent-based photosensitive resin compositions were prepared according to the formulations shown in Table 1 (unsaturated resins indicate solid content).

A circuit board was manufactured from the obtained compositions of Examples and Comparative Examples by the following method.

The above composition is spray-coated on a copper-clad laminate for a circuit so as to have a dry film thickness of 5 to 10 μm, and after the organic solvent is volatilized, a desired resist film (image) is obtained. Is exposed and cured through a negative mask (a negative mask prepared so as to obtain 100 linear copper wires having a width of 50 μm) using the exposure apparatus and the exposure amount shown in Table 1, and cured with an aqueous alkaline solution. To 0.
A resist film is formed on the substrate by developing using a 5% by weight aqueous solution of sodium carbonate at 25 ° C. for 60 seconds, and the copper layer not protected by the resist film is formed using an aqueous cupric chloride solution. After performing an etching treatment at 50 ° C. for 140 seconds, the product was washed with water and dried.

[0072]

[Table 1]

The following formulations in Table 1 have the following meanings:

IC-907: Ciba Specialty Chemicals (Irgacure 907) DETX: Nippon Kayaku (Kayacure DETX) M-245: Toa Gosei Co. (Aronix M-245) M-310: Toa Gosei Co. ( (Aronix M-310) The evaluation of resist adhesion was performed as follows.

Resist adhesion (* 1): 100 linear resist coatings were visually observed, and the number of peeled resist coatings was counted.

Resist adhesion (* 2): 100 linear resist coatings were visually observed and evaluated according to the following criteria. Those with practicality ○, those without practicality ×

[0077]

The composition of the present invention, having the above-mentioned constitution, exhibits a remarkable effect that a resist film having excellent adhesion to a metal substrate such as copper during etching can be formed.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/032 G03F 7/032 7/085 7/085 H05K 3/06 H05K 3/06 H (72) Inventor Naozumi Iwasawa Higashi-Hachiman, Hiratsuka-shi, Kanagawa 4-17-1 Kansai Paint Co., Ltd.

Claims (2)

[Claims] 1. A resin having an ionic group (A), a sulfide unsaturated compound having (B) a sulfide bond in a molecular skeleton and having at least one photopolymerizable unsaturated group at a molecular terminal, and (C) A photosensitive resin composition comprising a photopolymerization initiator. 2. On an insulating substrate having a metal layer such as copper on the surface, (1) (A) an ionic group-containing resin, (B) a sulfide bond in a molecular skeleton, and 1 A step of coating a photosensitive resin composition containing a sulfide-based unsaturated compound containing at least two or more photopolymerizable unsaturated groups and (C) a photopolymerization initiator; (2) a desired step for the coated photosensitive resin film; Curing by directly exposing with a laser beam or through a negative mask to obtain a resist film (image) of (3) developing a non-cured portion with an aqueous solution of alkali or acid to form a resist film on the substrate A circuit board obtained by: (4) a step of removing a metal layer such as copper which is not protected by the resist film; and (5) a step of removing the resist film.