JPH05160557A - Method of manufacturing printed circuit board - Google Patents

Abstract

PURPOSE:To form a solder resist pattern with high precision in an excellent processing capacity by a method wherein the process between the silk screen printing process and the liquid photosolder resist process is used. CONSTITUTION:The whole surface of a printed board with a copper foil pattern formed by etching step thereon is printed with the first solder resist ink and then preset by a conveyer ultraviolet ray setting furnace, model HMW-713, at a light quantity of 600mJ/cm<2> to form solder resist into a film. Next, the whole surface is pattern-printed with the second solder resist ink to be set by the setting furnace at the light quantity of 500mJ/cm<2>. Next, the printed board wherein a patterned resist film is formed on the solder resist film is dipped in 3Wt% of NaOH solution for three minutes so as to develop and remove the solder resist film on the part where no patterned resist exists at all. Finally, the second solder resist ink is exposed by the setting furnace at a light quantity of 1000mJ/cm<2>.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a method for manufacturing a printed wiring board, which comprises forming a solder resist pattern using one solder resist ink.

[0002]

2. Description of the Related Art Electronic components mounted on a printed wiring board are usually fixed by soldering. At that time, in order to prevent a conductor circuit or the like from being short-circuited by soldering, a portion other than a portion required for soldering is covered with a solder resist. As a method for forming this solder resist, methods such as a silk screen printing method, a dry film photo solder resist method, and a liquid photo solder resist method are well known and widely used. Among them, the method of forming the solder resist pattern by the silk screen printing method is such that the solder resist ink is pattern-printed on the substrate on which the conductor circuit is formed as shown in FIG. The method of repeating ultraviolet curing is widely used because of its high processing capacity and easy and easy operation.

However, recently, with the surface mounting of printed wiring boards, high-precision solder resist patterns have been required. Therefore, the silk-screen printing method which has been conventionally performed can meet this requirement. Not only is it impossible, but new problems have arisen. That is, in the printed wiring board, the thickness of the copper circuit is 35 μm.
It is ~ 100 μm and is not a smooth surface printing, the printed surface is made of two kinds of materials with different properties of the laminated plate base material and copper, and further, the pattern interval is narrow, etc. When printing, not only complicated operations such as changing the screen mesh and adjusting the ink application amount are required, but even if such operations are performed, the soldering and connecting parts are However, the problems such as the bleeding of the solder resist, the skipping of the non-soldered copper circuit portion, the resistance of the coating film, and the undercut were unavoidable.

Therefore, in order to solve these problems, the double-printing method and the scooping method are partially adopted, but the essential solution has not been reached. Further, the above-mentioned conventional liquid photo solder resist method, that is, FIG.
Print the entire surface of the solder resist ink on the substrate on which the conductor circuit shown in is formed, then align the negative film,
The method of exposure, development, and heat curing is good in terms of accuracy as in the photographic method such as dry film photo solder resist, but alignment takes too much time, which is about 1/3 to 1/4 that of the screen printing method. It is not always a satisfactory method because it cannot be processed. Therefore, it is possible to utilize the technology and production process of the screen printing method, which is easy and easy to handle, and has excellent processing ability, and, like the photographic methods such as liquid photo solder resist and dry film photo solder resist, bleed and skip. There has been a strong demand for the development of a method for manufacturing a printed wiring board for forming a solder resist pattern with high accuracy and without causing such problems.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation. That is, the object of the present invention is to prevent the occurrence of bleeding, skipping, etc., prevent undercut, and improve the resistance of the coating film, showing higher accuracy than the conventional screen printing method, and also excellent in processing capacity. Another object of the present invention is to provide a method for manufacturing a printed wiring board for forming a solder resist pattern.

[0006]

Means for Solving the Problems As a result of earnest studies, the present inventors have focused on a construction method intermediate between the silk screen printing method and the liquid photo solder resist method in order to solve the above problems. This is a method in which a solder resist film is first formed and then a solder resist pattern is formed thereon. When this method is adopted and in this method, the first solder resist ink and the second solder resist ink are used.
It has been found that the above object can be achieved when one of the solder resist inks of (1) and (2) contains a reducing agent and the other contains an oxidizing agent, and the present invention has been completed.

That is, the method for manufacturing a printed wiring board according to the present invention is (1): applying the first solder resist ink to the entire surface of the printed wiring board on which the conductor circuit is formed, and drying it.
A step of forming a solder resist film soluble in an alkaline aqueous solution or an organic solvent, (2), a step of pre-curing the solder resist film of the printed wiring board with active energy rays, (3), a step of forming the pre-cured resist film. A step of pattern-printing with a second solder-resist ink thereon, and (4) a step of protecting the solder-resist film by curing the patterned resist film pattern-printed with the second solder-resist ink with active energy rays. , (5), the step of developing the solder resist film with an alkaline aqueous solution or an organic solvent to form a solder resist pattern, and (6) the step of post-curing the pre-cured resist film and the patterned resist film. It is characterized by

In the method for manufacturing a printed wiring board according to the present invention, it is preferable that one of the first solder resist ink and the second solder resist ink contains a reducing agent and the other contains an oxidizing agent.

The present invention will be described in detail below. Figure 1
It is explanatory drawing which shows the pattern formation process which forms the solder resist pattern of this invention. In FIG. 1, A indicates a substrate on which the conductor circuit 2 is formed, B indicates a state in which the solder resist film 3 is formed in the first step, and C indicates
Indicates a state in which the patterned solder resist pattern 4 is formed in the third step, D indicates a state in which the patterned solder resist pattern 4 is developed in the fifth step, and E indicates a state in which the patterned resist film 3 and the solder are formed in the sixth step. The state where the resist pattern 4 is post-cured is shown.

The method of the present invention will be described with reference to FIG. 1. In the first step and the second step, the first solder resist ink is applied and dried on the entire surface of the printed circuit board 1 on which the predetermined conductor circuit 2 is formed. Then, when the formed film is pre-cured, a solder resist film 3 soluble in an alkaline aqueous solution or an organic solvent is formed on the entire surface of the substrate. (See Figure 1B)

The coating operation in the first step may be carried out only once, or may be repeated a plurality of times by repeating coating and drying. The coating may be performed by any method, and for example, a screen printing method, an offset printing method, a spray coating method, a curtain coater coating method, a magnetic image forming method or the like can be used.

Pre-curing in the second step can be carried out by irradiating with active energy rays such as ultraviolet rays or electron beams. The degree of curing depends on the solubility of the solder resist film 3 in an alkaline aqueous solution or an organic solvent or It must be carried out to the extent that the swelling property is maintained.
A low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used as a light source for irradiating active energy rays. The thickness of the solder resist film is 5 to 40 μm, especially 10 to 2
It is preferable to set in the range of 5 μm.

The formation of the patterned resist film 4 in the third step is performed by printing a predetermined pattern on the solder resist film 3 using the second solder resist ink by a screen printing method. Yes (see Figure 1C). The thickness of the patterned resist film formed by pattern printing is preferably set in the range of 10 to 50 μm, particularly 10 to 25 μm.

Curing of the patterned resist film 4 in the fourth step can be performed by the same means as the irradiation means used in the preliminary curing in the second step.

Next, in a fifth step, the solder resist film formed by using the first solder resist ink as described above is developed. The development treatment is performed with an alkaline aqueous solution or an organic solvent, whereby the portion where the patterned resist film 4 is not formed is removed (see FIG. 1D).

Finally, in the sixth step, the solder resist film remaining in a pattern and the patterned resist film thereon are post-cured by active energy rays such as ultraviolet rays or electron beams. Irradiation with active energy rays can be performed by the same means as in the case of the second step (FIG. 1).
(See E).

Next, the materials used in the present invention will be described. The first solder resist ink contains an alkaline aqueous solution or an organic solvent-soluble resin, a photosensitive diluent and a photopolymerization initiator as main components.
A filler, a coloring pigment, an antifoaming agent, a thixotropic agent, a leveling agent, an adhesion-imparting agent or the like may be added. As the above-mentioned alkaline aqueous solution or organic solvent-soluble resin, any resin component can be used as long as it exhibits either the characteristics of dissolution or swelling and peeling by the alkaline aqueous solution or the organic solvent.

As the organic solvent-soluble resin, phenol resin, xylene resin, urea resin, melamine resin, epoxy resin, alkyd resin, vinyl resin, acrylic resin, chlorinated rubber resin, polyamide resin , Terpene-based resins, butyral-based resins, cyclized rubber-based resins, ketone-based resins and cellulose derivatives. Among them, thermosetting resins such as vinyl resins, rubber resins and cellulose derivatives are particularly preferable.

The phenolic resin includes a resol type phenolic resin and a novolac type phenolic resin. Specifically, in the case of the resol type, super beccasite 10
01, Novolak type, Super Becca site 301
1 (above, manufactured by Dainippon Ink and Chemicals, Inc.).

The urea resin includes butylated urea resin, and specifically, Uban 10S-60 (above, manufactured by Mitsui Toatsu Chemicals, Inc.) can be mentioned.

Examples of melamine resins include hexamethoxymethylol melamine and methylated melamine. Specifically, hexamethoxymethylol melamine includes Cymel 300 (manufactured by Mitsui Toatsu Kagaku Co., Ltd.) and Nicalac MW-3.
0 (manufactured by Sanwa Chemical Co., Ltd.), methylated melamine,
Cymel 301 (manufactured by Mitsui Toatsu Chemicals, Inc.) may be mentioned.

Alkyd resins include alkyd resins,
There are modified alkyd resins and the like. Among the alkyd resins, there is Beccosol J-557 (Dainippon Ink and Chemicals, Inc.).
Manufactured by Beckosol J-61.
1. Styresol 4440 (above, manufactured by Dainippon Ink and Chemicals, Inc.). Examples of the butyral-based resin include S-REC BL-1 (manufactured by Sekisui Chemical Co., Ltd.) and Denka Butyral # 6000-C (manufactured by Denki Kagaku Kogyo).

Examples of the alkaline aqueous solution-soluble resin include novolac resin, rosin resin, rosin-modified resin, and carboxyl-containing polymer. These resins are preferable because they are simultaneously soluble in organic solvents.
The rosin-modified resin is a resin represented by a rosin-modified maleic acid resin, and is usually a resin obtained by reacting rosin with an acid or alcohol to modify. Specific examples thereof include Harimack R-80 and Harimack 145P (all manufactured by Harima Kasei Co., Ltd.).

The carboxyl group-containing polymer is a polymer containing a carboxyl group in the polymer chain, and is a polymer of monomers such as acrylic acid, methacrylic acid and maleic acid, or their acrylic acid ester and methacrylic acid. Examples thereof include copolymers with esters and styrene. Specifically, SMA-1000, SMA-2000, SM
A-3000 (above, Alco Chemical Co., Ltd.), John Cryl-67 (Johnson Polymer Co., Ltd.), CB-MH
P, CB-1, (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), H
OA-MPL (Kyoeisha Yushi Co., Ltd.), Viscoat # 2
100 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Further, the novolak resin means a phenol resin, a cresol resin and an alkylphenol resin which are soluble in an alkaline aqueous solution. Specifically, the phenol novolac resin includes BRG-556 and BRG-557.
(These are Showa High Polymer Co., Ltd.) and Resin-X (Mitsubishi Petrochemical Co., Ltd.). For cresol resin, PSM-22
46, PSM-4402 (above, manufactured by Gunei Chemical Co., Ltd.) and the like. In addition, for alkylphenol resin, MCM
-709, MCM-726 (above, Showa high polymer company make). The content of the alkaline aqueous solution or the organic solvent-soluble resin is preferably 10 to 50% by weight with respect to the first solder resist ink.

The photosensitive diluent dissolves the resin and photopolymerizes, and a known photosensitive diluent is used depending on the resin used. Typically, a vinyl monomer having an ethylenically unsaturated double bond, methoxyethyl acrylate (or methacrylate), ethoxyethyl acrylate (or methacrylate), butoxyethyl acrylate (or methacrylate), methoxyethoxyethyl acrylate (or methacrylate). ), Stearyl acrylate (or methacrylate), lauryl acrylate (or methacrylate), tetrahydrofurfuryl acrylate (or methacrylate), benzyl acrylate (or methacrylate), phenoxyethyl acrylate (or methacrylate), 2-hydroxyethyl acryloyl (or methacryloyl) phosphate , 2-hydroxyethyl acrylate (or methacrylate), 2-hydroxypropyl acrylate Relate (or methacrylate), ethylene glycol diacrylate (or methacrylate), diethylene glycol diacrylate (or methacrylate), triethylene glycol diacrylate (or methacrylate), polyethylene glycol diacrylate (or methacrylate), propylene glycol diacrylate (or methacrylate) , Polypropylene glycol diacrylate (or methacrylate), 1,6-hexanediol diacrylate (or methacrylate), trimethylolpropane triacrylate (or methacrylate), 2-ethylhexyl acrylate (or methacrylate), 1,3-butylene glycol diacrylate (Or methacrylate), 1,4-butylene glycol diacryle (Or methacrylate), neopetyl glycol diacrylate (or methacrylate), dipropylene glycol diacrylate (or methacrylate), tetramethylolmethane triacrylate (or methacrylate), tetramethylolmethane tetraacrylate (or methacrylate), hydroxypivalic acid neo Examples thereof include pentyl glycol diacrylate (or methacrylate), dipentaerythritol hexaacrylate (or methacrylate), hydroxyalkyl acrylate (or methacrylate) half-esterified product of polybasic acid (or its anhydride), and the like. The content of these is not particularly limited, but is 10 to 40 with respect to the ink.
A weight% range is preferred.

Next, as the photopolymerization initiator used in the present invention, α-carbonyl alcohols such as benzoin, butyroin, toluoin and acetoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and pivalo are used. Acyloin ethers such as inethyl ether and anisoin ethyl ether, α-side chain acyloines such as α-methylbenzoin and α-phenylbenzoin 9,10
-Anthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 1,
Polycyclic quinones such as 4-naphthoquinone and 2,3-benzanthraquinone, diacetyl, dibenzoyl, diphenyl ketone, phenylglyoxal, pentadione-2,
Substituted polyketone compounds such as 3,1-phenylbutanedione-1,2, octadione-2,3, diphenyltriketone, benzophenone, α-bromoacetophenone,
2-hydroxy-2-methylpropiophenone, 4 '
-Isopropyl-2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-2-phenylacetophenone, p-tert-butyltrichloroacetophenone, p
There are aromatic ketones such as -tert-butyl monochloroacetophenone, 2,2-diethoxyacetophenone, and 4,4'-bis-dialkylaminobenzophenones.

The second solder resist ink is
It hardens with active energy rays such as ultraviolet rays and electron beams to protect the solder resist film in the portion that needs to be protected from the developer, and to form a strong coating film that permanently protects the substrate. The composition is mainly composed of a photosensitive diluent and a photopolymerization initiator similar to those used in the first solder resist ink, together with the active energy ray-curable resin. As with the ink, additives such as a filler, a coloring pigment, a defoaming agent, a thixotropic agent, a leveling agent or an adhesion-imparting agent may be added if necessary.

As the active energy ray-curable resin, a known active energy ray-curable resin, for example, an acrylic oligomer such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, polyether acrylate, melamine acrylate, or active energy ray is used. Examples of the resin include curable unsaturated polyester. Epoxy acrylates and urethane acrylates are particularly preferable for solder resists that are hardened in a short time and are required to have electrical insulation properties, heat resistance, hardness, adhesion and chemical resistance.

Further, it is preferable to add an oxidizing agent to either one of the first solder resist ink and the second solder resist ink and a reducing agent to the other. By adding an oxidizing agent to one of the first solder resist ink and the second solder resist ink, and a reducing agent to the other, a reaction occurs between the solder resist film layer and the patterned resist film. Occurs, the resistance of the entire coating film is improved, and undercut is prevented.

As the oxidant, ketone peroxide,
Examples thereof include peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, etc., but diacyl peroxide is preferable. The amount used can be set in the range of 0.1 to 10% by weight with respect to the total amount of the composition. However, it is particularly preferable to use it in the range of 0.1 to 5% by weight from the viewpoint of the effect of addition, storage stability and handling.

Examples of the reducing agent include amines such as triethylamine, diethylenetriamine and triethylenetetramine, anilines such as dimethylaniline and diethylaniline, organic metal salts such as cobalt naphthenate, copper naphthenate, manganese naphthenate and tin octenoate. , Thiourea, ethylenethiourea, and thiols are preferable, and dimethylaniline is preferable, and the amount thereof can be set in the range of 0.01 to 20% by weight based on the total amount of the composition. However, from the viewpoint of addition effect, discoloration of copper foil and electrical insulation characteristics,
It is particularly preferred to use in the range of 5% by weight. These are preferably added to the solder resist film layer and the solder resist pattern layer, respectively.

Further, the organic solvent used in the present invention is, for example, 1,1,1-trichloroethane, trichloroethylene, perchlorethylene, methylene chloride, carbon tetrachloride, chloroform, trichlorotrifluoroethane. , Tetrachlorodifluoroethane, trichloromonofluoromethane, dichlorofluoroethane, dichlorotrifluoroethane, trichlorotrifluoroethane, n-pentane, n-hexane, aliphatic petroleum naphtha, kerosene, methanol, ethanol, isopropanol, ethyl ether, isopropyl ether , Methyl cellosolve, cellosolve, butyl cellosolve, cellosolve acetate, carbitol, butyl carbitol, carbitol acetate, butyl carbitol acetate, acetone, methyl Ethyl ketone, ethyl acetate, benzene, toluene, xylene, aromatic petroleum naphtha.

The alkaline aqueous solution includes sodium hydroxide aqueous solution, sodium carbonate aqueous solution, sodium hydrogen carbonate aqueous solution, sodium silicate aqueous solution, sodium metasilicate aqueous solution, potassium hydroxide aqueous solution, ammonia aqueous solution,
Methylamine aqueous solution, monoethylamine aqueous solution, isopropylamine aqueous solution, monoethanolamine aqueous solution, monoisopropanolamine aqueous solution, propylamine aqueous solution, butylamine aqueous solution, diethylamine aqueous solution, diethanolamine aqueous solution, diisopropanolamine aqueous solution, dimethylamine aqueous solution, dibutylamine aqueous solution, triethylamine aqueous solution , Triethanolamine aqueous solution,
A triisopropanolamine aqueous solution, a trimethylamine aqueous solution, a tributylamine aqueous solution or the like can be used.

Further, in the present invention, the first and second
It is preferable to use a filler for the solder resist ink of (1). Screen printing properties are imparted by the use of fillers. As the filler to be used, silicon dioxide, aluminum silicate, magnesium silicate, aluminum hydroxide, barium sulfate or the like which is used as a general resin filler can be used. The amount used is 3 to 90% by weight, preferably 10 to 30% by weight, based on the total amount of the alkaline aqueous solution or organic solvent-soluble resin and the photosensitive diluent, and the average particle size thereof is 15 μm.
The following are preferred.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples. In addition, "part" means "part by weight" unless otherwise specified. The solder resist ink used in the present invention has the following composition.

Composition 1 Styrene-maleic acid resin 20 parts (SMA-2000, manufactured by Arco Chemical Co.) Maleic anhydride-2-hydroxy 30 parts Ethyl methacrylate (half ester) Photosensitive diluent: Pentaerythritol triacrylate 7 parts (light Ester PE-3A, Kyoeisha Yushi Co., Ltd. Photopolymerization initiator (IRG-651, manufactured by Ciba Geigy) 4 parts Talc (LMP-100, manufactured by Fuji Talc Industry Co., Ltd.) 30 parts Silicone defoamer (KS-66, Shin-Etsu Silicone) 1)

Composition 2 Styrene-maleic acid resin 25 parts (SMA-2000, manufactured by Arco Chemical Co.) Maleic anhydride-2-hydroxy 35 parts Ethyl methacrylate (half ester) Photosensitive diluent: Pentaerythritol triacrylate 5 parts (light Ester PE-3A, Kyoeisha Yushi Co., Ltd. Photopolymerization initiator (IRG-651, manufactured by Ciba Geigy) 4 parts Talc (LMP-100, manufactured by Fuji Talc Industry Co., Ltd.) 30 parts Silicon defoamer (KS-66, Shin-Etsu Silicone) 1 part triethylamine 2 parts

Composition 3 Phenolic resin 25 parts (Resin-X, manufactured by Mitsubishi Petrochemical Co., Ltd.) Maleic anhydride-2-hydroxy 30 parts Ethyl methacrylate (half ester) Photosensitive diluent; 2-HEMA (2-hydroxy 10 parts ethyl Methacrylate) Photopolymerization initiator (IRG-651, manufactured by Ciba Geigy) 4 parts Talc (LMP-100, manufactured by Fuji Talc Industry Co., Ltd.) 30 parts Silicone defoamer (KS-66, manufactured by Shin-Etsu Silicone Co., Ltd.) 1 part Peroxidation Benzoyl 2 parts

Composition 4 Novolac type epoxy acrylate 20 parts (SP-4010, Showa Highpolymer Co., Ltd.) TMPTA (trimethylolpropane triacrylate) 30 parts Photosensitive diluent; 2-HEMA 15 parts Photopolymerization initiator (IRG) -651, manufactured by Ciba Geigy) 2 parts Talc (LMP-100, manufactured by Fuji Talc Industry Co., Ltd.) 25 parts Coloring pigment; Cyanine green 0.7 parts

Composition 5 Novolac type epoxy acrylate 20 parts (SP-4010, manufactured by Showa Highpolymer Co., Ltd.) TMPTA 30 parts Photosensitive diluent; 2-HEMA 10 parts Photopolymerization initiator (IRG-651, manufactured by Ciba Geigy) 2 parts Talc (LMP-100, manufactured by Fuji Talc Industry Co., Ltd.) 25 parts Coloring pigment; Cyanine green 0.7 parts Dimethylaniline 2 parts

Composition 6 Novolak type epoxy acrylate 25 parts (SP-4010, Showa Highpolymer Co., Ltd.) Light ester (PE-3A, Kyoeisha Yushi Co., Ltd.) 25 parts Photosensitive diluent; 2-HEMA 10 parts Photopolymerization Initiator (IRG-651, manufactured by Ciba Geigy) 2 parts Talc (LMP-100, manufactured by Fuji Talc Industry Co., Ltd.) 25 parts Colored pigment; Cyanine green 0.7 parts Benzoyl peroxide 2 parts

Example 1 A printed circuit board having a copper foil pattern formed by etching treatment (paper phenol substrate, copper foil 35 μm, plate thickness 1.6 m)
On the surface of m), the first solder resist ink represented by the composition 1 is entirely printed with a 180-mesh Tetron plate (bias), and a light amount of 600 mJ is produced by a conveyor type ultraviolet curing furnace HMW-713 type (manufactured by Oak Manufacturing Co., Ltd.). / Cm and pre-cured to form a solder resist film. Next, the second solder resist ink represented by the composition 4 is added to
Print the pattern with 5 mesh Tetron version (bias),
Light intensity of 500 mJ / cm by conveyor type UV curing furnace
Cured at ² . In this way, the printed board on which the patterned resist film is formed on the solder resist film is immersed in a 3 wt% NaOH solution (30 ° C.) for 3 minutes to remove the solder resist film in the portion where the patterned resist does not exist. The development was removed. Then, it was exposed with a light amount of 1000 mJ / cm ² in a conveyor type ultraviolet curing furnace.

Example 2 A printed circuit board having a copper foil pattern formed by etching treatment (paper phenol substrate, copper foil 35 μm, plate thickness 1.6)
(mm) the surface of the first solder resist ink represented by Composition 1 with 180 mesh Tetron plate (bias)
Then, the entire surface is printed with, and the light amount is 600 mJ in the same manner as in Example 1.
/ Cm ² was pre-cured to form a solder resist film. Next, a second solder resist ink represented by Composition 5 was pattern-printed with a 225 mesh Tetron plate (bias) and cured with a light amount of 500 mJ / cm ² . In this way, the printed board on which the patterned resist film is formed on the solder resist film is treated with 3 wt% NaO.
It was immersed in a H solution (30 ° C.) for 3 minutes to develop and remove the portion of the solder resist film where the patterned resist film does not exist. Then, it was exposed to light of 1000 mJ / cm ² .

Example 3 A printed circuit board having a copper foil pattern formed by etching (paper phenol substrate, copper foil 35 μm, plate thickness 1.6)
(mm) the surface of the first solder resist ink represented by Composition 1 with 180 mesh Tetron plate (bias)
Then, the entire surface is printed with, and the light amount is 600 mJ in the same manner as in Example 1.
It was cured at / cm ² to form a solder resist film.
Next, a second solder resist ink represented by Composition 6 was pattern-printed with a 225 mesh Tetron plate (bias) and cured with a light amount of 500 mJ / cm ² . The printed board on which the solder resist pattern was formed was immersed in a 3% by weight NaOH solution (30 ° C.) for 3 minutes to develop and remove the solder resist film exposed from the solder resist pattern uncoated portion. Next, light intensity 1000mJ / c
It was exposed at m ² .

Example 4 A printed circuit board having a copper foil pattern formed by etching (paper phenol substrate, copper foil 35 μm, plate thickness 1.6)
mm) surface with the first solder resist ink represented by the composition 2 and 180 mesh Tetron plate (bias)
Then, the entire surface is printed with, and the light amount is 600 mJ in the same manner as in Example 1.
/ Cm ² was pre-cured to form a solder resist film. Next, a second solder resist ink represented by Composition 4 was pattern-printed with a 225 mesh Tetron plate (bias) and cured with a light amount of 500 mJ / cm ² . In this way, the printed board on which the patterned resist is formed on the solder resist film is immersed in a 3 wt% NaOH solution (30 ° C.) for 3 minutes to remove the solder resist film in the portion where the patterned resist film does not exist. The development was removed. Then, it was exposed to light of 1000 mJ / cm ² .

Example 5 A printed circuit board having a copper foil pattern formed by etching (paper phenol substrate, copper foil 35 μm, plate thickness 1.6)
mm) surface with the first solder resist ink represented by the composition 2 and 180 mesh Tetron plate (bias)
Then, the entire surface is printed with, and the light amount is 600 mJ in the same manner as in Example 1.
/ Cm ² was pre-cured to form a solder resist film. Next, a second solder resist ink represented by Composition 6 was pattern-printed with a 225 mesh Tetron plate (bias) and cured with a light amount of 500 mJ / cm ² . The printed board on which the solder resist pattern is formed is immersed in a 3 wt% NaOH solution (30 ° C.) for 3 minutes,
The portion of the solder resist film where the patterned resist film does not exist was developed and removed. Next, light intensity 1000mJ
Exposure was performed at / cm ² .

Example 6 A printed circuit board having a copper foil pattern formed by etching treatment (paper phenol substrate, copper foil 35 μm, plate thickness 1.6)
(mm) the surface of the first solder resist ink represented by Composition 3 with 180 mesh Tetron plate (bias)
Then, the entire surface is printed with, and the light amount is 600 mJ in the same manner as in Example 1.
/ Cm ² was pre-cured to form a solder resist film. Next, a second solder resist ink represented by Composition 4 was pattern-printed with a 225 mesh Tetron plate (bias) and cured with a light amount of 500 mJ / cm ² . In this way, the printed board on which the patterned resist is formed on the solder resist film is immersed in a 3 wt% NaOH solution (30 ° C.) for 3 minutes to remove the solder resist film in the portion where the patterned resist film does not exist. The development was removed. Then, it was exposed to light of 1000 mJ / cm ² .

Example 7 A printed circuit board having a copper foil pattern formed by etching treatment (paper phenol substrate, copper foil 35 μm, plate thickness 1.6)
(mm) the surface of the first solder resist ink represented by Composition 3 with 180 mesh Tetron plate (bias)
Then, the entire surface is printed with, and the light amount is 600 mJ in the same manner as in Example 1.
/ Cm ² was pre-cured to form a solder resist film. Next, a second solder resist ink represented by Composition 5 was pattern-printed with a 225 mesh Tetron plate (bias) and cured with a light amount of 500 mJ / cm ² . In this way, the printed board on which the patterned resist is formed on the solder resist film is immersed in a 3 wt% NaOH solution (30 ° C.) for 3 minutes to remove the solder resist film in the portion where the patterned resist film does not exist. The development was removed. Then, it was exposed to light of 1000 mJ / cm ² .

Example 8 A printed circuit board having a copper foil pattern formed by etching treatment (paper phenol substrate, copper foil 35 μm, plate thickness 1.6)
(mm) surface is coated with the diluted first solder resist ink represented by the composition 3 by spraying, and pre-cured at a light amount of 600 mJ / cm ² in the same manner as in Example 1 to form a solder resist film. did. Next, the second solder resist ink represented by the composition 5 is pattern-printed with a 225 mesh Tetron plate (bias), and the light amount is 5
It was cured at 00 mJ / cm ² . In this way, the printed board on which the patterned resist is formed on the solder resist film is immersed in a 3 wt% NaOH solution (30 ° C.) for 3 minutes to remove the solder resist film in the portion where the patterned resist film does not exist. The development was removed. Then, light quantity 1
It was exposed at 000 mJ / cm ² .

Example 9 A printed circuit board having a copper foil pattern formed by etching treatment (paper phenol substrate, copper foil 35 μm, plate thickness 1.6)
(mm) surface is coated with the diluted first solder resist ink represented by the composition 3 by a curtain coater and pre-cured at a light amount of 600 mJ / cm ² in the same manner as in Example 1 to form a solder resist film. Formed. next,
The second solder resist ink represented by the composition 5 is added to 2
A pattern was printed using a 25-mesh Tetron plate (bias) and cured with a light amount of 500 mJ / cm ² . In this way, the printed board on which the patterned resist was formed on the solder resist film was treated with a 3 wt% NaOH solution (30
(3 ° C.) for 3 minutes to develop and remove the portion of the solder resist film where the patterned resist film does not exist. Then, it was exposed to light of 1000 mJ / cm ² .

Comparative Example 1 A printed circuit board having a copper foil pattern formed by etching (paper phenol substrate, copper foil 35 μm, plate thickness 1.6)
mm), UVR 150G (manufactured by Taiyo Ink Mfg. Co., Ltd.) on the surface of 225 mesh Tetron plate (bias)
And printed at 1100 mJ / cm ² .
Further, UVR 150G was pattern-printed with a 225 mesh Tetron plate (bias) and cured with a conveyor type ultraviolet curing furnace at a light intensity of 1100 mJ / cm ² (FIG. 2).
reference).

Comparative Example 2 A printed circuit board having a copper foil pattern formed by etching treatment (paper phenol substrate, copper foil 35 μm, plate thickness 1.6)
mm surface), PSR-4000 (manufactured by Taiyo Ink Mfg. Co., Ltd.), 100 mesh Tetron version (bias)
Printing on the whole surface, and after temporary drying at 80 ° C for 30 minutes, the exposure machine (HM
W-680GW, manufactured by Oak Manufacturing Co., Ltd.)
Exposure at mJ / cm ² , development, and 140 ° C, 60
Cured in minutes (see Figure 3).

Regarding the above Examples 1 to 9 and Comparative Examples 1 and 2, the first solder resist ink had a finger-touch curability,
The printability of the solder resist ink of No. 1 and the second solder resist ink were evaluated for the developability, undercut, resolution, edge embedding property and productivity of the first solder resist ink after coating. The evaluation results are shown in Table 1. The evaluation criteria are as follows. ◎ is very good, ○ is good, △ is slightly inferior,
X means inferior.

The evaluation method and evaluation standard for productivity are as follows. The productivity was evaluated by the length of the solder resist formation time on the substrate. The case of the same degree as Comparative Example 1 was marked with ⊚, the case of Example 7 with the same degree was marked with ◯, and the case of Comparative Example 2 was marked with x. The solder resist formation time (two-layer printing) was measured under the following conditions. Substrate used: 500 mm x 500 mm single-sided substrate. Number of substrates: 12 in each example. Printing speed: UV: 12 sheets / min, Liquid: 6 sheets /
Minutes. Curing oven used: UV curing oven with an effective length of 4 m. Curing time: 4 m / min. Exposure time: 1 sheet / minute. Comparative Example 1 L1 printing, curing, L1 ′ printing, curing (see FIG. 2). 1 minute 1 minute 1 minute 1 minute Total 4 minutes Comparative Example 2 Printing, drying, negative alignment, exposure, development and curing (see FIG. 3). 2 minutes 30 minutes 2 minutes 12 minutes 2 minutes 50 minutes Total 98 minutes Example 7 L1 printing, curing, L2 printing, curing, developing, polishing, curing. 1 minute 1 minute 1 minute 1 minute 3 minutes 2 minutes 1 minute Total 10 minutes Note: L1 and L1 ′ represent the first solder resist ink, and L2 represents the second solder resist ink.

[0056]

[Table 1]

[0057]

As is apparent from the results shown in Table 1 above,
According to the present invention, it is possible to manufacture a high-density printed wiring board having a resolution equivalent to that of a liquid photo solder resist, with productivity almost equal to that of the screen printing method, without burying edges and undercutting of a solder resist film. ..

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process of forming a solder resist pattern by the solder resist of the present invention shown in Example 7.

FIG. 2 is an explanatory diagram showing a process of forming a solder resist pattern by the conventional screen printing method shown in Comparative Example 1.

FIG. 3 is an explanatory diagram showing a process of forming a solder resist pattern by the liquid photo solder resist method of the conventional method shown in Comparative Example 2;

[Explanation of symbols]

 1. Substrate 2. Conductor circuit 3. Solder resist film 4. Solder resist pattern 5. UV-curable solder resist ink 6. Liquid photo solder resist 7. Negative film 8. undercut

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location G03F 7/027 7/028 7/038 505 7/40 501 7124-2H H01L 21/027

Claims (2)

[Claims] (1) A step of applying a first solder resist ink on the entire surface of a printed wiring board on which a conductor circuit is formed and drying it to form a solder resist film soluble in an alkaline aqueous solution or an organic solvent, (2), a step of pre-curing the solder resist film of the printed wiring board with an active energy ray, (3), a step of pattern printing with a second solder resist ink on the pre-cured resist film, ( 4), a step of protecting the solder resist film by curing the patterned resist film pattern-printed with the second solder resist ink with active energy rays, (5), the solder resist film with an alkaline aqueous solution or an organic solvent. Developing process to form a resist pattern, and (6) the pre-cured solder -A method for producing a printed wiring board having a solder resist pattern, comprising a step of post-curing a resist film and a patterned resist film. 2. A reducing agent in one of the first solder resist ink and the second solder resist ink,
The method for producing a printed wiring board according to claim 1, wherein the other contains an oxidizing agent.