JPH02305807A - Production of photosensitive composition, photosensitive laminate and printed wiring board - Google Patents

Abstract

PURPOSE:To form a photosensitive composition which can simultaneously form solder resists which leave no undeveloped area due to fogging and have sharp edge formed on both sides of a printed wiring board. CONSTITUTION:This photosensitive composition comprises a compound (A) having at least one ethylenically unsaturated group, a sensitizer and/or a sensitizer system (B) which forms free radicals with actinic radiation, and a compound (C) of formula I (wherein R is a hydrogen atom, an alkyl or an alkoxy). In addition to components A, B, C, a film-forming resin may be used. A combination of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1 with 4,4'-bis(diethylamino)benzophenone is desirable as component B.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a photosensitive composition, a photosensitive laminate using the photosensitive composition, and a method of soldering on both sides using the photosensitive composition or the photosensitive laminate. The present invention relates to a method of manufacturing a printed wiring board on which a resist is formed.

[Conventional technology]

Printed wiring boards have insulating layers and conductor pattern layers alternately laminated, and when soldering, the outermost conductor pattern layer is usually used to prevent solder bridging between conductors or to permanently protect the conductor patterns. A solder resist is formed on top.

In recent years, for the purpose of improving precision and workability, the formation of solder resist has been replaced by the screen printing method with a photoprinting method using photosensitive resin. There is.

FIG. 1 is an explanatory diagram of a solder resist forming process when manufacturing a printed wiring board having a solder resist using a photosensitive composition. In FIG. 1, photosensitive composition IA is first applied to both surfaces of a printed wiring board having conductive patterns 3 on insulating layer (or inner layer) 2 (step A), and then light in the direction of the arrow is passed through negative 4. In step B) of selective exposure, the unexposed areas of the photosensitive composition IA are removed by development, and a pattern corresponding to the exposure, ie, solder resist IB, is formed on both sides of the printed wiring board (step C).

The edges of the formed solder resist IB need to be sharp as shown in FIG. 2(A). If the shape is not sharp as shown in Figure 2CB), the solder may not adhere to the conductor sufficiently during soldering, or the solder may not adhere to the edges where solder is not required as shown in Figure 3. Solder adhesion occurs. In Figure 3,
5 is attached solder, and 6 is solder. Tsuruda Regis 1-
In order to obtain a good edge shape in No. 18, a photosensitive composition with good resolution is used, negative 4 and photosensitive composition IA are brought into close contact with each other during exposure, and the exposure light is irradiated at right angles. However, since the insulating layer (or inner layer) 2 allows the exposure light to pass through, when exposed from both sides, the photosensitive compositions on opposite sides will also be exposed, and the parts that do not want to be exposed will also be exposed to light. A reaction occurs, resulting in undeveloped images due to back fog or lack of sharpness in the edge shape.

In order to avoid this phenomenon, coating and
A method of exposing and developing one side at a time is considered, but compared to simultaneous exposure on both sides, the work is twice as much, the manufacturing cost increases, and the solder resist on the side that has been developed first has to be recoated on one side. - There is a problem that various quality deteriorations such as peeling of solder resist occur due to exposure to unnecessary steps during exposure and development.

[Problem to be solved by the invention]

The object of the present invention is to provide a photosensitive composition that solves the problems of the prior art and can simultaneously form a solder resist with sharp edges on both sides of a printed wiring board without any development residue due to back-fogging. It is an object of the present invention to provide a method for producing a photosensitive laminate using the composition and a printed wiring board using the photosensitive composition or the photosensitive laminate and having solder resists formed on both sides.

[Means for Solving the Problems] As a result of various studies, the present inventors have developed a compound that absorbs an emission spectrum of 405 nm in the emission spectrum of a high-pressure mercury lamp, which is the light source of an exposure machine, and that causes a photocuring reaction. We discovered that by forming a layer of a photosensitive composition on both sides of a printed wiring board, exposing it to light, and then developing it, we could form a solder resist with sharp edges and no development residue due to back-fogging. invention has been achieved. .

That is, the present invention provides (A) a compound having at least one ethylenically unsaturated group, (B) a sensitizer and/or sensitizer system that generates free radicals upon actinic light, and (C
) The present invention relates to a photosensitive composition containing a compound represented by the general formula (wherein R means a hydrogen atom, an alkyl group, or an alkoxy group).

The present invention also relates to a photosensitive composition further comprising (D) a film-forming resin in addition to the photosensitive composition, and a photosensitive laminate obtained by coating and drying the composition on a support film. Further, the present invention is characterized in that, after the layers of the photosensitive composition are formed on both sides of the printed wiring board on which the conductor pattern is formed, both sides are irradiated with imagewise actinic rays and developed. The present invention relates to a method of manufacturing a printed wiring board on which a solder resist is formed.

The photosensitive composition of the present invention contains a compound having at least one ethylenically unsaturated group as an essential component (A). The compound includes, for example, polyhydric alcohol with α
, a compound obtained by reacting β-unsaturated carboxylic acid,
For example, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethanetetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and their corresponding methacrylates and glycidyl group-containing compounds. Compounds obtained by adding α,β-unsaturated carboxylic acids to, for example, trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, and the corresponding methacrylates, polyhydric carboxylic acids, for example, Esterified products of phthalic anhydride, etc., and substances having hydroxyl groups and ethylenically unsaturated groups, such as β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate, alkyl esters of acrylic acid or methacrylic acid,
For example, urethane diacrylates obtained by reacting trimethylhexamethylene diisocyanate, dihydric alcohols, and monoesters of acrylic acid or methacrylic acid of dihydric alcohols, such as methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, etc. Alternatively, a urethane diacrylate or dimethacrylate compound obtained by reacting a dimethacrylate compound, trimethylhexamethylene diisocyanate, a dihydric alcohol, and 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate can also be used. Two or more of these compounds may be used in combination.

The photosensitive composition of the present invention further contains, as an essential component (B), a sensitizer and/or a sensitizer system that generates free radicals when exposed to actinic light. As the sensitizer, for example, 2-
Substituted or unsubstituted polynuclear quinones such as ethyl anthraquinone, 2-L-butylanthraquinone, octylanthraquinone, 1,2-benzanthraquinone, 2.3-diphenylanthraquinone, ketoaldonyl compounds such as diacetyl and benzyl, benzoin, pyruron α-ketaldonyl alcohols and ethers, α-phenyl-
α such as benzoin, α, α-jethoxyacetophenyl, etc.
- Hydrocarbon-substituted aromatic acyloins, benzophenone,
4. Aromatic ketones such as 4'-bis(dialkylamino)benzophenone, 2-methylthioxanthone, 2.4
- Thioxanthone such as diethylthioxanthone, 2-chlorothioxanthone, 2-isopro, pyruthioxanthone, and 2-ethylthioxanthone are used. These compounds may be used alone or in combination of two or more.

As a sensitizer system, combinations of 2,4.5-triarylimidazole dimer and 2-mercaptobenzoquinazole, leuco crystal violet, tris(4-diethylamino-2-methylphenyl)methane, etc. are used. used. Also, additives which do not have photoinitiating properties by themselves but which, when used in combination with the above compounds, result in a sensitizer system with better photoinitiating performance as a whole, such as:
Tertiary amines such as triethanolamine for benzophenone can also be used.

(B) Preferred sensitizers and/or sensitizer systems are:
From the viewpoint of the properties of the solder resist formed, 2-meth2
It is a combination of 1-[4-(methylthio)phenyl]-2-morpholino-propanone-1 and 4°4'-bis(diethylamino)benzophenone.

The photosensitive composition of the present invention contains a compound represented by the above general formula (1) as an essential component (C). General formula (I
) Examples of the compound represented by 2-chloroacridone, 10-methyl-2-chloroacridone, 10-ethyl-2-chloroacridone, 10-propyl-2-chloroacridone, IO-butyl- 2-chloroacridone, 10-pentyl-2-chloroacridone, 10-methoxy-2-chloroacridone, 10-ethoxy-2-chloroacridone, 10-propoxy-2-chloroacridone, 10-butoxy -2-chloroacridone, 10-
Examples include pentoxy-2-chloroacridone. These compounds are available from Kyoko Kasei.

These compounds absorb the 405 nm emission spectrum of the high-pressure mercury lamp, are effective in preventing backfogging, and can initiate photocuring reactions.These compounds can be used alone or in combination of two or more. can be used. Among these compounds, 10-butyl-2-chloroacridone is preferred from the viewpoint of the properties of the solder resist formed.

In the present invention, essential components (A
) 0.1 to 30 of essential component (B) per 100 parts by weight
It is preferable to use parts by weight and essential component (C) in a range of 0.01 to 30 parts by weight.

A photosensitive laminate is produced by applying and drying a photosensitive composition containing the film-forming resin (D) of the present invention onto a support film.

(D) As the film-forming resin, for example, a linear polymer compound can be used. Examples of linear polymer compounds include thermoplastic polymers described in Japanese Patent Publication No. 41-15932.

Preferred linear polymer compounds include, for example, vinyl monomers such as methyl methacrylate, ethyl acrylate, acrylic acid, styrene, 2-hydroxyethyl methacrylate, t-butylaminoethyl methacrylate, acrylamide, acrylonitrile, and vinyl acetate. Vinyl polymer compound obtained by polymerizing or copolymerizing butadiene/
Examples include synthetic rubbers such as acrylonitrile copolymers and butadiene/acrylonitrile/styrene copolymers, linear polyurethane compounds, and alcohol-soluble nylons. Two or more of these linear polymer compounds may be used in combination.

Moreover, a thermosetting compound can also be used as (D) film-forming resin. Examples of the thermosetting compound include epoxy resin, melamine resin, etc., and these may be used in combination of two or more kinds, or may be used in combination with the linear polymer compound.

Furthermore, (E) a compound having both a thermally crosslinkable functional group and a polymerizable vinyl group can be mixed in the photosensitive composition of the present invention. Examples of such compounds include oligomers having an epoxy group and a polymerizable vinyl group in their side chains. = Boar oligomer is disclosed in JP-A-61-132947, Japanese Patent Application No. 60-107785 and JP-A-60-107.
No. 786, it is preferred that a compound having at least two epoxy groups and an unsaturated carboxylic acid be subjected to an addition reaction at an acid equivalent/epoxy equivalent ratio of 0.1 to 0.98. In the resulting unsaturated compound, isocyanate ethyl methacrylate is added to the hydroxyl group of the unsaturated compound, and the isocyanate equivalent/hydroxyl group equivalent ratio is from 0.1 to
It is an oligomer obtained by reacting in the range of 1.2.

Examples of the above-mentioned compounds having two epoxy groups include bisphenol A type epoxy resins obtained by reacting bisphenol A and epichlorohydrin (for example, manufactured by Shell Chemical Co., Ltd., trade names Epicote 812, Epicote 828, Epicote 1001). etc.), brominated bisphenol A type epoxy resin (for example, manufactured by Tobu Kasei Co., Ltd., trade name Epicote YDB-340, YDB-400, etc.),
Bisphenol F type epoxy resins (for example, manufactured by Tobu Kasei Co., Ltd., trade name Potote YDF-170, YDF-190, etc.), epoxy compounds obtained by adding alkylene oxide to bisphenol A and then reacting with epichlorohydrin (for example, manufactured by Kyoeisha Yushi Co., Ltd., Product Master Borite 30
02, etc.), hydrogenated bisphenol A type epoxy resin (for example, manufactured by Tobu Kasei Co., Ltd., trade name Santoto 5T-1000,5
T-3000, etc.), glyoxal type epoxy resin (e.g. manufactured by Tobu Kasei Co., Ltd., trade name Evo)-) YDG-414 etc.), glycidylamine type epoxy resin (e.g. manufactured by Tobu Kasei Co., Ltd., trade name Evo)-) YDM-120 , YH-434
etc.), orthocresol novolac type epoxy resin (for example, manufactured by Nippon Kapaku Co., Ltd., trade name EOCN102, etc.), phenol novolac type epoxy resin (for example, manufactured by Tobu Kasei Co., Ltd.,
(trade name: YDPN-638, etc.), brominated phenol novolac type epoxy resin (for example, manufactured by Nippon Kapaku Co., Ltd., trade name: BR)
EN, etc.), alicyclic epoxy compounds (for example, manufactured by Chisso Corporation,
(trade name Chissonox 221, Chissonox 201, etc.), glycidyl ether type epoxy resin obtained by the reaction of dicarboxylic acid such as phthalic acid with epichlorohydrin (for example, manufactured by Showa Denko K.K., trade name Shodyne 508,
Shodyne 540, Shodyne 550, etc.), glycidylamine type epoxy resins (manufactured by Shell Chemical Co., Ltd., trade name Epicote 604, etc.), trimethylolpropane polyglycidyl ether, and the like.

As the unsaturated carboxylic acid, acrylic acid, methacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, etc. are used.

(E) Two or more compounds having both a thermally crosslinkable functional group and a polymerizable vinyl group may be used in combination.

Further, the linear polymer compound and the thermosetting compound may be used in combination.

Furthermore, other subsidiary components may be added to the photosensitive composition of the present invention. The secondary components include, for example, thermal polymerization inhibitors, dyes, pigments, fillers, coatability improvers, antifoaming agents, flame retardants, flame retardant aids, adhesion improvers, and latent curing of epoxy resins. agents, etc.

When forming a photosensitive layer on a substrate using the photosensitive composition described above, for example, the photosensitive composition is dissolved in an organic solvent such as methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, etc., and this solution is dipped. The substrate is coated directly onto the substrate to be processed and protected by a conventional method such as coating method, flow coating method, roll coating method, screen printing method, etc., and after drying, the substrate is further turned over and the same process is performed. A photosensitive layer having a thickness of 10 to 150 μm can be easily formed on both sides of the film.

Further, the solution is coated on a support film such as a polyethylene terephthalate film or a polyimide film by a knife coating method or a roll coating method, and dried to form a photosensitive layer or, if necessary, a cover such as a polyethylene film. The films are laminated to obtain a photosensitive laminate (photosensitive film). A photosensitive layer can also be formed by laminating this material on both sides of the substrate simultaneously under heat and pressure using a known method, for example, using a hot roll. At this time, if the board has irregularities of 10 μm or more, such as a printed wiring board on which conductor wiring lines are formed, a 200I
It is preferable to laminate under reduced pressure of IIIHg or less. As a device for this purpose, for example,
A laminating apparatus described in Japanese Patent No. 41 is used. In addition, when using a support film that is opaque to actinic light, it is necessary to peel off the support film at the time of exposure.

Exposure and development of the formed photosensitive layer are performed by conventional methods. That is, using an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, or the like as a light source, the layer of the photosensitive resin composition is imagewise exposed directly or through a negative mask through a support film. After exposure, if a support film remains, the support film is peeled off and then developed.

The type of developer used in the development process is not particularly limited as long as it does not damage the exposed areas and selectively elutes the unexposed areas.

The image-like solder resist (protective film) obtained by the above method is a corrosion-resistant film for ordinary etching, plating, etc., but after development, it is further exposed to active light and heated at 80 to 200°C.
By performing the heat treatment, a solder resist having even better properties can be obtained.

When manufacturing a printed wiring board using the photosensitive composition of the present invention, the printed wiring board on which a conductive pattern is formed may be a multilayer printed wiring board.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

In addition, parts in Examples and Comparative Examples indicate parts by weight.

Example 1 (a) Synthesis of urethane diacrylate compound A Trimethylhexamethylene 1680 parts diisocyanate (16 equivalents) Toluene (solvent)
1200 parts di-n-1 part butyltin dilaurate (catalyst) B 1,6-hexanediol 472 parts (8 equivalents) C2-hydroxyethyl 928 parts acrylate (8 equivalents) Toluene (solvent) 88 parts hydroquinone (thermal polymerization inhibitor) 0.4 part D methanol (terminating agent)
The above A was added to a reactor with a capacity of about 52 which can be heated and cooled and equipped with a 32-part thermometer, a stirrer, a cooling tube, a nitrogen gas introduction tube, and a dropper, and the temperature was raised to 60 ° C while stirring. . B was uniformly added dropwise over about 3 hours while maintaining the reaction temperature at 55-65°C. After the completion of dropping B, the temperature was maintained at 60°C for about 2 hours, and then C was uniformly dropped at a temperature of 60°C over about 3 hours. After the dropwise addition of C was completed, the reaction temperature was gradually raised to 80°C over about 5 hours. Then increase the temperature to 60°
The temperature was lowered to C, D was added, and stirring was continued for about 1 hour. In this way, a solution of the urethane diacrylate compound was obtained. Thereafter, it was dried under reduced pressure to obtain a viscous urethane diacrylate compound.

(b) Preparation of photosensitive composition Urethane diacrylate compound obtained in (a) above 40 parts Trimethylolpropane triacrylate 10 parts Methyl methacrylate 47 parts methacrylic acid Tetrahydrofurfuryl methacrylate (88/2/20 weight Ratio) Copolymer (weight average molecular weight approximately 150,000) Benzophenone 4 parts 4.4'
-Bis(diethylamine) 062 parts Benzophenone 10-butyl-2-chloroacridone 2 parts p-methoxyphenol 0.1 part Crystal violet 0.1 part Methyl ethyl ketone
80 parts Micro Ace P-4 (manufactured by Nippon Talc Co., Ltd. 10 parts ultrafine talc average particle size 1.5 μm) A solution of the photosensitive composition was prepared using the above formulation.

(C) Formation of solder resist (protective film) The photosensitive composition prepared in (b) was applied to both sides of the printed wiring board on which the pattern was formed by dip coating, and dried at 80"C for 20 minutes. , a photosensitive layer was formed.The thickness of the photosensitive layer was 3
It was 0 μm.

A negative film was brought into close contact with the photosensitive layers on both sides of a printed wiring board with a thickness of 0.6 mm on which a conductor pattern was formed, and a photosensitive layer of the photosensitive composition was formed, and a Phoenix 3000 type exposure machine (
(manufactured by Oak Seisakusho Co., Ltd.), and was exposed at 200□J/cm. Next, spray development was performed using 1.1.1-trichloroethane at 20°C for 50 seconds.

When the printed wiring board on which the solder resist was formed through the above steps was observed, there was no development residue. Furthermore, the printed wiring board on which this solder resist was formed was irradiated with ultraviolet irradiation equipment (manufactured by Toshiba Denzai Co., Ltd., rated voltage 200cm, rated consumption type cuff, 2KW, compatible lamp H5600L/2, number of lamps 1) for 2J/2. CD amount of ultraviolet rays were irradiated and then heat treated at 160° C. for 20 minutes to obtain a printed wiring board on which a sharp edge-shaped solder resist was formed.

After this printed wiring board was subjected to flux treatment, it was immersed in a solder bath heated at 260°C for 10 seconds and then observed. As a result, there was no abnormality such as thermal damage to the solder resist, and there was no adhesion of solder.

Example 2 In Example 1, 4 parts of benzophenone contained in the photosensitive composition was replaced with 2-methyl-1-(4-(methylthio)phenyl]-2-monopholino-propanone-1 (manufactured by Ciba Geigy, trade name Irgacure 907). ) A photosensitive composition was prepared by changing the amount to 4 parts, and the same treatment as in Example 1 was performed, and a printed wiring board was obtained in which a solder resist with sharp edges and excellent surface gloss was formed. After this printed wiring board was subjected to flux treatment, it was immersed in a solder bath heated at 260° C. for 10 seconds and then observed. As a result, there was no abnormality such as thermal damage to the solder resist, and there was no adhesion of solder.

Comparative Example 1 Example 1 except that 10-butyl-2-chloroacridone was not added to the photosensitive composition prepared in Example 1(b).
When a photosensitive composition similar to the above was prepared and treated in the same manner as in Example 1 (c), development residues due to back fogging were observed on both sides of the printed wiring board. Although development was performed for an additional 50 seconds, the residual development did not disappear.

Comparative Example 2 A photosensitive composition similar to Example 2 was prepared except that 10-butyl-2-chloroacridone was not added to the photosensitive composition of Example 2, and the same photosensitive composition as Example 1(C) was prepared. When this process was carried out, there was development residue due to back fogging on both sides of the printed wiring board. Although development was performed for an additional 50 seconds, the residual development did not disappear.

Example 3 (a) Synthesis of photopolymerizable unsaturated compound A Orthocresol novolak 1095 parts epoxy resin, EOCN 102 (epoxy equivalent weight 230) Methyl ethyl ketone 800 parts B Acrylic acid 69 parts Benzyltrimethylammonium chloride 7 parts p-methoxyphenol
3 parts methyl ethyl ketone 10
0 parts C isocyanate ethyl methacrylate 163 parts di-n-butyltin acrylate dilaurate 0.5 parts methyl ethyl ketone 100 parts D methanol
10 parts Heating and cooling possible with thermometer, stirrer, cooling tube and dropper 5! The above A was added to the reactor, and the temperature was raised to 60°C while stirring to uniformly dissolve. While maintaining the reaction temperature at 60°C, B was added dropwise to this over about 1 hour. After dropping B, the temperature was raised to 80°C over 2 hours, and stirring was continued at 80'C for about 15 hours to bring the acid value of the reaction system to 1 or less. Then increase the temperature to 60
°C, while maintaining the reaction temperature at 60 °C.
C was evenly added dropwise over time. After dropping C, the reaction temperature was gradually raised to 80°C over about 5 hours, and then the temperature was increased to 60°C.
The temperature was lowered to 0°C, D was added, and stirring continued for about 1 hour.

In this way, orthocresol novolac type epoxy resin with nonvolatile content of 57% by weight/acrylic acid/isocyanatoethyl methacrylate (acid equivalent/epoxy equivalent ratio = 0.2,
A solution of a photopolymerizable unsaturated compound (I/hydroxyl equivalent ratio = 1.1) was obtained.

(b) Preparation of photosensitive composition Solution of photopolymerizable unsaturated compound 88 parts 4.4'
-Bis(diethylamine) 0.3 parts Benzophenone 10-butyl-2-chloroacridone 3 parts Micro Ace P-4 (manufactured by Nippon Talc Co., Ltd. 30 parts ultrafine talc average particle size 1.5 μm) Phthalocyanine blue 0.1 part above A solution of the photosensitive composition was prepared by mixing and dispersing the formulation using a roll mill.

(C) Formation of solder resist (protective film) The solution of the photosensitive composition obtained in (b) was applied onto a copper-clad printed wiring board, dried at room temperature for 20 minutes and then at 80°C for 20 minutes, and then The printed wiring board was reversed and the same process was performed to form a photosensitive layer with a thickness of 40 μm on both sides of the printed wiring board with a thickness of 0.6 m on which a conductive pattern was formed. Then, using a Phoenix 3000 type exposure machine through a negative mask,
Both sides were exposed simultaneously at 0 mJ/c4. 5 at 80°C after exposure
After heating for 30 minutes at room temperature, 1゜1.1-1
- Spray developed using dichloroethane at 20°C for 90 seconds.

When the printed wiring board on which the solder resist was formed after development was observed, there was no development residue. Furthermore, after irradiating at IJ/cml using a Toshiba ultraviolet irradiation device,
Heat treatment was performed at 150° C. for 30 minutes to obtain a printed wiring board on which a solder resist with excellent dimensional accuracy suitable for a negative mask was formed.

This printed wiring board was soldered using rosin-based flux A-226 (manufactured by Tamura Kaken Co., Ltd., trade name) at 260°C for 10 seconds, and then with Triclean at 25°C for 10 seconds.
After purification for minutes, MIL-3TD-202E107
D Condition B (-65°C for 30 minutes, room temperature within 5 minutes, 125
C. for 30 minutes) for 50 cycles, but no cranking or peeling of the coating was observed in the solder resist. These results showed that the solder resist has excellent cold and thermal shock resistance and that a printed wiring board with excellent long-term reliability can be obtained.

Example 4 In Example 3, 2 parts of benzophenone contained in the photosensitive composition was changed to 1,2 parts of 2-methyl-1-(4-(methylthio)phenyl]-2-monopholino-propanone-1, and the composition was photosensitive. When a composition was prepared and treated in the same process as in Example 3(c), it showed the same characteristics as Example 3,
Printed wiring boards with sharp edges and a solder resist with excellent surface gloss were obtained, and these boards had excellent resistance to cold and thermal shock.

Comparative Example 3 Example 3 except that 1°-butyl-2-chloroacridone was not added to the photosensitive composition prepared in Example 3(b).
When a photosensitive resin composition similar to the above was prepared and processed in the same manner as in Example 3(c), development residues due to back fogging were observed on both sides. Although development was performed for an additional 90 seconds, the residual development did not disappear.

Example 5 (a) Synthesis of photopolymerizable unsaturated compound A Poly(p-hydroxystyrene) 500 parts (Maruzen Petrochemical Co., Ltd., Maruzen Resin M, hydroxyl equivalent: 120) Methyl ethyl ketone 700 parts B Isocyanate ethyl methacrylate 323 parts Rate Di-n-butyltin dilaurate 0.3 parts P-methoxyphenol 0.03 parts C methanol
1 part Heating and cooling capacity with thermometer, stirrer, cooling tube and dropper approx. 51.
The above A was added to the reactor, and the temperature was raised to 60'C while stirring. While maintaining the reaction temperature at 60'C, B was uniformly added dropwise over about 3 hours. Next, the reaction temperature was gradually raised to 80°C over about 5 hours, and then the temperature was lowered to 60°C, C was added, and stirring was continued for about 1 hour. A solution of a photopolymerizable unsaturated compound based on (isocyanate equivalent/hydroxyl group equivalent ratio -0.5) was obtained.

(b) Preparation of photosensitive composition 2. 4-diethylthioxanthone 3 parts dimethylamine isoamyl benzoate 3 parts IO-butyl 2
-Chloracridone 3 parts Victoria Pure Blue
A solution of the photosensitive composition was prepared using 0.01 part of the above formulation.

(C) Forming a solder resist (protective film) A solution of the photosensitive composition obtained in (b) is applied onto a copper-clad laminate,
Dry at room temperature for 20 minutes and then at 8°C for 20 minutes, then turn the printed wiring board over and repeat the same process to dry both sides of the printed wiring board with a conductor pattern and a thickness of 0.6 mm. A photosensitive layer with a thickness of 40 μm was formed. Next, it was exposed through a negative mask at 200 mJ/c using a HMW-201B type exposure machine (Oak Seisakusho!!). After exposure, the temperature was 8°C.
After heating for 5 minutes at room temperature and leaving it for 30 minutes at room temperature, it was developed using cyclohexanone at 20'C for 90 seconds. When the printed wiring board on which the solder resist was formed through the above steps was observed, no development residue was observed. Furthermore, the printed wiring board was coated with IJ/- using a Toshiba ultraviolet irradiation device.
After irradiation with 150° C. for 30 minutes, a printed wiring board on which a sharp edge-shaped solder resist was formed was obtained. After fluxing this printed wiring board,
After being immersed in a solder bath heated to 260°C for 10 seconds, observation revealed that there was no abnormality such as thermal damage to the solder resist, and there was no adhesion of solder.

Comparative Example 5 Example 5 except that 10-butyl-2-chloroacridone was not added to the photosensitive composition prepared in Example 5(b).
When a photosensitive composition similar to the above was prepared and processed in the same manner as in Example 5(c), development residues due to back fogging were observed on both sides. Although the process was continued for an additional 90 seconds, the residual development did not disappear.

Example 6 (a) Synthesis of photopolymerizable unsaturated compound A TEPIC-G (manufactured by Nissho Kagaku Kogyo Co., Ltd. 1100 parts 1 triglycidyl isocyanurate, epoxy equivalent) B Acrylic acid 480 parts p-methoxyphenol 1 part C propylene glycol Monomethylene 527 parts ether acetate Add the above A to a reactor with a capacity of about 22 that can be heated and cooled and equipped with a thermometer, a stirring device, a cooling tube, and a dropper, and raise the temperature to 140 ° C. with stirring, and uniformly dissolve. After dissolving, 11
Cool to 0°C and keep the reaction temperature at 110°C, about 1
B was evenly added dropwise over time. After dropping B, 110℃
Stirring was continued for about 7 hours, and after the acid value after the reaction was reduced to 1 or less, C was added and stirred uniformly. Thus, the non-volatile content is 75
A solution of triglycidyl isocyanurate/acrylic acid (acid equivalent/epoxy equivalent ratio = 2/3) type photopolymerizable unsaturated compound in a weight percent manner was obtained.

(b) Preparation of photosensitive composition Poly(p-vinylphenol) 35 parts (Maruzen Resin MS-2, weight average molecular weight 5000, manufactured by Maruzen Petrochemical Co., Ltd.) Ethylene glycol monoether 35 parts Acetate 2-methyl-1-( 4-(Methylthio) 8 parts Phenyl]-2-monopholino-propanone-1 4,4,'-bis(dimethylamino) 0.8 parts Benzophenone 2-chloroacridone 3 parts Propylene glycol monomethyl 100 parts Ether Sensitized with the above composition A solution of the sexual composition was prepared.

(C) Formation of solder resist (protective film) The solution of the photosensitive resin composition obtained in (b) is applied onto a copper-clad laminate and dried at room temperature for 20 minutes and then at 80°C for 20 minutes. Then, the printed wiring board was reversed and the same process was performed to form a photosensitive layer with a thickness of 40 μm on each side of the printed wiring board with a thickness of 0.6 tm on which a conductive pattern was formed. Then pass through a negative mask (newly manufactured by Oak) HMW-201
Exposure was performed at 500 mJ/cIII using a B-type exposure machine. After exposure, the film was heated at 80° C. for 5 minutes, left at room temperature for 30 minutes, and then spray-developed using a 1% aqueous sodium carbonate solution at 30° C. for 60 seconds, and immediately washed with spray water for 60 seconds. When the printed wiring board on which the solder resist was formed through the above steps was observed, no development residue was observed. Further, the printed wiring board was heat-treated at 150° C. for 30 minutes to obtain a printed wiring board on which a sharp edge-shaped solder resist was formed. After this printed wiring board was subjected to flux treatment, it was immersed in a solder bath heated to 260° C. for 10 seconds and then observed. As a result, there was no abnormality such as thermal damage to the solder resist, and there was no adhesion of solder.

Comparative Example 6 A photosensitive composition was prepared in the same manner as in Example 6, except that 2-chloroacridone was not added to the photosensitive composition prepared in Example 6(b), and the same was prepared as in Example 6(C). When the same process was carried out, there was development residue on both sides due to back fogging.

Further, development was performed for 120 seconds, but the residual development did not disappear.

(Effects of the Invention) If the photosensitive composition or photosensitive laminate of the present invention is used, there will be no development residue due to back-fogging, sharp edges, no adhesive solder adhering to undesired areas, and solder heat resistance. Printed wiring boards having good solder resists on both sides can be manufactured with good workability and industrial advantage.

[Brief explanation of the drawing]

Figure 1 is an explanatory diagram of the solder resist forming process, Figure 2 (
A) and (B) are schematic diagrams of edge formation of solder resist, and FIG. 3 is an explanatory diagram of solder adhesion when edge formation of solder resist is inappropriate. Explanation of symbols IA...photosensitive composition, IB...solder resist,
2... Insulating layer (or inner layer), 3... Conductor pattern,
4...Negative, 5...Adhesive solder, 6...Solder. 1B Nordaresist 2 Insulating layer (or inner layer) 3 Conductor pattern 4 Negative Figure 1

Claims (6)

[Claims] 1. (A) Compound having at least one ethylenically unsaturated group, (B) Sensitizer and/or sensitizer system that generates free radicals by actinic light, and (C) General formula ▲ Numerical formula, chemical formula, table, etc. A photosensitive composition containing a compound represented by ▼ (wherein R means a hydrogen atom, an alkyl group, or an alkoxy group). 2. The photosensitive composition according to claim 1, further comprising (D) a film-forming resin. 3. Sensitizers and/or sensitizers that generate free radicals by actinic light
or the sensitizer system is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1 and 4
, 4'-bis(diethylamino)benzophenone. 4. Sensitizers and/or sensitizers that generate free radicals by actinic light
or the sensitizer system is 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1 and 4
3. The photosensitive composition according to claim 2, which is 4'-bis(diethylamino)benzophenone. 5. A photosensitive laminate obtained by coating and drying the photosensitive composition according to claim 2 on a support film. 6. After forming layers of the photosensitive composition according to claim 1, 2, 3, or 4 on both sides of a printed wiring board on which a conductive pattern is formed, developing treatment is performed by irradiating both sides with imagewise actinic light. A method for manufacturing a printed wiring board on which a solder resist is formed, characterized by: