JPS59107344A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition with high suitability to image formation by adding an initiator which generates free radicals, an org. halogen compound, a dye which develops color under light and other dye to an ethylenic unsatd. compound and a film forming polymer. CONSTITUTION:A photosensitive resin composition is obtd. by blending 100pts.wt. in total of an ethylenic unsatd. compound (A) such as trimethylolpropane triacrylate and a film forming polymer (B) such as polymethyl methacrylate with an initiator (C) which generates free radicals under active rays such as benzophenone, 0.5-5pts.wt. org. halogen compound (D) such as tribromomethylphenylsulfone, 0.5-3.5pts.wt. dye (E) which absorbs ultraviolet rays of 100-400nm wavelengths and develops color under light such as leucocrystal violet, and 0.01-0.05pts.wt. other dye (F) such as malachite green. By using the composition, a sharp image can be formed, and defects after development can be easily detected, so the working speed can be increased.

Description

[Detailed description of the invention] The present invention relates to a photosensitive resin composition.

More details: Etching resist used for example in the production of printed wiring boards, metal precision processing, etc.

The present invention relates to a photosensitive resin composition that is removed from a substrate after the substrate is processed into a plating resist or the like.

Chemistry of base materials such as etching and plating in fields such as printed wiring board manufacturing and metal precision processing.

It is known to use a photosensitive resin composition and a photosensitive element using the same as a resist material during processing and modification using an electrical method. As a photosensitive element, one in which a photosensitive resin composition layer is formed on a support is widely used.

The properties required of such a photosensitive resin composition and a photosensitive element using the same include sufficient chemical resistance to be used as an etching resist or plating resist, adhesion to a substrate, and practical properties. Not only is it necessary to have sufficient photosensitivity, but it is also important that workability is good in each step of manufacturing printed wiring boards.

Particularly in recent years, there has been a strong demand for cost reduction and reduction of defect rate by shortening the time of each process in the field of printed wiring board manufacturing, and there is a strong demand for photosensitive elements that are easy to work with in each process.

A conventional photosensitive element has nine colored photosensitive film layers, a colorless and transparent peelable support, and a colorless and transparent peelable support.

It consists of a colorless and transparent removable protective film, and when manufacturing printed wiring boards using such photosensitive elements, the removable protective film is usually peeled off and the photosensitive film layer is placed on the board surface. The layers are laminated, exposed through a negative film to image the appropriate electrical circuit, and the peelable support is peeled off and developed to form the circuit.

After that, it goes through processes such as plating and etching.

The circuit of the printed wiring board is formed by peeling off the resist film.

Normally, photosensitive elements used in this way are laminated onto a base material and then irradiated with radically active light through a negative film so that the exposed areas, which are not blocked by the negative film, develop color due to the radically active light. The composition has been designed to suit. Therefore, after exposure, a contrast between the exposed area and the unexposed area usually appears. (Hereinafter, the contrast between the exposed area and the unexposed area is referred to as imaging, and a strong contrast is referred to as good or strong imaging.) This is usually done in the process of manufacturing printed wiring boards9. This is to enable circuit modification after exposure and development. Correcting the circuit after exposure and development means that if a defect is discovered, the board must be reprocessed immediately.
This is because it is possible to prevent defects. Therefore, strengthening the imaging has an industrial advantage in that defects after exposure and development, ie, circuit defects such as disconnections, chips, serrations, and notches, can be easily detected and the work speed can be further increased.

However, conventional photosensitive elements cannot fully satisfy this requirement.1 In the normal manufacturing process of printed wiring boards, corrections after exposure and development are performed visually because there is no other good method. This puts an extremely heavy burden on the workers.

In addition, in conventional photosensitive elements, the hue of the photosensitive layer itself is deep and the imaging is weak, so the photosensitivity of the photosensitive layer itself is low, the correction time after exposure is extremely long, and negative adjustment is difficult. It has some drawbacks such as jerkiness.

Therefore, the inventors of the present invention have conducted extensive research in order to improve the "minor defects" described in E., and as a result, have arrived at the present invention.

The present invention comprises (A) an ethylenically unsaturated compound, (B) an initiator that generates free radicals by actinic rays, (C) a polymer that imparts film properties, (D) an organic halogen compound, (E) a photochromic dye, and (F) A photosensitive resin composition containing a dye, (D)
α5 to 5 parts by weight of organic halogen compound, 0.5 to 3.5 parts by weight of (E) photochromic dye, and 0.01 part of (F) dye.
It relates to a photosensitive resin composition containing ~0.05 part by weight.

The photosensitive resin composition 9 of the present invention is JI) IA31.

It contains organic halogen compounds, photochromic dyes, and dyes as essential components.

As an imaging material, 1% 147829
As disclosed in Japanese Unexamined Patent Publication No. 55-13780, combinations of fluoran compounds and diazonium metal salts and combinations of proton donors and norogen compounds are known. The halogen compounds used in these photosensitive resin compositions are mainly low-molecular, sublimable, and easily volatilized when heated, such as trichloroacetamide and tribromoacetamide. However, during the printed wiring board manufacturing process, in order to laminate a photosensitive element onto a substrate, it is customary to heat the photosensitive element to 120 DEG C. to 160 DEG C. to laminate the substrate. Therefore, under such conditions, low-molecular and volatile compounds sublime or volatilize, thereby reducing the photosensitivity of the photosensitive layer and weakening imaging.

In particular, in high-temperature lamination at around 160° C., the volatilization rate further increases, and such low molecular weight compounds are not suitable.

Therefore, an organic compound such as tribromomethylphenylsulfone, which has a suitable molecular weight, sublimation property, and volatility, can satisfy this requirement. However, such organic halogen compounds alone do not produce imaging, but can be produced by combining them with photochromic dyes.

Such photochromic dyes are also required to have a relatively large molecular weight and not be sublimable. Moreover.

It must absorb the ultraviolet light used during exposure during the printed wiring board manufacturing process, that is, 100 to 400 nm. A leuco dye such as leuco crystal violet, which has a maximum absorption wavelength in the vicinity of 25 Q nm and has no sublimation property, is suitable as a material that meets these requirements. Furthermore, by optimizing the amount of the dye in the combination of the organic compound and the leuco dye described above, it is possible to obtain imaging that is much better and more stable than the imaging of conventional photosensitive resin compositions. This is because the dye in the photosensitive resin composition only plays a role in coloring the film, and when looking at the photosensitive layer alone,
The structure of the dye itself includes many phenyl rings and covalent double bonds, and it is light absorbing and inhibits the light absorption rate and photoreactivity of the photosensitive layer. Increasing the amount is nothing but reducing the photoreactivity, that is, the photosensitivity, of the photosensitive layer. Therefore, the smaller the amount of dye, the better, as long as it is within a distinguishable range, and there is no need to add a large amount. Malachite green is known for its good coloring properties and stability in nine colors even in small amounts.

A photosensitive resin composition containing these compounds, and
A photosensitive element using this has excellent imaging properties, and circuit correction work after exposure and development can be easily performed.

As the organic halogen compound used in the present invention, example t
Examples include tryp-a-moacetophenone, bis-(trifluoromethyl)sulfone, tribromomethylphenylsulfone, and chlorinated olefin, with tribromomethylphenylsulfone being particularly suitable. In addition, from the viewpoint of imaging properties of the photosensitive resin composition, the blending amount is set to 0.5 to 5 parts by weight per 100 parts by weight of the ethylenically unsaturated compound and the polymer imparting film properties.

Examples of photochromic dyes include 9, such as leuco crystal violet and its trimethyl substituted product, and examples of dyes include fuchsin, auramine base, and calcocyto green S.
, Bala Mazienta, Crystal Violet, Crystal Violet Lactone, Methyl Orange, Nile Blue 2B, Victoria Pure Blue, Malachite Green, Paysic Blue 20. Iosing Green, Night Clean B,) Riparosan, New Marienta, Acid Violet R, RH, Rhett Violet 5T'
Examples include tS, new methylene blue GG, etc., but leuco crystal violet is particularly suitable as a photochromic dye, and malachite green is particularly suitable as a dye. In addition, from the viewpoint of imaging properties of the photosensitive resin composition, the blender contains 0.5 to 3 parts by weight of a photochromic dye per 100 parts by weight of the ethylenically unsaturated compound and the polymer imparting film properties.
．． 5 parts by weight, and 0.01 to 0.05 parts by weight of the dye.

As for the other components contained in the photosensitive resin composition of the present invention, there are no restrictions, and already known compounds can be used.

Examples of ethylenically unsaturated compounds include trimethylolpropane triacrylate, pentaerythritol triacrylate, 1,6-hexanediol diacrylate, 2,2-bis(4-methacryloxyethoxyphenyl)propane, 2,2-bis( (4-acryloxyethoxyphenyl)furopane, dipentaerythritol pentaacrylate, trimethylolpropane trimethacrylate, acrylic acid or methacrylic acid adduct of trimethylolpropane triglycidyl ether, acrylic acid or methacrylic acid adduct of bisphenol A-epichlorohydrin epoxy resin Acid adducts, low-molecular unsaturated polyesters such as 1:1°2 adducts of 7-talic anhydride-neopentyl glycol-acrylic acid, diethylene glycol diacrylate, tetodiethylene glycol diacrylate, nonaethylene glycol di-acrylate, polyethylene glycol ( 400-600) diacrylate.

Tetraethyleneglyfur dimethacrylate.

Also included are nonaethylene dimethacrylate and the like.

There is no particular limit to the initiator that generates free radicals by actinic radiation, and conventionally known compounds can be used. For example, benzophenone, p,p-dimethylaminobenzophenone, p,p-dichlorobenzophenone, mixtures thereof, anthraquinones such as 2-ethylanthraquinone, 2-1-butylanthraquinone, 2- Chlorothioxanthone, benzoin, benzoin alkyl ether.

Benzyl, 2,4.5-) Reallylimidazole 21
There are three examples.

Examples of film-like polymers include methacrylic esters such as polymethyl methacrylate and methyl methacrylate-ethyl acrylate copolymers, polymers or copolymers of acrylic esters, polystyrene, styrene-methacrylic ester copolymers, Polyvinyl formal, polyvinyl butyral, cellulose acetate butyrate, etc. are used depending on the purpose.

Note that the photosensitive resin composition of the present invention may contain other additives such as additives and flame retardants, if necessary.

Stabilizers etc. may be added.

The present invention will be explained below with reference to two examples and comparative examples. Parts are by weight.

Examples and Comparative Example 1, Production of Photosensitive Element *Copolymer dissolved in ethylcelonorb (35% solution)? Hs HCH2CH20 replacement C-C= CH2 1 n-4-m, 10 (manufactured by Shin Nakamura Chemical) the above polymer,
An initiator and a polymerization inhibitor are added to the solution obtained by mixing and stirring the ethylenically unsaturated compound.

A photochromic dye, a dye, and a halogen compound dissolved in a solvent were added and mixed to form photosensitive resin compositions C-1 to C-.
I got 4.

Photosensitive resin compositions C-1 to C-4 were coated on a 25 μm thick polyester film (Toshi Co., Ltd. Kema product name: Lumirror).
FK was applied uniformly and dried for 10 minutes in a hot air drying oven at 100°C. The thickness of the photosensitive layer is 25μrT! Met. Further on this photosensitive layer is a polyethylene film (Hitachi Kasei Koushiba Co., Ltd. product name: Hitachi Polyester Film CT, -40).
were laminated to form photosensitive elements E-1 to E-4. The embodiment of the present invention is E-1 and the other three are comparative examples.

2. Exposure and development A copper-clad laminate with a 35 μm copper foil was puff-polished with Scotchbrite 0, and the substrate was dried at 80° C. for 10 minutes. The photosensitive nilemens) E-1 to E-4 prepared above were laminated on a copper-clad laminate at 160° C. while removing the polyethylene film. This was done in 3K using negative film.
14 with W high pressure mercury lamp (HMW-6-N type, manufactured by Oak Company)
Exposure was carried out at a distance of 50 Crn per second. For development, the polyester film was peeled off and an image was obtained by spraying with a 2% aqueous sodium carbonate solution at 30°C for 75 seconds at a spray pressure of 1.5 Kq/cIn2.

Table 2 shows the photosensitive characteristics of E-1 to E-4. or.

- Color difference ΔE was used as an imaging index.

ΔE is the difference in color density between the unexposed area and the exposed area, and ΔE
The larger the value, the better the imaging.Table 2 The results in Table 2 show that E-1 is superior to the other three photosensitive elements in terms of photosensitivity, imaging, and adhesion.

Claims (1)

[Claims] 1. (Al ethylenically unsaturated compound, (B) an initiator that generates free radicals by actinic rays, (C) a polymer that imparts film properties, (D) an organic...rogen compound, (E) A photosensitive resin composition containing a photochromic dye and a (Fl dye), in which (D) an organic compound is added to 100 parts by weight of a total of (A) an ethylenically unsaturated compound and a (Cl film property imparting polymer). 0.5 to 5 parts by weight of a rogen compound, 0.5 to 3.5 parts by weight of (E) a photochromic dye, and 0.01 part of fF) a dye.
A photosensitive resin composition containing ~0.05 part by weight. 2. The photosensitive resin composition according to claim 1, which contains tribromomethylphenylsulfone as the organic/logogen compound, leuco crystal violet as the photochromic dye, and malachite green as the dye.