JPS60240715A - Photosensitive resin composition and photosensitive resin composition laminate - Google Patents

Abstract

PURPOSE:The titled composition excellent in plating resistance, etchant resistance, chemical resistance, laminatability with a base, developability, etc., comprising at least two specified addition-polymerizable substances, a photopolymerization initiator, a linear copolymer, etc. CONSTITUTION:A mixture is formed by mixing 30-60pts.wt. (A) total of 25- 35pts.wt. addition-polymerizable substance of formula I (wherein R1-4 are each H or CH3, and n+m=8-12) and 5-15pts.wt. addition-polymerizable substance of formula II with 0-30pts.wt. (B) addition-polymerizable substance other than the above, 0.5-10pts.wt. (C) photopolymerization initiator, 40-70pts.wt. (D) linear copolymer of a COOH content of 17-50mol%, a water absorption of 4- 30wt% and a weight-average MW of 30,000-400,000 obtained by copolymerizing a carboxylic acid (anhydride) containing one unsaturated group (e.g., acrylic acid) with a monomer having one unsaturated group and an MW<=300 (e.g., alkyl acrylate), and optionally (E) a radical-polymerization inhibitor and a colorant.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a photosensitive resin composition and a photosensitive resin composition laminate, and more particularly to a photosensitive resin composition and a photosensitive resin that can be developed with an alkaline aqueous solution. The present invention relates to a composition laminate.

(Prior Art) Photoresists formed from photosensitive resin compositions are used, for example, in manufacturing printed wiring boards. Conventionally, these photosensitive resin compositions contain a solvent in a printed wiring board substrate (hereinafter simply referred to as a substrate). is removed to form a dry film, which is then imagewise exposed to actinic light and developed to form a photoresist image.

However, in recent years, flexible three-layer laminates have been developed to improve their low workability, air pollution, and low yield.

That is, a photosensitive resin composition laminate (hereinafter simply referred to as a photosensitive film) consisting of a support film layer, a dried photosensitive resin composition layer (hereinafter simply referred to as a photosensitive layer), and a protective film layer is used. It has become. As a photosensitive resin composition, the unexposed areas are removed (developed) with an alkaline aqueous solution and an alkaline developing type and an organic solvent are used.
Both solvent-developed types are known.

The method for using an alkali-developable photosensitive film is to remove the protective film layer from the photosensitive film to form a laminate consisting of two layers, a photosensitive layer and a supporting film layer, and then heat and press (laminate) the photosensitive layer so that it is in contact with the substrate. do. After imagewise exposure using a negative film or the like, unexposed areas are removed (developed) using an alkaline aqueous solution to form a j-photoresist image. Using this formed photoresist image as a mask, the metal surface of the substrate is processed by etching or plating, and then the photoresist image is peeled off using a developer or a strongly alkaline aqueous solution.
Printed wiring boards, etc. are manufactured.

It goes without saying that the photoresist image must have sufficient resistance as a mask against the etching or plating treatment of the metal surface of the substrate during the above steps. The etching process is a process of removing metal (usually porcelain) forming the surface layer of the substrate using an aqueous solution of ferric chloride, cupric chloride, ammonium persulfate, or the like.

There are many types of plating solutions used for plating, but in the case of alkaline-developable photosensitive film.

The plating solution used is usually an acidic plating solution.

The metal surfaces not masked by the photoresist image are plated using solder plating or a combination of copper sulfate plating and solder plating.

Since plating involves passing an electric current through a highly concentrated chemical solution, it can be said to be a much more severe process than etching.

This type of alkali-developable photosensitive film was developed in Japanese Patent Application Laid-open No. 52
-94388 Publication 9% Publication No. 130701/1982, * Publication No. 128688/1982, Japanese Patent Application Publication No. 1977-14
It is disclosed in Publication No. 7323 and the like. However, the photoresist images obtained from these conventional alkali-developable photosensitive films have a drawback in that they do not have sufficient electroplating resistance. That is, it can withstand electroplating with a copper sulfate plating solution and a solder plating solution with a low concentration of fluoroboric acid, but it is resistant to a general solder plating solution with a concentration of fluoroboric acid exceeding 3509/L. In such solder plating, the resist film peels off, lifts up,
Solder plating stains (development in which solder plating precipitates under the resist) occur. In the case of the most common solder plating solution, the concentration of borofluoric acid is asog, 'z
It is used in the range of ~500 g/l, and it is said that within this range, the liquid for obtaining eutectic solder with dense particles can be stably managed.

As a result of intensive research to improve these conventional problems, we have found that it has excellent plating resistance, etching liquid resistance, chemical resistance, and other characteristics of alkaline-developable photosensitive films ( For example, the inventors have found a photosensitive resin composition that satisfies the requirements (for example, lamination properties with a substrate and developability), leading to the present invention.

(Objective of the Invention) The present invention provides a novel photosensitive resin composition, which has excellent plating resistance, and also has good etching liquid resistance, chemical resistance, and laminability with substrates.

An object of the present invention is to provide an alkali-developable photosensitive film having good developability.

(Structure of the Invention) That is, 1 the present invention provides (al) an addition polymerizable substance represented by the following formula [I] (wherein R1, R2, Rs and 'Ra HAH'! ucHs)
D.

These may be the same or different (, n and m are n
(10m is a positive integer such that B to 12) (bl is an additional polymerizable substance represented by the following formula (II) (in the formula, R1, & , Rs and CF R4tj: H1fc
HACHs tea 夛.

These may be the same or different) (C) Photopolymerization initiator (dl Carboxyl group content is 17 to 50 mol.

A photosensitive resin composition containing a linear copolymer having a water absorption rate of 4 to 30% by weight and an average weight of 30,000 to 400,000, and at least -10,000 of the photosensitive resin composition layer. In the photosensitive resin composition laminate formed by laminating a film support on the surface of the photosensitive resin composition layer.

(a) Additive polymerizable substance represented by the following formula (I) 0 (e
HcH2U import CU=toth 1 (& , R2, R4 and R4 are H or CHs.

These may be the same or different, and n and m are n
tbl is an addition polymerizable substance represented by the following formula (If) (wherein R1, R2, R3 and R4 are H or CH3;

These may be the same or different) (C) Photopolymerization initiator (d) Carboxyl group content is 17 to 50 mol.

Water absorption rate is 4 to 30 weight tS, weight average molecular weight is 30,000 to 40
The present invention relates to a photosensitive resin composition laminate, which is a photosensitive resin composition layer containing a linear copolymer of 10,000 yen.

The photosensitive resin composition in the present invention contains an addition polymerizable substance represented by formula 2 (1).

Examples of the addition polymerizable substance represented by formula [I] include λ2bis(4-methacryloxypentaethoxyphenyl)propane, 2.2bis(4-acryloxypentaethoxyphenyl)propane, and 2.2bis(4-methacryloxyphenyl)propane. Examples of commercially available products include BPE-10 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

The addition polymerizable substance represented by formula (1) may be used as a single compound, or may be used as a mixture of two or more compounds. When n-1-m is 7 or less, the compatibility with the carboxyl group-containing linear copolymer decreases, and when a photosensitive film is laminated onto a substrate, it is likely to peel off. Also n
-) When -m is 13 or more, the hydrophilicity of the system increases, the resist image tends to peel off during development, and the solder plating resistance also decreases. The compound represented by formula [II') is
It is easily produced by an addition reaction between 2,6-toluene diisocyanate or 2,4-4-toluene diisocyanate and an acrylic or methacrylic monomer having an OH group at the β position. Examples of the above-mentioned acrylic monomers or methacrylic monomers having an OH group at the β-position include:
β-hydroxyethyl acrylate.

Examples include β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, and β-hydroxypropyl methacrylate. This addition reaction is 1
For example 2.6-) luene diisocyanate, 2.4-
20 to 2.2 moles of the above acrylic monomer or methacrylic monomer are placed in a solvent per mole of toluene diisocyanate or a mixture thereof.

Adding 0.05 to 0.5% by weight of dibutyltin silaurylate or zinc acetate as an addition catalyst to the monomer,
The process is carried out at room temperature to 60°C for 8 to 12 hours while blowing air. For example, toluene is used as a solvent.

Methyl ethyl ketone or the like is used, and the amount thereof can be appropriately selected. The compound represented by the formula (nll) may be used as a mixture.
It may also contain an addition polymerizable substance other than the addition polymerizable substance represented by the formula [■]. The addition-polymerizable substances other than the addition-polymerizable substances shown in the formula [former] may be liquid addition-polymerizable substances having at least one terminal ethylenically unsaturated group; examples thereof include polyvalent polymerizable substances. Products obtained by adding α,β-unsaturated carboxylic acid to alcohol 9 For example, tetraethylene glycol di(meth)acrylate (indicates acrylate or methacrylate).

The same applies hereinafter), polyethylene glycol di(meth)acrylate (those having 2 to 14 ethylene groups), 1 trimethylolpropane di(meth)acrylate.

Trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetrametholmethanetetra(meth)acrylate, polypropylene glycol di(meth)acrylate (with 2 to 14 propylene groups), dipenta Erythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, compound with n 10 m: 2 to 7 in addition polymerizable substance represented by formula [■], α,β-unsaturated carpon in glycidyl group-containing compound Products obtained by adding acids 9 For example, trimethylolbrono(triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, etc.), polyhydric carboxylic acids 9 For example, phthalic anhydride, etc. and hydroxyl groups and ethylenically unsaturated groups substance that has

For example, there are esterified products with β-human, roxyethyl (meth)acrylate, and the like.

The total amount of the addition polymerizable substance represented by formula (1) and formula [■] and other addition polymerizable substances is preferably 30 to 60 parts by weight, more preferably 40 parts by weight.
~50 parts by weight. If the amount is less than 30 parts by weight, the photosensitive layer will have poor flexibility and will easily peel off from the substrate during lamination. If the amount is more than 60 parts by weight, the photosensitive layer will soften and cause cold flow while being wound up into a roll and stored.

When the addition polymerizable substance is 30 to 60 parts by weight, the formula [!
] It is preferable that the amount of the addition polymerizable substance is in the range of 25 to 35 parts by weight. Copper sulfate plating resistance when the content is within the range of 25 to 35 parts by weight.

If the solder plating resistance is sufficient, the resolution and adhesion of the resist image will be high.

The amount of the addition polymerizable substance represented by formula (II) is 5 to 15
The range is preferably 7 parts by weight, more preferably 7 parts by weight.
-13 parts by weight. When the amount is in the range of 5 to 15 parts by weight, the resolution, especially the adhesion of the resist image during and after development, photosensitivity, developability, and plating resistance become high. The photopolymerization initiator contained in the photosensitive layer in the present invention is a substance that is not thermally activated at a temperature of 200° C. or lower, but a substance that is activated by actinic light 1, such as ultraviolet rays, is recommended. These substances include substituted or unsubstituted polynuclear quinones9, such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone,
2.3-Benzanthraquinone, 2-phenylanthraquinone, 2゜3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, II4-naphthaquinone, 9.10
-7 enanthraquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 3-chloro-2
- Examples include methylanthraquinone. Other aromatic ketones, such as benzophenone, Michler's ketone [4,
4'-bis(dimethylamino)benzophenone), 4.
Examples include 4'-bis(diethylamine)benzophenone and 4-methoxy-4'-dimethylaminopenzophenone. Also benzoin.

Benzine ethers such as benzoin methyl ether, benzoin ethyl ether, penzoin phenyl ether, methylbenzoin, ethylbenzoin, and the like. Furthermore, combinations of the 2.4.5-triarylimidazole dimer and 2-mercaptobenzoxazole, leuco crystal violet, tris(4-diethylamine-2-methylphenyl)methane, etc. can also be used.

What is the amount of photopolymerization initiator in the photosensitive resin composition?

0.5 to 10.01 parts is preferable, more preferably 1 part
．． It is 0 to 5.0 parts by weight. When the amount is less than 0.5 parts by weight, it is used when curing the photosensitive layer by irradiating it with actinic rays.

Curing does not proceed sufficiently, producing a photoresist with poor resistance. If it is more than 10.0 parts by weight.

This is because the sensitivity of the photosensitive layer to actinic rays is too high.

This results in drawbacks such as decreased resolution and decreased stability.

In the present invention, the carboxyl group content is 17 to 50
Molch, water absorption rate is 40-30% by weight.

It is necessary that a linear copolymer having a weight average molecular weight of 30,000 to 400,000 be present. The general characteristics of the photoresist image in the present invention, such as excellent resistance to electroplating and resistance to plating pretreatment liquids, as well as adhesion with the substrate and developability, are due to the combination of the addition polymerizable substance and the linear copolymer. It can be achieved by both parties.

Linear copolymers are obtained by polymerizing two or more types of monomers, and the monomers are broadly classified into two types. The first monomer imparts developability to the linear copolymer and is a carboxylic acid having one unsaturated group or an acid anhydride.

For example, acrylic acid, methacrylic acid, fumaric acid.

Cinnamic acid, propiolic acid, itaconic acid, maleic acid,
Maleic anhydride, maleic acid half ester, etc. are used. The second monomer to be used is selected so that the photoresist image retains plating resistance, etching resistance, developer resistance, flexibility, and plasticity.

As the second monomer, one having one unsaturated group is used, and the solubility of water in the monomer at 20°C is preferably 2% by weight or less, but 2% by weight. There is no problem even if a small amount of a hydrophilic monomer exceeding . The molecular weight of the second monomer is preferably 300 or less; if a monomer with a larger molecular weight is used, developability will be impaired.

Examples of second monomers include alkyl acrylates or alkyl methacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate. ; Nine examples of esters of vinyl alcohol include vinyl-o-butyl ether; polymerizable styrene derivatives or styrene substituted at the α-position or the aromatic ring; A preferable monomer among the above-mentioned first monomers is acrylic acid or methacrylic acid, and a preferable monomer among the second monomers is alkyl acrylate t or alkyl methacrylate.

The linear copolymer in the present invention is obtained by copolymerizing the above-mentioned first monomer and second monomer. The carboxyl group content of the linear copolymer of the first and second monomers is from 17 to
It is selected so that the water absorption rate is 4 to 30% by weight at 50%. The water absorption rate in this case is based on the standards shown in JIS K 6911, ie, diameter 50±1mm, thickness 3±0.
It is expressed as the weight increase rate when a 2 mm sample is immersed in water at 23°C for 24 hours. The carboxyl group content herein refers to the percentage (mole ratio) of the number of moles of the first monomer to the number of moles of all monomers used in the linear copolymer.

The resistance of the above-mentioned linear copolymer to various processing solutions is not determined uniquely by either its carboxyl group content or its water absorption rate (hydrophilicity), but by both of them, and each of them is determined by the above-mentioned properties. Must be within range. If the carboxyl group content is defined as only 17-50 moles, then if the second monomer is chosen an extremely hydrophobic monomer.

If the water absorption rate of the linear copolymer is less than 4 cm,
Even if the carboxyl group content is within the range of 17 to 50 moles, development becomes difficult.

On the other hand, even if the carboxyl group content is 17 to 50 moles, if the water absorption rate exceeds the upper limit of the above range, the developability of the unexposed areas is greatly promoted, but the exposed areas are hydrophilic. Beyond the limits of the photoresist image, its edges (
The boundary between the exposed area and the unexposed area is most severely attacked by the developer, resulting in poor image sharpness and reduced resolution.As a result, the apparent sensitivity also decreases, and furthermore, the resistance to plating and etching solutions decreases. decreases and development such as peeling occurs.

Similarly, the content of carboxyl groups is important as a determinant of developability. Even if the water absorption rate is within the above range, development cannot be carried out if the carboxyl group content is less than 17 moles. On the other hand, if the carboxyl group content exceeds the upper limit of the above-mentioned range, even if the water absorption rate is within the above-mentioned range, the surface gloss of the resist image will be lost and the resistance will be reduced.

The molecular weight of the linear copolymer is a factor that imparts film-forming properties and secondarily determines developability and resistance to processing solutions. The range of this molecular weight must be 30,000 to 400,000 in weight average molecular weight, preferably 50,000 to 200,000.
Ten thousand. If it is less than this range, film forming properties will be impaired and resistance to processing solutions including developing solutions will be reduced.

If it exceeds this range, the film forming properties and resistance will be very good, but the developability will deteriorate.

The amount of linear copolymer contained in the photosensitive resin composition is 4
It is preferably 0 to 70 parts by weight, more preferably 50 to 60 parts by weight.
This is the heavy electrical department. If the amount is less than 40 parts by weight, the photosensitive layer will be softened and cold-two will occur during storage. Also, 70
If the amount is higher than the weight part, the photosensitive layer becomes brittle and easily peels off during lamination. Generally, in order to prevent thermal polymerization during the heating process and during storage, it is preferable that the photosensitive layer contains a radical polymerization inhibitor.

Such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine, and pyridine.

Nitrobenzene, dinitrobenzene, p-torquinone, chloranil, arylphosphite, etc. are used, but it is preferable that they have low volatility at 200°C or less, such as alkyl-substituted hydroquinone, tc
rt-butylcatechol, cuprous chloride, slojite
rt-butyl p-cresol, 2,2-methylenebis(
4-ethyl-6-t-butylphenol), 2,2-methylenebis(2-methyl-6-t-butylphenol)
etc.

The photosensitive resin composition described above may contain coloring substances such as dyes and pigments. The colored substance is preferably one that does not affect the properties of the photoresist and does not decompose or volatilize at temperatures below 200°C. Coloring agents that can be used include, for example, fuchsin, auramine base, calcocytogreen S, bala madienta, crystal violet, methylnare di, Nile blue 2B, and picto 11 a blue.

Malachite green, Paythic blue 20. Examples include Iosing Green, Night Green B,) Livarosan, New Magenta, Acid Violet fLRJH, Red Violet 5R8, and New Methylene Blue GG.

Additives such as star-forming agents and adhesion promoters may be added to the photosensitive layer of the photosensitive film.

A film-like support is laminated on at least one surface of the photosensitive layer. Use it as a film-like support.

For example, films made of polyethylene terephthalate, polypropylene, and polyethylene are preferably 1) polyethylene terephthalate films.

Since these must be removable later from the photosensitive layer, they must not be made of materials or subjected to surface treatments that would make their removal impossible. The thickness of these films is suitably 5 to 100 μm, preferably 10 to 3 μm.
It is 0 μm. Further, one of these films may be laminated on both sides of the photosensitive layer, with one serving as a support film for the photosensitive layer and the other serving as a protective film for the photosensitive layer.

To prepare a photosensitive resin composition laminate, that is, a photosensitive film, first, the photosensitive resin composition is uniformly dissolved in a solvent. Any solvent may be used as long as it dissolves the photosensitive resin composition, and one or more types of solvents may be used. Examples of the solvent include acetone, methyl ethyl ketone, methyl imbutyl ketone, methyl cellosolve, ethyl cellosolve, dichloromethane, chloroform, and methyl alcohol.

Common solvents such as ethyl alcohol are used.

Next, the photosensitive resin composition in the form of a solution is uniformly applied onto the film support as the support film layer described above, and then the solvent is removed by heating and/or blowing hot air to form a dry film. The thickness of the dried film is a normal thickness, and there is no particular restriction, and the thickness is 10~. 100 μm is appropriate;
Preferably it is 20 to 60 μm.

A photosensitive film consisting of two layers, a photosensitive layer and a film-like support, is stored as it is or after a protective film is further laminated on the other side of the photosensitive layer and wound into a roll.

In the production of photoresist images, the protective film, if present, is removed and then laminated by pressing the photosensitive layer against the substrate while heating. The surface to be laminated is usually preferably a metal surface, but is not particularly limited. Heating of the substrate is not necessary depending on the temperature at which the photosensitive layer is heated (laminate temperature).

Of course, heating may be performed to further improve lamination properties.

The laminated photosensitive layer is then imagewise exposed to actinic light using a negative or positive film. At that time, if the polymer film present on the photosensitive layer is transparent, it may be exposed as is. If it is opaque, it will of course need to be removed. From the viewpoint of protecting the photosensitive layer, it is preferable that the polymer film is transparent and that the exposure is carried out through it while the polymer film remains.

As the active light, light generated from a known active light source 1 such as a carbon arc, mercury vapor arc, xenon arc, etc. is used. The sensitivity of the photoinitiator contained in the photosensitive layer is 1
It is usually maximum in the ultraviolet region, so in that case,
The active light source should effectively emit ultraviolet light. Of course, if the photoinitiator is sensitive to visible light or rays, such as 9.10-phenanthrenequinone, then visible light is used as the active light, and the light source may be one of those mentioned above, Photographic flood light bulbs, solar lamps, etc. are also used. After exposure, if a film support is present on the photosensitive layer, it is removed and treated with an alkaline aqueous solution using known methods 9, such as spraying, oscillating dipping, brushing, scraping, etc. Develop by removing the unexposed areas. As a base for alkaline aqueous solutions.

Alkali hydroxides, i.e. hydroxides of lithium, sodium and potassium; alkali carbonates, i.e.

Lithium, sodium and potassium carbonates and bicarbonates; alkali metal phosphates 2 e.g.

Potassium phosphate or sodium phosphate; Alkali metal birophosphate 9 For example, sodium pyrophosphate or potassium birophosphate can be exemplified, and an aqueous solution of sodium carbonate is particularly preferred. What is the pH of the 0.5 to 3 weight alkaline aqueous solution used for development?

The temperature is preferably between 9 and 12, and the temperature can be adjusted depending on the developability of the photosensitive layer. A small amount of a surfactant, an antifoaming agent, or a small amount of an organic solvent for accelerating development may be mixed into the alkaline aqueous solution.

Furthermore, in the manufacture of printed wiring boards, the developed photoresist image is used as a mask to etch or plate the exposed surface of the board.

Process using known methods. Thereafter, the photoresist image is usually peeled off using an aqueous alkaline solution used for development and a strongly alkaline aqueous solution, but there are no particular restrictions on this. As a strong alkaline aqueous solution, 1, for example, 2
~10% by weight of sodium hydroxide or the like is used.

(Examples) The present invention will be explained in more detail with reference to the following examples. Here, CH indicates weight %.

Example 1 [Synthesis of addition polymerizable substance] Mixture 3 of 2.6-1 luene/diisocyanate and 2.4-) luene diisocyanate 80:20 (weight ratio)
209 ('2.0 mol), β-hydroxyethyl methacrylate 5469 (4.2 mol) and toluene 1000
9 to 21! , into a flask, and then add 2.69 g of zinc acetate.
(0.3% by weight based on the monomer) was added and stirred at 60° C. for 12 hours while blowing 7 min of air into the mixture to prevent polymerization, to obtain reaction product 9 (46.4 liters of toluene solution). When the NCO group was quantified by a conventional method, N0
The zero value was 0. The structure of the reaction product is shown in formula CII).

[Preparation of photosensitive film]

Solution A and solution A' were uniformly applied onto a 25 μm thick polyethylene terephthalate film.

It was dried for about 3 minutes in a hot air convection dryer at 100°C.

The dry thickness of the photosensitive layer was approximately 25 μm. A polyethylene film was pasted as a protective film on the photosensitive layer (on the surface not in contact with the polyethylene terephthalate film). The photosensitive film (referred to as FA) obtained from solution A is:

Examples of the present invention are shown, and a photosensitive film (referred to as FA') obtained from solution X is a comparative example (the additive polymerizable substance is different from that of the present invention).

Solution A, 1 0-phthalate 2-ethyl anthraquinone 2.5 g Victoria Pier Blue 0.099 Ethyl cellosolve 130 g Methyl ethyl ketone 109 Chloroform 109 H3 (where n and m are positive integers such that n+m=1Q) Solution A' and thinning 2-ethylanthraquinone 2.5 g Victoria Pier Blue 0.099 Ethyl cellosolve 130 g Methyl ethyl ketone 109 Chloroform 109 A substrate made of glass epoxy material with copper foil (thickness 35 μm) laminated on both sides (Hitachi Chemical Co., Ltd. Manufactured by MCL, trademark
The copper surface of -E-61) was polished with 800-grit sandpaper, washed with water, and dried with a stream of air. Next, the substrate was
℃, and the polyethylene film was removed from the copper surface of the photosensitive film F A ! : F A' to 160
Each while heating to ℃.

Laminated on separate boards. Both samples had good adhesion between the photosensitive layer and the substrate. Using negative film on these substrates, 50C for 10 seconds with a 3KW high pressure mercury lamp (manufactured by Oak Seisakusho, trademark Phoenix-3000).
Exposure was performed at a distance of m. Development was accomplished in about 45 seconds for both samples by spraying a 2% aqueous solution of sodium carbonate at 30° C. after removing the polyethylene terephthalate film, showing good developability. Furthermore, the photoresist images obtained from both photosensitive films have good resolution, capable of resolving line widths up to 80 μm, and are also compatible with ferric chloride aqueous solution, cupric chloride aqueous solution, ammonium persulfate aqueous solution, etc. It had sufficient resistance to ordinary etching solutions.

In the plating process shown in Table 1, although the photoresist image obtained from the photosensitive film FA had sufficient resistance, the photoresist image obtained from the photosensitive film FA' had poor resistance and soldered. After plating, the resist film peeled off.

Margin below Table 1 Plating process Example 2 Using the same method as in Example 1 from solution B and solution B'.

Photosensitive film FB (film thickness of photosensitive layer obtained from solution B: 25 μm) and photosensitive film FB' (solution B'
A photosensitive layer having a thickness of 25 μm was prepared. Photosensitive film FB shows an example of the present invention, and photosensitive film FB' shows a comparative example (different polymerizable substance from the present invention).

Solution B Benzophenone 2.5 g Victoria Pier Blue 0.149 Ethyl Cellosolve 130 g Methyl Ethyl Ketone 109 Chloroform 109 Solution B' Benzophenone 2.5 g 4.4'-Bis(diethylamino)pen 0.69 Siphenon Victoria Pier Blue 0.14 g Ethyl Cellosolve 130 g Methyl ethyl ketone 109 Chloroform 109 The obtained photosensitive films FB and FB' were laminated, exposed and developed in the same manner as in Example 1.

When comparing the adhesion to the substrate, the photosensitive film FB was good, but the photosensitive film FB' was poor.

It came off. Next, resistance to an etching solution as shown in Example 1 was investigated, and it was found that the resist image formed from the photosensitive film FB had sufficient resistance, but the resist image formed from the photosensitive film FB' The resulting resist image showed partially low peel resistance. Furthermore, plating resistance was investigated in the plating process shown in Table 1 in Example 1, and the resist image formed from the photosensitive film F'B had sufficient resistance. Most of the resist images formed thereon had no peeling resistance at all.

Example 3 A photosensitive film PC (obtained from solution C) and a photosensitive film FC' (obtained from solution C') were prepared in the same manner as in Example 1 using solutions C and d. Photosensitive film FC shows an example of the present invention, and photosensitive film PC' shows a comparative example (below the lower limit of the carboxyl group content range of the linear copolymer in the present invention). The thickness of the photosensitive film FC and the pρ' layer was in the range of 23 to 26 μm, respectively.

Solution C Benzophenone 2.59 Victoria Pier Blue 0.149 Ethyl Cellosolve 1309 Methyl Ethyl Ketone - All the same except that β-hydroxyglobil methacrylate 6069 (4.2 mol) was used in place of hydroxyethyl methacrylate 5469] The same procedure as in Example 1 was carried out, including exposure. The adhesion to the substrate was the same for both photosensitive films PC and PC'. Development was also carried out in the same manner as in Example 1, by spraying two times a 30°C aqueous sodium carbonate solution after removing the polyethylene terephthalate film.
Development was achieved in about 40 seconds, showing good developability.

However, on the other hand, FC' was not developed even after being sprayed for 180 seconds.

Developability was poor. The substrate with the resist image formed by FC was further tested for etching liquid resistance and plating resistance in the same manner as in Example 1, and was found to have sufficient resistance.

(Effects of the Invention) As described above in detail in the Examples, the photosensitive film obtained using the photosensitive resin composition of the present invention has excellent plating resistance and also has excellent plating resistance. Other properties such as stickiness and developability are also excellent.

Claims (1)

[Claims] 1. (al) An addition polymerizable substance represented by the following formula (1) (
In the formula, R1, R2, R3 and R4 are H or CH3. These may be the same or different <+” and m is n
-1-m is a positive integer of 8 to 12) (bl is an addition polymerizable substance represented by the following formula [■] (in the formula, R1, 几2.R3 and R4 are Hl or CH3te) #) These may be the same or different) (C) Photopolymerization initiator (d) Carboxyl group content is 17 to 50 mole, water absorption rate is 4 to 30% by weight, 9% by weight A photosensitive resin composition containing an average of 30,000 to 400,000 linear copolymers. 2. The total amount of the addition polymerizable substance is 30 to 60 parts by weight, and the addition polymerizable substance represented by formula [I] is 25 to 35 parts by weight.
5 to 1 part by weight of the addition polymerizable substance represented by formula [111]
5 parts by weight 9 0 to 30 parts by weight of an addition polymerizable substance other than the addition polymerizable substance shown by formula (1) and the addition polymerizable substance shown by formula [11], and 0.5 to 10 parts by weight of a photopolymerization initiator. .0
The photosensitive resin composition according to claim 1, which contains 40 to 70 parts by weight of the linear copolymer. 3. The photosensitive resin composition according to claim 1 or 2, which contains a radical polymerization inhibitor and a coloring substance. 4. A photosensitive resin composition laminate comprising a film-like support laminated on at least one surface of the photosensitive resin composition layer. (al) Addition polymerizable substance represented by the following formula (1) (wherein R1, R2, Rs and R4 are H or CHs. These may be the same or different<+" and m is n
-1-m = a positive integer of 8 to 12) (b) An addition polymerizable substance represented by the following formula (II) (wherein R1, R2, Ra and R4 are H or CHs) These may be the same or different) (C1 photopolymerization initiator (d) Carboxyl group content is 17 to 50 mol, water absorption is 4 to 30% by weight, weight %9 is weight average is 3 A photosensitive resin composition laminate, which is a photosensitive resin composition layer containing a linear copolymer of 30,000 to 400,000.5.
~60 parts by weight, of which 25 to 35 parts by weight of the addition polymerizable substance represented by formula [■] and 5 to 15 parts by weight of the addition polymerizable substance represented by formula (II). The addition polymerizable substance other than the addition polymerizable substance represented by formula (1) and the addition polymerizable substance represented by formula [U] is 0 to 3
0 parts by weight, 0.5 to 10.0 parts by weight of a photopolymerization initiator, and 40 to 70 parts by weight of a linear copolymer. resin composition laminate. 6. The photosensitive resin composition laminate according to claim 4 or 5, which contains a radical polymerization inhibitor and a coloring substance in the photosensitive resin composition layer.