JPH02311846A - Photosensitive resin composition and photosensitive laminate using the same - Google Patents

Abstract

PURPOSE:To improve plating resistance and aging stability by incorporating a specified carboxybenzotriazole deriv., a linear high molecular compd., an ethylenic unsatd. compd. and a sensitizer and/or a sensitizer system. CONSTITUTION:This photosensitive resin compsn. contains a carboxybenzotriazole deriv. represented by formula I, a linear high molecular compd. having 10,000-300,000 wt. average mol. wt., contg. 15-50mol% carboxyl groups and soluble or swellable in an alkaline aq. soln., an ethylenic unsatd. compd. having >=100 deg.C b.p. under ordinary pressure and a sensitizer and/or a sensitizer system capable of generating free radicals under active light. In the formula I, Y is H, etc., and Z is a group represented by formula II (where each of R1 and R2 is alkyl or aryl) or -O<->X<+> (X is an alkali metal atom). Improved plating resistance and improved aging stability at the time of laminating on a substrate are ensured.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a photosensitive resin composition, more specifically a photosensitive resin composition developable with an alkaline aqueous solution used for making printed circuit boards, and the composition. The present invention relates to a photosensitive laminate using.

[Conventional technology]

Photosensitive resin compositions are widely used as resists used in the manufacture of printed circuit boards2.Furthermore, photosensitive laminates (hereinafter referred to as photosensitive films) in which this photosensitive resin composition is laminated on a support layer are used. ) is widely used. Most of these photosensitive films are of the alkaline development type, in which the uncured portions are removed with an alkaline aqueous solution.

The method for using this photosensitive film is to laminate a photosensitive layer on a printed circuit board substrate that has been polished or treated with chemicals, then expose it to light through a desired negative mask, remove the support, and
A resist image is formed on the substrate by development using an alkaline aqueous solution such as a ~3% by weight aqueous sodium carbonate solution.

Etching or plating is performed using the image thus formed as a resist, and then the hardened resist is peeled off using an aqueous sodium hydroxide solution or the like. Furthermore, in the case of plating, etching is performed using water containing ammonia or the like to produce a printed circuit board.

[Problem to be solved by the invention]

In the above process, it is necessary to have sufficient adhesion to copper in the etching or plating process, and it is also desired to improve the stability after lamination on the copper-clad laminate (no development residue will be left even if it is applied after lamination). ing.

Japanese Patent Publication No. 50-9177 discloses benzotriazole, 2-aminobenzothiazole, etc. as compounds effective for improving the plating resistance of the photosensitive layer.
Alkaline-developable photosensitive films using these compounds not only do not have sufficient resistance to plating, but also leave trace amounts of organic matter in the form of a very thin film on the surface of the copper foil after development (as if the copper foil had turned red). ), the precipitation of the plating deteriorates, and development residues are likely to occur due to drying after lamination. This publication also discloses 5-carboxybenzotriazole, which improves oral stability but reduces plating resistance.

An object of the present invention is to provide an alkali-developable photosensitive resin composition having excellent plating resistance and oral stability, and a photosensitive film using the composition.

[Means to solve the problem]

As a result of intensive examination of the plating resistance and stability over time of these alkali-developable photosensitive resin compositions, we have found a composition that is significantly superior in plating resistance and oral stability, which have been problems in the past.

That is, the present invention provides (A) general formula (■): [wherein, Y
is a hydrogen atom or -GHz-N-RzR.

(In the formula, R1 and R2 each independently have 1 to 1 carbon atoms.
15 substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group), and Z is 1○eX■ (in the formula, R
and R2 have the same meanings as above, and X is an alkali metal atom) Carboxybenzotriazole derivative (B) having a weight average molecular weight of 10,000 to 300,000
(C) an ethylenically unsaturated compound having a boiling point of 100"C or more at normal pressure, and (D ) A photosensitive resin composition containing a sensitizer and/or a sensitizer system capable of generating free radicals by actinic radiation, and a photosensitive film obtained by coating and drying this photosensitive resin composition on a support. Regarding.

The photosensitive resin composition of the present invention contains a carboxybencitriazole derivative represented by the above general formula (I) as an essential component as component (A).

These compounds include 5-carboxy-1-[di(2'-ethylhexyl)] obtained by a condensate of 5-carboxybenzotriazole or 4-carboxybenzotriazole with formaldehyde and a secondary alkylamine.
Aminocomethyl-1,2,3-benzotriazole-di(2''-ethylhexyl)amine salt, ζ (CsH+Jz 5-carboxy-1-[di(2'-ethylhexyl)
Dehydration tank hardware for aminocomethyl-1,2,3-benzotriazole-di(2″-ethylhexyl) amine salt, 4-carboxy-1-[di(2′-ethylhexyl)
Aminocomethyl-1,2,3-benzotriazole-di(2″-ethylhexyl)amine salt, dehydration tank hardware for the salt, 5-carboxy-1-(diphenylamino)methyl-1
, 2,3-benzotriazole-diphenylamine salt,
Dehydration tank hardware for the salt, 5-carboxy-1-(ditolylamino)methyl-1,
2,3-benzotriazole-ditolylamine salt, dehydration tank hardware of the salt, 5-carboxy-1-[di(2'-hydroxylethyl)aminocomethyl-1,2,3-benzotriazole-di(2''-hydroxylethyl) ) Amine salt, dehydration tank hardware for the salt, 5-carboxy-1-[di(2'-ethylhexyl)
Examples include sodium aminotumethyl-1,2,3-benzotriazole. These can be used alone or in combination of two or more.

The amount of these components (A) used is based on the total amount of the linear polymer compound (B) component and the ethylenically unsaturated compound (C) component in the photosensitive resin composition being 100 parts by weight (hereinafter referred to as weight). 0.01 to 5 parts by weight, preferably 0.01 to 5 parts by weight.
If the amount is less than 1 part by weight, the effect will be small, and if it exceeds 5 parts by weight, properties such as releasability will tend to deteriorate.

The photosensitive resin composition of the present invention further contains a polymer compound that is soluble or swellable in an alkaline aqueous solution as component (B). Such a polymer compound has a weight average molecular weight of 1
O,000 to 300,000, and contains 15 to 50 mol% of carboxyl groups in the molecule. You may use a mixture of two or more types of linear polymers.

The polymer compound of component (B) is preferably a vinyl copolymer, and the copolymerizable monomers used for producing the vinyl copolymer include, for example, methyl methacrylate, butyl methacrylate, methacrylic acid 2- Ethylhexyl, lauryl methacrylate, methyl acrylate, ethyl acrylate, styrene, α-methylstyrene, vinyltoluene,
Examples include N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylonitrile, methacrylaterile, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, acrylic acid, and methacrylic acid. Further, styrene/maleic acid copolymer Hafestel and the like can also be used.

The amount of component (B) added is preferably 40 to 80 parts by weight when the total of components (B) and (C) is 100 parts by weight. If it is less than 40 parts by weight, developability may deteriorate or photosensitive This increases the flexibility of the resin composition layer, and when it is formed into a laminate, there is a tendency for seepage from the end faces, that is, edge fusion, etc. to occur.

Moreover, if it exceeds 80 parts by weight, the photosensitive layer tends to deteriorate.

The ethylenically unsaturated compound used as component (C) in the present invention has a boiling point of 100'C or more at normal pressure, and is, for example, a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid. , tetraethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethanetetraacrylate, polypropylene glycol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Hexaacrylate, etc. and corresponding methacrylate compounds, compounds obtained by adding α,β-unsaturated carboxylic acid to glycidyl group-containing compounds, such as trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate etc. and corresponding methacrylate compounds, esterified products of polyhydric carboxylic acids such as phthalic anhydride and substances having hydroxyl groups and ethylenically unsaturated groups such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, acrylic Acid or alkyl ester of methacrylic acid, such as methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, etc., are used, trimethylhexamethylene diisocyanate, dihydric alcohol, and monomer of dihydric alcohol and acrylic acid or methacrylic acid are used. Also used are urethane diacrylate compounds or dimethacrylate compounds obtained by reacting esters, adducts of bisphenol A1 alkylene glycol and acrylic acid or methacrylic acid, β-phenoxyethoxyethyl acrylate, and the like. These compounds may be used alone or in combination of two or more, and the amount added is the same as that of component (B) and component (C).
When the total amount of components is 100 parts by weight, it is preferably 20 to 60 parts by weight. If the amount is small, sufficient curability cannot be obtained, and if the amount is too large, edge fumes may occur.

Sensitizers and/or sensitizers that can generate free radicals when exposed to actinic rays
Or, as the sensitizer system (D), for example, benzophenone, 4,4'-bis(dimethylamino)benzophenone [
Michler's ketone], 4,4'-bis(diethylamino)
Benzophenone, dimethylaminobenzoic acid ethyl ester, diethylaminobenzoic acid ethyl ester, dimethylaminobenzoic acid butyl ester, dimethylaminobenzoic acid isoamyl ester, benzyl dimethyl ketal, 2
-chlorothioxanthone, 2,4-diethylthioxanthone, 2-propylthioxanthone and the like. The amount added is preferably 0.01 to 30 parts by weight from the viewpoint of photosensitivity.

The photosensitive resin composition of the present invention includes dyes such as Victoria Pure Blue, pigments, plasticizers, imaging agents such as leuco crystal violet/tribromomethylsulfone,
Stabilizers and the like may be added as necessary.

The photosensitive resin composition of the present invention can also be used as a photosensitive film by coating it on a support and drying it. As supports, polymer films are used, for example films of polyethylene terephthalate, polypropylene, polyethylene, preferably polyethylene terephthalate films, since these polymer films must be removable later from the photosensitive layer. The thickness of these polymer films, which must not be made of materials that cannot be removed or subjected to surface treatments, is usually 5 to 1100 tI, preferably 10 to 30 μm.

One of these polymer films may be laminated on both sides of the photosensitive layer as a support film for the photosensitive layer and as a protective film for the other photosensitive layer.

When producing a photosensitive film, first components (A) to (
A photosensitive resin composition containing D) is uniformly dissolved in a solvent.

The solvent may be any solvent that dissolves the photosensitive resin composition.
For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, dichloromethane, chloroform, methyl alcohol, ethyl alcohol, etc. are used. These solvents may be used alone or in combination of two or more.

Next, the photosensitive resin composition in the form of a solution is uniformly applied onto the polymer film as the support, and then the solvent is removed by heating and/or blowing hot air to form a dry film (
photosensitive layer). The thickness of the dry film is not particularly limited and is usually 10 to 100 μm, preferably 20 to 60 μm.

The photosensitive layer and polymer film thus obtained
The photosensitive film of the present invention consisting of layers can be stored as it is or by further laminating a protective film on the other side of the photosensitive layer and winding it up into a roll.

When producing a photoresist image using the photosensitive film of the present invention, if the protective film is present, after removing the protective film, the photosensitive layer is laminated by pressing onto the substrate while heating. . The surface to be laminated is usually a metal surface, but there is no particular restriction.The heating and pressure bonding of the photosensitive layer is usually 90 to 130°C and a pressure of 3K.
g/aJ, but these conditions are not particularly limited.

When using the photosensitive film of the present invention, it is not necessary to preheat the substrate if the photosensitive layer is heated as described above. Of course, in order to further improve the lamination properties, the substrate can be preheated.

The photosensitive layer thus laminated is then imagewise exposed to actinic light using a negative or positive film. At this time, if the polymer film as a support existing on the photosensitive layer is transparent, it may be exposed as it is; if it is opaque, it must be removed. From the viewpoint of protecting the photosensitive layer, it is preferable that the polymer film used as the support is transparent and that the polymer film is exposed through it while remaining. The active light is a known active light source, such as carbon arc, mercury vapor arc,
Light generated from a xenon arc, etc. is used. Since the sensitivity of the photoinitiator contained in the photosensitive layer is usually greatest in the ultraviolet region, in that case the active light source should be one that effectively emits ultraviolet light. Of course, when the photoinitiator is sensitive to visible light, such as 9.10-phenanthrenequinone, visible light is used as the active light, and the light source may be a photographic flood light in addition to the above. Light bulbs, solar lamps, etc. are also used.

After exposure, if there is a polymer film as a support on the photosensitive layer, it is removed and then treated with an alkaline aqueous solution using known methods such as spraying, oscillating dipping, brushing, scraping, etc. The unexposed areas are removed and developed using a method.

Bases for the alkaline aqueous solution include alkali hydroxides such as hydroxides of lithium, sodium or potassium; alkali carbonates such as carbonates or bicarbonates of lithium, sodium or potassium; alkali metals such as potassium phosphate, sodium phosphate; phosphate, sodium birophosphate,
Alkali metal pyrophosphates such as potassium birophosphate are used, and an aqueous solution of sodium carbonate is particularly preferred.

The pH of the alkaline aqueous solution used for development is preferably 9 to 9.
11, and the temperature is adjusted depending on the developability of the photosensitive layer. The alkaline aqueous solution contains a surfactant,
An antifoaming agent and a small amount of an organic solvent for accelerating development may be mixed.

Further, the printed wiring board can be manufactured by a known method, for example, by using a developed photoresist image as a mask, the exposed surface of the substrate is processed by a known method such as etching or plating, and then , photoresist images are usually removed with an aqueous solution that is more strongly alkaline than the aqueous alkaline solution used for development. As this strongly alkaline aqueous solution, for example, a 2 to 10% by weight aqueous sodium hydroxide solution is used.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples. "%" in the following means "% by weight" unless otherwise specified.

Example 1 Using the apparatus shown in FIG. 1, a solution (solution A) 6 of a photosensitive resin composition having the following composition was uniformly applied onto a polyethylene terephthalate film with a thickness of 25 μm.
The solvent was removed by drying in a hot air convection dryer 7 at °C for about 3 minutes. To explain the above in detail, the polyethylene terephthalate film fed out from the polyethylene terephthalate film feeding roll 1 includes rolls 2.3 and 4.
A solution 6 of the photosensitive resin composition is applied uniformly by a knife 5 and a hot air convection dryer 7.
After the solvent is removed there, the polyethylene film fed out from the polyethylene film feeding roll 8 is laminated by rolls 9 and 10 and wound onto a photosensitive film winding roll 11.

The thickness of the photosensitive layer of the thus obtained photosensitive film after drying was about 40 μm.

Wataruto Methacrylic acid/Methyl methacrylate/Butyl methacrylate/2-ethylhexyl acrylate = 23151/6/
20 (%) copolymer, weight average molecular weight approximately 80. OO
150 parts by weight of 40% ethyl cellosolve solution of O BPE-10 (trade name of methacrylate of ethylene oxide adduct of bisphenol A manufactured by Shin-Nakamura Chemical Co., Ltd.)
30 parts AMP60GC Shin-Nakamura Chemical Co., Ltd. Product name of acrylate of phenoxytetraethylene oxide) 10 parts by weight Diethylaminobenzophenone 0.1 parts by weight Benzophenone 5 parts by weight F-803
” 0.1 parts by weight Victoria Pure Blue 0.2 parts by weight Leuco Crystal Violet 1.0 parts by weight Tribromomethyl sulfone 1.0 parts by weight Methyl ethyl ketone
30 parts by weight *l: Manufactured by Fuji Kasei Trading ■, prototype name (5-carboxybenzotriazole:formaldehyde:di(2-ethylhexyl)amine-1:1:2)
(molar ratio) condensate, 5-carboxy-1-[di(2'-ethylhexyl)aminocomethyl-1°2.3
-benzotriazole-di(2″-ethylhexyl)
A polyethylene film having a thickness of 30 μm was then laminated as a protective film on the photosensitive layer using the apparatus shown in FIG. 1 to obtain a photosensitive laminate of the present invention.

Separately, there is a substrate for printed wiring boards (trade name: MCL-E-6 manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material with copper plates laminated on both sides.
The copper surface of 1) was polished with a cleanser, washed with water, and dried with a stream of air. The photosensitive film was produced on this substrate (23°C) using a Uminator (Model HLM-1500) manufactured by Hitachi Chemical Co., Ltd. at a lamination temperature of IIO°C and a lamination pressure of 3 kg/cm. Immediately after its manufacture, the photosensitive layer was pulled by hand, but the photosensitive layer adhered well to the substrate and did not peel off.

Next, using a negative film on the obtained sample, 3-
Exposure was carried out for 60 seconds to a high pressure mercury lamp from a distance of 900 m.

Development was carried out for about 60 seconds by spraying a 1% aqueous sodium carbonate solution at 30°C after removing the polyethylene terephthalate film, and good developability was shown.

Next, the following plating process was performed, but no plating was observed. Furthermore, after lamination, the relative humidity is 9 at 30°C.
Although it was stored in a 0% environment for 2 days and developed, there was no development residue, and the subsequent plating was good.

亙 ゆ う l 工 Ｇ (i) Degreasing PC-455 (degreasing agent, Meltex Company trademark), 30%
, 50°C, immersion for 5 minutes (b) Washing with water, room temperature, 60 seconds, 3 times (c) Soft etching Ammonium persulfate aqueous solution, 25 g/i, room temperature, 90
Second (d) Water washing: Room temperature, 60 seconds (e) Sulfuric acid immersion, 20% sulfuric acid, room temperature, 60 seconds (f) Copper sulfate plating Plating solution composition Copper sulfate 75 g/l sulfuric acid (98%
) 190g/l reagent hydrochloric acid (36%)
0.12cc/j! CoverGrim PC5cc/l! (Trademark manufactured by Japan Ronal Co., Ltd.) Pure water Total amount 11. The remaining current density for...
・2. OA/d Bo, room temperature, 60 minutes (g) Washing with water, room temperature, 60 seconds, 3 times (h) Soaking in sulfuric acid, 20% sulfuric acid, room temperature, 60 seconds (su) Washing with water, room temperature, 60 seconds (nu) Soaking in borohydrofluoric acid 20 % borofluoric acid, room temperature, 60 seconds (l) Solder plating Plating solution composition Boric acid 25 g/j! Hydroborofluoric acid 400g/Il Lead borofluoride
11.5g/l tin borofluoride
23.1g/j! peptone
5 g/j! Pure water Remaining current density for total litβ...1.5A/dITf, room temperature, 18
Minutes (e) Washing with water at room temperature, 60 seconds, 3 times Comparative Example 1 The same evaluation as in Example 1 was conducted for a composition in which 0.1 part by weight of 5-carboxybenzotriazole was added in place of F-803 in Example 1. As a result, significant plating deterioration occurred.

Comparative Example 2 The same evaluation as in Example 1 was performed for a composition in which 0.05 parts by weight of 1.2.3-benzotriazole was added instead of F-803 in Example 1. As a result, the plating resistance was good. However, significant residual development occurred after one day of oral administration.

〔Effect of the invention〕

As described above, the photosensitive resin composition of the present invention has good adhesion to a support, developability, and plating resistance, does not leave any residue after development, and has excellent oral stability during lamination of substrates.

Further, by using the photosensitive resin composition of the present invention, a photosensitive film with excellent characteristics can be provided.

[Brief explanation of the drawing]

FIG. 1 shows the photosensitive film feed roll used in the examples, 2.3.4.9.10... Roll, 5... Knife, 6... Solution of photosensitive resin composition, 7 ...Hot air convection dryer, 8.Polyethylene film feed roll, 11.
...Photosensitive film take-up roll 5 and -g =' 1...Polyethylene terephthalate film feeding roll 2.3, 4, 9.10...Roll 5...Knife 6...Photosensitive resin composition Solution of substances 7...Hot air convection dryer

Claims (1)

[Claims] 1. (A) General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, Y is a hydrogen atom or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Formula R_1 and R_2 each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group having 1 to 15 carbon atoms, and Z is ▲ mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
or -O^■X^■ (in the formula, R_1 and R_2 have the same meanings as above, and X is an alkali metal atom)]
A carboxybenzotriazole derivative represented by (B) a weight average molecular weight of 10,000 to 300,000
(C) an ethylenically unsaturated compound having a boiling point of 100°C or higher at normal pressure; A photosensitive resin composition comprising a sensitizer and/or a sensitizer system capable of generating free radicals upon radiation. 2. The photosensitive resin composition according to claim 1, containing (B) 40 to 80 parts by weight of the polymer compound and 20 to 60 parts by weight of the ethylenically unsaturated compound in a total amount of 100 parts by weight. 3. The photosensitive resin composition according to claim 1 or 2, wherein in the general formula (I), Z is ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼. 4. A photosensitive laminate obtained by coating and drying the photosensitive resin composition according to claim 1, 2 or 3 on a support.