TWI400275B - Printed wiring board and manufacturing method thereof - Google Patents

Description

Printed wiring board and method of manufacturing same

The present invention relates to a printed wiring board comprising a protective layer formed of a photosensitive oxyalkylene polyimine resin composition.

An aromatic polyimine resin obtained by ruthenium imidation of an aromatic tetracarboxylic acid and an aromatic diamine is widely used as an interlayer insulating film and a coating layer for electronic parts because of its excellent heat resistance and insulation properties. The material, but for such an aromatic polyimide resin, it is required to have excellent flexibility and adhesion. Therefore, the use of a nonoxyalkylene polyimine resin in which a part of an aromatic diamine is replaced with a nonoxyl diamine and a polyoxyalkylene skeleton is introduced into a polyamidene skeleton is expanding.

However, the rhodium oxane diamine which is a raw material of the decyl alkoxyimine resin contains a cyclic dimethyl methoxy olefin oligomer which does not have an amine group as an impurity, and thus the produced oxirane When the polyimine resin is used as an interlayer insulating film or a cover layer and applied to an electronic component, if the electronic component is put into a heat treatment step such as a reflow step, there is a problem that the interlayer-to-line insulating film is interposed. Or the surface of the cover layer may again adhere or ooze the cyclic dimethyl methoxy olefin oligomer generated as a gas, thereby causing contact failure or decrease in conductivity in the electronic component, followed by decrease in strength and the like. In addition, the term "bleed out" in the present specification means a phenomenon in which a substance contained in a solid layer such as a film moves to a surface of a solid layer, liquefies or solidifies thereon, or volatilizes and diffuses.

In order to solve the problem, a method has been proposed in which a diamine compound containing at least a di-cavity polyoxyalkylene as a diamine component and a tetracarboxylic dianhydride are subjected to a ruthenium imidization reaction in a toluene or an ether solvent. For example, the solvent which is volatilized is discharged to the outside of the system several times, and the solvent is replenished (Patent Document 1). According to this method, the cyclic dimethyl methoxy olefin oligomer has a lower boiling point than the solvent, and thus is discharged to the outside of the system together with the solvent to be volatilized, thereby obtaining a cyclic dimethyl siloxane oligo. The concentration of the substance is reduced by the oxirane polyamine varnish.

Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2004-263058

However, in the method of Patent Document 1, since the volatilized solvent is discharged outside the system under normal pressure, the dimethyl methoxy olefin oligomer to the hexamer can be removed to a considerable extent, but the problem is that The hexamethoxane oligomer above the heptamer is sufficiently removed. Therefore, the problem is that when the oxime phthalimide varnish obtained by the method of Patent Document 1 is mixed with a sensitizer to impart photosensitivity, a decane coupling agent widely used as a crosslinking agent for polyimine is blended. In the case of epoxyamine, solid epoxy resin, etc., it is still difficult to suppress the impurity, that is, the cyclic dimethyl methoxy olefin oligomer, from forming the obtained photosensitive oxirane polyimine resin composition into a printed wiring. The thin protective layer (plating protective layer or solder protective layer) which is obtained by hardening and hardening on the board is oozing out.

Further, the printed wiring board having the protective layer formed of the photosensitive siloxane oxide polyimide composition is grown in a copper or copper alloy wiring pattern region (opening region) which is not covered by the protective layer. The plating treatment is performed without plating or plating, but the adhesion between the protective layer and the copper or copper alloy wiring pattern is insufficient, so that the peripheral portion of the opening region may be discolored, and thus the plating resistance is expected to be improved. Sex.

The object of the present invention is to solve the above problems of the prior art, and to provide a printed wiring board having a protective layer composed of a photosensitive oxyalkylene polyimine resin composition, which can sufficiently suppress the ring of impurities The methyl siloxane oligomer oozes out from the protective layer and is excellent in plating resistance.

The present inventors have found that a decyloxypolyimide resin is prepared by using a diphenylsilylene unit having a diphenylsilylene unit as a diamine component, and is used in combination with a specific type and amount. A photosensitive oxirane polyimine resin composition formed by a crosslinking agent to form a protective layer, thereby suppressing bleed out of the cyclic dimethyl methoxy olefin oligomer, and further, if copper or copper of the wiring board is to be formed When the alloy wiring pattern is subjected to surface roughening treatment in advance, the plating resistance of the protective layer formed thereon can be improved, and the present invention has been completed.

That is, the present invention provides a printed wiring board formed by forming a thermosetting substance composed of a photosensitive decyl oxymethylene iodide resin on at least a part of a copper or copper alloy wiring pattern of a printed wiring board. a protective layer; the photosensitive oxirane polyimine resin composition comprises a decyl alkoxy phthalimide resin, a crosslinking agent, and a photoacid generator; the oxirane polyimine resin is composed of four a carboxylic acid dianhydride, a nonyl fluorenylene unit having a diphenyl fluorenylene unit, and a hydrazine imidized with a non-oxane-containing diamine; wherein the crosslinking agent is used as a crosslinking agent. 100 parts by mass of the oxirane polyimine resin is at least one selected from the group consisting of liquid epoxy resins, benzoxazines, and resole resins; The sensitizer is a photoacid generator which is used in an amount of 5 to 30 parts by mass based on 100 parts by mass of the decyl iodide resin; the surface of the copper or copper alloy wiring pattern is subjected to surface roughening treatment.

In addition, the present invention also provides a method for manufacturing the above-mentioned printed wiring board, which is subjected to surface roughening treatment on the surface of a copper or copper alloy wiring pattern of a printed wiring board; copper or copper after surface roughening treatment At least a part of the alloy wiring pattern is formed by forming a film of a photosensitive decyl oxymethylene imide resin film, exposing it to development, patterning, and then thermally curing to form a protective layer by post-baking. It is required to perform electroless plating or electroplating; the photosensitive oxirane polyimine resin composition contains a decyl alkoxy phthalimide resin, a crosslinking agent, and a photoacid generator; the decyl alkoxy amide resin It is obtained by ruthenium imidization of tetracarboxylic dianhydride, a nonoxyalkylene diamine having a diphenylarylene unit, and a diamine containing no alkoxysilane; and is characterized in that as a crosslinking agent, Using at least one selected from the group consisting of a liquid epoxy resin, a benzoxazine, and a resol resin, in an amount of 1 to 20 parts by mass based on 100 parts by mass of the decyl iodide resin; Relative oxirane 100 parts by mass of the resin is 5 to 30 parts by mass of photoacid generator.

In the present invention, a non-oxyalkylene diamine having a diphenylarylene unit is used as a diamine component, and further, a protective layer such as a film composed of a photosensitive oxirane polyimine resin composition is formed. The three-dimensional structure caused by the thermosetting cross-linking agent captures the cyclic dimethyl methoxy olefin oligomer as an impurity in the three-dimensional structure, and as a result, it prevents or even inhibits the cyclic dimethyl oxyalkylene oligomerization. Exudation of the material, and further good plating resistance by thermal hardening. Further, since a specific amount of the photoacid generator is contained as a sensitizer, the decyl oxymethylene iodide resin composition has a positive photosensitive property and can be patterned by exposure or alkali development.

Further, since the copper or copper alloy wiring pattern of the printed wiring board is subjected to surface roughening treatment in advance, the adhesion between the copper or copper alloy wiring pattern and the protective layer can be improved, and the plating resistance of the protective layer can be improved.

The photosensitive oxirane polyimine resin composition for forming a protective layer of a printed wiring board of the present invention contains: a tetracarboxylic dianhydride, a nonoxyalkylene diamine having a diphenyl fluorenylene unit, 100 parts by mass of a decyl alkoxyimide resin obtained by ruthenium imidization with a non-oxane-containing diamine; and selected from the group consisting of liquid epoxy resins, benzoxazines, and resol phenol resins 1 to 20 parts by mass of the crosslinking agent of at least one of the groups; and 5 to 30 parts by mass of the photoacid generator as a sensitizer.

First, a decyloxypolyimine resin which is a main component of a photosensitive siloxane oxy-imide resin composition will be described. Since the decane polyimine resin is a diamine sulfoxane having a diphenyl fluorenylene unit as a diamine component, the amount of occurrence of the cyclic dimethyl methoxy olefin oligomer can be reduced.

Specific examples of the tetracarboxylic dianhydride which is a constituent unit of the oxirane polyimine resin used in the present invention include pyromellitic dianhydride and 3,4,3',4'-biphenyl. Tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'- Diphenylphosphonium tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)ruthenium anhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl茀 dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 1,2,3,4-cyclobutane Alkane tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, ethylene glycol trimellitate dianhydride, 2,2-double (4-(3,4-Dicarboxyphenoxy)phenyl)propane dianhydride or the like. Among them, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride is preferably used.

Further, the constituent unit of the oxirane polyimine resin used in the present invention, that is, a decane diamine, is a compound having at least a dimethyl fluorenylene skeleton in the molecule, and can be used conventionally for polyfluorene. Alkoxylate modified by imine resin. Among them, from the viewpoint of ensuring flame retardancy and compatibility, a structure having the following formula (1) can be preferably used.

In the formula (1), n is an integer of 1 to 30, preferably an integer of 1 to 20, and m is an integer of 1 to 20, preferably an integer of 1 to 10. Since m is 1 or more, the alkoxydiamine of the formula (1) has a diphenyl fluorene-based skeleton, and the flame retardancy of the decyl alkene polyimide resin is improved. Further, since m is 1 or more, bleed out of the impurity dimethyl methoxy siloxane oligomer, which is an impurity, can be suppressed to some extent. Specific examples of the above-mentioned oxime diamines include X-22-9409 (m>1) manufactured by Shin-Etsu Chemical Co., Ltd. Further, as the alkoxyalkylene diamine, an amine group such as a third butoxycarbonyl group, an anthracene group such as a fluorenyl group, or a sulfonamide such as a p-toluenesulfonyl group may be used. Protected by the system.

The constituent unit of the oxirane polyimine resin used in the present invention is a diamine containing no alkane, and a diamine having no dimethyl fluorenylene skeleton and a diphenyl fluorenylene skeleton in the molecule can be used. As specific examples thereof, 3,3'-diamino-4,4'-dihydroxydiphenylanthracene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane , 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxy-4 , a diaminophenol derivative such as 4'-diaminobiphenyl, 2,4-diaminophenol, 9,9-bis(3-amino-4-hydroxyphenyl)anthracene; p-phenylenediamine , 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)benzene碸, 1,3-bis(4-aminophenoxy)benzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 1,3-double ( 3-aminophenoxy)benzene, 4,4'-diaminobenzimidamide, 5,5'-methylene-bis(o-amine benzoic acid), 9,9-bis[4-(4 -aminophenoxyphenyl)]indole, 9,9-bis(4-aminophenoxy)anthracene, 4,4'-diaminodiphenylanthracene, 3,4'-diaminodiyl Phenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl] An aromatic diamine such as fluoropropane, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, ortho-toluidine oxime; An aliphatic diamine such as 1,4-cyclohexanediamine, cis-1,4-cyclohexanediamine or 4,4,-methylenebis(cyclohexylamine), but is not limited thereto These preferably include a diaminophenol derivative, particularly 3,3'-diamino-4,4'-dihydroxydiphenylanthracene.

The oxirane polyimine resin used in the present invention may be a solvent of tetracarboxylic dianhydride and a nonoxyalkylene diamine having a diphenyl fluorenylene unit and, if necessary, a non-oxane-containing diamine. It can be produced by performing a hydrazine imidation reaction under reflux conditions, or can be obtained by the production method which has the following steps (a) and (b).

Step (a)

First, a tetracarboxylic dianhydride and a nonyl fluorenylene diamine having a diphenylhydrazinyl unit are subjected to hydrazine imidation under reflux conditions to obtain an anhydride-containing terminal oxirane quinone imine oligomer. The reaction mixture.

In order to obtain an acid anhydride terminal oxime oxime imine oligomer, it is sufficient that the first tetracarboxylic dianhydride has more moles than the oxime diamine. In particular, the amount of the oxoxane diamine used is less than 1 mole per all of the tetracarboxylic dianhydride. If the amount is too small, it tends to be difficult to maintain the adhesion and flexibility. If the amount is too high, the heat resistance tends to decrease. It is 0.1 to 0.9 moles, more preferably 0.3 to 0.8 moles.

In the step (a), the reason for carrying out the hydrazine imidization reaction under reflux conditions is to remove the hydrazide water using a Dean-Stark separation tube or the like. Therefore, the solvent is a solvent which is refluxed at a temperature at which a quinone imidization reaction is carried out between a tetracarboxylic dianhydride and a decyloxydiamine, and a solvent which can separate water by azeotropy. As the solvent, glyceryl glycol such as diglyme or triglyme, an ether solvent such as dioxane or tetrahydrofuran, or γ-butyrolactone or γ-valerolactone may be used. Lactone solvent, a mixture of these. Further, an aromatic hydrocarbon solvent such as toluene, xylene, benzene or mesylene or a guanamine solvent such as N-methyl-2-pyrrolidone may be used in combination as long as the effects of the invention are not impaired. In the step (a), from the viewpoint of the reflux temperature and the like, a mixed solvent of a glyme and a non-polar solvent is preferred, and among them, triethylene glycol dimethyl ether and a benzene, toluene, and the like are preferably used. A mixed solvent of at least one of a group consisting of xylene and trimethylbenzene (w/wl/(0.1 to 10)).

The amount of the solvent used in the step (a) varies depending on the type of the solvent or the reaction substrate, but if it is too small, the monomer may be poorly dispersed or the reflux efficiency may be lowered. If too large, the heat of vaporization of the solvent may become large. Since the temperature inside is difficult to rise, it is preferable to use the total mass of the tetracarboxylic dianhydride and the decane diamine in an amount of 5 to 60% by mass.

The reaction temperature in the imidization reaction varies depending on the type of the solvent or the reaction substrate or the amount used, but if it is too low, the imidization reaction cannot be completed; and if it is too high, the oxime imidization reaction may occur. The side reaction is preferably from 150 to 220 ° C, more preferably from 160 to 200 ° C. The reaction time is a time required for removing the theoretical amount of hydrazine imidized water, and is usually from 0.5 to 12 hours, preferably from 1 to 8 hours.

In the step (a), when a ruthenium imidization is carried out, an alkali catalyst such as triethylamine, an aromatic isoquinoline or pyridine, or a benzoic acid or p-hydroxybenzoic acid may be added as needed. Acid catalyst.

Step (b)

After the reaction of the step (a) is completed, a dioxane-free diamine is added to the solution of the anhydride terminal oxirane quinone imine oligomer obtained in the step (a) so that the oxime-free The amine is subjected to a hydrazine imidization reaction with an acid anhydride terminal oxirane quinone imine oligomer, whereby a decyloxypolyimine resin is obtained. In this case, it is also possible to add a tetracarboxylic dianhydride which is the same as or different from the former user at the same time as the diamine containing no alkane. Further, a solvent may be added as needed. Therefore, the concentration of the solid component of the polyimine can be adjusted. The solvent can be used in step (a). In particular, when a decyloxypolyimide resin is used in the form of a varnish, an ether system which is a solvent having a low hygroscopic property may be used singly or in combination in order to prevent precipitation of polyamidene due to moisture absorption during coating. Solvent, lactone solvent, non-polar solvent, and the like. Especially in this step (b), a mixed solvent of triethylene glycol dimethyl ether (alias: triethylene glycol dimethyl ether) and γ-butyrolactone (w/w=1/(0.1~10) can be preferably used. )).

In order to ensure the molecular weight of the protective layer for obtaining sufficient mechanical properties, the amount of the diamine containing no alkane and the molar amount of the two-cavity two-cavity are preferably 1 mol with respect to the total tetracarboxylic dianhydride. It is 0.1 to 0.9 moles, more preferably 0.3 to 0.8 moles.

In the case of the imidization of the oxime in the step (b), as in the case of the step (a), an alkaline catalyst such as a tertiary amine such as triethylamine, an aromatic isoquinoline or a pyridine may be added as needed. Or an acid catalyst such as benzoic acid or p-hydroxybenzoic acid.

Regarding the temperature of the hydrazine imidization reaction in the step (b), when the acid dianhydride or diamine component having a polar group is used in the step (b), the oxime oxide generated by the Weistelberg effect The viscosity of the polyimide resin increases, and sometimes it occurs around the stirring rod. In order to avoid an increase in the viscosity of the produced oxyalkylene polyimine resin, it is preferred to have water present in the reaction system. In this case, if the amount of water is too small, the risk of increasing the viscosity is increased. If the molecular weight of the polyimide is decreased, the molecular weight of the polyamidene is preferably 0.01 to 1.1% by mass. .

The reaction temperature in the imidization of the hydrazine in the step (b) varies depending on the type or amount of the solvent or the reaction substrate, but if it is too low, the hydrazide reaction cannot be completed; and if it is too high, bismuth may occur. The side reaction other than the imidization reaction is preferably from 150 to 220 ° C, more preferably from 160 to 200 ° C. The reaction time is usually from 0.5 to 12 hours, preferably from 1 to 8 hours. Thereby, a decyl alkene polyimine resin having a small content of a cyclic dimethyl methoxy olefin oligomer can be obtained in a varnish state.

Next, the crosslinking agent used in the photosensitive oxirane polyimine resin composition will be described. The cross-linking agent, as it is literally, is itself polymerized by heating to form a three-dimensional crosslinked structure. Therefore, the cyclic dimethyl methoxy olefin oligomer as an impurity can be locked in a three-dimensional structure to inhibit or prevent it from oozing out.

The crosslinking agent may be at least one selected from the group consisting of a liquid epoxy resin, a benzoxazine, and a resol resin, which are compatible with the decyloxypolyimine resin. . In particular, from the viewpoint of preventing the volatilization and diffusion of the cyclic dimethyl methoxy olefin oligomer, a liquid epoxy resin and a benzoxazine may be used together, or a liquid epoxy resin or a benzoxazole may be used in combination. Pyrazines and resoles. At this time, the polymerization of the liquid epoxy resin is carried out after the amine group remaining in the oxirane polyimine resin is heated to become an anion polymerization starting point. The polymerization of benzoxazines is carried out by heating to open a ring of the oxazine ring to form a methylenium cation and a phenolic oxonium anion, and then the methyl sulfonium cation is subjected to nucleophilic substitution polymerization of the benzene ring. In the case of a resol phenol resin, the benzene ring is subjected to dehydration condensation polymerization by heating with a phenolic hydroxyl group.

The liquid epoxy resin and the resol resin are preferably from 1 to 100,000 mPa·s, more preferably from 1 to 50,000 mPa·s, in order to have good compatibility with the decyloxypolyimide resin. Here, the viscosity is measured at 25 ° C with a B-type viscometer. On the other hand, the benzoxazines are usually solid at normal temperature, but if the softening point is too high, the compatibility with the oxirane polyimine resin is lowered. Therefore, the softening point is preferably about 100 ° C or lower.

Preferred examples of the liquid epoxy resin used as the crosslinking agent include bisphenol F type epoxy resin (jER807, Japan Epoxy Resin Co., Ltd.) and bisphenol A type epoxy resin (for example). jER828, Japan Epoxy Co., Ltd.), alicyclic epoxy resin (Celloxide 2021, Daicel Chemical Industries, Ltd.), epoxy propylamine epoxy resin (jER604, Japan Epoxy Resin Co., Ltd.; GAN , Japan Chemical Pharmaceutical Co., Ltd., etc.). Among them, a bisphenol F type epoxy resin and a bisphenol A type epoxy resin are preferably used from the viewpoint of availability.

Preferable specific examples of the benzoxazines used as the crosslinking agent include bisphenol S-type benzoxazine of the following formula (1) and bisphenol F-type benzoxazine of the formula (2). The bisphenol A type benzoxazine of the formula (3) (all manufactured by Xiaoxi Chemical Industry Co., Ltd.). Among them, bisphenol F type benzoxazine is preferably used from the viewpoint of easiness of availability.

Moreover, as a preferable specific example of the resole phenol resin used as a crosslinking agent, the alkali-soluble phenol resin obtained using the hydroxide of an alkali metal or an alkaline earth metal as a catalyst, and ammonia are used. An ammonia-soluble phenol resin resin obtained by a catalyst, a high-ortho resol resin obtained by using a divalent metal salt as a catalyst, or the like. Among them, an alkali-soluble phenol resin can be preferably used from the viewpoint of availability.

The content of the crosslinking agent in the photosensitive oxirane polyimine resin composition used in the present invention is 1 to 20 parts by mass, preferably 1 to 1 part by mass per 100 parts by mass of the decyl alkoxyimide resin. 15 parts by mass, more preferably 1 to 10 parts by mass. When the content of the crosslinking agent is less than this range, the effect of suppressing volatilization and diffusion of the cyclic dimethyl methoxy olefin oligomer may be insufficient; if it exceeds, the flexibility will be lacking and the film tends to become hard. Not good.

Further, when a liquid epoxy resin and a benzoxazine are used together as a crosslinking agent, the benzoxazine is preferably used in a ratio of 0.5 to 10 parts by mass based on 1 part by mass of the liquid epoxy resin. The reason for this is that if the benzoxazine is too small, the effect of volatilization and diffusion inhibition of the cyclic dimethyl methoxy olefin oligomer is insufficient, and if it is too large, the flexibility is lacking and the film tends to be hard. Further, when a liquid epoxy resin, a benzoxazine or a resol resin is used in combination, the benzoxazine is preferably used in an amount of 0.5 to 10 parts by mass based on 1 part by mass of the liquid epoxy resin. The phenol resin is preferably used in a proportion of 0.5 to 10 parts by mass. The reason for this is that if the amount of the resol phenol resin is too small, the effect of volatilization and diffusion suppression of the cyclic dimethyl methoxy olefin oligomer is insufficient, and if it is too large, the flexibility is lacking and the film tends to be hard.

Next, the photoacid generator used in the photosensitive oxirane polyimine resin composition will be described. The photo-acid generator has the following characteristics and is used as a sensitizer: when a film of a oxime phthalimide resin composition containing a photo-acid generator is exposed to ultraviolet rays or the like, it is decomposed in the film to generate an acid, and is imparted thereto. The composition can develop the characteristics of the film alkali.

Examples of the photoacid generator include a diazonium salt, a guanamine diazonium sulfonate, a diazonium sulfonate, a diazonium sulfonate, a nitrobenzyl ester, a phosphonium salt, and a halide. Halogenated isocyanate, halogenated triazine, diarylsulfonyldiazomethane, dioxane, and the like. Among them, an o-quinonediazide compound having an effect of suppressing water solubility of an unexposed portion can be preferably used. Specific examples of the ortho-quinonediazide compound include 1,2-benzoquinone-2-azido-4-sulfonate or decylsulfonate, 1,2-naphthoquinone-2-diazepine -5-sulfonate or decylamine sulfonate, 1,2-naphthoquinone-2-diazide-4-sulfonate or decylamine sulfonate. These may be, for example, by 1,2-benzoquinone-2-azido-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone- An o-quinonediazidesulfonium chloride such as 2-diazide-4-sulfonyl chloride is obtained by a condensation reaction with a polyhydroxy compound or a polyamine compound in the presence of a dehydrochlorination catalyst.

The content of the photoacid generator in the photosensitive oxirane polyimine resin composition used in the present invention is 5 to 30 parts by mass, preferably 5 parts by mass based on 100 parts by mass of the decyl alkoxyimide resin. ~20 parts by mass. If the content of the photoacid generator is less than this range, sufficient sensitivity cannot be obtained. When the content exceeds this range, the heat resistance of the resin composition tends to be lowered, which is not preferable.

The photosensitive oxirane polyimine resin composition used in the present invention may optionally contain a conventional additive such as a metal deactivator, an antifoaming agent, a rust preventive agent, or an organic solvent.

The photosensitive oxirane polyimine resin composition used in the present invention can be produced by uniformly mixing a decane oxime polyimide resin, a crosslinking agent, a sensitizer, other additives or a solvent in a usual manner.

The protective layer (plating protective layer or solder protective layer, etc.) obtained by thermally curing the photosensitive oxirane polyimine resin composition used in the present invention can greatly suppress cyclic dimethyl oxirane The polymer oozes out, unlike the conventional oxirane polyimine resin.

The printed wiring board of the present invention is characterized in that a protective layer of a thermosetting material composed of the photosensitive siloxane oxy-imide resin composition is formed on at least a part of a copper or copper alloy wiring pattern of a printed wiring board, and is characterized in that It is that the surface of the copper or copper alloy wiring pattern is subjected to surface roughening treatment. Therefore, the unevenness of the anchor layer of the protective layer is formed on the surface of the copper or copper alloy wiring pattern, and as a result, the adhesion of the protective layer is improved, and the plating resistance is improved.

As the surface roughening treatment, a so-called chemical polishing treatment using a wet blasting treatment of an aqueous slurry of inorganic fine particles or a chemical etchant using copper or a copper alloy is preferably used. Further, the roughened layer has an Ra (average surface roughness) of from 50 to 500 nm from the viewpoint of balance with developability.

Examples of the inorganic fine particles used as the polishing agent dispersed in the aqueous slurry used in the wet blasting treatment include aluminum particles, cerium particles, zirconium particles, and resin particles. Among them, aluminum particles are preferably used from the viewpoint of availability.

When the average particle diameter of the inorganic fine particles is too small, it is less likely to be dispersed in the aqueous slurry; if it is too large, it is difficult to form fine unevenness on the surface of the copper or copper wiring pattern, and therefore it is preferably 1 to 200 μm, more preferably 2 to 200 μm.

These inorganic fine particles are used as an aqueous slurry, but in addition to water, a mixed organic solvent (methanol, ethanol, acetone, etc.) may be used in combination. Further, a conventional dispersion stabilizer may be blended in the aqueous slurry.

In the wet blasting treatment, the aqueous slurry is usually sprayed to the printed wiring board by compressed air at a speed of 80 to 200 m/sec.

As a preferable chemical polishing treatment, an etchant (containing sulfuric acid, hydrogen peroxide, an azole-based anti-embroidering agent, or an aromatic hydrogen peroxide decomposition inhibitor) can be used. Here, examples of the azole-based anti-emulsion agent include an imidazole-based compound, a triazole-based compound, and a tetrazole-based compound. Further, examples of the aromatic hydrogen peroxide decomposition inhibitor include benzenesulfonic acid, and for example, toluenesulfonic acid or phenolsulfonic acid may be added. Further, it is considered that, by the above chemical polishing treatment, the azole-based anti-embroidering agent or the aromatic hydrogen peroxide decomposition inhibitor is chemically or physically bonded to the surface of the copper or copper alloy to form a protective layer with the organic substance. The closeness of the relationship is even more enhanced.

When the content of the sulfuric acid etching solution (1 liter) is too small, the etching rate is slow; if it is too large, the effect corresponding to the compounding amount is still not obtained, so it is preferably 50 to 300 g. When the content in the etching solution of hydrogen peroxide is too small, the etching rate is slow, and if it is too large, it is difficult to uniformly etch, and therefore it is preferably 10 to 30% by mass per 100 g of sulfuric acid.

In the chemical polishing treatment, it is preferred to maintain the etching liquid at room temperature to 50 ° C, and to eject a copper or copper alloy wiring pattern surface facing the printed wiring board, or to immerse the printed wiring board in the etched liquid after stirring. in.

The printed wiring board of the present invention can be applied to a so-called flexible printed wiring board, a glass epoxy wiring board, a laminated printed wiring board, or the like. Further, as the copper or copper alloy pattern, any thickness formed by the conventional semi-additive method or the build-up method can be applied.

Further, the formation position of the protective layer of the printed wiring board is above at least a part of the copper or copper alloy wiring pattern. When the wiring pattern is exposed, since the boundary between the protective layer and the wiring pattern exists, the effect of improving the etching resistance of the protective layer can be easily confirmed. Further, in the case where the entire surface of the wiring pattern is covered by the protective layer, since it is impossible to form a boundary between the two, it is difficult to confirm the effect of improving the etching resistance.

The printed wiring board of the present invention described above can be manufactured in the following manner. First, the surface of the copper or copper alloy wiring pattern of the printed wiring board is subjected to surface roughening treatment in the above manner. Next, the photosensitive oxirane polyimine resin composition of the present invention is applied to the surface by a bar coater, a roll coater, a comma coater, a screen printing machine or the like. The wiring pattern after the roughening treatment is dried at 50 to 100 ° C to form a film, and then the film is exposed to an active energy ray such as ultraviolet rays through a mask, and then removed by alkali development using an aqueous solution of sodium hydroxide or the like. The exposed portion is patterned, and then thermally cured by heating to 120 to 250 ° C to form a protective layer, and may be subjected to electroless plating such as electroless nickel plating or electroplating as needed.

Example

The invention will now be described more specifically by way of examples.

Reference Example 1 (Photosensitive oxirane polyimine resin composition containing a crosslinking agent)

(1) Manufacture of oxoxane polyimine resin

862.65 g (0.639 mol) of diamino sulfoxane (diaminodiphenyl/dimethyl group) was placed in a reaction vessel of a synthesis apparatus equipped with a Dean-Stark Trap (Dean-Stark Trap). Oxane (amine equivalent: 675 g/mol), trade name: X-22-9409, manufactured by Shin-Etsu Chemical Co., Ltd.), 363.6 g (1.01 mol) of 3,3',4,4'-diphenylfluorene A carboxylic acid dianhydride (Rikacid DSDA, manufactured by Nippon Chemical Co., Ltd., purity: 99.6%), 547 g of triethylene glycol dimethyl ether, and 200 g of toluene, and the mixture was thoroughly stirred for 2 hours. Thereafter, the temperature was raised to 185 ° C, and the temperature was maintained at this temperature for 2 hours, and the water was recovered by a Dean-Stark separation tube, and the reaction liquid was stirred under reflux.

The resulting reaction mixture was applied to a ruthenium wafer from which the oxidized film had been removed, and dried at 100 ° C for 10 minutes, and then the terminal functional group was identified by FT-IR transmission. The absorption of the quinone imine carbonyl group occurred in the vicinity of 1780 cm ^-1 , and the absorption of the cyclic anhydride carbonyl stretching vibration was confirmed in the vicinity of 1860 cm ^-1 . Therefore, it was confirmed that the anhydride terminal siloxane oligomer was formed.

The reaction mixture was cooled to 80 ° C, and 101.44 g (0.361 mol) of 3,3'-diamino-4,4'-dihydroxydiphenyl hydrazine (BSDA, manufactured by Xiaoxi Chemical Industry Co., Ltd.; purity 99.7%) was charged. ) and stirred at room temperature for 12 hours. After stirring, the temperature was raised to 185 ° C, and the mixture was heated and stirred at this temperature for 2 hours. Thereafter, it was cooled to room temperature to obtain a varnish containing a diphenylarylene unit-based oxirane polyimine resin.

(2) Modulation of photosensitive oxirane polyimine resin composition

Adding sensitizer (4NT-300, Toyo Synthetic Industrial Co., Ltd.) 10 phr, metal deactivator (rust inhibitor) (CDA-10, ADEKA Co., Ltd.) 0.3 phr to the varnish of the decyl oxyalkylene resin , liquid epoxide (jER807, Japan Epoxy Co., Ltd.) as a crosslinking agent, 0.5 phr, benzoxazine (BF-BXZ, Xiaoxi Chemical Industry Co., Ltd.) 5 phr, resol phenolic resin (BRL- 274, Showa Polymer Co., Ltd.) 2 phr, uniformly mixed at room temperature to obtain a photosensitive oxirane polyimine resin composition. Here, phr means the amount (parts by mass) added when the solid content of the polyimine is 100 parts by mass.

Reference Example 2 (Photosensitive oxirane polyimine resin composition containing no crosslinking agent)

In addition to not using liquid epoxy resin as a crosslinking agent (jER807, Japan Epoxy Co., Ltd.), benzoxazine (BF-BXZ, Xiaoxi Chemical Industry Co., Ltd.), resol phenolic resin (BRL-274) In addition to the Showa Polymer Co., Ltd., the oxirane polyimine resin was obtained in the same manner as in Reference Example 1, and a photosensitive oxirane polyimine resin composition was further prepared.

Reference Example 3 (Production of wiring board after physical roughening treatment by wet blasting)

The copper surface of a copper-clad laminate (Upisel N, Ube Nitto Chemical Co., Ltd.) with an insulating layer thickness of 25 μm and a copper thickness of 12 μm is used by the wet blasting system of Macoho Co., Ltd. (refer to http://www.macoho. Co.jp), the surface roughening treatment was carried out by the following condition (WB1) to obtain a wiring board after physical roughening treatment (average surface roughness Ra: 73.95 nm).

(WB1 condition)

Abrasive: aluminum microparticles

Center particle size: 6.7μm

Abrasive concentration in aqueous slurry: 14% by volume

Use spray gun: wide format

Processing speed: 1.8m / min

Projection distance: 20mm

Projection angle: 90 degrees

Air pressure: 0.15MPa

Reference Example 4 (Production of wiring board after physical roughening treatment by wet blasting)

Except that the air pressure was set to 0.25 MPa (WB2 condition), the wiring board after the physical roughening treatment (average surface roughness Ra: 100.7 nm) was obtained by repeating the method of Reference Example 3.

Reference Example 5 (Production of wiring board subjected to chemical roughening treatment)

The copper surface of a copper-clad laminate (Upisel N, Ube Nitto Chemical Co., Ltd.) with an insulating layer thickness of 25 μm and a copper thickness of 12 μm is first diluted with a 10-fold dilution of an acidic cleaning solution (CB-7612, MEC Co., Ltd.). (liquid temperature 25 ° C) spray, spray tap water, and then pre-soaked with etching solution (25 ° C) (BO7770VP, MEC Co., Ltd.), and then officially etched (25 ° C) (BO7770VP, MEC Co., Ltd.) Soak, then spray pure water, remove the water with an air knife (50 ° C), and finally dry with a blower hot air (80 ° C) to obtain a chemically roughened wiring board on the copper surface (etching amount: about 0.5 μm) .

Reference Example 6 (Production of wiring board subjected to chemical roughening treatment)

The copper surface of a copper-clad laminate (Upisel N, Ube Nitto Chemical Co., Ltd.) with an insulating layer thickness of 25 μm and a copper thickness of 12 μm was first diluted 10 times with a soft etching solution (CPE-755, Mitsubishi Gas Chemical Co., Ltd.). The solution was immersed in a liquid (liquid temperature: 30 ° C). Then, it was washed with pure water, and then the water was removed by an air knife, and dried by a blower hot air (50 ° C) to obtain a wiring board on which the copper surface was chemically roughened.

Examples 1 to 6 and Comparative Examples 1 to 3

According to the combination shown in Table 1, the photosensitive oxirane polyimine resin composition of Reference Example 1 or 2 was applied to the wiring board of Reference Examples 3 to 6 by a bar coater to be predried to 10 μm. And dried at 80 ° C for 10 minutes. The resin composition was exposed to ultraviolet light (condition 2500 mJ/cm ² ) through a photomask. After the exposure, the substrate was immersed in a 3 % by mass aqueous sodium hydroxide solution at 40 ° C for 60 seconds, and the exposed portion of the resin composition film was removed for development. Then, the substrate was washed with water at 30 ° C for 60 seconds, and then washed with 10% by mass (room temperature) of a dilute sulfuric acid aqueous solution for 10 seconds, and further washed with distilled water (room temperature) for 120 seconds. Thereafter, post-baking (200 ° C, 60 minutes) was carried out under a nitrogen atmosphere, and finally, the resin composition film was thermally cured to obtain a wiring board having a protective layer.

<Evaluation of inhibition effect of exudation of cyclic dimethyl methoxy olefin oligomer>

Samples having a width of 4 mm and a length of 50 mm were cut out from the portions of the wiring sheet of the examples and the comparative examples, and heated at 260 ° C for 15 minutes at a flow rate of 50 ml/min. The volatile components were removed from the sample and the volatile components were collected elsewhere in a Tenax-TA collection tube at -20 °C. Next, the collected components were gasified in a helium gas stream under a predetermined condition, and then the helium gas was introduced into a GC-MS apparatus (JAS100, manufactured by JAI Co., Ltd.), and the amount of the cyclic dimethyloxane oligomer was used. Quantify. The results obtained are shown in Table 1.

<Evaluation of plating resistance>

The copper surface exposed on the wiring boards of the examples and the comparative examples was subjected to gold plating to form a gold plating film (0.03 μm thick). Alternatively, the exposed portion exposed on the copper surface is subjected to nickel plating/gold plating to form a hard Ni plating (3 μm)/gold plating (0.05 μm thick). The discoloration of the protective layer around the plating region in the obtained electroplated and protected layer and the wiring board of the comparative example was visually evaluated. The case where no discoloration was evaluated as good (G) and the case where there was some discoloration was evaluated as poor (NG).

As is clear from Table 1, in the wiring boards after the surface roughening treatment of Reference Examples 3 to 5, the wiring boards of Examples 1 to 6 (the protective layer provided has the crosslinking agent containing Reference Example 1). The three-dimensional crosslinked structure composed of a thermosetting product of a specific composition of a decane oxide polyimide composition can suppress the bleeding of a cyclic dimethyl methoxy olefin oligomer and has excellent plating resistance.

On the other hand, in the wiring board after the chemical polishing treatment of the conventional example of Reference 6, the wiring board of Comparative Example 1 (the protective layer provided was a photosensitive oxyalkylene polymerization of Reference Example 2 containing no crosslinking agent). The quinone imine resin composition does not inhibit the bleeding of the cyclic dimethyl methoxy olefin oligomer, and also has a problem of plating resistance. In the wiring board after the chemical polishing treatment of the conventional example of Example 6, the wiring board of Comparative Example 3 (the protective layer provided is obtained by using the photosensitive decane polyimine resin composition of Reference Example 1) The bleeding of the cyclic dimethyl methoxy olefin oligomer is not inhibited, and there is still a problem of plating resistance. On the other hand, in the case of Comparative Example 1, the wiring board of Comparative Example 2 (the protective layer provided was obtained by using the photosensitive siloxane oxyalkylene resin composition of Reference Example 1 containing a crosslinking agent) The bleed out of the cyclic dimethyl methoxy olefin oligomer was suppressed, and the plating resistance was improved as compared with Comparative Example 1, but the plating resistance was still higher than that of Comparative Example 3 and Further Examples 1 to 6. The problem.

Industrial availability

In the printed wiring board having the protective layer of the present invention, a nonoxyalkylene diamine having a diphenylarylene unit is used as a diamine component, and further, a photosensitive oxirane polyimine resin composition is used. A three-dimensional structure due to a specific thermosetting cross-linking agent is formed in the protective layer such as a film formed, so that it is possible to prevent or even inhibit the bleeding of the cyclic dimethyl methoxy olefin oligomer, and to obtain good by thermal hardening. Resistance to plating. In addition, since the copper or copper alloy wiring pattern of the printed wiring board is subjected to surface roughening treatment in advance, the adhesion between the copper or copper alloy wiring pattern and the protective layer can be improved, and the plating resistance of the protective layer can be further improved. . Therefore, it can be applied to a printed wiring board having high reliability.

Claims (12)

A printed wiring board formed with a protective layer composed of a thermosetting material of a photosensitive decyl oxymethylene imide resin composition on at least a part of a copper or copper alloy wiring pattern of a printed wiring board; The oxoxane polyimine resin composition contains a decyl alkoxyimide resin, a crosslinking agent, and a photoacid generator; the decyl oxymethylene amide resin is composed of tetracarboxylic dianhydride and has two a phenyl sulfinyl unit of a nonoxyalkylene diamine, which is obtained by hydrazine imidation with a non-oxane-containing diamine; characterized in that as a crosslinking agent, a relative oxyalkylene polyimide is used. 100 parts by mass of the resin is at least one selected from the group consisting of liquid epoxy resins, benzoxazines, and resole resins, and is used as a sensitizer, and is used as a sensitizer. 100 parts by mass of the quinone imine resin is 5 to 30 parts by mass of the photoacid generator; the surface of the copper or copper alloy wiring pattern is subjected to surface roughening treatment. The printed wiring board of claim 1, wherein the crosslinking agent is a liquid epoxy resin and/or a benzoxazine; or a liquid epoxy resin, a benzoxazine, and a resol resin. . For example, in the printed wiring board of claim 1 or 2, the viscosity of the liquid epoxy resin is 1~100000 mPa. s. The printed wiring board of claim 1 or 2, wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride. The printed wiring board according to claim 1 or 2, wherein the nonoxyalkylene diamine having a diphenylarylene unit has the structure of the formula (1): (where n is an integer from 1 to 30, and m is an integer from 1 to 20). A printed wiring board according to claim 1 or 2, wherein the diamine containing no alkane is a diaminophenol derivative. The printed wiring board of claim 6, wherein the diaminophenol derivative is 3,3'-diamino-4,4'-dihydroxydiphenylanthracene. The printed wiring board of claim 1 or 2, wherein the polyoxyalkylene polyimine resin is a reaction mixture of a tetracarboxylic dianhydride, a decane diamine, and a non-oxane-containing diamine. The yttrium imidization is carried out in the presence of 0.01 to 1.1% by mass of water. The printed wiring board of claim 1 or 2, wherein the photoacid generator is an o-quinonediazide compound. A manufacturing method for manufacturing a printed wiring board according to the first aspect of the patent application, which is characterized in that a surface roughening treatment is performed on a surface of a copper or copper alloy wiring pattern of a printed wiring board; and copper or a copper alloy is subjected to surface roughening treatment. On at least a part of the wiring pattern, a photosensitive decyl oxymethylene imide resin composition is formed into a film, exposed, developed, patterned, and then thermally cured to form a protective layer by post-baking; The oxoxane polyimine resin composition contains a decyl alkoxyimide resin, a crosslinking agent, and a photoacid generator; the decyl oxymethylene amide resin is composed of tetracarboxylic dianhydride and has two Phenyl fluorenylene unit The non-oxyalkylene diamine and the non-oxane-containing diamine are obtained by hydrazylation; and as a crosslinking agent, 100 parts by mass of the relative oxirane polyimide resin is used as 1~ 20 parts by mass of at least one selected from the group consisting of a liquid epoxy resin, a benzoxazine, and a resol resin; and as the sensitizer, 100 parts by mass of a relative oxirane polyimide resin is used. It is 5 to 30 parts by mass of a photoacid generator. The manufacturing method of claim 10, wherein the surface roughening treatment is a wet blasting treatment using an aqueous slurry. The manufacturing method of claim 10, wherein the surface roughening treatment is a chemical polishing treatment using an etchant.