TW201012851A - Printed wiring board and method for manufacturing same - Google Patents

Abstract

A printed wiring board having excellent plating resistance, wherein bleed-out of a cyclic dimethylsiloxane oligomer from a protective layer which is composed of a photosensitive siloxane polyimide resin composition is sufficiently suppressed. Specifically, a protective layer which is composed of a thermoset product of a photosensitive siloxane polyimide resin composition containing a siloxane polyimide resin, which is obtained by imidizing a tetracarboxylic acid dianhydride, a siloxane diamine having a diphenylsilylene unit and a diamine containing no siloxane, a crosslinking agent and a photoacid generator is formed on at least a part of a copper or copper alloy wiring pattern of a printed wiring board. A certain amount of at least one substance selected from the group consisting of liquid epoxy resins, benzoxazines and resols is used as the crosslinking agent, and a certain amount of the photoacid generator is used as a sensitizer. The surface of the copper or copper alloy wiring pattern of a printed wiring board has been subjected to a roughening treatment.

Description

[Technical Field] The present invention relates to a printed wiring board having a protective layer formed of a photosensitive oxymethylene polyienimine resin composition and a method for producing the same. [Prior Art]

An aromatic polyimine resin obtained by ruthenium imidization of aromatic tetracarboxylic acid and aromatic diamine is widely used as an interlayer insulating film and 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 by a nonoxyldiamine and a polyoxyalkylene skeleton is introduced into a polyimidazole skeleton is expanding. However, in the nonoxyldiamine diamine which is a raw material of the fluorinated polyimine resin, the cyclic dimethyl oxa oxime 11 which does not have an amine group as an impurity is contained, so that the produced oxy-combustion is sintered. When the imine 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 insulating film or the interlayer is covered. The surface of the layer reattaches or exudes the cyclic dimethyl methoxy olefin oligomer which is generated as an oxime, thereby causing contact failure or decrease in conductivity in the electronic component, followed by decrease in strength and the like. In addition, the term "exudation" in the book refers to a phenomenon in which a substance contained in a solid layer such as a film is transferred to a surface of a solid layer, liquefied or solidified therein, or volatilized and diffused. 201012851 In order to solve this problem, the following method has been proposed, that is, a ruthenium imidization reaction is carried out in a solvent of a diamine compound and a tetraacid in a toluene or an ether solvent; When, for example, eight: two, the solvent evaporated is discharged to the outside of the system, and the solvent is replenished (: Levin: small according to the method, the cyclic dimethyl ketone oligomer has a lower boiling point than the solvent. And the volatilized (4) is discharged to the outside of the system, and the concentration of the cyclic dimethyl 7 oxygen transpolymer can be reduced to reduce the oxygen-burning polyamine varnish. Patent Document 1: Japanese Patent Laid-Open No. 2004-263058 Disclosure of the Invention Problems to be Solved by the Invention However, in the method of Patent Document 1, since the volatilized solvent is discharged to the outside of the system under normal pressure, the dimethyloxane oligomer to the hexamer can be considerably obtained. The polymer is removed, but the problem is that one of the methyl oxime oligo-oligomers on the heptamer ruthenium cannot be sufficiently removed. Therefore, the problem is that the oxirane polysiloxane obtained by the method of Patent Document 1 is obtained. Amine varnish mixed sensitizer When a decane coupling agent, an epoxy amine, a solid epoxy resin, etc., which are widely used as a crosslinking agent of a polyimine, is added to the photosensitivity, it is still difficult to suppress an impurity, that is, a cyclic dimethyl alkoxysilane. A phenomenon in which a thin protective layer (plating protective layer or solder protective layer) obtained by forming a photosensitive stellite-oxygenated imide resin composition onto a printed wiring board and patterning and then hardening it is oozing out 201012851 Further, in the case of a printed wiring board having a protective layer formed of the photosensitive oxyalkylene polyimine resin composition, a copper or copper alloy wiring pattern region (opening region) for covering the unprotected layer ) plating 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 it is expected to improve resistance. Plating property. The object of the present invention is to solve the above problems of the prior art, and to provide a ruthenium protective layer composed of a photosensitive oxirane polyimine resin composition. In the present invention, the present inventors have found that the ring-shaped dimethyl gangrene oligopolymer is bleed out from the protective layer and is excellent in the resistance to the problem. A diphenylsilylene unit of a nonoxyldiamine is used as a diamine component to prepare a sulphuric acid imide resin, which is then used in combination with a specific type and amount of a crosslinking agent. The oxane polyimine resin composition can form a protective layer ′ to suppress bleed out of the cyclic dimethyl siloxane condensate, and further, the copper or copper alloy wiring pattern of the wiring board is surface roughened in advance. The present invention can be improved by improving the plating resistance of the protective layer formed thereon. That is, the present invention provides a printed wiring board which is at least a part of a copper or copper alloy wiring pattern of a printed wiring board. a protective layer composed of a thermosetting material of a photosensitive decyloxypolyimine resin composition; the photosensitive decyl oxymethylene amide resin composition containing a decyl oxyalkylene amide resin Crosslinker And a photoacid generator; the oxime oxygenated polyimine resin is a tetrabasic acid dianhydride, a decyl oxide having a diphenyl fluorenylene unit, 5 201012851 diamine' and a non-oxane-containing diamine The ruthenium imidization is carried out; and the crosslinking agent is used in an amount of 1 to 20 parts by mass based on 1 part by mass to 1 part by mass of the decyl oxymethylene imino resin. And at least one of the group consisting of an oxazine and a resole; and as the sensitizer, a light having a mass fraction of 5 to 30 parts by mass relative to the oxime phthalimide resin is used. The acid generator; the surface of the copper or copper alloy wiring pattern is subjected to surface roughening treatment. Further, the present invention also provides a method for manufacturing the above-described 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 one of the four metal knives of the alloy wiring pattern is formed by forming a film of a photosensitive smectite, and exposing and developing to form a film, and then thermally curing by post-baking. An electroless plating or an electric clock is required as the layer '$; the photosensitive oxalyl polyoxyimide resin composition contains a decyl alkoxy phthalimide resin, a crosslinking agent W & photoacid generating enthalpy; Shixi Oxygen-Poly-Polyimide Resin Resin is obtained by ruthenium imidization of tetrazoic acid dioxins, oxydiamine diamines having diphenyl sulfite units, and diamines containing no oxalate. It is characterized in that: as a crosslinking agent, it is selected from the group consisting of liquid epoxy resin, benzophenone, and resol type phenolic resin, with a mass loss of 1 to 20 parts by mass relative to the decyl alkoxyimide resin. At least one of the groups constituting _, as a sensitizer, a phase is used Silicon siloxane polyimide resin 100 parts by mass 201 012 851 amount of 5~30 parts by mass of photoacid generator. Advantageous Effects of Invention The present invention uses a diazonite diamine having a diphenyl sulfite unit as a diamine component, and further in a protective layer such as a film composed of a photosensitive oxirane polyimine resin composition. Since a three-dimensional structure due to a specific thermosetting crosslinking agent is formed, a cyclic dimethyl oxy-oxygen oligomer as an impurity is trapped in the three-dimensional structure, and as a result, the cyclic dimethyl hydrazine can be prevented or even suppressed. The osmolality of the oxyalkylene oligomer is further improved by thermal hardening to obtain a mineralization resistance. Further, since a specific amount of the photoacid generator is contained as a sensitizer, the oxime siloxane polyimide composition has a positive photosensitive property and can be patterned by exposure and 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. [Embodiment] The photosensitive oxy-oxygenated polyimine resin composition for forming a protective layer of a printed wiring board of the present invention contains: an oxygen-containing dianhydride having a diphenyl fluorenylene unit 100 parts by mass of a decyl iodide resin obtained by hydrazine imidization with a diamine containing no alkane, selected from liquid epoxy resins, benzoxazines, and resoles 1 to 20 parts by mass of the crosslinking agent of at least one of the groups of the resins; and 5 to 30 parts by mass of the photoacid generator as the sensitizer. First, the main component of the photosensitive oxirane polyimine resin composition will be described as a decyl oxyalkylene resin. Since the decyl alkoxyimine resin is a diamine sulfonium oxide having a diphenyl fluorenylene unit as a diamine component, the amount of occurrence of the cyclic dimercapto methoxy olefin oligomer can be reduced. Specific examples of the tetraoxo-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'-benzophenone tetracarboxylic dianhydride, 3,3,,4,4,- Diphenyl sulfone tetracarboxylic dianhydride, 9,9-bis(3,4·dicarboxyphenyl) second anhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl ] succinic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4,-(hexafluoroisopropylidene) bisphthalic 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, it is preferred to use a 3,3,4,4'-diphenyl base tetra-retensive two-needle. Further, 'the constituent unit of the oxirane polyimine resin used in the present invention is a fluorinated diamine, which is a compound having at least a fluorenylene fluorenylene skeleton in the molecule, and can be used for the polymerization. Alkoxylate modified by imine resin. From the viewpoint of ensuring flame retardancy and compatibility, it is preferable to use a structure having the following formula (1). H2N-(CH2)~-

201012851 is an integer from 1 to 20, preferably an integer from 1 to ι. Since ^ is more than or equal to, the alkoxydiamine of the formula 0) has a diphenyl fluorene-based skeleton, and the flame retardancy of the oxy-oxygenated imine resin is improved. Further, since m is 1 or more, the 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 diarrhea diamine are X-22-9409 (m> 1) manufactured by Shin-Etsu Chemical Co., Ltd. Further, as the alkoxyalkylene diamine, an amine group having an amine group such as a second butoxy group or the like, a sulfonium group such as a fluorenyl group, or a sulfonium group such as a p-toluene group can also be used. Protected by amines. © The constituent unit of the decane polyimine resin used in the present invention, that is, a diamine containing no alkane, and a molecular group having no dimercaptoarylene skeleton and a base sulfite skeleton can be used. As a specific example, the diamine '3,3'·diamino-4,4′-dihydroxydiphenyl sulfone, 2,2-bis(3-amino-4-hydroxyphenyl) 6 Fluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxyl _4,4,-Diaminobiphenyl, 2,4-diaminophenol, 9,9-bis(3-amino-4-hydroxyphenyl), etc. diaminophenol derivative; p-benzene Diamine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-amine-phenoxy)phenyl]propane, bis[4-(4-aminophenoxy) Phenyl]sulfone, iota, 3-bis(4-aminophenoxy)benzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 1,3- Bis(3-Amino-p-oxy)benzene, 4,4'-diaminobenzidine, 5,5'-arylene-bis(o-amine benzoic acid), 9,9-bis[4- (4-Aminophenoxyphenyl)] 9,9,9-bis(4-aminophenoxy), 4,4'-diaminodiphenyl, 3,4 -diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4,-bis(4-aminophenoxy)biphenyl , an aromatic diamine such as 1,4-bis(4-aminophenoxy)benzene or o-toluidinesulfone; trans-1,4-cyclohexanediamine, cis-cyclohexane 201012851 diamine An aliphatic diamine such as 4,4,-arylene bis(cyclohexylamine), but is not limited to these, preferably a diaminophenol derivative, particularly a 3,3,-diamino group. -4,4--Phenyldiphenyl. The oxirane polyimine resin used in the present invention may be a solvent of dihydrochatty acid dihydrogen and a diphenyl fluorenylene unit having a diphenyl fluorenylene unit and optionally an oxy-free diamine in a solvent. The ruthenium imidization reaction is carried out under reflux conditions, and can also be obtained by a production method having the following steps (a) & (b). Step (a)

First, the tetracarboxylic dianhydride and the fluorinated diamine having a diphenylarylene unit are subjected to hydrazylation under reflux conditions to obtain an acid anhydride terminal oxime oxime imine oligomerization. The reaction mixture of the materials. In order to obtain an anhydride terminal oxime oxime imine oligomer, as long as the amount of moles of the second valence acid di-if is more than that of the diarrhea diamine. Among them, the use amount of Shixi oxygen sea diamine is relative to all the four moles of tetradecanoic acid, and if it is too small, it is difficult to maintain the adhesion and tend to scratch; if too much, there is a tendency to heat resistance. Therefore, it is preferably ... _9 moles, more preferably 0.3 to 0.8 moles. '

In the case of (4), the reason for the ruthenium imidization reaction under the trickle condition is to remove the hydrazide water by using a Dean-StarV eight-touch knife. Therefore, the solvent is used for refluxing at the temperature of the four (four) and the reaction, and the solvent is separated from the amine by the imide. The above-mentioned solvents are known as glyme, such as monomethyl ether, _^-agent, or r-butyrolactone, r-pentane vinegar, etc.; The solvent and the mixture are not damaged as long as the effects of the invention are not impaired. The effect is also to use an aromatic hydrocarbon solvent such as f benzene, dif benzene, benzene, 10 201012851 mesitylene, or N_methyl_2_. It is slightly more than the rest of the amide/valency. In the step (4), from the viewpoint of the reflux temperature and the like, a mixed solvent of a glycol diether ether and a non-polar solvent is preferable, and among them, triethylene glycol diterpene ether and a substance selected from the group consisting of stupid, toluene and diterpene are preferably used. A mixed solvent of at least one of a group consisting of stupid and triterpenic benzene (w/wl/(〇丨~1〇)). 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; and if too much, the heat of vaporization of the solvent may become large. Since the temperature inside is difficult to rise, it is preferable to use an amount of the total mass of the tetrasodium oxyhydride and the sulphuric acid diamine to be 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. However, if the reaction temperature is too low, the ruthenium imidization reaction cannot be completed; if it is too high, the ruthenium reaction may occur. The side reaction is preferably 150 to 220 ° C, more preferably 160 to 200 ° C. The reaction time is a period of time required for removing the theoretical amount of the imidized water, and is usually from 5 to 12 hours, preferably from 1 to 8 hours. Wherein, in the step (a), when the imidization is carried out, a tertiary amine such as triethylamine, an aromatic isophthalocyanine, a B-biting test catalyst, or a benzoic acid or a para-hydroxy group may be added as needed. An acid catalyst such as benzoic acid. Step (b) After the end of the reaction of the step (a), the diamine-free diamine-free diamine is added to the solution of the anhydride-terminated oxy-oxyn imide polymer obtained in the step (a) so as to be free The dioxane diamine is reacted with the anhydride terminal oxirane quinone imine to carry out the oxime imidization reaction, thereby obtaining a decyl alkoxyimide resin. In this case, 11 201012851 can also be added to the same as the former user or the same as the former user without the addition of a sputum a __ milk to one of the amines. Further, a solvent may be added as needed. Therefore, it is possible to adjust the concentration of the polyethyleneimine solid 忐8, A ^ bottle. The solvent can be used in the step (a). In particular, when a decyloxypolyimide resin is used in the form of a varnish, 'the ether which is a solvent having a low hygroscopicity, which is a solvent having a low hygroscopicity, may be used singly or in combination to prevent precipitation of the polyimine by moisture absorption during coating. Solvent, lactone solvent, non-polar ☆ agent, etc. In particular, in this step (8), a mixed solvent of triethylene glycol dimethyl compound C dimethyl hydrazine dimethyl hydrazine and γ _ butyl vinegar can be preferably used (w/w=l/(〇.l 〜10) )) 〇 In order to ensure the molecular weight of the protective layer used to obtain sufficient mechanical properties, the amount of diamine containing no alkane and the molar amount of the total amount of oxime diamine relative to the total tetracarboxylic dianhydride i mole Preferably, it is 01 to 0 9 m, more preferably 〇·3 to 0.8 m. In the case of the imidization of the oxime in the step (b), as in the case of the step (a), an alkali 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 imidation reaction in the step (b), when the bismuth or diamine component having a polar group is used in the step (b), the enthalpy generated by the Weiseiberg effect The viscosity of the oxyalkylene polyimide resin increases, and sometimes it occurs around the stirring rod. In order to avoid an increase in the viscosity of the produced oxirane 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 Μ% by mass. . 12 201012851 The reaction temperature for the imidization 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 imidization reaction cannot be formed, and if it is too high, it may be A side reaction other than the ruthenium imidization reaction may occur, so it is preferably 15 Torr to 22 (TC, more preferably 160 to 200 ° C. The reaction time is usually 0.5 to 12 hours, preferably 1 to 8 hours. In this varnish state, it is known that the content of the cyclic monomethyl alkane oligomer is less than that of the oxirane polyimide resin 0. Next, it is used for the photosensitive oxirane polyimine resin composition. The cross-linking agent is described. The cross-linking agent, as it is literally, is itself kneaded by heat and hardens to form a two-dimensional crosslinked structure. Therefore, the cyclic dimethyl gangue as an impurity can be gathered. The object is locked in a three-dimensional structure to inhibit or prevent it from oozing out. As the crosslinking agent, a liquid epoxy resin, a benzo oxime, or the like, which is compatible with the cerium oxide polyimine resin, may be mentioned. And at least one of the group consisting of soluble resins, especially from the prevention of cyclic dimethyl From the point of view of the volatilization and diffusion of the oxylate oligomers, the liquid epoxy resin and the sigma scorpion, the erythraea root field, and the liquid epoxy resin and benzo can be used together. Oxazine, and soluble (tetra) resin. At this time, the polymerization of the liquid epoxy resin is carried out by heating the amine group remaining in the sulphur oxide smelting imine resin to become an anionic polymerization =:= two: open °_ The polymerization is carried out by heating (4) ring:, - post == rthylenium) cation _ oxo anion ' and then methyl _ ion to benzene ring nucleophilic to obtain soluble (iv) resin, by 朌through. The reaction is carried out by subjecting the ring to dehydration condensation polymerization. Soil, two U heat and p-benzene 13 201012851 As the above liquid epoxy resin and soluble resin, in order to have good compatibility with the dream oxygenated polyimine resin, preferably 1~1 〇〇 〇〇〇mPa · s, more preferably uoooompa · s. The viscosity here is measured at 25 艽 with a B-type viscometer. On the other hand, the benzoate is usually a solid at normal temperature, but if the softening point is too high, the phase coldness of the decyl alkane resin decreases. Therefore, it is preferred that the softening point is about 1 〇〇 or less. By. As a preferable specific example of the liquid epoxy resin used as the crosslinking agent, it is possible to exemplify the double epoxy resin (10), the Japanese epoxy resin, and the public epoxy resin (for example, Qing 28, Japanese epoxy resin). <A 5 &amp; % epoxy resin (CellGxide 2021, Daicel

Chemical Industries Ltd), 搭, (JER604 a ^ - 5 丙基 propyl amine epoxy resin (teacher 6 〇 4, Japan Epoxy Epoxy Co., Ltd., etc.), etc. From the viewpoint of the bisphenol F-type ring, it is preferable to use L as a double-type epoxy resin. The following formula (1) is a double-looking S type stupid:: a vicious type (3) Benzophenazine (all are small westernized and oxazine, system). Its I obtained from the viewpoint of the ease of the observation of the industry, the limited company F type stupid and oxazide. See 'better bisphenol can be used 201012851

Further, as a soluble example used as a crosslinking agent, an organic phenolic resin obtained by using a hydroxide of a metal as a catalyst can be used as a preferred phenolic resin obtained by using a hydroxide of a metal as a catalyst. Ammonia is used as a catalyst; a cereal resin resin, a high ortho-group (phenolic resin) resin obtained by using a divalent metal salt as a catalyst, and the like. Among them, from the viewpoint of easiness of availability, it is preferred to use an insoluble aldehyde resin. 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 part by weight based on 100 parts by mass of the decyl alkoxyimide resin. ~ 丨 5 parts by mass, more preferably 1 to 10 parts by mass. If the content of the cross-linking agent is less than this range, the inhibition effect of the volatilization and diffusion of the cyclic dimethyl methoxy alkane polymer 15 will not be sufficient; if it exceeds the lead, the film may be hardened. The tendency is not good. In addition, a liquid epoxy resin and benzopyrene are used in combination. When Qin is used as a crosslinking agent, it is preferable to use a ratio of 0.5 to 10 f parts relative to the amount of the liquid epoxy resin 丨f. The reason for this is that if there are too few benzoxazines, the volatilization of the cyclic bismuth-based oxy-enrichment polymer will be insufficient, and if it is too large, the flexibility will be lacking and the film tends to become hard. In addition, when the liquid epoxy resin 'stupid B and the soluble (iv) resin are used in combination, the benzo compound is preferably used in an amount of 0.5 to 10 by mass relative to the liquid epoxy resin 丨f. The fraction of the resole phenolic resin is preferably a ratio of 〇·5 to 〇 〇 by mass. The reason is that if the number of soluble chain-chain resins is too small, the effect of volatilization and diffusion inhibition of the methyl onium oxide oligomer is insufficient, and if it is too large, the flexibility is lacking, and the film is changed. Hard tendency. Next, the photoacid generator used in the photosensitive oxirane polyimine resin composition will be described. The photoacid generator has the following characteristics and is used as a sensitizer: when a photoacid generator is used. When the film of the polyimide composition is exposed to ultraviolet light or the like, it is decomposed in the film to generate an acid', and the composition is provided with the property of developing the film alkali. Examples of the photoacid generator include a diazonium salt, a diazonium sulfonate, a diazonium sulfonate, a diazonium sulfonate, a nitrobenzyl ester, a rust salt, a halide, and the like. Halogenated isocyanate, halogenated triazine, diarylsulfonyldiazomethane, diterpene, etc. " Among them, an ortho-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 sulfonic acid 201012851 decylamine, 1,2-naphthoquinone-2_double stack Nitrogen _5_ _ A or acid amide, 1,2-naphthoquinone-2-azide-4-ester or acid 醯 face. Λ and so on. These may be, for example, 1,2-benzoquinone-2-azide·4_sulfonium chloride, anthracene naphthalene. ” 2-azido-5-sulfonyl chloride, 1,2-naphthoquinone-2_ The adduct of the diazide-4-sulfuric gas, etc. _.^ sleep- azide sulfonium chloride and a polyhydroxy compound or a polyamine compound are obtained by a condensation reaction in the presence of a dehydrochlorinated hydrazine 0 The content of the photoacid generator in the photosensitive sarcophagus &amp; A w* oxy-oxygenated imide resin composition used in the present invention is relative to &amp;&amp; amp relative to the decyl alkoxyimine The amount of the resin is 5 to 30 parts by mass, and is 5 to 20 parts by mass relative to 祛ic and 隹. If the content of the photoacid generator is less than the range, sufficient sensitivity cannot be obtained; and if it exceeds this range, the resin is not. The heat resistance of the composition tends to be lowered, which is not preferable. The photosensitive oxirane polyimine resin composition used in the present invention may optionally contain a metal deactivator, an antifoaming agent, a rust preventive agent, or an organic compound. A conventionally used additive such as a solvent. The photosensitive oxirane polyimine resin composition used in the present invention can be obtained by using a decyl oxyalkylene resin and a crosslinking agent. The sensitizer, other additive agent or solvent is uniformly mixed by a usual method. The photosensitive siloxane oxide polyimide composition used in the present invention is thermally cured to obtain a protective layer (plating protective layer or solder) The protective layer or the like is capable of greatly suppressing the bleed out of the cyclic dimethyl methoxy olefin condensate, and is different from the conventional oxime siloxane polyimide resin. The printed wiring board of the present invention is applied to a printed wiring board. A protective layer of a thermosetting material composed of the photosensitive Xanthoxynitrile imine resin composition is formed on at least a part of the copper or steel alloy wiring pattern, and is characterized in that: · face IA 17 201012851 or copper alloy wiring The surface of the 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. Or the chemical used for copper or steel alloy. In addition, the roughening level, the apparent Ra (average surface roughness) is 50~. As the surface roughening treatment, water using inorganic fine particles is preferably used. From the viewpoint of balancing the so-called chemical polishing treatment of the wet blasting treatment of the slurry, 500 nm is obtained. 无机 The inorganic fine particles dispersed in the aqueous charge used in the wet blasting treatment can be used. Listed in the Ming particles, the Shixi particles, the wrong particles, the moon particles, etc. Among them, from the point of view of the ease of availability of aluminum particles, 衩佳 is the average particle size of the particles in use, if it is too small, it is scattered in the aqueous slurry. If it is too large, it will be difficult to form fine concavities on the surface of the copper or copper wiring pattern. Therefore, it is preferably (9)^, more preferably 2~%. No.: The microparticles are used as an aqueous slurry, as a medium. It can also be mixed with water and organic solvent (I I :: sand two: water-based slurry with a well-known dispersion stabilizer C

It is preferred that the SO twist is sprayed onto the printed wiring board. As a preferred chemical polishing treatment, there are a tracer acid, a hydrogen peroxide, an azole system, and an etchant (including a sulfur, an embroidering agent, or an aromatic peroxide preparation). Here, as the wow-based performance-prevention agent, a miso system is mentioned: an aryl group such as a salivary compound or a tetra-salt compound is inhibited. Compounds and threes are used as a peroxidation of the genus of the genus. 18 201012851 Hydrogen decomposition inhibitors include benzoic acids, for example, toluene acid, benzoquinone sulfonic acid, and the like. In addition, it is generally believed that by the above chemical polishing treatment, the azole-based anti-winding agent or the aromatic bismuth peroxide can be used to chemically or physically bind to the surface of the copper or copper alloy. ;,, · ««', and the adhesion between it and the protective layer of organic matter is further enhanced. If the content of the combing acid etching solution (1 彳 彳 φ + l A liter) is too small, the etching speed is slow; if too much, the effect corresponding to the compounding amount is still not obtained, so it is preferably 50 to 3 〇〇g. . If the content of the (4) liquid in the hydrogen peroxide is too small, the residual Ο is slow; if it is too large, it is difficult to be about ± 1 ^ scoop, so it is preferably 10 to 30% by mass per sulphuric acid. In the process of handling the button armor, it is preferable to maintain the etching solution at room temperature until the surface of the copper or copper alloy wiring pattern of the printed wiring board is sprayed, or the printed wiring board is immersed in (4). (4) In the liquid. The printed wiring board of the present invention can be applied to a so-called pullable printed wiring board, a glass epoxy wiring board, a laminated printed wiring board, or the like. Or a copper alloy pattern can also be applied to any thickness of the copper crucible. The formation of the protective layer of the printed wiring board is formed above at least a part of the copper or copper σ gold wiring pattern. When the wiring pattern is exposed, the boundary between the protective layer and the wiring pattern is made, so that the effect of improving the performance can be easily confirmed. Further, in the case where the entire surface of the wiring pattern is covered by the protective layer, it is impossible to confirm that the etching resistance is difficult to confirm. The printed wiring board of the present invention described above can be manufactured by the following method 19 201012851. 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 light coater, a comma coater, a screen printing machine or the like. On the wiring pattern after the roughening treatment, 50 to 1 〇〇 is used. (: drying the film, and then exposing the film to an active energy ray such as ultraviolet rays through a mask, and then removing the exposed portion by patterning with an alkali solution such as an aqueous solution of sodium hydroxide or the like, followed by heating to 120 to 25 (TC is then baked and thermally cured to form a protective layer, and may be subjected to electroless plating such as electroless nickel plating or electroplating, if necessary.) EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. Reference Example 1 (Photosensitive oxirane polyimine resin composition containing a crosslinking agent) (1) The production of a sulphur-oxygenated yoke resin was carried out with a Dean-Stark Trap. Polyethylene sulfoxide resin was charged with 862.65 g (0.639 mol) of diamine-based oxyn (diaminodiphenyl/diindolyl oxo-oxane (amine equivalent 675 g/mol)' in the reaction vessel of the synthesis apparatus. :χ·22-9409 'Shin-Etsu Chemical Industry Co., Ltd.'' 33.6' (1.〇1111〇1) 3,3',4,4,-diphenylfluorene tetracarboxylic dianhydride (Rikacid DSDA, new Made by Japan Physicochemical Co., Ltd., purity 99 6%), 547 g of diglyme, 200 g of the product was stupid, and the mixture was thoroughly stirred for 2 hours. Thereafter, the temperature was raised to 1851, and maintained at this temperature for 2 hours, at 20 201012851, the water was recovered by a Dean-Stark separation tube, and the reaction liquid was stirred under reflux. The reaction mixture was applied to a crucible wafer from which the oxide film had been removed. 'The sample was dried at 100 ° C for 10 minutes and then identified by the FT-IR transmission method. The absorption of the quinone imine carbonyl occurred near 1780 cm·1. The absorption of the cyclic anhydride carbonyl stretching vibration was confirmed in the vicinity of 1860 cm·1, so that it was confirmed that an acid anhydride terminal oxime condensate was formed. The reaction mixture was cooled to 80 C, and 101.44 g (0.361 mol) of 3, 3 was charged. '_Diamino-4,4,-dihydroxydiphenyl sulfone (BSDA, manufactured by Xiaoxi Chemical Industry Co., Ltd.; purity: 99.7%), and stirred at room temperature for 12 hours. After stirring, the temperature was raised to 1 85 °C. And heating and stirring at this temperature for 2 hours. Thereafter, it was cooled to room temperature' to obtain a varnish of a nonylphenylidene group-containing oxirane polyimine resin. (2) Photosensitive oxirane polyfluorene Preparation of imine resin composition in Shixi oxygen burning polyimine resin Lacquer A is added to the sensitizer (4NT-300, Toyo Synthetic Industrial Co., Ltd.) 1 phr, metal deactivator (rust inhibitor) (CDA-l〇, ADEKA Co., Ltd.) 0.3 phr, as a cross-linking agent Liquid epoxy resin (jER807, Sakamoto Epoxy Co., Ltd.) 0.5 phr, benzoxazine (BF_BXZ, Xiaoxi Chemical Industry Co., Ltd.) 5 Phr, resol phenolic resin (BRL_274, Showa Polymer Co., Ltd.) 2 phr was 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 fluorinated polyoxyimide resin group 21 without cross-linking agent; 201012851 product) Except that liquid epoxy resin as a crosslinking agent was not used (jER807, Sakamoto Epoxy Co., Ltd.) In the same manner as in Reference Example 1, except for the pheno-oxazine (BF_Bxz 'Xiaoxi Chemical Industry Co., Ltd.) and the resol phenolic resin (BRL-274, Showa Polymer Co., Ltd.), the oxime-agglomeration was obtained in the same manner as in Reference Example 1. The imine resin' is further prepared to obtain a photosensitive sulphur oxide polyimine resin composition. Reference Example 3 (Production of wiring board after physical roughening treatment by wet blasting) Copper-clad laminate with insulating layer thickness 25 &quot;m and copper thickness 12#m (Upisel N, Yubu Toho Kasei Copper surface of the company, using Mac〇h〇c〇.,

The blasting system of Ltd. (refer to http://www.macoho.co.jp), the surface roughening treatment is carried out by the following conditions (WB 1) to obtain the wiring board after physical roughening (average Surface roughness Ra: 73.95 nm). (WB1 condition) Abrasive: Aluminum particle size Center particle size: 6.7/zm Abrasive concentration in aqueous slurry: 14% by volume Using spray gun: Wide processing speed: 1.8m/min Projection distance: 20mm Projection angle: 90 degrees Air pressure: 0.15 MPa 22 201012851 Reference Example 4 (Production of wiring board after physical roughening by wet blasting) Except that the air pressure is set to 〇.25 MPa (WB2 condition), the rest is repeated by reference. In the manner of Example 3, a wiring board after physical roughening treatment (average surface roughness Ra: l 〇〇. 7 nm) was obtained. Reference Example 5 (Production of wiring board subjected to chemical roughening treatment)

© The copper surface of the copper-clad laminate (UpiseI N, Ube Nitto Chemical Co., Ltd.) with a thickness of 25 m and a copper thickness of 12 m, first with an acidic cleaning solution (CB-7612, MEC Co., Ltd.) Spray 1 〇 dilution (liquid temperature 25 °c), spray tap water, and then pre-soak with etchant (25 C) (BO7770VP, MEC Co., Ltd.), then use the original solution (25 C (BO7770VP, MEC Co., Ltd.) formally soaked, then sprinkle pure water, then remove the water with an air knife (5 (TC), and finally dry by blower hot air (80 C) to obtain copper surface chemically roughened Wiring board 〇 (etching amount · about 0.5 private m) 〇 Reference Example 6 (Production of wiring board subjected to chemical roughening treatment) Copper-clad laminate N with insulating layer thickness 25 &quot;m and copper thickness 12 hearts The copper surface of Ube Mindong Chemical Co., Ltd. is firstly diluted with a 1 〇 dilution of CPE-755 (CPE-755, Mitsubishi Gas Chemical Co., Ltd.) (liquid temperature 30. 浸泡, then washed with pure water) Net, then remove the water with an air knife and dry it with a blower hot air (5 (rc) A wiring board having a copper surface subjected to chemical 23 201012851 roughening treatment. Examples 1 to 6 and Comparative Examples 1 to 3 According to the combination shown in Table 1, the photosensitive oxygen of Reference Example 1 or 2 was used by a bar coater. The fired polyimine resin composition was applied to the wiring board of Reference Examples 3 to 6 to be pre-dried to become 10 β τη, and then dried by 8 (rc for 1 minute. The resin composition was irradiated through a reticle) Ultraviolet light (condition: 25 〇〇mJ/cm2) was exposed. After the exposure, the substrate was immersed in 4 (rc 3 mass% sodium hydroxide aqueous solution for 60 seconds, and the exposed portion of the resin composition film was removed for development. Then, ❹ was 30°. The substrate of C was washed with water for 60 seconds, and then washed with a dilute sulfuric acid aqueous solution of 10% by mass (room temperature) for 0.25 hours, and further washed with distilled water (room temperature) for 12 seconds. Thereafter, post-baking was performed under a nitrogen atmosphere. (200t, 6〇), and finally, the resin composition film is thermally cured to obtain a wiring board having a protective layer. <Evaluation of the effect of suppressing the bleeding of the %-form monomethyl oxysulfide granules> The wiring board of the example and the comparative example is such that the film of the resin composition film is cut. a sample having a width of 4 mm and a length of 50 mm and heating at 26 Gt for 15 minutes under a helium circulation of 5 〇 ml / * ❾ = flow rate, thereby removing volatile components from the sample and volatilizing it elsewhere The ingredients were collected in a 抓 η ΤΑ ΤΑ collection tube. Then, the collected components were vaporized under a predetermined condition in a sputum air sling, and then the gas was introduced into a gC_ms device (JAS100, manufactured by JAI Corporation). The amount of the cyclic dimethyloxy oxymethylene oligomer was quantified. The results obtained are shown in Table i. 24 201012851 &lt;Evaluation of mineralization resistance&gt; The wiring boards of the examples and the comparative examples were exposed. The copper surface is gold plated to form a gold plated film (〇.〇3 μp thick). Alternatively, the exposure exposed on the copper surface is nickel-plated/gold plated to form a hard ore Ni(3 V m)/gold plating (〇 ν m 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 the case of no discoloration was evaluated as good and slightly discolored was evaluated as poor (NG). Table 1 Comparative Example Example 1 2 3 1 2 3 4 5 6 PSIP*1 with or without cross-linking 刽 no*3 Yes*4 No*3 Yes*4 Yes*4 Yes*4 Yes*4 Yes*4 Yes*4 PWB*2 Surface Roughening Condition Conventional*5 Conventional*5 WB1*6 WB1*6 WB1*6 WB2*7 WB2*7 CE*8 CE*8 Soft Plating Au Implementation Implementation Implementation Implementation Hard Plating Ni/ Au _ _ ____ Implementation implementation of plating resistance evaluation NG NG GGGGGGG dimethyl methoxy olefin oligomer ϋ, ϋ quantity (len g / cm2) triploid D3 0.27 0.06 0.31 0.08 0.08 0.05 0.08 0.05 0.04 Tetraploid D4 0.11 0.02 0.09 0.04 0.05 0.03 0.04 0.03 0.04 Pentaploid D5 0.03 0.01 0.03 0.01 0.01 0.01 0.01 0.01 hexaploid D6 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Total of D3~D6 0.42 0.09 0.43 0.13 0.14 0.09 0.13 0.09 0.09 Other alkane 2.56 1.01 2.70 1.01 1.10 1.10 1.01 1.10 1.11 Total alkane 2.97 1.10 3.13 1.14 1.24 1.19 1.14 1.10 1.20 * 1 : Photosensitive fluorinated polyaniline resin composition 25 201012851 氺2 : Wiring board* 3 : The oxirane polyimine resin composition of Reference Example 2 * 4 : The oxygen of Reference Example 1 Polyimine resin composition * 5 : wiring board after chemical polishing treatment of Reference Example 6 * 6 : Distribution board after physical roughening treatment by wet blasting of Reference Example 3 : Reference Example 4: The wiring board after the physical roughening treatment by the wet blasting treatment * 8 : The wiring board after the chemical roughening treatment of Reference Example 5 ❹ It is clear from Table 1 that Reference Examples 3 to 5 In the wiring board after surface roughening treatment, the wiring board of Examples 1 to 6 (the protective layer provided has a specific decyl oxymethylene imide resin composition containing the crosslinking agent of Reference Example 1). The three-dimensional crosslinked structure composed of the heat-cured material can suppress the bleeding of the cyclic dimethyl anthrax and the excellent plating resistance. On the other hand, in the conventionally known chemically polished wiring board of Reference Example 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 exudation of the cyclic dimethyl methoxy olefin oligomer, and also has the problem of steep mineralization resistance. Referring to the conventionally known chemically polished wiring board of the example 6, the wiring board of Comparative Example 3 (the protective layer provided is obtained by using the reference example 1 sensitizing the yttrium-oxygenated yttrium imide resin composition) The bleed out of the cyclic dimethyl anthracycline oligomer is not inhibited, and there is still a problem of plating resistance. In contrast, in the case of Comparative Example 1, the wiring board of Comparative Example 2 (the only layer provided was a photosensitive siloxane oxide containing the cross-linking agent of Reference Example 1). Obtaining, ^ A , ) can inhibit the exudation of the cyclic dimethyl anthracene, and the plating resistance is improved compared with the 疋 疋 衩 衩 衩 , , , , 衩 衩 衩For example, ~6 phase kernels have a problem with plating resistance. Industrial Applicability The printed wiring board having the protective layer of the present invention is used as a diamine component by using a gas generator having a base of a dream base unit. Further, the protective layer such as a film formed by the photosensitive (tetra) oxysulfide sub-material (4) forms a three-dimensional structure caused by a specific thermosetting cross-linking agent, thereby preventing or even suppressing the cyclic dimethyl methacrylate The bleed out of the smoldering oligomer is further improved by thermal hardening, and the plating resistance of the squid is improved. In addition, since the copper or copper gold wiring pattern of the printed wiring board is subjected to surface roughening treatment in advance, the adhesion between the copper or steel alloy wiring pattern and the protective layer can be improved, and the plating resistance of the protective layer can be further improved. Sex. Therefore, it can be applied to a printed wiring board with high reliability. [Simple description of the diagram] ❹ None [Main component symbol description] None 27

Claims (1)

201012851 VII. Patent application scope: 1 . A printed wiring board formed on a copper or copper alloy wiring pattern of a printed wiring board, formed with a thermosetting substance composed of a photosensitive decyl oxymethylene imide resin. a protective layer; the photosensitive anthraquinone polyimine resin composition comprising a decyl alkoxyimine resin, a crosslinking agent, and a photoacid generator; the decane polyimine resin system It is obtained by the imidization of a tetracarboxylic dianhydride having a diphenylarylene unit of a nonoxyalkylene diamine and an amine containing no anthracene; characterized by: The crosslinking agent is one selected from the group consisting of liquid epoxy resins, benzoxazines, and resol phenol resins, in an amount of from 1 to 20 parts by mass based on 1 part by mass of the cerium oxide polyimine resin. At least one of the group; as the sensitizer, a photoacid generator having a mass fraction of 5 to 30 parts by mass relative to the oxime phthalimide resin, and a surface system of a copper or copper alloy wiring pattern; After surface roughening treatment. 2 · The printed wiring board according to the scope of the patent application, in which the crosslinking agent ^ liquid epoxy resin and / or benzopyrene; or liquid epoxy resin, benzene; oxazines, and resol phenolic resin class. 3. For the printed wiring board of Patent No. 1 or Brother Z, the viscosity of the liquid epoxy resin is 1~1〇〇〇〇〇mPa.s. 4. For the printed wiring board of the patent range 1~3 ..^ T, the s-tetracarboxylic dianhydride is 3 3, 4 4, _ lean and also 1 heart), 4, 4 _ one Based on tetracarboxylic dianhydride. 5. For example, in the printed wiring board of the Gans a term in the first to fourth patent applications, there are two bases in the base of the product. _ Made: / Milky one amine has the formula (1) 掮 28 (1 ) 201012851 Γ3 r?% ___sj-〇] I k I J CH3 U (where n is an integer of i~3〇, and the claw is an integer of 丨~2〇). 6. The printed wiring board according to any one of claims 5, wherein the diamine containing no alkane is a diaminophenol derivative. Ο 7. The printed wiring board of claim 6, wherein the diaminophenol derivative is 3,3'-diamino-4,4,dihydroxydiphenyl. 8. The printed wiring board according to any one of claims 1 to 7, wherein the polyoxyalkylene polyimine resin is tetracarboxylic dianhydride, terpene diamine, and no alkane. The reaction mixture of the diamine is obtained by the hydrazine imidation in the presence of 5% by mass of water. The printed wiring board according to any one of claims 1 to 8, wherein photoacid generation occurs. The agent is an ortho-quinone diazide compound. 〇10· A method for producing a printed wiring board according to item 1 of the patent application section is to perform surface roughening treatment on the surface of a copper or copper alloy wiring pattern of a printed wiring board. Forming a photosensitive decyl oxymethylene imide resin composition on at least a portion of the copper or copper alloy wiring pattern after surface roughening treatment, forming a film, exposing, developing, patterning, and borrowing Thermally hardened by post-baking to form a protective layer; the photosensitive oxirane polyimine resin composition contains a hair emulsion polyimine resin, a crosslinking agent, and a photoacid generator; The quinone imine resin is composed of tetracarboxylic dianhydride and diphenyl phenyl矽基单位 29 201012851 The shovel-imidation of diamine and dioxane-free diamine is obtained by shovel imidization; it is characterized by: using as a cross-linking agent 1 part by weight to 20 parts by mass of at least one selected from the group consisting of liquid epoxy resins, benzoxazines, and resole phenolic resins; θ as a sensitizer, using a relative oxime group The amine resin is a photoacid generator in an amount of 5 to 30 parts by mass per part by mass. The manufacturing method of the first aspect of the invention, wherein the surface roughening treatment is a wet blasting treatment using an aqueous slurry. 12. For example, the scope of patent application is treated as a chemical grinding treatment using an etchant, in which the surface is roughened. 8. Pattern: (none) 30