WO2011061899A1 - Procédé de traitement de base pour matériau à base de cuivre et matériau à base de cuivre sur lequel est fixée une couche de revêtement de traitement de base - Google Patents

Procédé de traitement de base pour matériau à base de cuivre et matériau à base de cuivre sur lequel est fixée une couche de revêtement de traitement de base Download PDF

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WO2011061899A1
WO2011061899A1 PCT/JP2010/006511 JP2010006511W WO2011061899A1 WO 2011061899 A1 WO2011061899 A1 WO 2011061899A1 JP 2010006511 W JP2010006511 W JP 2010006511W WO 2011061899 A1 WO2011061899 A1 WO 2011061899A1
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Prior art keywords
copper
copper material
aqueous
base
treatment agent
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PCT/JP2010/006511
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English (en)
Japanese (ja)
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宮崎雅矢
森和彦
石井均
中山隆臣
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日本パーカライジング株式会社
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Publication of WO2011061899A1 publication Critical patent/WO2011061899A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/383—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by microetching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H05K2203/0796—Oxidant in aqueous solution, e.g. permanganate

Definitions

  • the present invention relates to a copper material base treatment method for forming a base treatment film on the surface of a copper material, a copper material with a base treatment film, and a laminated member.
  • a method of forming an anchor has been used for a long time.
  • the surface of the metal material or the resin material may be roughened, and chemical processing methods such as mechanical processing such as blasting, etching, plating, and chemical conversion treatment are used.
  • the coating type treatment mainly composed of an elastomer disclosed in International Publication No. WO2009 / 066665 can obtain a practical level of adhesive strength to a thermosetting resin without surface roughening.
  • unevenness is formed in this coating type process between the copper wiring portion and the portion where no wiring exists, so that it is uniform.
  • a coating film is formed not only on the copper wiring but also on the surface of the insulating resin, which tends to be unfavorable in the industry from the viewpoint of influence on insulation reliability and electrical characteristics.
  • a technique (hereinafter referred to as “resin self”) can be used to form an organic resin film on the metal surface by bringing an iron-based or aluminum-based metal surface into contact with an acidic coating composition containing an organic resin.
  • Precipitation treatment is known and disclosed in Patent Documents 1 to 4 and the like.
  • a feature of conventionally known coating compositions is that an organic resin film whose thickness or weight increases with the immersion time can be formed by immersing a clean metal surface in the coating composition. Furthermore, this film formation is achieved by the chemical action of the coating composition on the metal surface (metal ions eluted from the metal surface by etching act on the resin particles and precipitate on the metal surface).
  • a resin film can be effectively formed on a metal surface without using external electricity.
  • the conventional autodeposition coating composition as described above can form an expected coating when the target metal is an iron-based metal, but when the target metal is copper. Has a problem that no film is formed or only a film having low adhesion to the resin is formed. That is, although there are many materials in the industry including a printed wiring board material having a copper wiring portion as a copper material, there is a current situation where this self-deposition coating technology cannot be applied.
  • the present invention provides a resin film that is expected to have a high adhesive force with respect to an adhesive resin material (for example, a thermosetting resin material) only on a copper member (for example, a copper wiring portion) by the above resin self-deposition treatment.
  • the object is to provide means that can be formed.
  • the present invention provides a method for grounding a copper material, which is advantageous in terms of the environment, using a grounding agent for copper material that does not use a substance that causes environmental pollution, such as hexavalent chromium, and has a low environmental load. It is another object of the present invention to provide a copper material with a base treatment film and a laminated member obtained by the method.
  • the present inventor treated a copper material with a predetermined liquid aqueous base treatment agent containing an organic resin, an anionic surfactant, an acid and a predetermined oxidizing agent.
  • a resin material for example, a thermosetting resin material
  • the present invention (1) comprises an aqueous liquid containing an iron (III) ion as an organic resin (A), an anionic surfactant (B), an acid (C) and an oxidizing agent (D) having a pH of 3 or less. It has an application process for bringing a copper material into contact with an aqueous base treatment agent, a water washing process for washing the ground treatment film formed on the copper material by the application process, and a drying process for drying after the water washing process. This is a copper material ground treatment method.
  • the present invention (2) is the ground treatment method of the invention (1), wherein the organic resin (A) is an elastomer.
  • elastomer means a generic name for industrial materials having rubber-like elasticity.
  • the anionic surfactant (B) is one or more selected from alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl diphenyl ether disulfonate, and alkane sulfonate, and the total content is In the ground treatment method according to the invention (1) or (2), the content is 500 to 3000 ppm.
  • the range of the carbon number of the “alkyl” part or “alkane” part of the surfactant is preferably 1 to 15.
  • the present invention (4) provides an anion source (E) having a first complex stability constant ⁇ 1 -Fe (III) of 5 or more with iron (III) ions at 25 ° C. and an ionic strength of 0.5 M. Further, it is a surface treatment method according to any one of the inventions (1) to (3).
  • the present invention (5) is the surface treatment method according to any one of the inventions (1) to (4), wherein the aqueous surface treatment agent further contains 1 to 1000 ppm of copper ions (F).
  • the present invention (6) is the ground treatment method according to any one of the inventions (1) to (5), wherein the copper material is a printed wiring board material.
  • the present invention (7) is a copper material with a base coating film obtained by any one of the base processing methods of the inventions (1) to (6).
  • the ratio of the copper element in the base treatment film is 0.1 to 10 atomic%, and the iron element content in the base treatment film is 0.003 g / m 2 or less. This is a copper material with an undercoat film.
  • the change ⁇ Ra of the copper material surface roughness (Ra 1 ) after the base treatment relative to the copper material surface roughness (Ra 0 ) before the base treatment is 0.5 ⁇ m or less.
  • it is a copper material with a base-treatment film of (8).
  • the present invention (10) is a laminated member comprising the copper material with a base treatment film of any one of the inventions (7) to (9) and a resin layer provided on the base treatment film.
  • the ground treatment coating film according to any one of the inventions (7) to (9) is formed only on the surface of the copper circuit.
  • the present invention (12) is an aqueous liquid having an organic resin (A), an anionic surfactant (B), an acid (C) and an oxidizing agent (D) containing iron (III) ions and having a pH of 3 or less. It is the aqueous
  • This invention (13) is the aqueous
  • the anionic surfactant (B) is one or more selected from alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl diphenyl ether disulfonate, and alkane sulfonate, and the total content is
  • the present invention (15) provides an anion source (E) having a first complex stability constant ⁇ 1 -Fe (III) of 5 or more with iron (III) ions at 25 ° C. and an ionic strength of 0.5 M.
  • the aqueous base treating agent for copper materials according to any one of the inventions (12) to (14), further contained.
  • the present invention (16) is the aqueous base treatment agent for copper materials according to any one of the inventions (12) to (15), further containing 1 to 1000 ppm of copper ions (F).
  • the present invention (17) is the aqueous base treating agent for copper materials according to any one of the inventions (12) to (16), which is for printed wiring board materials.
  • an autodeposition film having a high adhesive force is formed on a resin material to be adhered (for example, a thermosetting resin material).
  • a resin material to be adhered for example, a thermosetting resin material.
  • the positive charge of the iron ion as the oxidant can be prevented without affecting the film formation reaction between the copper (II) ion and the organic resin or the like. As a result, the liquid stability can be improved.
  • the composition for autodeposition coating according to the present invention does not affect the performance of the autodeposition coating formed even if copper ions are contained. In this case, there is no problem even if copper ions are eluted and remain in the composition for self-deposited self-deposited film from copper, which is the target metal, so the same composition for self-deposited film can be repeated several times without frequent replacement. Also has the effect of being usable.
  • the autodeposition coating does not substantially contain iron, there is an effect that it is possible to provide a copper material having higher adhesive force.
  • the transmission loss can be reduced as compared with the case where the copper material surface is roughened. There is an effect that can be done.
  • a wiring board can be provided.
  • FIG. 1 is a schematic cross-sectional view showing a laminated member of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing the structure of the printed wiring board of the present invention.
  • FIG. 3 is a cross-sectional photograph of a copper circuit part of a single-sided copper circuit-formed epoxy resin plate.
  • 4 is a cross-sectional photograph of a copper circuit part of a single-sided copper circuit-forming epoxy resin plate with a base coating obtained in Example 4.
  • FIG. FIG. 5 shows the XPS depth direction analysis results for the autodeposition coating for Example 5.
  • FIG. 6 shows the XPS depth direction analysis results for the autodeposition coating for Comparative Example 5.
  • the aqueous surface treating agent for copper material of the present invention contains an organic resin (A), an anionic surfactant (B), an acid (C), and iron (III) ions as an oxidizing agent (D), and has a pH of 3 It consists of the following aqueous liquid.
  • the said processing agent is by adding an acid (C) and an oxidizing agent (D) essential in the aqueous liquid containing organic resin (A) and anionic surfactant (B), for example. It is a liquid obtained.
  • the object of the surface treatment with the ground treatment liquid of the present invention is a copper material.
  • the copper material is not particularly limited, and specific examples thereof include pure copper and a copper alloy.
  • the shape, structure, etc. of the copper material used in the present invention are not particularly limited, and may be, for example, a plate shape, a foil shape, a rod shape, a granular shape, or the like.
  • the copper material used also in the present invention may be a material coated with another metal material, ceramic material, or organic material base material by a technique such as plating or vapor deposition.
  • the copper alloy preferably contains 50% by mass or more of copper, and examples thereof include brass. Examples of alloy components other than copper in the copper alloy include Zn, P, Al, Fe, Ni, and the like.
  • Organic resin (A)> First, the organic resin (A) that is the first essential additive component of the aqueous base treatment agent according to the present invention will be described.
  • the organic resin (A) is a main component of the base treatment film obtained by treating the copper material.
  • the organic resin (A) is forcibly emulsified using (1) an anionic surfactant (B) described later, (2) sulfone group, carboxyl group, phosphone group, phenolic It may be a self-emulsifying agent to which a hydrophilic group such as a hydroxyl group, a hydroxyl group, or ethylene oxide is added, or (3) a combination thereof.
  • an anionic surfactant (B) described later, (2) sulfone group, carboxyl group, phosphone group, phenolic It may be a self-emulsifying agent to which a hydrophilic group such as a hydroxyl group, a hydroxyl group, or ethylene oxide is added, or (3) a combination thereof.
  • the organic resin (A) and the anionic surfactant (B) exist as separate compounds.
  • Surfactant (B) exists as the same compound.
  • the organic resin (A) may be any type, and for example, a conventionally known water-dispersible or water-soluble organic resin can be used. Specifically, elastomer, acrylic resin, epoxy resin, urethane resin, polyester resin, polyamide resin, vinyl chloride resin, vinylidene chloride resin, fluorine resin, silicon resin, polyolefin resin, phenol resin, urea resin, melamine resin, polyimide, Examples include polyamine, nylon resin, polyphenylene sulfide and the like dissolved or dispersed in a solvent.
  • the elastomer is not particularly limited, and a conventionally known elastomer dissolved or dispersed in water can be used.
  • Specific examples of the elastomer include diene rubbers such as natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, acrylonitrile butadiene styrene rubber, and methyl methacrylate butadiene rubber; butyl rubber, ethylene Examples include propylene rubber, urethane rubber, silicone rubber, chlorosulfonated rubber, chlorinated polyethylene, acrylic rubber, epichlorohydrin rubber, fluorine rubber, and the like dissolved or dispersed in water.
  • the glass transition temperature (Tg) of the elastomer ⁇ glass transition temperature measured using a differential scanning calorimeter (for example, DSC6200: manufactured by Seiko Instruments Inc.) ⁇ is preferably ⁇ 100 to 350 ° C., and ⁇ 65 to More preferably, it is 110 degreeC.
  • the specific gravity of the elastomer is preferably 0.8 to 2.0.
  • butadiene rubber, acrylonitrile butadiene styrene rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, methyl methacrylate butadiene rubber, and acrylic rubber are the reason for their high affinity with the thermosetting resin to be bonded. To preferred.
  • ⁇ Essential additive component 2 Anionic surfactant (B)> Next, the anionic surfactant (B) that is the second essential additive component of the aqueous ground treatment agent according to the present invention will be described.
  • An anionic surfactant (B) is not specifically limited, A conventionally well-known anionic surfactant can be used.
  • the anionic surfactant (B) is adsorbed to the water-dispersible or water-soluble organic resin (A) in the surface treatment agent by being contained in the surface treatment agent. It is a component necessary for generating a negative charge for electrostatic aggregation with copper ions in the water-dispersible or water-soluble organic resin (A).
  • anionic surfactant examples include alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl diphenyl ether disulfonate, alkane sulfonate, alkyl sulfate ester, polyoxyethylene alkyl ether sulfate ester, carboxy Examples thereof include rate surfactants, phosphate surfactants, naphthalenesulfonic acid formalin condensates, and polycarboxylic acid type surfactants.
  • anionic surfactants (B) one or more selected from alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl diphenyl ether disulfonates, and alkane sulfonates
  • the mechanism of action is not clear at present, Furthermore, when it is contained in the aqueous base treatment agent, there is an effect of reducing the film thickness of the base treatment film deposited on the surface of the copper material.
  • the aqueous base treatment agent of the present invention When considering the effect of the base coating on the electrical characteristics of the printed wiring board, especially when considering the application of the aqueous base treatment agent of the present invention as a process for improving the adhesion between the copper circuit and the interlayer insulating resin material of the printed wiring board In some cases, it is better to use a thin film as much as possible, and it becomes possible to stably form a base treatment film having a film thickness of 1 ⁇ m or less, which is considered to be less affected by the addition of the anionic surfactant.
  • an elastomer is suitable as the organic resin (A), but as a commercial product of an aqueous liquid containing an elastomer and an anionic surfactant, as for butadiene rubber, BATERACOL E-301 of DIC Corporation, acrylonitrile the butadiene-styrene rubber, Emerald Performance Materials, Inc. of Nychem1570X75, Nychem1562X160, Nychem1577,1578X1, are exemplified, for acrylonitrile butadiene rubber, EmeraldPerformance Materials Co.
  • NipolLX811B NipolLX814, NipolLX816, NipolLX820A, NipolLX821, NipolLX844B, NipolLX851C, NipolLX851E, NipolLX851F, NipolLX852, NipolLX854E, NipolLX855EX1, NipolLX857X2, NipolLX874, NipolSX1706, Lubrizol Corp.
  • Hycar26843 HycarT-122, HycarT-9202, Hycar26-1042, Hycar26477, Hycar26717, Hycar26479, Hycar26-1199, Hycar26083, Hycar26322, Hycar26552, Hycar26-0202, Hycar26092, Hycar2671, Hycar26120, HycarT-9207, Hycar26319, Hycar26871, Hycar26345, Hycar26- 0912, Hycar2679, Hycar26779, Hycar26084, Hycar26349, Hycar26091, Hycar26288, Hycar26-1265, Hycar26138, Hycar26523, Hycar26-1084, Hy ar26106, Hycar26348, Hycar26450, Hycar26688, Hycar26172, Hycar26391, Hycar26256, Hycar26-1475, Hycar26315, Hycar26459, Hycar594, Hycar595, Hycar2003, HystretchV-60, HystretchHystretchV-43, Hycar2631
  • the acid (C) which is the third essential additive component of the aqueous base treatment agent according to the present invention will be described.
  • the acid (C) is a component necessary for forming a surface treatment film having high water-washing resistance that does not fall off even when washed with water on the copper material.
  • the action mechanism of the acid (C) is not clear at the present time, but the treatment agent pH is lowered by containing the acid (C) in the aqueous base treatment agent as one action.
  • Examples of the acid (B) include at least one selected from zircon hydrofluoric acid, titanium hydrofluoric acid, silicohydrofluoric acid, borohydrofluoric acid, hydrofluoric acid, phosphoric acid, nitric acid, and the like. More preferably, at least one selected from hydrofluoric acid is used.
  • oxidizing agent (D) which is the fourth essential additive component of the aqueous ground treatment agent according to the present invention.
  • the oxidizing agent (D) is formed by electrostatically aggregating the water-dispersible or water-soluble organic resin (A) on the surface of the copper material by oxidizing and dissolving the copper material. It is a source of copper ions necessary for deposition.
  • the standard hydrogen electrode potential E 0 (25 ° C.) in the reaction of the formula (1) is 0.34 V
  • the standard hydrogen electrode potential E 0 (25 ° C.) in the reaction of the formula (2) is 0 V
  • oxidizing agent for copper for example, nitric acid compounds such as nitrous acid, peroxonitric acid, peroxonitrous acid, nitroxylic acid, trioxodinitric acid, tetraoxodinitric acid, Sulfuric acid compounds such as nitrous acid, peroxonitric acid, peroxonitrous acid, nitroxylic acid, trioxodinitric acid, tetraoxodinitric acid, salts thereof; halogen acid-based compounds such as perchloric acid, chloric acid, nitrous acid Chloric acid, hypochlorous acid, perbromic acid, bromic acid, bromous acid, hypobromite, periodic acid, iodic acid, hypoiodous acid, salts thereof; organic peroxides such as hydrogen peroxide , Ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, per
  • an iron (III) ion supply source for supplying iron (III) ions into the liquid, specifically, for example, iron (III) fluoride, iron chloride (III), iron bromide (III) , Iron (III) iodide, iron (III) sulfate, iron (III) nitrate, iron (III) acetate, iron (III) acetylacetone, iron (III) citrate, iron (III) glycine, iron (III) oxalate , Iron (III) picolinate, iron (III) L-phenylalanine, iron (III) malonate, and the like, and these may be used alone or in combination of two or more.
  • the aqueous base treatment agent according to the present invention may contain conventionally known various components and additives.
  • the anion supply source (E), the copper ion (F), and the hydrogen peroxide (G) will be described in particular, but this does not exclude the inclusion of other optional components.
  • anion supply source (E) which is an optional component of the aqueous ground treatment agent according to the present invention
  • An anion source (E) in which the first complex stability constant ⁇ 1 -Fe (III) with iron (III) ions at 25 ° C. and ionic strength 0.5 M is 5 or more is added to the treatment agent.
  • the electrostatic force due to the positive charge of the iron (III) ion can be weakened, thereby improving the liquid stability. Can be increased.
  • the iron (III) ion supply source for supplying iron (III) ions as the oxidizing agent (D) into the liquid and the anion supply source (E) may be derived from the same compound.
  • iron (III) fluoride, iron (III) oxalate, and iron (III) citrate exemplified as the iron (III) ion supply source correspond to this.
  • Copper ion (F) The copper ion (F) that is an optional component of the aqueous base treatment agent according to the present invention will be described.
  • copper ions (F) include copper (I) ions and copper (II) ions, and these may be used alone or in combination of two or more.
  • These metal ions are present in the surface treatment agent of the present invention by adding or immersing at least one selected from a copper (II) compound, a copper (I) compound, and metal copper in the aqueous surface treatment agent. You can make it.
  • a copper (I) compound copper (I) chloride etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.
  • the copper (II) compound examples include copper formate (II), copper (II) acetate, copper (II) propionate, copper (II) valerate, copper (II) gluconate, and copper tartrate.
  • Copper salts of organic acids such as (II); copper chloride (II), copper bromide (II), copper hydroxide (II), copper acetate (II), copper nitrate (II), copper sulfate (II), carbonic acid
  • Examples thereof include copper (II), copper oxide (II), copper fluoride (II), copper sulfide (II); these may be used alone or in combination of two or more.
  • the metal copper the above copper material can be used.
  • hydrogen peroxide (G) is further contained as an oxidizing agent.
  • iron (III) ions act as an oxidizing agent, they themselves become iron (II) ions, but if they contain hydrogen peroxide, the iron (II) ions are oxidized and returned to iron (III) ions. This is because there is an effect.
  • the aqueous base treatment agent according to the present invention is an aqueous liquid medium (aqueous liquid) containing (or containing) the above-described components.
  • the “aqueous liquid medium” is a liquid medium mainly composed of water.
  • the “main body” means that at least 50% by volume or more is water based on the total mass of the liquid medium.
  • It may contain a liquid medium other than water, for example, alkanes such as hexane and pentane; aromatics such as benzene and toluene; alcohols such as ethanol, 1-butanol and ethyl cellosolve; tetrahydrofuran, dioxane and the like Suitable ether systems; ester systems such as ethyl acetate and butoxyethyl acetate; amide systems such as dimethylformamide and N-methylpyrrolidone; sulfone solvents such as dimethyl sulfoxide; phosphate amides such as hexamethylphosphate triamide; Can be used.
  • alkanes such as hexane and pentane
  • aromatics such as benzene and toluene
  • alcohols such as ethanol, 1-butanol and ethyl cellosolve
  • tetrahydrofuran, dioxane and the like Suitable
  • the organic resin (A) is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass, based on the total amount of the surface treatment agent.
  • the content of the organic resin (A) is within this range, after the copper material used in the present invention is treated with the ground treatment agent, the ground treatment film is prevented from falling off during washing.
  • the concentration of the elastomer in an elastomer dispersion solution (also referred to as an emulsion) in which the elastomer is dissolved or dispersed in water is not particularly limited, but from the viewpoint of ease of handling of the treatment agent, 1 ⁇ 80% by mass is preferable, and 10 to 60% by mass is more preferable.
  • the viscosity of the dispersion is not particularly limited, but is preferably 5 to 3000 cP from the viewpoint of easy handling of the treatment agent.
  • the particle size of the elastomer in the dispersion is not particularly limited, but is preferably 0.001 to 10 ⁇ m, and more preferably 0.01 to 2 ⁇ m.
  • the content of the anionic surfactant (B) is preferably 100 to 10,000 ppm, more preferably 500 to 3000 ppm, based on the total amount of the surface treatment agent.
  • the substrate with a film thickness of 1 ⁇ m or less It becomes possible to form a treatment film stably.
  • the acid (C) is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, based on the total amount of the aqueous surface treatment agent.
  • the content of the acid (C) is within this range, after the copper material used also in the present invention is treated with the ground treatment agent, the ground treatment film drop-off preventing property at the time of washing with water becomes better.
  • the oxidizing agent (D) is preferably 0.01 to 10% by mass, and 0.05 to 5% by mass, based on the total amount of the aqueous surface treatment agent. More preferred. When the content of the oxidizing agent (D) is within this range, the metal material used also in the present invention is treated with the base treatment agent, and then the self-deposited film is prevented from falling off during washing.
  • the anion (E) is preferably 0.01 to 10% by mass, and 0.05 to 5% by mass, based on the total amount of the aqueous surface treatment agent. More preferred. When the content of the oxidizing agent (D) is within this range, the liquid stability becomes good while maintaining the reactivity of the base treatment agent.
  • the copper ion (F) is preferably 0.0001 to 0.1% by mass, and 0.001 to 0.05% by mass with respect to the total amount of the aqueous base treatment agent. It is more preferable that When the content of copper ions (F) is within this range, when a metal material used also in the present invention is treated with a ground treatment agent, a stable ground film deposition amount can be obtained even when treated with a treatment load. It is done.
  • the concentration of the oxidant is sufficient to oxidize and maintain all iron ions present in the liquid to iron (III) ions. It needs to be an appropriate amount.
  • the concentration of the oxidizing agent can be managed by an oxidation-reduction potential measured with a commercially available ORP electrode using a platinum electrode as a working electrode.
  • the preferable oxidation-reduction potential is at least 300 mV or more, preferably 350 mV or more. If it is lower than 300 mV, ferrous ions having a low complex stability with fluoride ions may be present in the treatment liquid, and as a result, the stability of the treatment liquid may be reduced.
  • the copper material ground treatment method according to the present invention includes a liquid contact step of bringing the aqueous base treatment agent of the present invention into contact with a copper material, and the above liquid contact After the step, the copper material is ground-treated with a step of removing acid (C) and oxidant (D) by washing with water and a drying step of drying after the washing step.
  • the liquid contact step is a step of bringing the aqueous base treatment agent of the present invention described above into contact with the copper material used in the present invention.
  • the liquid contact method in the liquid contact step is not particularly limited, and can be applied by a method such as a dipping method, a spray method, or a combination thereof.
  • the use conditions of the surface treatment agent of this invention in the said liquid-contacting process are not specifically limited.
  • the temperature of the treating agent when applying the base treating agent and the copper material used in the present invention is preferably 10 to 90 ° C., more preferably 20 to 50 ° C. Since the use of useless energy can be suppressed as the temperature is 50 ° C. or less, it is preferable from an economical viewpoint.
  • the time for contacting the substrate treatment agent can be set as appropriate.
  • the water washing method in the water washing step is not particularly limited, and for example, water washing can be performed by a method such as a dipping method, a spray method, or a combination thereof.
  • the washing time can be set as appropriate.
  • the said drying process is a process of drying after a water washing process and forming a base film.
  • the drying temperature is not particularly limited because it varies depending on the solvent used. For example, when water is used as the solvent, it is preferably in the range of 50 to 200 ° C.
  • the copper material with an undercoat of the present invention is a copper material obtained by surface treatment using the above-described undercoat agent of the present invention.
  • the formed undercoat is described in detail.
  • the film thickness of the resulting undercoat is preferably from 0.01 to 20 ⁇ m, more preferably from 0.05 to 5 ⁇ m.
  • the base coat on the metal material obtained by the base treatment method of the present invention contains a copper element in addition to the water-dispersible or water-soluble organic resin (A).
  • A water-dispersible or water-soluble organic resin
  • the copper elemental content (atomic ratio) is 0.01 to 10 atomic%, and when the iron element content (atomic ratio) derived from the oxidant (D) is similarly calculated, the signal-to-noise ratio When the detection limit was 2 or less, it was below the detection limit.
  • X-ray fluorescence analysis apparatus; ZSX-Primus (manufactured by Rigaku) was performed and a calibration curve was obtained.
  • the iron content in the film was measured by the method, it was below the detection limit (0.003 g / m 2 ), and iron element was present in the base film on the metal material obtained by the base treatment method of the present invention. Not contained is a factor in high adhesive performance as will be described later. At the moment I think that it is.
  • the change ⁇ Ra of the metal surface roughness (Ra 1 ) after the treatment with respect to the thickness (Ra 0 ) can be 0.5 ⁇ m or less, preferably 0.3 ⁇ m or less.
  • the transmission loss can be reduced as compared with the case where the surface of the copper material is roughened.
  • the surface of the copper material is roughened, and even when a copper foil having a surface roughness Ra of 0.2 ⁇ m or less is used, the surface average roughness Ra is usually It exceeds 1 ⁇ m, and the effect of the present invention cannot be obtained.
  • the metal material with an undercoat according to the present invention and the metal material before processing are embedded in a resin, cross-sectional SEM observation is performed at a magnification of 10,000 times, and Ra 1 is determined from the metal surface roughness profile.
  • the average surface roughness Ra (arithmetic average surface roughness Ra) is a value represented by an abbreviation of Ra according to JISB 0601, and represents an average value of absolute value deviations from an average line of surface roughness values.
  • the laminated member of the present invention is a laminated member having the above-described copper material with an undercoat of the present invention and a thermosetting resin material provided on the undercoat.
  • the structure of the laminated member of the present invention is not particularly limited, and may be, for example, a plate shape, a foil shape, a rod shape, or a complicated shape.
  • FIG. 1 is a schematic cross-sectional view showing a plate-like laminated member of the present invention as an example of the laminated member of the present invention.
  • a laminated member 1 shown in FIG. 1 includes a copper material 2, a base film 3 formed thereon using the base treatment agent of the present invention, and a thermosetting resin material layer 4 provided on the base film 3. And have.
  • the cause of the copper material treated with the copper material ground treatment agent according to the present invention is not clear at the present time, but unlike the prior art, surface roughening of the metal material is suppressed.
  • thermosetting resin material As the material of the thermosetting resin layer, a conventionally known resin having a functional group expected to be crosslinked by heating can be used. Specific examples include acrylic resins, epoxy resins, phenol resins, urea resins, melamine resins, urethane resins, thermosetting polyimides, unsaturated polyesters, bismaleimide triazine resins, and the like. Examples of functional groups that are expected to be crosslinked by heating include hydroxyalkyl groups such as amino groups, hydroxyl groups, and methylol groups, phenol groups, carboxyl groups, epoxy groups, isocyanate groups, and carbodiimide groups. These may be used alone or in combination of two or more. These resins may be modified with a functional group.
  • the resin layer is made of metal such as glass fiber, calcium carbonate, aramid fiber, graphite, carbon black, alumina, aluminum nitride, boron nitride, silver, copper, etc. from the viewpoint of improving reinforcement, thermal conductivity, and electrical conductivity. It may contain a filler such as powder.
  • One preferred embodiment of the resin layer material is a prepreg.
  • a prepreg means a sheet-like fiber base material impregnated with a thermosetting resin to be in a semi-cured state.
  • Examples of the material of the sheet-like fiber base material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as aramid, polyimide, polyester, and polytetrafluoroethylene, and mixtures thereof. Etc. These fiber base materials have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfacing mats, but the materials and shapes are selected according to the intended use and performance of the molded product, and as required. , Alone or in combination of two or more materials and shapes.
  • the laminated member of the present invention can be obtained by bonding a thermosetting resin layer to the above-described metal material with a base coating of the present invention via the base coating.
  • the bonding method is not particularly limited. Specifically, in the case of a thermosetting resin layer epoxy resin, for example, (1) An uncured liquid epoxy resin is applied to a base film of a metal material with a base film. Then, a coating method in which a resin layer is formed by drying and curing, and (2) an epoxy resin film is laminated on the base film of the metal material with the base film so that the base film and the epoxy resin film are in contact with each other.
  • An epoxy resin layer is formed by injecting a molten epoxy resin into the mold so that the metal material with the base coat is set in the mold and in contact with the base coat.
  • an injection molding bonding method may be used.
  • the laminated member of this invention is excellent in the adhesive strength with the thermosetting resin layer adhere
  • the surface treatment agent of the present invention can be suitably used as a treatment for improving the adhesion between the copper circuit and the interlayer insulating resin material of the printed wiring board.
  • the substrate treating agent of the present invention can be applied to conventionally known types of printed wiring boards, specifically, single-sided printed wiring boards, double-sided printed wiring boards, multilayer printed wiring boards, build-up printed wirings. Examples are a substrate, a collective laminated printed wiring board, a flex-rigid printed wiring board, a component built-in printed wiring board, and a metal-based printed wiring board.
  • the surface treatment agent of the present invention is not particularly limited with respect to the number of layers in the printed wiring board, the copper wiring pattern, the copper wiring width, the copper wiring height, the gap width, the insulating resin layer thickness, and the like. Applicable to
  • the surface treatment agent of the present invention is not limited with respect to a method for forming a copper circuit in a printed wiring board, and conventionally known methods can be applied. Specifically, a subtractive method, an additive method, an additive-subtractive method, and the like are exemplified.
  • the surface treatment agent of the present invention is not particularly limited with respect to the interlayer insulating resin layer, and can be applied to conventionally known thermosetting resins.
  • FIG. 2 is a schematic cross-sectional view of a four-layer printed wiring board as an example of a printed wiring board manufactured using the ground treatment agent of the present invention.
  • a ground coating film is formed only on the surface of the copper circuit. Since a film is not formed on the surface of the insulating resin layer where the copper wiring circuit is not formed, it is preferable from the viewpoint of influence on insulation reliability and electrical characteristics.
  • the film thickness of the undercoat film is not particularly limited, but is preferably 0.01 to 20 ⁇ m, and more preferably 0.05 to 5 ⁇ m.
  • the surface roughness of the copper material surface is 0. 0 in terms of skin effect. It is preferably 35 ⁇ m or less, preferably 0.2 ⁇ m or less.
  • Copper foil electrolytic copper foil (purity 99.8% by mass or more), thickness 18 ⁇ m, Ra 0.3 ⁇ m Nickel foil: (purity 99% by mass or more), thickness 20 ⁇ m -Single-sided copper circuit forming epoxy resin plate, LS12.5 ⁇ m, epoxy resin layer thickness 0.1mm
  • Example 1 As a water-soluble and water-dispersible organic resin (A), an aqueous dispersion of acrylonitrile butadiene styrene rubber having a carboxyl group and a methylol group (solid content concentration: 47%, pH: 8, viscosity: 45 cP, Tg: 18 ° C., Specific gravity: 1.01) 5 parts by weight, anionic surfactant (B), sodium alkyldiphenyl ether disulfonate (Kao Co., Ltd., Perex SS-H, solid content concentration 50%) as solid content 0
  • An aqueous liquid containing a water-dispersible organic resin (A) and an anionic surfactant (B) is prepared by mixing .15 parts by weight and 89.5 parts by weight of deionized water, The base treatment was performed by adding and dissolving 5 parts by weight of nitric acid (active ingredient 60%) as the acid (C) and 0.35 parts by weight of iron fluoride as the oxid
  • a surface treatment was performed in which the copper foil of the material to be treated was immersed in the treatment agent (temperature: 25 ° C.) for 3 minutes.
  • anionic surfactant (B) a sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, demole NL, solid content concentration 41%) as a solid content of 0.25 parts by weight, deionized Except for adding 88.5 parts by weight of water, a surface treatment agent (b
  • Example 3 As water-soluble and water-dispersible organic resin (A), an aqueous dispersion of acrylic rubber having a carboxyl group (solid content concentration: 48.5%, pH: 8, viscosity: 70 cP, particle size: 0.24 ⁇ m, Tg) : -29 ° C, specific gravity: 1.04, surface tension: 42 dyne / cm) and 10 parts by weight of anionic surfactant (B), sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, Neoperex G- 15 by mixing 0.02 parts by weight with a solid content of 16%) and 84.63 parts by weight of deionized water, thereby dissolving the water-soluble organic resin (A) and the anionic surfactant (B An aqueous liquid containing 5 parts by weight of nitric acid (active ingredient 60%) as the acid (C) and 0.1% of iron fluoride as the oxidizing agent (D) and the anion (E).
  • Example 4 Using the ground treatment agent (a), a surface treatment was performed in which the single-sided copper circuit forming epoxy resin plate of the material to be treated was immersed in the treatment agent (temperature: 25 ° C.) for 10 minutes.
  • Example 5 A surface treatment agent (d) having the same composition as the surface treatment agent (a) except that 10.9 parts by weight of iron (III) ammonium oxalate trihydrate is added as the oxidizing agent (D) and the anion (E). )
  • a surface treatment was performed in which the copper foil of the material to be treated was immersed in the treatment agent (temperature: 25 ° C.) for 3 minutes.
  • FIG. 3 shows a cross-sectional photograph of a copper circuit portion of a single-sided copper circuit-formed epoxy resin plate
  • FIG. 4 shows a cross-sectional view of the copper circuit portion of the single-sided copper circuit-formed epoxy resin plate with an undercoat obtained in Example 4. It is a photograph. It was confirmed that an undercoat having a thickness of 1 ⁇ m or less was uniformly formed on the copper circuit portion, and no undercoat was formed on portions other than the copper circuit portion. In addition, the underlying film thickness was measured from cross-sectional observation. The results are shown in Table 1.
  • the iron element content (atomic%) was estimated from the element content (atomic%) other than the iron element obtained by the XPS analysis and the film thickness measurement result.
  • ⁇ Fluorescence X-ray analysis> ⁇ Device: ZSX-Primus (manufactured by Rigaku) Excitation: Rh-K ⁇ , 30kV-100mA ⁇ Measurement area: 10mm ⁇
  • the base coating film obtained in Example 1 is below the detection limit (the signal-to-noise ratio is 2 or less) at the measurement depth, and the fluorine element and the iron element derived from the oxidant (D) are below.
  • the carbon element derived from acrylonitrile butadiene styrene rubber, which is a water-soluble organic resin (A) is also below the detection limit (0.003 g / m 2 ) for the measurement of iron content in the film using fluorescent X-ray analysis. It was confirmed that it was composed of nitrogen element and copper element derived from the metal substrate to be treated. The copper element content was 6 atomic% at the outermost surface with a sputtering time of 1 sec, and thereafter 1-2 atomic%.
  • the undercoat obtained in Comparative Example 5 is similar to Example 1 in the measurement depth, and the carbon element and nitrogen element derived from acrylonitrile butadiene styrene rubber, which is a water-soluble organic resin (A).
  • the copper element derived from a to-be-processed metal base material was detected.
  • iron atoms derived from the oxidant (D) were detected only on the outermost surface with a sputtering time of 1 sec, and the content was 1.5 atomic%.
  • the iron content in the film obtained by the technique using fluorescent X-ray analysis was 0.02 g / m2. When the iron element content was estimated, it was 0.5 atomic%.
  • the copper element content was 14 atomic% at the outermost surface with a sputtering time of 1 sec, and thereafter 3-4 atomic%.
  • Adhesiveness A glass cloth base epoxy resin sheet (manufactured by Hitachi Chemical Co., Ltd.) having a thickness of about 100 ⁇ m was applied to the copper material with an undercoat obtained in Examples 1 to 3 and 5 and Comparative Examples 1 to 6. (Product name: GEA-679N), and further laminated with the roughened surface of the copper foil facing the back side of the glass cloth base epoxy resin sheet, heating temperature 180 ° C., pressure 45 kgf / cm 2 , heating time 1 It was press-bonded under time conditions to obtain a metal material-epoxy resin laminated member.
  • ⁇ Heat resistant secondary adhesion test> The laminated member was cut to a width of 1 cm, heated in an oven at 275 ° C. for 1 minute, and then allowed to stand at room temperature for 30 minutes. Then, a 90 ° peel test similar to the primary adhesive property was performed, and the peel strength was measured. .
  • the copper material with the undercoat of the present invention (Examples 1 to 3, 5) obtained by the surface treatment method of the present invention using the surface treatment agent of the present invention was laminated with an epoxy resin. And when it was set as the laminated member of this invention, it was confirmed that the outstanding adhesiveness between a copper material and an epoxy resin, especially the outstanding adhesiveness under high temperature is shown.
  • Comparative Example 2 containing no anionic surfactant (B), Comparative Example 3 using Ni foil as the material to be treated, and Comparative Example 4 in which no acid (C) was added, no film was deposited, and in any adhesive strength was confirmed to be inferior.
  • the ground treatment agent of the present invention is not only bonded to the copper material and the resin in the printed wiring board described in the background art, but also to various copper materials by a method such as a coating method, a laminate bonding method, and an injection molding bonding method. It is also useful as a base treatment agent for forming a thermosetting resin.

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Abstract

Cette invention concerne des moyens de formation d'une couche de revêtement en résine conçue pour avoir une forte adhérence sur un matériau en résine d'intérêt (par exemple, un matériau thermodurcissable) uniquement sur un matériau en cuivre (par exemple, une partie de câblage en cuivre) dans une technique de formation de couche par autodéposition. Cette invention concerne spécifiquement un procédé de traitement de base pour un matériau à base de cuivre, caractérisé en ce qu'il comprend : une étape d'application consistant à mettre en contact avec le matériau à base de cuivre un agent de traitement de base aqueux comprenant (A) une résine organique, (B) un agent de surface anionique, (C) un acide, et (D) un oxydant comprenant une solution aqueuse contenant un ion de fer (III) et ayant un pH inférieur ou égal à 3 ; une étape de rinçage à l'eau consistant à rincer à l'eau une couche de revêtement de traitement de base formée sur le matériau à base de cuivre lors de l'étape d'application ; et une étape de séchage consistant à sécher la couche de revêtement après l'étape de rinçage.
PCT/JP2010/006511 2009-11-17 2010-11-05 Procédé de traitement de base pour matériau à base de cuivre et matériau à base de cuivre sur lequel est fixée une couche de revêtement de traitement de base WO2011061899A1 (fr)

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JP6837332B2 (ja) * 2016-12-28 2021-03-03 日本パーカライジング株式会社 化成処理剤、化成皮膜の製造方法、化成皮膜付き金属材料、及び塗装金属材料
CN112064003B (zh) * 2020-08-20 2022-06-17 华帝股份有限公司 一种前处理剂及其制备方法和应用

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JP2003129254A (ja) * 2001-10-22 2003-05-08 Nikko Materials Co Ltd 銅及び銅合金の表面処理剤
JP2004140268A (ja) * 2002-10-18 2004-05-13 Matsushita Electric Works Ltd 高周波用多層プリント配線板の製造方法
JP2004346410A (ja) * 2003-05-26 2004-12-09 Nippon Paint Co Ltd 防錆皮膜の形成方法
JP2007291448A (ja) * 2006-04-25 2007-11-08 Hitachi Chem Co Ltd 銅箔の表面処理方法及び銅箔
JP2008274311A (ja) * 2007-04-02 2008-11-13 Mec Kk 基板の製造方法及びこれに用いる銅表面処理剤
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JPH1143778A (ja) * 1997-07-24 1999-02-16 Mec Kk 銅および銅合金の表面処理法
JP2003129254A (ja) * 2001-10-22 2003-05-08 Nikko Materials Co Ltd 銅及び銅合金の表面処理剤
JP2004140268A (ja) * 2002-10-18 2004-05-13 Matsushita Electric Works Ltd 高周波用多層プリント配線板の製造方法
JP2004346410A (ja) * 2003-05-26 2004-12-09 Nippon Paint Co Ltd 防錆皮膜の形成方法
JP2007291448A (ja) * 2006-04-25 2007-11-08 Hitachi Chem Co Ltd 銅箔の表面処理方法及び銅箔
JP2008274311A (ja) * 2007-04-02 2008-11-13 Mec Kk 基板の製造方法及びこれに用いる銅表面処理剤
WO2009066658A1 (fr) * 2007-11-19 2009-05-28 Nihon Parkerizing Co., Ltd. Agent de traitement de base pour matériaux métalliques et procédé de traitement de base pour matériaux métalliques

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