TW201132803A - Method for treating a foundation surface of copper material and a copper material having a treated foundation surface coating - Google Patents

Abstract

This invention provides a method for treating a foundation surface of a copper material with a film forming by self-precipitation, the method being capable of forming a resin film only on a copper member (e.g. a copper wiring), the resin film being adapted for providing a high adhesive strength to a resin material (e.g. a thermosetting resin material) to be bonded therewith. The method comprises an application process of contacting a copper material with an aqueous foundation surface treating agent constituted of an aqueous liquid having a pH of 3 or less, the aqueous liquid containing an organic resin (A), an anion surfactant agent (B), an acid (C) and an iron (IIL) ion as an oxidizing agent; a washing process of washing the foundation surface coating formed on the copper material by the above said application process, and a drying process of drying the foundation surface coating after the above washing process.

Description

[Technical Field] The present invention relates to an underlayer treatment method for forming an underlayer treatment material on a surface of a copper material, a copper material with a primer film, and a laminate member. [Prior Art] In industrial products, there are many cases in which a joint between a resin material and a metal material exists, and countermeasures for improving the adhesion force are considered. In the same way, the adhesion between metal materials and resin materials has been improved. Since ancient times, straight ribs have been used (the method of anehQ〇. For the sake of the shape, the surface of the material or the resin material is used to make the surface secret, and each is used separately. Chemical processing methods such as mechanical reinforcement, surname engraving, electroplating, and chemical processing such as blasting. However, there has recently been a phenomenon in which no anchor is formed and an adhesive force is required. In the case of the board, the high density of the printed wiring board, the speed of the signal, the thinning of the copper wiring, and the wideness of the width increase the thickness of the copper conductor circuit and the insulating resin layer. Chemical rough treatment of copper materials and insulating resin materials, but limited in the formation of fine patterns and devices used in high frequency bands above Giga (billion) Hz, because the skin effect is large, copper When the surface of the material is roughened, the transmission loss will become large, so it is eager to develop the surface to be roughened and improve only with chemical affinity 眭322497 4 201132803 and the county of Resin Surface treatment. ... and the non-chemical surface treatment known as surface roughening is known to be used in the treatment of copper materials. Although it is known to use the coating of 'Xi Xing coupling agent', it is still not available. The adhesive strength of the practical degree is further improved by the coating type treatment of the main component of the elastomer disclosed in the international publication WO2009/066658, and the practical strength is obtained for the thermosetting resin having no rough surface. When the printed wiring board is manufactured, the insulating resin laminated layer after the formation of the copper wiring is followed, the processing of the coating type is formed in the convex-concave state due to the portion where the copper wiring portion and the wiring are not present, and it is difficult to perform uniform film processing, and Not only on the copper wiring, but also on the surface of the insulating resin, a coating film is formed. From the viewpoint of the influence on the reliability of the insulation or the electrical characteristics, there is a tendency in the industry that it is not preferred. In such a case, it is required only in copper. The wiring portion does not roughen the surface and is subjected to the reactive treatment of the underlying treatment method. As a metal reactive surface treatment, it is known that A technique in which an acidic coating composition containing an organic resin of an iron-based or metal-based metal surface is contacted, and an organic resin coating film can be formed on the surface of the metal (hereinafter referred to as "resin self-precipitation treatment")" has been disclosed in Patent Documents 1 to 4, etc. The conventionally disclosed coating composition is characterized in that an organic resin film having an impregnation time and an increased thickness or weight can be formed by impregnating the cleaned metal surface in the coating composition. The film formation is further advanced. This is because the chemical action of the coating composition on the metal surface (by etching the metal ions eluted from the metal surface acts on the resin particles and precipitates on the metal surface) without electrode deposition (elctr〇de p 〇siti〇n) is the electricity from the outside forgetting 322497 5 201132803, which can effectively form a resin film on the metal surface. [PRIOR ART DOCUMENT] Patent Document 1: Japanese Patent Publication No. Sho 47-17630 (Patent Document 2) Japanese Patent Publication No. Sho 52-21006 (Patent Document 3) Japanese Patent Publication No. Sho 54-13435 (Patent Document 4) [Problems to be Solved by the Invention] However, in the case where the coating material for the film is applied as an iron-based metal, the film is expected to be formed, but the film is expected to be formed. When the metal to be coated is copper, there is a problem that a film is not formed or a film having a low adhesion to a resin is formed. In other words, although various materials including a material for a printed wiring board having a copper wiring portion as a copper material are widely used in the industry, it is still impossible to apply this self-precipitating film technology. Here, an object of the present invention is to provide a resin film which can be expected to have a high adhesion to a resin material to be bonded (for example, a thermosetting resin material) by the above-described resin self-precipitation treatment, only in a copper member material ( For example, a means of forming on a copper wiring portion. Further, the present invention provides a method for treating a copper material which is advantageous in environmental aspects, without using a material such as hexavalent chromium which is a cause of environmental/loss, and a primer for treating a steel material having a small environmental load. The steel material and the laminated member with the underlying treated film are obtained by the underlayer processing method. 322497 6 201132803 [Means for solving the problem ^

The inventors of the present invention found that the oxidizing agent was set as the result of the oxidizing agent = the sub-interface active agent, the acid, and the predetermined liquid aqueous treatment agent for treating the copper material, and the obtained curable resin was coated. With the invention of the invention (for example, the invention of the heat (10). Excellent adhesion. The following (1) to the present invention (1) are as follows - the following steps are included: a method for treating the underlying copper material, which is characterized by an application step. a step of contacting a copper material with an aqueous underlayer treatment agent comprising an organic resin (1), an anionic interface (4) (β), an acid (C), and an iron (ΙΠ) ion as an oxidizing agent (D); Washing step: a step of performing water washing on the underlying treatment film formed on the copper material through the aforementioned application step; and a drying step: a step of drying the underlayer treatment film after the water washing step. (2) The method of treating the underlayer of the invention (1), wherein the organic resin is an elastomer. Here, the "elastomer" is a general term for a rubbery elastic industrial material. The invention (3) is the aforementioned The underlayer treatment method of (1) or (2), wherein the anionic surfactant (Β) is selected from the group consisting of an alkyl sulfonate, an alkylnaphthalene sulfonate, an alkyl diphenyl ether disulfonate, The alkane sulfonate has a total content of 500 to 3000 ppm, and the carbon number of the "alkyl" portion or the "alkane" portion of the surfactant is preferably 1 to 15. The present invention (4) Is the underlying treatment of any one of the aforementioned inventions (1) to (3) s 7 322497 201132803 The method of 'comprising the first wrong body stability coefficient of the iron (1) D ion at 25 ° C ' and the ionic strength 〇 5 M The anion supply source (E) of 5 or more. In the underlayer treatment method according to any one of the above aspects (1) to (4), the aqueous base treatment agent further contains 1 to 1 ppm of copper ions (F). The invention (6) is the underlayer treatment method of any one of the inventions (1) to (5), wherein the copper material is a material of a printed wiring substrate. The invention (7) is a copper material to which an underlying treatment film is attached, via The invention is directed to the underlying processing method of any of the items (1) to (6). The present invention (8) In the copper material to which the undercoat film is applied, the ratio of the copper element in the underlayer treatment film is 1 to atom%, and the iron element content in the undercoat film is 〇3 g/m2 or less. 9) The copper material of the above-mentioned invention (7) or (8), which adheres to the underlying film, wherein the surface roughness (Ra〇) of the copper material before the underlayer treatment is the surface roughness of the copper material (Rai) The change ΔRa is 〇. 5/ζιη. The present invention (10) is a laminated member comprising the copper material of the underlying treated film of any one of the inventions (7) to (9), and the setting The resin layer on the film is treated in the underlayer. The invention (11) is a printed wiring substrate having a structure of 1 to 1 〇〇 layer, wherein the structure is in the insulating resin layer of the copper wiring circuit, Forming an underlayer treatment film according to any one of the above aspects (7) to (9) on the surface of the copper circuit, forming an insulating resin on the surface of the above-mentioned underlying treatment film and the surface of the above-mentioned insulating resin layer which is not formed with a copper circuit 8 322497 201132803 line circuit Layer knot . The invention (12) is an aqueous base treatment agent for copper materials, which comprises an organic resin (A), an anionic surfactant (B), an acid (c), and an iron (III) ion as an oxidant (D). And an aqueous liquid having a pH of 3 or less. The invention (13) is the aqueous base treatment agent for copper materials of the invention (12), wherein the organic resin (A) is an elastomer. The invention (14) is the aqueous base treatment agent for copper materials of the invention (12) or (13), wherein the anionic surfactant (8) is selected from the group consisting of a pyridyl acid salt, an alkylnaphthalene sulfonate, an alkyl group. One or more of the diphenyl ether disulfonate and the alkanesulfonate are combined in an amount of from 500 to 3,000 ppm. The present invention (15) is the aqueous underlayer treatment for a copper material according to any one of the items (12) to (14), which comprises a first error of 25 Å and an iron (III) ion having an ionic strength of 5 m. (1) The anion supply source (E) of the steel material according to any one of the inventions (12) to (15) The present invention (17) is the aqueous base treatment agent for a feed material according to any one of the items (12) to (16), which is used in a material of a printed wiring substrate. According to the inventions (1) and (12), when the metal to be coated is copper, it is possible to form a self-precipitating film having a t-resistance to the resin material to be bonded (for example, a thermosetting resin material). Because it does not use a substance such as hexavalent chromium which is a cause of word dyeing, it is a step-by-step process that causes less environmental load, and it can form a self-precipitating film that is substantially free of iron. 201132803 The surface of the copper material is suppressed to be rough. The effect of degree change. In accordance with (4) (2) and (10), in the _: The effect of forming a coating film on the epoxy-based thermosetting resin is exhibited by the force of the film. According to the inventions (3) and ((4), the effect of reducing the film thickness of the formed film can be exhibited. According to the present invention (4) And (15), it is possible to exert an effect that the steel (π) is not affected by the reaction with the organic resin, and the effect of the liquid stability can be improved by the positive charge of the iron ion of the chemical inhibitor. According to the inventions (5) and (16), the composition for the self-precipitating film of the present invention does not affect the performance of the formed self-precipitating film even if it contains copper ions. Therefore, when it is used, the self-applying metal is used. The copper does not have any problem of eluting the copper ions by depositing the composition for the coating film on the film, so that it is possible to use the same self-precipitating composition for the film even if it is not frequently exchanged. According to the invention (6) and (17) In the case where the material of the printed wiring board is applied, it is possible to selectively form a self-precipitating film in the material of the printed wiring substrate. According to the invention (7), it is possible to exert a copper material which is provided with a self-precipitating film having a high adhesion force by a resin material (for example, a thermosetting resin material). According to the invention (8) 'Because of self-precipitation Since the film is substantially free of iron, it can exhibit the effect of providing a copper material having a higher adhesion. According to the invention (9), since the surface roughness of the copper material changes little, 322497 10 201132803 is suitable for the copper of the printed wiring board. In the case of a circuit, it is possible to exert an effect of less transmission loss than the case where the surface of the copper material is roughened. According to the invention (10), between the copper material and the underlying layer between the coating film and between the underlying film and the resin layer, It can exert the effect of providing a laminate with a stronger reinforcement. According to the present invention, the copper material and the underlying treatment film and the underlayer treatment film and the resin layer are more strongly adhered to each other, and an effect of providing a printed wiring board having a circuit for forming a primer layer on the copper portion can be provided. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, an underlayer treatment method for a copper material using an aqueous underlayer treatment agent for a copper material according to the present invention will be described in detail, and an underlayer treatment is obtained by the underlayer treatment method. The steel material of the film and the laminated material. (Aqueous base treatment agent for copper material) The aqueous base treatment agent for the raw material of the present invention contains a fat (Α) and a negative material (4) _) (for the iron (III) ion of Weishu, and ρΗ is In the aqueous solution containing 3 or less, the treating agent 'for example, in the aqueous liquid containing (iv) linoleum (1) and _ sub-, it is necessary to add acid (6) and oxidizing agent (8) to obtain &lt;surface treatment target&gt; The surface treatment object of the underlying treatment liquid is a material. The copper material is not limited, as the case of (4), copper and copper alloy. The shape and structure of the steel material used in the present invention are also 322497 11 201132803 without special limitation. For example, it may be in the shape of a plate, a foil, a rod, a pellet, etc. Further, the copper material used in the present invention may be on a substrate of another metal material, ceramic material or organic material, for example, by In the case of a copper alloy, it is preferable that the copper alloy is 5% by mass or more of copper. For example, a sheet steel is used. For example, in a copper alloy, an alloy component other than copper is exemplified as 'Zn. , P, Al, Fe, Ni, etc. &lt; Addition of component 1: organic resin (A)&gt; First, the organic resin (A) which is the first essential additive component of the aqueous base treatment agent according to the present invention will be described. Here, among the aqueous primer treatment agents of the present invention, an organic resin ( A) is a main component of the underlying treatment film by treating the copper material. Here, the organic resin (A) may be (1) forcedly emulsified using a negative surfactant (B) described later, or may be used. (2) A self-emulsifier of a hydrophilic group such as a sulfo group, a carboxyl group, a phosphino group, a phenolic hydroxyl group, a hydroxyl group or an alkoxyethane, or (3) may be used in combination with (1) and (2). In the case of (1), the organic resin (A) and the negative surfactant (B) are present as individual compounds, and in the case of (2), the organic resin (A) and the negative surfactant (B) are the same. The organic resin (A) may be any one, and it is possible to use, for example, a conventional water-dispersible or water-soluble organic resin. Specific examples thereof include an elastomer, an acrylic resin, an epoxy resin, and a polyurethane ( Urethane) resin, polyester Resin, polyamide resin, gas vinyl resin, ethylene oxide resin, fluorine resin, enamel resin, polyolefin resin, phenol resin, urea resin, melamine resin, polyimine resin, polyamine resin, nylon resin, Polyphenylene sulfide 322497 12 201132803 A state in which an ether resin or the like is dissolved or dispersed in a solvent. Among them, 'elastomer is preferred. The above-mentioned bomb is not particularly limited, and it is possible to use water to dissolve or disperse conventionally. Specifically, the above-mentioned bullets may be: natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, chloroprene rubber, acrylonitrile, butadiene rubber, acrylonitrile-butyl Diene rubber such as olefin-styrene rubber, methyl methacrylate, butadiene rubber, butyl rubber, vinyl ruthenium rubber, polyurethane rubber, silicone rubber, chlorosulfonate Chemical rubber, vaporized polyethylene, acrylic rubber, epichl〇r〇hydrin rubber, fluorine-containing rubber, etc., which are dissolved or dispersed in water. These may be used alone or in combination. the aboveFurther, as the elastomer, an hydroxyalkyl group such as an amine group, a hydroxyl group or a hydroxymethyl group, a carboxyl group, a sulfonic acid group, a phosphine group, an epoxy group, an isocyanate group or a carbodiimide group may be used. Specialized functional reformers. Among the above elastomers, the glass transition temperature (Tg) of the elastomer is used [the glass transition temperature measured by a differential scanning calorimeter (for example, 6200: manufactured by Seiko Instruments Inc.); | at _1 〇〇 to 35 ( Rc is preferably from -65 to ll (Tc is better. Further, in the above elastomer, the specific gravity of the elastomer is preferably from 0.8 to 2.0. Among these elastomers, because of butadiene rubber, acrylonitrile-butyl The diene-styrene rubber, the acrylonitrile-butadiene rubber, the styrene-butadiene rubber, the decyl acrylate-based butadiene rubber, and the acrylic rubber have high affinity with the thermosetting resin to be the target. The reason is preferable. <Required addition component 2: anionic surfactant (B)> Next, the second essential s of the aqueous low-layer treatment agent according to the present invention will be described. 13 322497 201132803 Anionic interfacial activity of the added component (A) The anionic surfactant (B) is not particularly limited, and a conventional anionic interfacial activity agent can be used. Among the aqueous low-layer treatment agents of the present invention, an anionic surfactant (B) ·- By being contained in the bottom layer In the physicochemical agent, the water-dispersible or water-soluble organic resin (A) is adsorbed in the lower layer treating agent, and the water-dispersible or water-soluble organic resin (A) is generated to cause the copper ions and the static electricity to be agglomerated. The charge is a necessary component. As the anionic surfactant, specific examples include: a hospital-based besylate, an alkylnaphthalenesulfonate, an alkyldiphenyloxide di-acid salt, and a sulfonate. Acid salt, alkyl sulfate salt, polyethylene oxide alkyl ether sulfate salt, tartrate surfactant, citrate surfactant, naphthoate condensate, polycarboxylic acid type interface An active agent, etc. Although currently, the above anionic surfactant (β) is selected from the group consisting of a pyridyl acid salt, a pyromy a naphthyl acid salt, a pyridyl group, a dibasic acid salt, and a pharmaceutically acceptable acid salt. The mechanism of action of the above is not clear, but the film thickness of the underlying treatment film can be precipitated on the surface of the copper material by being contained in the aqueous underlayer treatment agent, and the effect of thinning is obtained. In particular, the aqueous underlayer treatment agent of the present invention is considered. Applied in copper circuits and layers as a printed wiring board In the case of the adhesion between the resin materials, in consideration of the influence on the electrical characteristics of the printed wiring board of the underlying film, it is preferable to form the film as much as possible, and by adding the above anionic surfactant, it can be stably formed. In the case of an organic resin (A), an elastomer is suitable as an organic liquid (A), but it is a commercially available product containing an aqueous solution of an elastomer and an anionic surfactant. 322497 201132803 '_, about butadiene rubber, for example, DIC (share) company

Pateracole E-301, acrylonitrile butadiene styrene rubber, for example, Nycheml 570X75, Nychem 1562X160, Nycheml 577, 1578X1 manufactured by Emerald Performance Materials, and acrylonitrile butyl rubber, exemplified by Emerald Nycheml 561X87, Nycheml 561, Nycheml 571, Nychem 1581, Nycheml 552, Nycheml 562, Nychem 1562X103, Nycheml 562X 117, Nycheml 572X64, Nychem 1572, Nycheml 570X79, Nychem N4000, DAC Co., Ltd., Lacstar DN-703, Lacstar-1570 B, manufactured by Performance Materials. Lacstar-6541G, NA-11, NA-13, NA-20 made by Japan A&amp;L Co., Ltd., Nipol 156, Nipol 1571H, Nipoll571C, Nipoll571CL, Nipoll577, NipolLX5U, manufactured by Zeon Co., Ltd., Japan , NipolLX513, NipolLX517A, NipolLX53, NipolLX531B, NipolLX550, Nipol550L, Nipol55, Nipol552, NipolSX1503, and styrene butadiene rubber, for example, Nychem 2570X59, Nychem 1800X73, and DIC (manufactured by Emerald Performance Materials) Lacstar-7300A Lacstar-DS-602, Lacstar-7310-K, Lacstar-2800A, Lacstar-3009A, Lacstar-DS-410, Lacstar-CB-2, Lacstar-DS-407H, Lacstar-3307BE, Lacstar-DS-205, Lacstar- 7440N, SB0695, SB0696, SB0561, SB0589, SB0602, SB2108, SB0533, SB0545, SB0548, SB0568, SB0569, SB0573, SB0597C, day 15 322497 201132803 made by JSR Co., Ltd. -100, SR-102, SR-103, SR-104, SR-107, SR-110, SR-112, SR-113, SR-115, SR-116, SR-117, SR-118, SR-130 , SR-140, SR-142, SR-143, Nipol LX407AS series manufactured by Zeon Co., Ltd., Nipol LX407F series, Nipol LX407G series, Nipol LX407H series, Nipol LX407K series, Nipol LX407S series, Nipol LX407BP series, Nipol V1004, Nipol MH5055, NipolC4850A, NipolLXllO, NipolLX112, Nipol LX119, Nipol LX206, Nipol2507H, NipolLX303A, Nipol2518FS, Nipol2518GL, NipolLX603, Nip〇lLX415A, NipolLX416, NipolLX426, NipolLX430, NipolLX432A, NipolLX433C, NipolLX435, NipolL X438C, NipolLX473B, NipolLX476, Nipol2570X5, NipolSX1105, Lubrizol's StycarTM SB-1168, StycarTM SB-1177, StycarTM SB-0738, StycarTM SB-1170, StycarTM SB-0706, StycarTM SB-1459, StycarTM 1780, StycarTM 1795, About Methyl Methacrylate The olefin rubber can be exemplified by Lacstar-DM-886, Lacstar-DM-801, Lacstar-DM-808, manufactured by DIC Co., Ltd., MR-170, MR-17, MR-made by Japan ML Co., Ltd. 172, MR-173, MR-174, Nipol LX811B, Nipol LX814, Nipol LX816, Nipol LX820A, Nipol LX82, Nipol LX844B, Nipol LX851C, Nipol LX851E, Nipol LX851F, Nipol LX852, Nipol LX, manufactured by Zeon Co., Ltd., Japan 854E, Nipol LX855EX, Nipol LX85H2, Nipol LX874, Nipol SX1706, Hycar26843, HycarT-122, HycarT-9202, 16 322497 201132803 by Hybrizol ' Hycar26-1042, Hycar26477, Hycar 26717, Hycar26479, • Λ

Hycar26-1199, Hycar23083, Hycar 26322, Hycar26552, Hycar26-0202, Hycar26092, Hycar 2671, Hycar26120, HycarT-9207, Hycar26319, Hycar 26871, Hycar26345, Hycar26-0912, Hycar2679, Hycar26796, Hycar26084, Hycar26349, Hycar26091, Hycar26288, Hycar26 -1265, Hycar26138, Hycar26523, Hycar26-1084, Hycar26106, Hycar26348, Hycar26450, Hycar26688, Hycar26172, Hycar26391, Hycar26256, Hycar26-1475, Hycar26315, Hycar26459, Hycar594, Hycar595, Hycar2003, HystretchV-60, HystretchV-43, HystretchV-43FDA , Hystretch V-43FF, Hystretch V-29, and acrylic rubber, such as Bonkote AB-901, Bonkote AN-155-E, Bonkote AN-200, Bonkote ED-85E, Bonkote R, manufactured by DIC Corporation -3380-E, Bonkote AN-782-E, Bonkote AB-886, Bonkote AN-l190, Bonkote H-5, BonkoteS-5, Bonkote AC-501, Bonkote HV-E, Bonkote TA-96, Bonkote SFA-33 , Bonkote AK-261E, Bonkote AK-3090, Bonkote AK-2100 , Bonkote SEP-119, AE610H, AE200A, AE337, AE945H, AE981A, AE120A, AE982, AE986B, SX8900C, SX8900D, AE116, AE150B manufactured by JSR. &lt;Required Addition of Component 3: Acid (C)&gt; Next, the acid (C) of the third essential component of the aqueous low-layer treatment agent according to the present invention will be described. In the aqueous low-layer treatment agent of the present invention, the acid (〇 is s 17 322497 201132803 2: ί is not detached from the copper material even when washed, and the water-washing resistance is high, but it is thought to be acid-based. In the eye =!, to reduce the treatment agent, whereby the copper ion can be _ ~ or the coordination of the steel in the treatment agent, etc., and the positive charge from the Nazi will make The coui_force of the reservoir becomes larger, and it is therefore assumed that the water-dispersible or water-soluble organic resin (4) having a negative charge has a stronger electrostatic aggregation on the surface Φ of the anion-based anionic agent. The underlying treatment film is formed so that it does not fall off when washed. The acid (C) can be used, for example, selected from the group consisting of a gasified gas, a hydrogenated gas, a sulphuric acid, a hydrogen fluoride, and a fluorinated acid. At least one of nitrogen acid, scaly acid, nitric acid, and the like is used, and it is more preferable to use one or more selected from the group consisting of nitric acid and gas acid. &lt;Must add component 4: oxidizing agent (£)) &gt; Next, the present invention will be described. The fourth essential component of the aqueous low-layer treatment agent is the added oxidizing agent (9). The aqueous low-layer treating agent (9) of the present invention is a copper ion generating source which is required to electrostatically agglomerate the surface of the bake material by oxidizing and dissolving the copper material as described above in order to make the water octagonal or water-soluble (4) dragon (4). Here, in the reaction of the formula (1), the standard hydrogen electrode potential ΐ (25 ΐ) is 0.34 V' (2) in the reaction of the formula (2). (b) Yes Unlike iron, zinc and materials, hydrogen ions usually do not become the oxidation sword of steel. Therefore, oxidants for oxidizing dissolved steel are especially needed.

Cu - Cuz+ + 2e- Formula (1) 322497 18 201132803 2H+ + 2e~ ^H2 Formula (2) According to such a theory, as an oxidizing agent for copper, the user may have a good time (for example, a nitric acid compound such as a shale Acid (nitr〇us acid), peroxyacid, peroxynitrite, nitric acid (H2NO2), trioxanediamine (H2N2O3), tetraoxydinitrogen, salts of these; sulfuric acid a compound, for example, a sub->6 octanoic acid, a peroxy phthalic acid, a hypotrimic acid, a trioxane sulphate, a tetraoxymononitrate, a specific salt thereof; a tart acid compound, for example, chlorous acid, Chloric acid, sulphuric acid, sub-sulphuric acid, high bromic acid, bromic acid, bromic acid, hypobromous acid, high acid breaking, hard acid, cleavage acid, sub-acid exchange, and the like; organic Peroxides such as 'hydrogen peroxide, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, dinonyl peroxides, peroxyesters, peroxydicarbonates, ... ). However, the present inventors have found that iron (ΙΠ) ions can be significantly exhibited in the case where the liquid composition of the aqueous underlayer treatment agent of the present invention is applied and the object is a copper material, which is capable of exerting various performances. Performance. Here, 'the source of iron (III) ion as the iron (ΠΙ) ion in the supply liquid' may specifically be, for example, iron (III) fluoride, iron (III) chloride, iron (III) bromide, Iron(III) iodide, iron (strontium) sulfate, iron nitrate (iron), iron (III) acetate, iron (III) acetate, iron (citrate), iron (III), iron oxalate (III), iron (III) picoline, iron (III) L-phenylalanine, iron (III) malonate, and the like may be used alone or in combination of two or more. Next, the optional components of the aqueous low-layer treatment agent according to the present invention will be described. The aqueous low-layer treatment agent according to the present invention may contain various components or additives known from the prior art. The anion source (8), copper ion (7) and hydrogen peroxide (6) therein are specifically described below, but any components other than the above are not excluded. &lt;Required addition component 1: Anion supply source (Ε)> Next, an anion supply source (8) containing any component of the aqueous underlayer treatment agent according to the present invention will be described. An anion supply source (E) having a first-substrate stability coefficient pi pe(1)1} of iron (III) ions and an ion intensity difference of 5 or more is added to the treatment agent, and is derived from the anion supply source (8). The anion is coordinated to the iron (in) ion to attenuate the electrostatic force formed by the positive charge held by the iron ion, thereby improving the liquid stability. Specifically, it can be exemplified by: oxyacid (red coffee) = 5.2 〇), oxalic acid (red 卩 side = 7.53), acetamidine acetone, citric acid, glycosaminoglycan, picolinic acid, l-phenylpropylamine Acid, malonic acid or the like (sodium salt, potassium salt, ammonium salt, etc.) ^ Here, the iron (III) ion supply source in the iron (1) cesium ion supply liquid as the oxidant (D) and the anion described above The supply source (8) may also be derived from the same compound. For example, gasified iron (ruthenium), iron oxalate (iron) or iron citrate (Ιπ) which is an example of a source of iron (111) ions is used. &lt;Optional component 2: Copper ion (f)> Copper ion (7) which is an optional component of the aqueous underlayer treatment agent according to the present invention. As the copper ion (F), the copper (1) ion and the copper ion (II) may be used alone or in combination of two or more. The metal ions of the present invention are added or impregnated into the aqueous underlayer treatment agent from one or more of the steel (10) compound, the copper (1) compound, and the metal copper towel, and may be present in the present invention. Examples of the copper (1) 322497 20 201132803 compound include copper chloride (such as ruthenium or the like, and these may be used alone or in combination of two or more kinds thereof as copper gi), and specific examples thereof include copper antacid ( II), copper (II) acetate, copper (II) propionate, copper (U) pentoxide, copper gluconate (yttrium), copper tartrate (11), etc. (4); gasified copper (Π), bromine Copper (Π), copper hydroxide (11), copper acetate (11), copper nitrate (11), copper sulfate (11), copper carbonate (11), copper oxide (11), copper sulfide (11), etc. These may be used alone or in combination of two or more. As the metal copper, the above copper material can be used. Further, it is suitable as the oxidizing agent to further contain hydrogen peroxide (G). This is because iron (III) ions act as oxidants, although they themselves become iron (II) ions, but when hydrogen peroxide is contained, the effect of oxidizing the iron (11) ions back into iron (III) ions The reason. The aqueous underlayer treatment agent according to the present invention is an aqueous liquid medium (aqueous liquid) obtained by blending (or containing) each of the above components. Here, the "aqueous liquid medium" means a liquid medium/main body mainly composed of water, and means that at least 5 % by volume or more of water is used as a reference based on the total mass of the liquid medium. Further, a liquid medium other than water may be contained, for example, an alkane system such as hexane dioxane, an aromatic system such as benzene or anthracene; an alcohol such as ethanol, butanol or ethyl cellosolve; Hydrogen gnat, two Wei and other vinegar; acetic acid ethyl vinegar, acetic acid butoxy vinegar and other vinegar; second 曱 to 曱 amine, 曱 曱. An anthraquinone-based solvent such as anthraquinone or a hydrazine-based solvent such as dimercaptosulfoxide; a phosphonium amide such as hexamethylenephosphoric acid triamide; and the like can be suitably used. Next, the amount (or content) of each component described above in the aqueous underlayer treatment agent will be described. S' 322497 21 201132803 &lt;Must add component (A) &gt; In the aqueous underlayer treatment agent of the present invention, the organic resin 00 is preferably from 0.5 to 80% by mass based on the total amount of the lower layer treatment agent, and the mass machine is more preferable. When the content of the above-mentioned organic resin (4) is within this range, the undercoating agent used in the present invention is treated with a primer to prevent the undercoating film from being detached during washing. Further, in the case where the organic resin is an elastomer, the concentration of the elastomer in the elastomer dispersion solution (also referred to as latex) in which the elastomer is dissolved or dispersed is not particularly limited, but is easy to handle from the treatment agent. The viewpoint ^^, to 80 mass is preferable, and preferably 1 to 60% by mass. Further, although the viscosity of the above-mentioned dispersion solution is not limited, it is preferably from 5 to 3,000 cP from the viewpoint of the degree of __^. Further, the particle diameter ' of the elastomer in the dispersion solution is not particularly limited, but is preferably 〇1 to 10/zm, more preferably 〇1 to 2/ζιη. &lt;Must add component (B) &gt; In the aqueous base treatment agent of the present invention, the total amount of the anionic surfactant (B) relative to the underlying treatment agent is preferably from 1 〇〇 to loooo ρριη, from 500 to 3000 ppm is better. In particular, in the case where the above-mentioned concentration selected from the above-mentioned alkyl sulfonate, alkylnaphthalenesulfonate, alkyldiphenyloxide disulfonate or alkanesulfonate is selected, it is possible to stably An underlayer treatment film having a film thickness of 1 / zm or less is formed. &lt;Must be added (〇> In the aqueous underlayer treatment agent of the present invention, the total amount of the underlying treatment agent is preferably from 5 to 20, and from 1 to 10% by mass to 22 322497. 201132803

good. When the content of the acid (c) is within this range, the underlying treatment agent is treated with the underlayer treating agent to prevent the undercoating film from becoming good after washing with water. , &lt;Must add component (D)&gt; In the aqueous underlayer treatment agent of the present invention, the oxidizing agent (D) is preferably 〇.01 to 10 by mass, and 〇〇5 to 5 by mass relative to the total amount of the underlying treatment agent. % is better. When the content of the oxidizing agent (9) is within this range, the metal material used in the present invention is treated with the underlying treatment agent, and the release property of the film during water washing is improved. Å &lt;optional addition component (E)&gt; The present invention _ aqueous bottom treatment shot, relative to the aqueous bottom layer:: Anion (E) is preferably 〇 1 to 1 〇 mass, with mass ❶ /. For better. When the content of the oxidizing agent (8) is within this range, the reactivity of the pharmaceutically acceptable agent is maintained and the liquid stability is improved. f bottom layer &lt;optional addition component (F)&gt; The hair _ _ _ bottom layer 4 physics, (four) Cai Quan, steel ion (7) to 〇.0 thank you (M quality is good to the agent to 〇.05 quality % is better. The content of copper ion (8) is in this range ^ · 001 The bottom layer is processed in the case of the tree (10), and the case of the gold is used to deal with the negative financial situation, and the stable bottom can be obtained. In the case of adding hydrogen peroxide (G) as an oxidizing agent, it is necessary to transfer a sufficient amount of the (10) ion present in the liquid towel. Here, the concentration of the oxidizing agent: from: oxidation to iron The electrode is managed in the state of the electrode 322497 201132803 for the working electrode. In the state in which the self-precipitated ferrous ion of the present invention is oxidized to iron ions, the state in which the remaining hydrogen peroxide is present is Preferably, the value obtained by using a plurality of oxidants is kept at a minimum value of ▲ 匕 to reduce the potential state. Here, the preferred oxidation-reduction potential, at least = maintaining the foregoing shape is preferably 350 or more. Below _ mV, With fluorination 2, ferrous ions with low stability can exist in the treatment of 2 The reason for the decrease in the stability is... the result is the treatment layer "the underlying treatment of steel f&quot; (the use of the aqueous underlayer treatment agent, the underlying treatment method of the relevant steel material of the present invention = method)" is "the underlying treatment method of the present invention" )), under the squat, simply contact the copper substrate with the contact agent = after the water of the invention, remove the acid by washing with water (c) after the liquid-contacting step, the drying step of the steel step , and the washing step <liquid-contacting step> Saki (four) the bottom layer processing method. The liquid step is the above-mentioned liquid-feeding step of the above-mentioned aqueous underlayer of the present invention. The underlayer treatment of the present invention can be used by a dipping method, a mouth mist method or this == specifically defined by, for example, the underlying treatment method of the invention. Further, the conditions of use of the agent are not the same as the treatment agent of the bottom layer of the present invention in the above-mentioned liquid-contacting step, and the temperature limit of the coating agent is preferably limited to the temperature of 30 to Λ. In 10 to 90, the energy is wasted, so when the temperature is below 5 °C, it is suitable temperature because it can be, left, and from the viewpoint. Again, 322497 24 201132803

The time for the underlying treatment agent to be connected to the liquid can be appropriately set. &lt;Washing Step&gt; In the bottom layer treatment method of the present month, the water washing method in the water washing step is not particularly limited. For example, the method may be washed by a dipping method, a mouth mist method, or a combination thereof. X, washing time, can be set appropriately. By the water washing step, the iron ions of the acid (C) and the oxidizing agent (9) contained in the undertreatment agent of the present invention can be removed, whereby the adhesion can be improved. &lt;Drying step&gt; The step of drying the step after the water washing step and (4) forming the underlayer film. In the underlying treatment method of the present invention, the drying temperature is not determined depending on the solvent to be used, and for example, when water is used as the solvent, it is preferably in the range of 50 to 200 °C. <<Copper Material Attached to Underlayer Film>> The copper material to which the underlayer film of the present invention is attached is obtained by using the surface layer of the above-described present invention. Here, the underlying film formed is detailed. &lt;Thickness&gt; The film thickness of the obtained underlayer film is preferably 0.01 to 2 Å #m, more preferably 0·05 to 5 // m. &lt;containing ingredients&gt;

S The underlying film on the metal material obtained by the underlayer treatment method of the present invention, except for the water-dispersible or water-soluble organic resin (A), is a human copper element. Due to such a film structure, the adhesion performance is further improved: XPS analysis (device name · ESCA-850M (Shimadzu Corporation (share) system = 322497 25 201132803 = 2 analysis software carried in the device, theoretical calculation In the film, the ratio of the bottom layer of the copper element U to the sub-"the production of oxygen 峨D) contains the ratio of the syrup. The same is true for the signal noise ratio (SignaI t〇_如〇) to 2 When the = is the detection limit, the result is below the detection limit. In order to more detail the presence or absence of the inclusion of the 70, the X-ray analysis (device: nmus (science system)) is performed by the calibration curve. In the method, the result of the iron content in the film is also below the detection limit (〇〇〇3g/m2). Currently, the underlying film on the metal material obtained by the underlayer treatment method of the present invention is pushed, &lt;,. The fact that the iron element is not contained is a cause of high performance. The following description will be continued. Next, the physical property change of the copper material on the side where the underlying film is formed can be described by using the underlying treatment agent for the metal material of the present invention. Suppress changes in the thickness of the metal surface The surface can be improved with the resin ===two-body' can change the rough surface degree D of the treated metal surface relative to the surface roughness (Ra.) of the metal surface before treatment. The ARa is controlled at 〇.5^m or It is better to be below 3.3_. Especially in the printed wiring board 2, 'compared with the case where the surface of the copper material is roughened, the surface of the steel material that can be used as the copper material is roughened. When a copper foil having a surface roughness Ra of 0.2 μm曰 or less is used, the surface roughness of the surface is generally more than 1 Å, and the effect of the present invention is not obtained. The aforementioned method for measuring ARa is based on the present invention. The metal material with the underlying film and the metal material before the treatment are embedded in the resin. The SEM observation of the cross-section i thousand times is performed, and the Rai and Ra are calculated from the metal surface 322497 26 201132803 coarse k-degree shell material respectively. Correction—(5). The surface roughness Ra of the flat sentence (arithmetic mean surface roughness (8) is the absolute value deviation of the mean line offset from the value of the rough surface of the surface by the value of (10) 0601 with the abbreviated sign of Ra'. The average value of the building. The laminated member of the present invention is a laminated material of the above-described copper material with a primer film of the present invention and a thermosetting resin material provided on the underlying film. The structure of the laminated member of the present invention is not It is particularly limited, for example, a plate shape, a foil shape, a rod shape, or the like, or a complicated shape. The second drawing is an example of the laminated member of the present invention, and shows a schematic cross-sectional view of the plate-shaped laminated member of the present invention. The laminated structure shown in the figure is a copper material 2, a primer film 3 formed thereon using the underlayer treatment agent of the present invention, and a thermosetting resin material layer 4 provided on the underlayer film 3. The copper material treated by the underlayer treatment agent of the copper material according to the present invention can suppress the roughening of the surface of the metal material unlike the prior art, and the reason for this is not known at present. (Thermosetting resin) As the material of the thermosetting resin layer, a conventionally known resin having a functional group which is crosslinked by heating can be used. Specifically, for example, an acrylic resin, an epoxy resin, a phenol resin, a urea resin, a melamine resin, a polyurethane resin, a thermosetting polyimide, an unsaturated polyester, a bismaleuric acid imide triazine resin Wait. The functional group which can be crosslinked by heating is exemplified by a hydroxyalkyl group such as an amine group, a hydroxyl group or a hydroxymethyl group, a phenol group, a carboxylic acid, an epoxy group, an isocyanate group or a carbodiimide group. These can be used as separate ζ 27 322497 201132803, or two or more types can be used in combination. These resins can also be modified by functional groups. Further, the resin layer may contain glass fibers, calcium carbonate, aromatic amide fibers, graphite, carbon black, aluminum oxide, aluminum nitride, boron nitride, or the like from the viewpoint of enhancing reinforcement, thermal conductivity, and improving electrical conductivity. A filler such as silver or copper metal powder. One of the suitable aspects of the material of the resin layer may be a prepreg. The prepreg is a one in which a thermosetting resin is impregnated into a sheet-like fibrous base material to be semi-hardened. Examples of the material of the sheet-like fibrous base material include fibers of an inorganic material such as E glass, D glass, s glass, and Q glass, aromatic aramide, polyimine, polyester, and polytetrazole. A fiber of an organic substance such as fluoroethylene, and a mixture thereof. Such fibrous base materials include, for example, woven fabrics, non-woven fabrics, rovings, short glass mats, and surface weld mats, and the materials and shapes are selected depending on the purpose and performance of the intended molded product, and may be used alone or in combination as necessary. 2 or more types of materials and shapes. (Manufacturing method of laminated member) The laminated member of the present invention can be obtained by bonding a thermosetting resin layer to a metal material with a primer film of the present invention and a base film. The bonding method is not particularly limited. Specifically, the thermosetting resin layer is an epoxy resin. For example, (1) drying is performed on the underlying film of the metal material to which the underlying film is attached, (4) unweiwei-like epoxy. (2) coating method of forming a resin layer by hardening, (2) laminating film of a metal material to which an underlayer film is attached, laminating an epoxy resin film, and bringing the underlying film into contact with the epoxy resin film, and then laminating by heating, (3) The metal material &amp; with the underlying film is placed in the mold, and the molten epoxy is shot out of the mold 28 322497 201132803, so that the _ county _ and the bottom layer are formed by the formation of the epoxy layer. Wait. (Characteristics of the laminated member) In the laminated member of the present invention, the copper material and the thermosetting resin layer which is adhered to the underlying film are excellent in adhesion strength. Since the underlying film formed also has excellent acid resistance, it is possible to suppress an unsuitable phenomenon such as a pink ring during the production of a printed wiring board, as described in the following suitable application examples. In the further step, the underlying film also exhibits excellent adhesion strength under high temperature and high humidity conditions. (Application example of the printed wiring board) The underlayer treatment agent of the present invention can also be suitably used as a treatment for improving the adhesion between the insulating resin materials between the layers of the copper circuit of the printed wiring board. The type of printed wiring board to which the underlying treatment agent of the present invention can be applied is applicable to conventional ones, and specifically, for example, a single-sided printed wiring board, a double-sided printed wiring board, a multilayer printed wiring board, and a combined printed wiring board ( Build up printed circuit board, 骈 volume layer type printed wiring board, flexible rigid printed wiring board, part built-in type printed wiring board, and metal base printed wiring board. The underlayer treatment agent of the present invention is not particularly limited 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, and the thickness of the insulating resin layer, and can be applied to conventionally used ones. .

In addition, the method of forming the copper circuit in the printed wiring board of the underlying treatment agent of the present invention is not particularly limited, and a conventional method can be applied. Specifically, for example, a subtractive method, an additive method 322497 29 201132803 (additive), an addition subtraction method, and the like, the underlayer treatment agent of the present invention is not particularly limited in the interlayer insulating resin layer. A conventional thermosetting resin can be applied. Fig. 2 is a cross-sectional view showing a mode of a four-layer printed wiring board as an example of a printed wiring board produced by using the underlayer treating agent of the present invention. The insulating resin layer formed by the copper wiring circuit is subjected to surface treatment by using the underlayer treating agent of the present invention. The underlying film is formed only on the surface of the copper circuit. Since the surface of the above-mentioned insulating resin layer on which the copper wiring circuit is not formed is not opened, it is preferable from the viewpoint of the influence on the insulation reliability or electrical characteristics. Further, the film thickness of the underlayer treatment film is not particularly limited, and is preferably from 0.01 to 20 v m, more preferably from 0.05 to 5 /z m. Further, in the case of a printed wiring board, in the case of using a high-frequency waveform as a signal, as in the case of the Japanese Patent Application Laid-Open No. Hei 7-314603, the surface roughness Ra of the copper turning surface is 〇 from the point of the skin effect. Below, and 0. 2 &quot; m or less is preferred. EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the invention is not limited to these embodiments. I. Preparation of Copper Material Containing Underlayer Film As shown in the examples and comparative examples described later, various underlayer treatment agents were used and the following treatment steps were carried out on the material to be treated to obtain a copper material with a primer layer attached thereto. [Materials to be treated] 30 322497 201132803 The symbols and definitions of the materials to be treated are as follows. • Copper foil: electrolytic copper foil (purity of 99.8 mass% or more), thickness 18#m,

Ra 0. 3 ^ m • Nickel foil: (purity of 99% by mass or more), thickness 20/zm • Single-sided copper circuit to form epoxy resin sheet, LSI 2. 5# m, epoxy layer thickness 0. 1mm [Processing procedure The process steps are performed in the order of the following steps (1) to (7). (1) Degreasing (60 ° C, 10 minutes, dipping method, using a 5 mass % aqueous solution prepared by Fine Cleaner 4360 manufactured by Parkerizing Co., Ltd.) (2) Washing (normal temperature, 30 seconds, dipping method) ( 3) Pickling (normal temperature, 30 seconds, dipping method, using 10% aqueous solution prepared by commercially available sulfuric acid) (4) Washing (normal temperature, 30 seconds, dipping method) (5) Surface treatment (as described later) (6) Washing (normal temperature, 30 seconds, dipping method) (7) Heating and drying (100 ° C, 5 minutes, hot air oven) [Surface treatment] Example 1 As a water-soluble, water-dispersible organic An aqueous dispersion of acrylonitrile butadiene styrene rubber having a carboxyl group and a methylol group of resin (A) (solid content concentration: 47%, pH: 8, viscosity: 45 cP, Tg: 18 ° C, specific gravity: 1. 01) 5 parts by weight of solid alkyl diphenyl ether disulfonate (made by Kao, PELEXSS-H, solid concentration: 50%) as an anionic surfactant (B) 31 322497 201132803 0. 15 parts by weight, mixed with deionized water 89. 5 parts by weight to prepare a water-dispersible organic resin (A), an anionic surfactant ( An aqueous liquid of B) to which is added: nitric acid as an acid (C) (active ingredient 60 «5 parts by weight, as an oxidizing agent (D) and an anion (magic iron fluoride 0.35 parts by weight, dissolved to obtain an underlying treatment agent) (a) e. The pH of the underlying treatment agent (3) was measured to obtain pH = 1.5 (25 ° C.) Then, in the above treatment agent (temperature: 25 ° C), the copper foil of the material to be treated was impregnated 3 The surface treatment was carried out in a minute. Example 2 In the present example, a sodium salt of a naphthalenesulfonic acid formaldehyde condensate (addition of Kao (manufactured by Co., Ltd.), DEMOLNL, and solid concentration was prepared in addition to the anionic surfactant (B). The bottom layer treatment agent (b) having the solid content of 0.25% by weight and the deionized water of 88.5 parts by weight, which is the same as the bottom treatment agent (a). The pH of the underlying treatment agent (bj is obtained. Η Η . . . Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在(A) An aqueous dispersion of a propylene-based rubber having a carboxyl group (solid concentration concentration: πρ, particle diameter: .24&quo t; ^ expensive,: heavy '1〇4 surface tension: 42dyne/an) 1G parts by weight, with = (8) (tetra) 12-dozen benzene sister prince ceremonial trr 彡 concentration: 16%) solid fraction Q.G2 By weight, and mixed with detachment_water 84.63 parts by weight', an aqueous solution containing water-soluble organic resin (4), ^ 322497 32 201132803 • ionic surfactant (B), prepared and contained as an acid (C) 5 parts by weight of nitric acid (60% of active ingredient), and an aqueous solution of 0.53 parts by weight of iron fluoride as the oxidizing agent (d) and the anion (E), to obtain an underlying treatment agent (c). The pH of the underlying treatment agent (c) was determined to obtain pH = 2. 〇 (25 〇 C). Next, in the above treatment agent (temperature: 25 ° C), the surface of the copper box of the material to be treated was immersed for 10 minutes. (Example 4) Using the underlayer treatment agent (a), the surface treatment was carried out by subjecting the single-sided copper circuit of the material to be treated to an epoxy resin sheet for 1 〇 minutes in the above treatment agent (temperature: 25 °C). Example 5 In the present example, an underlayer treatment agent ("the same composition of the underlying treatment agent" was prepared in addition to the addition of 10.9 parts by weight of iron (111) ammonium oxalate 3 as an oxidizing agent (D) and an anion (E). (d) The pH of the underlying treatment agent (d) was measured to obtain pH = 0.4 (25 c), and then the copper foil of the material to be treated was impregnated for 3 minutes on the surface of the treatment agent (temperature: 25 Å). Comparative Example 1 In this comparative example, it was prepared by adding oxidizing agent (D) and anion (Ε), and adding 1 part by weight of oxidized hydrogen peroxide (active ingredient 3〇%) to deionized water. 7 parts other than the portion of the underlying treatment agent (e) which is composed of the underlying treatment agent (a). The pH of the bottom treatment agent (e) is measured to obtain ρ Η = 0.33 (25 ΐ). Medium (temperature: 25. 〇, the copper box of the treated material is impregnated with 3 322497 33 201132803 minutes of surface treatment. Comparative Example 2 In this comparative example: bis aqueous liquid "_4D", solid-shaped two-pointed rubber ( The first industrial music (stock) system 'product name young workers p % ♦ degree 2 dip ' ρ Η = 8 · 5) 10 parts by weight, adding deionized water 79. 7 The amount of the mixture is 3 旦, the knives are added as the acid (C) nitric acid (the active ingredient is 60%) • the parts by weight, and the anionic surfactant (8) is not added, and the underlying treatment agent (a) is composed of the underlying treatment agent. (〇. The bottom treatment agent was measured (pH of Ο, pH=2.9 (25 ° C) was obtained. Then, in the above treatment agent (temperature · 25 C), the surface of the copper foil of the material to be treated was dipped for 3 minutes. Comparative Example 3 Using the underlayer treatment agent (a), the surface treatment of the Ni foil of the material to be treated was immersed for 10 minutes in the treatment agent (temperature: 25 ° C). Comparative Example 4 In this comparative example, : The bottom treatment agent (g) which is composed of the same as the treatment agent (a), except for the addition of the acid (C). The pH of the undertreatment agent (g) is measured to obtain a pH of 3. 4 (25 t) 0 followed by In the above treatment agent (temperature: 25.0), the surface of the material to be treated was dipped for 3 minutes. Comparative Example 5 Using the underlying treatment agent (a), metal copper pigs were immersed in the treatment agent. After 3 minutes, the above treatment step (6) is not washed and (?) heated and dried (l〇〇t, 5 minutes, hot air baking) Surface treatment. 322497 34 201132803 Comparative Example 6 After performing the above treatment steps to (4) water washing, in a blackening treatment bath (containing sodium sulfite 30 g / L, sodium phosphate 12 water and 10 g / L, the aqueous solution of sodium hydroxide 15 g / L), the copper foil was immersed for 3 minutes at a treatment temperature of 90 ° C. After that, it was washed with water in a hot air oven, 1 〇 0. € heat drying for 5 minutes to make a blackening treatment Sample 2. Evaluation of the underlying coated steel material The evaluation of the underlying coated copper material obtained in Examples 1 to 5 and Comparative Example 1 was carried out as follows. (1) Evaluation of arithmetic mean surface roughness of the surface of the copper material and film thickness measurement of the underlying film. Samples in which the underlying film copper material obtained in Examples 1 to 5 was embedded in the % oxygen resin were used. Microscope (magnification: 1 〇〇〇〇) observed the wearing surface of the sample, and estimated the arithmetic mean surface roughness Ra of the surface of the metal material with the underlying film metal material, and it was found that Ra of each sample was 〇·50 //m or less, and confirm that the surface roughness change ARa of the metal material before and after the treatment is less than 20am. Fig. 3 is a view showing a copper circuit portion in which a single-sided copper circuit is formed into an epoxy resin sheet, and Fig. 4 is a view showing a copper circuit portion in which a single-sided copper circuit having an underlying film obtained in Example 4 is formed into an epoxy resin sheet. Cross-section photo. As a result, it was confirmed that the circuit portion formed a uniform thickness of 1, the underlying film, and the copper circuit. [The outer layer of the UX does not form the underlying film. Further, the thickness of the underlayer film was measured from the cross section. The results are shown in Table i. (2) Analysis of the film structure of the underlying film 35 322497 201132803 The underlying film-coated copper material prepared in the first embodiment and the comparative example 5 was subjected to the depth direction analysis of the film by XPS under the following conditions, and the XPS analyzer was used. The analysis software installed in the medium calculates the content ratio of the elements shown below by theory. Fig. 5 shows the results obtained in Example 1, and Fig. 6 shows the results obtained in Comparative Example 5. &lt;XPS depth direction analysis> Device: ESCA850 manufactured by Shimadzu Corporation (issued): X-ray: Mg-K α measured area; approx. 50 mm2 field of measurement · Cls, 〇ls, Nls, Cu2p, FIs, Fc2p sputtering Time: 6 minutes (Si 〇 2 conversion oscillating speed 60 nm / min) For the iron element, the X-ray analysis was carried out under the following conditions, and the iron content in the sputum was measured by the calibration line method (g/m 2 ) . Using the obtained value, the element content other than the iron element obtained by the above XPS analysis (the atomic and film thickness measurement results, the iron element content (atomic %) is estimated. &lt;fluorescence X-ray analysis> Apparatus: ZSX~primus ( Science system): Rh, Ka, 30kV-100mA measured area, 10 mm § It is confirmed from Fig. 5 that the underlying film obtained in Example 1 is 'in the measured depth, fluorine element and derived from oxidant ( D) The iron element is below the detection limit (signal-to-noise ratio is below 2), and sister, because the use of fluorescent X-ray analysis to determine the iron content in the sputum is also the detection limit (0·003g/m2) In the following, it is considered to be composed of the carbon element and the element of the olefinic rubber of the organic resin (A) which is derived from the water-soluble organic resin (A). The steel is made of ginseng and is derived from the metal to be treated. The % of the copper element of the material, the surface has a rate of 3, and the surface of the first time of the splash time has 6 original dips of 1 to 2 atomic %. The latter, by the 笫β country, in the depth of measurement, ' In the same manner as in Example 1 of the underlying film organic resin (A) obtained in Comparative Example 5, the detection originated from The water-soluble element, the copper element derived from the carbon element derived from the treated ethylene-olefin rubber, and the iron atom of the nitrogen element (8). The source and the self-oxidizing agent are the atomic ^ time of 1 second. The surface was detected, and the iron content in the content rate was 〇η9 9 by the (4) optical X-ray analysis method, and the film obtained was 0·5 atom g/lfl2. The result of estimating the iron element content was found to be 14 atom%. The content of the content is 1 second on the surface of the splash time. (3) The adhesion table is 3 to 4 atom%. In the example; | s Q r The layer of the film steel is compared with the age of 6 and the bottom is made. In the case of a glass cloth substrate having a thickness of about 1 〇〇/Zm, the epoxy resin is made into an industrial (stock) system, trade name; GEA-679N), and the inside of the #3 is broken inside the epoxy resin sheet. The coarse tread of the copper foil faces and the laminate is heated at a temperature of 180 Ϊ, a pressure of 45 kgf/cm 2 , and a heating time of 1 hour, followed by a laminate of a metal material—epoxy resin. &lt;One-time adhesion test&gt; The above-mentioned laminated structure material was cut into a width of 1 cm, and a portion of the metal material with the underlying film which was not subsequently adhered was vertically oriented while the glass cloth substrate epoxy resin sheet was fixed. The peeling test was carried out in a direction of 9 degrees, and the peel strength of 37 322497 201132803 was measured. &lt;Heat-resistant secondary adhesion test&gt; The above-mentioned laminated member was cut into a width of 1 cm, heated in a furnace at 275 ° C for 1 minute, and then left at room temperature for 30 minutes, and then subjected to the same adhesion as once. Peel test, peel strength was measured. &lt;Moisture-resistant secondary adhesion test&gt; The above-mentioned laminated structure was cut into a width of 1 cm, and heated in a furnace at 121 ° C, 2 atm, and 100% relative humidity for 1 hour, after which the temperature was lowered to the chamber. After the temperature was removed, the water vapor was removed, and the 90-degree peeling test was performed in the same manner as the primary adhesion, and the peel strength was measured. &lt;Acid resistance secondary adhesion test&gt; The above-mentioned laminated structure was cut into a width of 1 cm, and immersed in a 1 M hydrochloric acid aqueous solution at 25 ° C for 15 minutes, and then washed at room temperature for 30 seconds to remove water vapor. The 90-degree peeling test was performed in the same manner as the primary adhesion, and the peel strength was measured. &lt;Secondary test of the second test&gt; The above-mentioned laminated structure was cut into a width of 1 cm, and immersed in a 1 M sodium hydroxide aqueous solution at 25 ° C for 15 minutes, and then washed at room temperature for 30 seconds. After the moisture was removed, a 90-degree peeling test was performed in the same manner as the primary adhesion, and the peel strength was measured. [Evaluation Criteria] If the peel strength is below 0.4 kgf/cm, it is evaluated as poor adhesion. The results obtained are shown in Table 1 below. 38 322497 201132803 [Table 1] Laminated structure Metal material Bottom treatment agent Film thickness (^m) Then strength (kgf/cm)

It can be seen from Table 1 that the steel material (Examples 1 to 3, 5) of the present invention obtained by the underlayer treatment method of the present invention, which is obtained by the underlayer treatment method of the present invention, is laminated with an epoxy resin. When the laminated member of the present invention is used, it exhibits excellent adhesion between the copper material and the epoxy resin, and particularly excellent adhesion at south temperature. In Comparative Example 1 in which iron as an oxidizing agent was replaced with hydrogen peroxide, the primary adhesion, the wet resistance secondary adhesion, the acid resistance secondary adhesion, and the alkali resistance were repeated twice. The sex was good, but it was confirmed that the heat resistance was poor. In Comparative Example 2, in which the anionic surfactant (B) was not contained, the material to be treated was Comparative Example 3 using a Ni box, and Comparative Example * in which no acid (c) was added was confirmed to have no precipitation of the film. Comparative Example 5 containing iron was confirmed in the film which was not washed with water, and any of the subsequent strengths were inferior. In Comparative Example 6 in which the blackening treatment s 39 322497 201132803 was used in the subsequent processing of the printed wiring board, the primary adhesion and the alkali resistance were good. However, the heat resistance was confirmed to be 2 times and the humidity was 2 times. Subsequent and acid-resistant secondary adhesions are poor. [Industrial Applicability] The underlayer treatment agent of the present invention is applied not only to the copper material and the resin in the printed wiring board or the like described in the background art, but also to various copper materials by a coating method or a laminate method. A method of forming a thermosetting resin by a method such as injection molding followed by a method, and is also a useful underlayer treatment agent. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a laminated material pattern of the present invention. Fig. 2 is a cross-sectional view showing a structural mode of a printed wiring board of the present invention. Fig. 3 is a photograph of a cross section of a copper circuit portion in which a single-sided copper circuit is formed into an epoxy resin sheet. Fig. 4 is a photograph showing a cross section of a copper circuit portion in which an epoxy resin sheet is formed by a single-sided copper circuit having a primer film obtained in Example 4. Fig. 5 is a graph showing the results of the xps depth direction analysis of the film deposited by itself in Example 5. Fig. 6 is a graph showing the results of the xps depth direction analysis of the film of Comparative Example 5 itself. [Explanation of main component symbols] 1 Laminated material 2 Copper material 3 Underlayer film 4 Thermosetting resin material layer 40 322497

Claims (1)

201132803 VII. Patent application scope: 1. A method for treating the underlying material of copper material, which has the following steps: Application steps: using copper material with organic resin (A), anionic surfactant (B), acid ( C) a step of contacting the aqueous underlayer treatment agent formed by the aqueous solution of the iron (111) ion of the oxidant (D) and having a pH of 3 or less; a water washing step: treating the underlayer formed on the copper material via the aforementioned application step a step of performing water washing on the film; and a drying step: a step of drying the film by the underlayer treatment after the water washing step. 2. The underlayer treatment method according to claim 1, wherein the organic resin (A) is an elastomer. 3. The underlayer treatment method according to claim 1 or 2, wherein the anionic surfactant (B) is selected from the group consisting of alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyldiphenyls One or more of the ether disulfonate and the alkanesulfonate are contained in a total amount of from 500 to 3,000 ppm. 4. The underlayer treatment method according to any one of claims 1 to 3, which further comprises a first wrong body stability coefficient of iron (III) ions at 25 ° C and an ion intensity of 0.5 M. /3 ! -Fe(III) is an anion supply source (E) of 5 or more. 5. The underlayer treatment method according to any one of claims 1 to 4, wherein the aqueous underlayer treatment agent is a composite of 1 to 1000 ppm of copper ions (F). 6. The method of the underlying treatment method of s 322497 to 201132803, wherein the copper material is a material for a printed wiring board. A copper material to which an underlying treatment film is attached is obtained by the underlayer treatment method according to any one of claims 1 to 6. 8. 003 g/ The content of the copper element in the underlying treated film is 0.1 to 10 atom%, and the content of the iron element in the underlying film is 0. 003 g/, as described in claim 7, wherein the ratio of the copper element in the underlying film is 0.1 to 10 atom%. Below m2. 9. The copper material to which the underlying treated film is attached as described in claim 7 or 8, wherein the surface roughness of the copper material after the underlying treatment with respect to the surface roughness (Ra.) of the copper material before the underlayer treatment ( 5的以下以下。 The variation of Ra Ra) Δ Ra at 0.5 or less from m. A laminated material comprising the copper material to which the underlying film is attached as described in any one of claims 7 to 9 and the resin layer provided on the underlying film. A printed wiring board having the following structure of a j to 1 , layer, wherein the structure is in an insulating resin layer of a copper wiring circuit, and only a patent application is formed on the surface of the copper circuit _ 7 to 9 The underlayer processing film described in the above-mentioned item is characterized in that the surface of the film is processed on the surface of the underlayer and the surface of the insulating layer of the copper wiring circuit is not formed to form an insulating resin layer. 12. An aqueous base treatment agent for a copper material, characterized by comprising an organic resin (A), an anionic surfactant (B), an acid (C), and an iron oxide as an oxidant (D) ion and having a pH of 3 The following aqueous solution. 13. The aqueous base treatment of copper material as described in item 2 of Uij, 2 322497 201132803 ', wherein the organic resin (Α) is an elastomer. 14. The aqueous base treatment agent for copper materials according to claim 12, wherein the anionic surfactant (B) is selected from the group consisting of alkylbenzenesulfonates, alkylnaphthalenesulfonates, and alkane. One or more of the diphenyl ether disulfonate and the alkanesulfonate are contained in a total amount of from 500 to 3,000 ppm. The first error of the iron (III) ion with an ionic strength of 0. 5M, at 25 ° C, with an aqueous base treatment agent for copper material according to any one of claims 12 to 14 The body stability coefficient (1) is an anion supply source (E) of 5 or more. The aqueous base treatment agent for copper materials according to any one of claims 12 to 15, which contains 1 to 1000 ppm of copper ions (F). The aqueous base treatment agent for copper materials according to any one of claims 12 to 16, which is used in a material of a printed wiring board. s 3 322497