Copper-based material, method for producing copper-based material, and laminate

Abstract

The invention provides a copper-based material, a manufacturing method of the copper-based material, and a laminate. A first surface treatment layer is arranged on the surface of the copper material, and a second surface treatment layer is arranged between the copper material and the first surface treatment layer; the first surface treatment layer is a layer formed from a first agent containing a styrene-butadiene-acrylic copolymer and a copolymer A having a vinyl silane compound, a hydrolysate thereof, or a polycondensate thereof, and water; the second surface treatment layer is a layer formed from a second agent containing a metal compound B and a compound D, the metal element of the metal compound B being selected from at least one of zirconium, titanium, and trivalent chromium, and the compound D containing a vanadium element. The copper-based material satisfying the above-mentioned characteristics has excellent heat resistance, improves the adhesion of the laminate, and improves the adhesion.

Description

Technical Field

[0001] The present application relates to the technical field of copper materials, and in particular to a copper material, a method for manufacturing the copper material, and a laminate. Background Art

[0002] In recent years, with the further high-speed communication, the high-frequency of electrical signals has continued to develop, and a high-frequency printed circuit board capable of coping with the above situation is needed. In the high-frequency region, it is ideal to use a resin material with excellent dielectric properties (relative dielectric constant and dielectric loss tangent are low), but due to weak electrostatic interaction with copper foil, there is a tendency for low adhesion. In addition, with the integration of printed circuit boards, heat resistance is required.

[0003] Copper-clad laminates formed by laminating a resin substrate and a copper-based material substrate are used in the manufacture of printed circuit boards, for example. For example, Patent Document 1 discloses a technique in which a surface-treated copper foil having a roughening treatment layer, a heat-resistant treatment layer, and a chromate treatment layer is treated with a silane coupling agent to form a silane coupling agent layer, thereby improving adhesion and corrosion resistance.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2024 / 116475. Summary of the Invention

[0007] The purpose of this application is to provide a copper-based material, a method for manufacturing a copper-based material, and a laminate to improve adhesion and heat resistance. The specific technical solution is as follows:

[0008] The first aspect of the present application provides a copper-based material having a first surface treatment layer on or on the surface of the copper-based material, and a second surface treatment layer is arranged between the copper-based material and the first surface treatment layer; the first surface treatment layer is a layer formed by a first agent containing a styrene-butadiene-acrylic copolymer and a copolymer A having a vinyl silane compound, its hydrolyzate, or their condensation product and water; the second surface treatment layer is a layer formed by a second agent containing a metal compound B and a compound D, the metal element of the metal compound B is selected from at least one of zirconium, titanium and trivalent chromium, and the compound D contains vanadium.

[0009] In one embodiment of the present application, copolymer A comprises a structure represented by formula (I):

[0010]

[0011] In formula (I), R1 and R2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, R3 represents a hydrogen atom or a methyl group, M, X, Y and Z are the average values ​​of the number of repeating units, X is an integer from 1 to 100, M / X is from 0.01 to 10, Y / X is from 0.01 to 10, and Z / X is from 0.01 to 20.

[0012] In one embodiment of the present application, the second agent further comprises compound C, and compound C comprises fluorine element.

[0013] In one embodiment of the present application, in the second dose, at least one of the following conditions is met: (I) the ratio of the metal element converted mass BM g of the metal compound B to the vanadium element converted mass DM g of the compound D satisfies: BM / DM is 500 to 1200; (II) the ratio of the fluorine element converted mass CM g to DM g of the compound C satisfies: CM / DM is 500 to 3200.

[0014] In one embodiment of the present application, the first agent further comprises a metal compound E, wherein the metal element of the metal compound E is selected from at least one of zirconium, titanium and trivalent chromium.

[0015] In one embodiment of the present application, in the first dose, at least one of the following conditions is met: (III) the ratio of the solid content mass AM g of the copolymer A to the metal element converted mass EM g of the metal compound E satisfies: EM / AM is 0.01 to 50; (IV) the pH of the first dose is 1 to 6.

[0016] The second aspect of the present application provides a method for manufacturing the copper material described in the first aspect of the present application, which includes: step a of forming a second surface treatment layer on the surface or surface of the copper material, step a including: a step of contacting a second agent containing metal compound B and compound D with the copper material and a drying step after the contact step; step b of forming a first surface treatment layer, step b including: a step of contacting a first agent of copolymer A, its hydrolyzate, or their condensation product with water and a drying step after the contact step.

[0017] In one embodiment of the present application, step a includes making the second surface treatment layer 2 mg / m 2 Up to 500 mg / m 2 The contact process and the drying process at 100 ℃ to 180 ℃ after the contact process; Step b includes: making the first surface treatment layer 2mg / m 2 Up to 500 mg / m 2 contact process.

[0018] The third aspect of the present application provides a laminate, which comprises the copper material described in the first aspect of the present application or the copper material obtained according to the manufacturing method described in the second aspect of the present application, and the first surface treatment layer of the copper material comprises a resin film layer, and the resin film layer comprises a hydrocarbon resin.

[0019] Beneficial effects of this application:

[0020] The present application provides a copper-based material having a first surface treatment layer on or on the surface of the copper-based material, and a second surface treatment layer disposed between the copper-based material and the first surface treatment layer. The first surface treatment layer is formed from a first agent containing a styrene-butadiene-acrylic acid copolymer and a copolymer A containing a vinyl silane compound, a hydrolyzate thereof, or a polycondensate thereof, and water. The second surface treatment layer is formed from a second agent containing a metal compound B and a compound D, wherein the metal element of the metal compound B is selected from at least one of zirconium, titanium, and trivalent chromium, and the compound D contains vanadium. The copper-based material meeting the above characteristics has excellent heat resistance and improves the adhesion and tightness of the laminate.

[0021] Of course, it is not necessary to achieve all the advantages described above at the same time when implementing any product or method of the present application. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solutions in this application. Obviously, the embodiments described are only part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those skilled in the art based on this application are within the scope of protection of this application.

[0023] In a first aspect, the present application provides a copper-based material having a first surface-treated layer on or on the surface of the copper-based material, and a second surface-treated layer disposed between the copper-based material and the first surface-treated layer. The first surface-treated layer is formed from a first agent comprising a styrene-butadiene-acrylic copolymer and a copolymer A containing a vinyl silane compound, a hydrolyzate thereof, or a polycondensate thereof, and water. The second surface-treated layer is formed from a second agent comprising a metal compound B and a compound D, wherein the metal element of the metal compound B is selected from at least one of zirconium, titanium, and trivalent chromium, and the compound D contains vanadium. The copper-based material meeting the above characteristics has excellent heat resistance and improves the adhesion and tightness of the laminate.

[0024] In one embodiment of the present application, copolymer A comprises a structure represented by formula (I):

[0025]

[0026] In formula (I), R1 and R2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, R3 represents a hydrogen atom or a methyl group, M, X, Y and Z are the average values ​​of the number of repeating units, X is an integer from 1 to 100, M / X is from 0.01 to 10, Y / X is from 0.01 to 10, and Z / X is from 0.01 to 20. For example, X can be 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, or a range consisting of any two thereof; M / X can be 0.01, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or a range consisting of any two thereof; Y / X can be 0.01, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or a range consisting of any two thereof; and Z / X can be 0.01, 0.5, 1, 3, 5, 7, 9, 10, 12, 14, 16, 18, 20, or a range consisting of any two thereof. When copolymer A meets the above characteristics, the resulting copper-based material has excellent heat resistance, which is beneficial for improving the adhesion and tightness of the laminate.

[0027] The weight average molecular weight of the copolymer A of this embodiment is 50 to 12000. For example, the weight average molecular weight of the copolymer A is 50, 100, 500, 1000, 2000, 4000, 6000, 8000, 10000, 12000, or a range consisting of any two of these values. The weight average molecular weight values ​​in this specification are measured by GPC (gel permeation chromatography) and are converted to polystyrene.

[0028] In one embodiment of the present application, the second agent further comprises compound C, and compound C comprises fluorine. When the second agent comprises compound C, it is beneficial to improve the adhesion of the laminate and the initial adhesion.

[0029] In one embodiment of the present application, in the second dose, at least one of the following conditions is satisfied: (I) the ratio of the metal element-converted mass BM g of the metal compound B to the vanadium element-converted mass DM g of the compound D satisfies: BM / DM is 500 to 1200; (II) the ratio of the fluorine element-converted mass CM g to DM g of the compound C satisfies: CM / DM is 500 to 3200. For example, the value of BM / DM may be 500, 600, 700, 800, 900, 1000, 1100, 1200, or a range consisting of any two thereof; the value of CM / DM may be 500, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, or a range consisting of any two thereof. By adjusting the values ​​of BM / DM and CM / DM within the range of this application, the second agent has better adhesion and heat resistance, which is beneficial to improving the adhesion and initial adhesion of the laminate, while also improving the heat resistance.

[0030] In one embodiment of the present application, the first agent further comprises a metal compound E, wherein the metal element of the metal compound E is selected from at least one of zirconium, titanium, and trivalent chromium. When the first agent comprises the metal compound E, it is beneficial to improve the adhesion of the laminate and the initial adhesion.

[0031] In one embodiment of the present application, the first agent satisfies at least one of the following conditions: (III) the ratio of the solid content mass AM g of the copolymer A to the metal element-converted mass EM g of the metal compound E satisfies: EM / AM is 0.01 to 50; (IV) the pH of the first agent is 1 to 6. For example, the EM / AM value can be 0.01, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, or a range consisting of any two of these ratios; the pH of the first agent can be 1, 2, 3, 4, 5, 6, or a range consisting of any two of these ratios. By regulating the EM / AM and pH values ​​of the first agent within the ranges of the present application, the first surface treatment layer formed by the first agent exhibits good affinity with the resin film layer to which it is bonded, and exhibits good initial adhesion.

[0032] In the present application, when the metal element of the metal compound B includes zirconium, as a compound including zirconium, as long as zirconium is included as an element, there is no particular limitation, and it can be any one of an inorganic zirconium compound and an organic zirconium compound. As an inorganic zirconium compound, for example, zirconyl sulfate, zirconyl nitrate, zirconyl nitrate, zirconyl chloride, zirconium chloride, zirconium oxide sol, zirconium oxide, hexafluorozirconic acid, etc. can be mentioned, but it is not limited to these. In addition, as an organic zirconium compound, for example, zirconium lactate, zirconium tetraisopropoxide, zirconium acetylacetonate, n-propyl zirconate, n-butyl zirconate, zirconium tetraacetylacetonate, etc. can be mentioned, but it is not limited to these. These compounds can be used in the preparation of the second dose in one or more than two kinds.

[0033] In the present application, when the metal element of the metal compound B includes titanium, as a compound including titanium, as long as it includes titanium as an element, there is no particular limitation, and it can be any one of an inorganic titanium compound and an organic titanium compound. As an inorganic titanium compound, for example, titanium oxysulfate, titanium oxynitrate, titanium nitrate, titanium oxychloride, titanium chloride, titanium dioxide sol, titanium oxide, hexafluorotitanic acid, etc. can be mentioned, but it is not limited to these. In addition, as an organic titanium compound, for example, potassium oxalate titanate, titanium lactate, tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, titanium acetylacetonate, diisopropyl diacetylacetonate titanium, diisopropoxy bis (acetylacetonate) titanium, etc. can be mentioned, but it is not limited to these. These compounds can be used in the preparation of the second agent alone, or two or more can be used.

[0034] In the present application, when the metal element in the metal compound B includes trivalent chromium, the compound containing trivalent chromium is not particularly limited as long as it is a compound containing trivalent chromium as an element, and may be any of an inorganic trivalent chromium compound and an organic chromium compound. Examples of inorganic trivalent chromium compounds include, but are not limited to, chromium acetate, chromium hydroxide, chromium trichloride, chromium sulfate, chromium nitrate, and chromium fluoride. In addition, examples of organic trivalent chromium compounds include, but are not limited to, chromium (III) acetate and chromium (III) acetylacetonate. These compounds may be used alone or in combination in the preparation of the second agent.

[0035] In the present application, when the metal element of the metal compound E includes zirconium, as a compound including zirconium, as long as zirconium is included as an element, there is no particular limitation, and it can be any one of an inorganic zirconium compound and an organic zirconium compound. As an inorganic zirconium compound, for example, zirconyl sulfate, zirconyl nitrate, zirconyl nitrate, zirconyl chloride, zirconium chloride, zirconium oxide sol, zirconium oxide, hexafluorozirconic acid, etc. can be mentioned, but it is not limited to these. In addition, as an organic zirconium compound, for example, zirconium lactate, zirconium tetraisopropoxide, zirconium acetylacetonate, n-propyl zirconate, n-butyl zirconate, zirconium tetraacetylacetonate, etc. can be mentioned, but it is not limited to these. These compounds can be used in the preparation of the first dose in one or more than two kinds.

[0036] In the present application, when the metal element of the metal compound E includes titanium, as a compound including titanium, as long as it includes titanium as an element, there is no particular limitation, and it can be any one of an inorganic titanium compound and an organic titanium compound. As an inorganic titanium compound, for example, titanium oxysulfate, titanium oxynitrate, titanium nitrate, titanium oxychloride, titanium chloride, titanium dioxide sol, titanium oxide, hexafluorotitanic acid, etc. can be mentioned, but it is not limited to these. In addition, as an organic titanium compound, for example, potassium oxalate titanate, titanium lactate, tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, titanium acetylacetonate, diisopropyl diacetylacetonate titanium, diisopropoxy bis (acetylacetonate) titanium, etc. can be mentioned, but it is not limited to these. These compounds can be used alone or in combination in the preparation of the first dose.

[0037] In the present application, when the metal element in the metal compound E includes trivalent chromium, the compound containing trivalent chromium is not particularly limited as long as it is a compound containing trivalent chromium as an element, and may be any of an inorganic trivalent chromium compound and an organic chromium compound. Examples of inorganic trivalent chromium compounds include, but are not limited to, chromium acetate, chromium hydroxide, chromium trichloride, chromium sulfate, chromium nitrate, and chromium fluoride. In addition, examples of organic trivalent chromium compounds include, but are not limited to, chromium (III) acetate and chromium (III) acetylacetonate. These compounds may be used alone or in combination in the preparation of the first agent.

[0038] In the present application, compound C is not particularly limited as long as it is a compound that can supply fluoride ions when mixed with the second agent. The compound containing fluorine element is hydrofluoric acid, an inorganic fluoride salt, a fluoride of a metal, a complex of hydrofluoric acid and a metal, etc., and can include, for example, hexafluorozirconic acid, hexafluorotitanic acid, hexafluorohafnic acid, hydrofluoric acid, ammonium fluoride, ammonium bifluoride, germanium fluoride, sodium fluoride, potassium fluoride, potassium bifluoride, iron fluoride, fluorosilicic acid, sodium fluoride, sodium bifluoride, etc., but is not limited to these. Various fluorine-containing element compounds can be used only one, or two or more can be used.

[0039] In the present application, compound D is not particularly limited as long as it is a compound capable of supplying vanadium-containing ions when combined with the second agent. The compound containing vanadium can be either an inorganic vanadium compound or an organic vanadium compound. Examples of inorganic vanadium compounds include sodium vanadate, potassium vanadate, ammonium metavanadate, vanadium sulfate, and vanadium pentoxide; examples of organic vanadium compounds include, but are not limited to, vanadyl acetylacetonate. The various vanadium-containing compounds may be combined alone or in combination of two or more.

[0040] In the present application, the method for producing copolymer A is not particularly limited, and any method known in the art can be used, as long as the purpose of the present application can be achieved. For example, the method for producing copolymer A can be as follows: in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, styrene and butadiene at a molar ratio of 0.01 to 10 relative to styrene are dissolved in an organic solvent 5-10 times the mass of styrene, and an acrylic acid compound at a molar ratio of 0.01 to 10 relative to styrene and a vinyl silane compound at a molar ratio of 0.01 to 20 relative to styrene are added under a nitrogen atmosphere, and stirring is continued at 70 to 120° C. for 12 to 24 hours to obtain a reaction mixture a. Subsequently, benzoyl peroxide at a molar ratio of 0.005 to 0.01 relative to styrene is dissolved in an organic solvent and then slowly added dropwise to the reaction mixture a, with the addition time controlled to 20 to 40 minutes. After the addition is completed, stirring is continued at 70 to 120° C. for 12 to 24 hours. After the reaction was completed, the mixture was cooled to room temperature, precipitated with an excess amount of an organic solvent, and filtered to obtain a copolymer A having a solid content concentration of 100 wt%.

[0041] In the present application, the acrylic compound includes at least one of acrylic compounds, methacrylic compounds, methacrylate compounds, and acrylate compounds; the vinylsilane compound includes at least one of vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinyltributoxysilane.

[0042] As an organic solvent, as long as it can dissolve styrene, butadiene, acrylic compounds, and vinyl silane compounds, the present application has no particular restrictions on it. For example, alcohol solvents, glycol ether solvents, ketone solvents, and amide solvents can be used. As alcohol solvents, methanol, ethanol, propanol, 2-propanol, butanol, etc. can be used; as glycol ether solvents, ethylene glycol ethyl ether, ethylene glycol n-butyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, etc. can be used; as ketone solvents, methyl ethyl ketone, methyl isobutyl ketone, etc. can be used; as amide solvents, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, etc. can be used. These organic solvents can be used alone or in combination of two or more.

[0043] The reaction catalyst is not particularly limited as long as it is a catalyst that promotes the polymerization reaction. Tertiary amines, organometallic carboxylates, titanates, etc. can be used. Examples of tertiary amines include dimethylbenzylamine, triethylamine, and tributylamine. Examples of organometallic carboxylates include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, tin(II) acetate, lead naphthenate, zinc octoate, and cobalt naphthenate. Examples of titanates include titanium tetraethoxide, titanium tetraisopropoxide, and titanium tetrabutoxide. These reaction catalysts can be used alone or in combination of two or more.

[0044] Whether the copolymer A produced as described above contains styrene, butadiene, an acrylic compound, or a vinylsilane compound can be confirmed by measuring the Si-CC-derived wavelength at 1290 cm-1 using an infrared spectrophotometer by the ATR method. -1 ~1320cm -1 to the peak.

[0045] In the present application, styrene, butadiene, acrylic compounds, vinyl silane compounds, and organic solvents may also be commercially available, as long as they can meet the purpose of the present application.

[0046] In the present application, the metal compound B, compound C, compound D, and metal compound E may also be purchased from the market, as long as they can meet the purpose of the present application.

[0047] In the present application, the pH of the first agent forming the first surface treatment layer is not particularly limited as long as it can be adjusted to the desired pH, and is preferably adjusted using an oxyacid of an inorganic compound. "Oxyacid of an inorganic compound" refers to a compound that does not contain carbon in the elements constituting the molecule and has an oxo group and a hydroxyl group showing proton donating properties bonded to the central atom. For example, as oxyacids of inorganic compounds containing sulfur atoms, sulfuric acid, sulfurous acid, etc. can be mentioned; as oxyacids of inorganic compounds containing phosphorus atoms, phosphoric acid, polyphosphoric acid, etc. can be mentioned; as oxyacids of inorganic compounds containing nitrogen atoms, nitric acid, nitrous acid, etc. can be mentioned, but are not limited to these. The oxyacids of inorganic compounds can be used alone or in combination of two or more.

[0048] In the present application, the first agent may contain various additives as needed. As additives, for example, surfactants, defoaming agents, leveling agents, cross-linking agents, pH regulators, thickeners, antioxidants, antibacterial and antifungal agents, colorants, etc. can be cited, but are not limited to these. By adding these additives to the first agent, the storage and drying properties of the first agent can be improved, or the operability in the manufacture of the first surface treatment layer formed using the first agent can be improved, or the smoothness and stability of the manufactured first surface treatment layer can be improved. These additives can be added within the range that does not damage the effect of the present invention, and the content of the additives in the first agent is at most 0.1% to 10% relative to the mass of the first agent.

[0049] In the present application, the pH of the second agent is preferably 1 to 6, more preferably 2 to 5. The second surface treatment layer formed by the second agent having a pH within the above numerical range has high affinity with the copper material and the first surface treatment layer and excellent initial adhesion.

[0050] The pH of the second agent may be adjusted using an inorganic oxygen-containing acid or an acid other than an inorganic oxygen-containing acid.

[0051] In the present application, the second agent may contain various additives as needed. The second agent may contain various additives as needed. As additives, for example, surfactants, defoaming agents, leveling agents, cross-linking agents, pH regulators, thickeners, antioxidants, antibacterial and antifungal agents, colorants, etc. may be cited, but are not limited to these. By adding these additives to the second agent, the storage and drying properties of the second agent can be improved, or the operability in the manufacture of the second surface treatment layer formed using the second agent can be improved, or the smoothness and stability of the manufactured second surface treatment layer can be improved. These additives can be added within the range that does not impair the effect of the present invention, and the content of the additives is at most 0.1% to 10% relative to the mass of the second agent.

[0052] The second aspect of the present application provides a method for manufacturing the copper material described in the first aspect of the present application, which includes: step a of forming a second surface treatment layer on the surface or surface of the copper material, step a including: a step of contacting a second agent containing metal compound B and compound D with the copper material and a drying step after the contact step; step b of forming a first surface treatment layer, step b including: a step of contacting a first agent of copolymer A, its hydrolyzate, or their condensation product with water and a drying step after the contact step.

[0053] In the present application, the copper-based material is not particularly limited as long as the entire or a portion of the surface of the material contains copper or a copper alloy, and the entire or a portion of the surface of the material is at least composed of copper or a copper alloy. Examples of copper or copper alloys include electrolytic copper foil and rolled copper foil.

[0054] In one embodiment of the present application, step a includes making the second surface treatment layer 2 mg / m 2 Up to 500 mg / m 2 The contact process and the drying process at 100 ℃ to 180 ℃ after the contact process; Step b includes: making the first surface treatment layer 2mg / m 2 Up to 500 mg / m 2 For example, in the contact process, the second surface treatment layer can be 2mg / m 2 , 5mg / m 2 , 10mg / m 2 , 50mg / m 2 , 100mg / m 2 , 150mg / m 2 , 200mg / m 2 , 250mg / m 2 , 300mg / m2 , 350mg / m 2 400mg / m 2 450mg / m 2 , 500mg / m 2 or a range consisting of any two values ​​therein; the temperature of the drying process can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C or a range consisting of any two values ​​therein; the first surface treatment layer can be 2mg / m 2 , 5mg / m 2 , 10mg / m 2 , 50mg / m 2 , 100mg / m 2 , 150mg / m 2 , 200mg / m 2 , 250mg / m 2 , 300mg / m 2 , 350mg / m 2 400mg / m 2 450mg / m 2 , 500mg / m 2 The single-sided adhesion weight of the first surface treatment layer and the second surface treatment layer and the temperature of the drying process within the above ranges are beneficial to improving the adhesion and initial adhesion of the laminate and enhancing the heat resistance.

[0055] In the present application, as a contact step of contacting the copper-based material with the second agent in the step of forming the second surface treatment layer on the surface of the copper-based material or on the surface thereof, the contact step method may include, but is not limited to, dipping, coating, spraying, flow coating, etc. The present application does not particularly limit the contact temperature and contact time. For example, the contact temperature may be 5° C. to 50° C., and the contact time may be 0.1 second to 1 hour.

[0056] In the present application, when the drying process is performed after the copper material is brought into contact with the second agent, the drying time may be 5-10 minutes.

[0057] In the present application, as the contact step of the first agent in the process of forming the first surface treatment layer on the second surface treatment layer, the contact method of the first agent can be, for example, dipping, coating, spraying, flow coating, etc., but is not limited to these. The contact temperature and contact time are not particularly limited. For example, the contact temperature can be 5°C to 50°C, and the contact time can be 0.1 second to 1 hour.

[0058] In the present application, the drying temperature and time in the drying process after contacting the first agent are not particularly limited. The drying temperature may be 100° C. to 180° C., and the drying time may be 5-10 minutes.

[0059] The manufacture method of present embodiment can also carry out degreasing process to the surface of copper material or before the process of forming the second surface treatment layer on the surface.Degreasing can be carried out by known method using appropriate degreasing agent according to material.In addition, as degreasing agent, for example known acidic degreasing agent, alkaline degreasing agent, solvent degreasing agent etc. can be enumerated, but is not limited to these.As degreasing method, there is no particular limitation, for example methods such as scrubbing cleaning, spray cleaning (spray cleaning), immersion cleaning can be enumerated.

[0060] The manufacturing method of this embodiment may perform a water washing step on the surface of the copper material after the degreasing step and before the step of forming the second surface treatment layer on the surface. Alternatively, a pickling step or an alkali washing step may be performed after the water washing step. Alternatively, the water washing step and the pickling step or the alkali washing step may be repeated before the step of forming the second surface treatment layer. The pickling step and the alkali washing step may be applied by known methods.

[0061] A third aspect of the present application provides a laminate comprising the copper-based material described in the first aspect of the present application or the copper-based material obtained according to the manufacturing method described in the second aspect of the present application, wherein the first surface treatment layer of the copper-based material comprises a resin film layer, and the resin film layer comprises a hydrocarbon resin. The laminate meeting the above characteristics has good adhesion and heat resistance, and is therefore suitable for copper-clad laminates.

[0062] In the present application, a resin film layer containing a hydrocarbon resin is bonded to a surface treated layer of a copper material by a bonding process. The bonding method in the bonding process may be a commonly used bonding method, such as thermocompression bonding.

[0063] Example

[0064] The following examples and comparative examples are provided to more specifically illustrate the embodiments of the present invention. Various tests and evaluations were performed according to the following methods. In addition, unless otherwise specified, "parts" and "%" are based on mass.

[0065] Test methods and equipment:

[0066] Fit test:

[0067] Initial adhesion test: For various laminates, the initial adhesion was measured using a tensile testing machine according to the IPC-TM-650 test method and evaluated according to the following evaluation criteria:

[0068] 5: 0.6N / mm or more;

[0069] 4: 0.5N / mm or more and less than 0.6N / mm;

[0070] 3: 0.4N / mm or more and less than 0.5N / mm;

[0071] 2: 0.3N / mm or more and less than 0.4N / mm;

[0072] 1: Less than 0.3N / mm.

[0073] Adhesion test after solder float test: After floating various laminates in a solder bath at 288° C. for 180 seconds, the adhesion was evaluated using the same test method and evaluation criteria as the initial adhesion test.

[0074] Heat resistance test:

[0075] Each laminate was floated on lead-free solder at 288°C according to the evaluation rules in IPC TM-650 2.4.13 test method. The time required for the resin film layer to peel from the copper material was measured and evaluated according to the following evaluation criteria.

[0076] 5: The time required to peel the resin film layer and the copper foil is more than 400 seconds;

[0077] 4: The time required to peel the resin film layer and the copper foil is 300 seconds or more and less than 400 seconds;

[0078] 3: The time required to peel the resin film layer and the copper foil is 200 seconds or more and less than 300 seconds;

[0079] 2: The time required to peel the resin film layer and the copper foil is 100 seconds or more and less than 200 seconds;

[0080] 1: The time required for peeling the resin film layer and the copper foil is less than 100 seconds.

[0081] Synthesis example 1

[0082] <Synthesis of Copolymer A>

[0083] As shown in Table 1, in a reaction vessel equipped with a stirrer, dropping funnel, and thermometer, 10.42 g of styrene (butadiene at a molar ratio of 1 to styrene) was dissolved in toluene (5 times the mass of styrene). Methyl methacrylate (at a molar ratio of 1 to styrene) and vinyltrimethoxysilane (at a molar ratio of 0.5 to styrene) were then added under a nitrogen atmosphere. Stirring was continued at 90°C for 16 hours to obtain a reaction mixture a. Next, benzoyl peroxide (at a molar ratio of 0.005 to styrene) was dissolved in 30 mL of toluene and slowly added dropwise to the reaction mixture a over a 30-minute period. Stirring was continued at 90°C for 16 hours. After the reaction was complete, the mixture was cooled to room temperature, precipitated with excess methanol, and filtered to obtain copolymer A1 (X=50, Y / X=1, Z / X=0.5, M / X=1, R1 is methyl, R2 is methyl, and R3 is methyl) with a solids concentration of 100 wt%. The infrared absorption spectrum of the obtained copolymer A1 is at 1290 cm -1 ~1320cm -1 Has a peak.

[0084] Synthesis Examples 2 to 5

[0085] Adjust the relevant parameters according to Table 1, and the rest are the same as in Synthesis Example 1 to obtain copolymers A2 to A5 (all with X=50) as shown in Table 1. The infrared absorption spectra of the obtained copolymers A2-A5 are at 1290 cm -1 ~1320cm -1 Has a peak.

[0086] Example 1

[0087] <Copper materials>

[0088] As the metal material, electrolytic copper foil for PCB (glossy surface, thickness: 12 μm, Rz ≤ 1 μm) was used.

[0089] <Preprocessing>

[0090] The copper material surface was degreased by diluting FC-315S (manufactured by Japan Parkersin Co., Ltd.), an alkaline degreasing agent, in 20 g / L deionized water and immersing the material at 60°C for 1 minute. After degreasing, the copper material surface was rinsed with water by immersing it in ion-exchanged water at 25°C for 1 minute. After rinsing, the copper material surface was pickled by immersing it in 10% sulfuric acid at 25°C for 1 minute. After pickling, the copper material surface was rinsed with water by immersing it in ion-exchanged water at 25°C for 1 minute.

[0091] <Manufacturing of the Second Agent and the Second Surface Treatment Layer>

[0092] As shown in Table 2, metal compound B3 and compound D1 were mixed in 500 mL of deionized water, and stirred at 20°C-30°C and 200 rpm for 0.5-2 hours. The pH of the second agent was adjusted with nitric acid and ammonia water to obtain the second agent.

[0093] The vanadium element equivalent mass DM in D1 is 1 g, the metal element equivalent mass BM in the metal compound B3 is 300 g, and the value of BM / DM is 300.

[0094] After pretreatment, a second coating (0.1 ml) was applied to the copper surface using a #3 SUS Meyer rod at a contact temperature of 30°C for 30 seconds. The coating was then dried in a hot air oven for 5 minutes at the ambient temperature shown in Table 2 to form a second surface treatment layer with the single-sided adhesion weights shown in Table 2.

[0095] <Manufacturing of the First Agent and the First Surface Treatment Layer>

[0096] As shown in Table 2, copolymer A1 prepared as shown in Table 1 was mixed in 500 ml of deionized water, heated to 40°C-80°C, and stirred at 200 rpm for 0.5-2 hours. The pH of the first agent was adjusted with nitric acid and ammonia to obtain the first agent.

[0097] The mass AM of the copolymer A1 is 100 g.

[0098] After forming the second surface treatment layer, 0.1 ml of the first agent was applied to the surface of the second surface treatment layer using a #3 SUS Meyer rod at a contact temperature of 30° C. for 30 seconds. The material was then dried in a hot air oven at the ambient temperature shown in Table 2 for 5 minutes to form a first surface treatment layer having a single-sided adhesion amount shown in Table 2, thereby obtaining a copper-based material having a second surface treatment layer and a first surface treatment layer.

[0099] <Manufacturing of Laminated Body>>

[0100] The first surface treatment layer of the copper-based material contains a resin film layer of a hydrocarbon resin (with a styrene content of 50% and a butadiene content of 30 wt %).

[0101] A vacuum laminator, Morton CVA725, was used at a temperature of 190°C and a pressure of 70 kgf / cm 2 Vacuum lamination was performed under conditions of for 150 minutes to obtain the laminate shown in Example 1.

[0102] Examples 2 to 35

[0103] The same procedures as in Example 1 were followed, except that the preparation of the first and second surface treatment layers was adjusted according to Table 2. The pH of the first and / or second agents was adjusted using nitric acid and aqueous ammonia as shown in Table 2. The solid content of the first and / or second agents was adjusted by varying the amount of deionized water, such that the single-sided adhesion of the first and / or second surface treatment layers was as shown in Table 2.

[0104] Comparative Example 1

[0105] <Copper materials>

[0106] As the metal material, electrolytic copper foil for PCB (glossy surface, thickness: 12 μm, Rz ≤ 1 μm) was used.

[0107] As shown in Table 2, the copper material is not provided with the first surface treatment layer and the second surface treatment layer, and the rest is the same as in Example 1.

[0108] Comparative Example 2

[0109] Except that the copper material is not provided with the first surface treatment layer as shown in Table 2, the rest is the same as Example 5.

[0110] Comparative Example 3

[0111] The styrene-butadiene-acrylic acid copolymer A0a synthesized in Synthesis Example 1 without adding vinyltrimethoxysilane was used.

[0112] Except that A0a replaces copolymer A1 and the copper material shown in Table 2 is not provided with the second surface treatment layer, the rest is the same as Example 1.

[0113] Comparative Examples 4 to 6

[0114] The styrene-butadiene-acrylic acid copolymer A0a synthesized in Synthesis Example 1 without adding vinyltrimethoxysilane was used.

[0115] Except that A0a replaces copolymer A1 and relevant parameters are adjusted according to Table 2, the rest is the same as Example 5.

[0116] Comparative Example 7

[0117] After synthesizing styrene-butadiene-acrylic acid copolymer without adding vinyltrimethoxysilane in Synthesis Example 1, deionized water was added to adjust the solid content concentration to 30 wt %; then vinyltrimethoxysilane was added and stirred at 25° C. for 1 hour to obtain A0b.

[0118] Except that copolymer A1 was replaced by A0b and relevant parameters were adjusted according to Table 2, the rest was the same as Example 5.

[0119] The manufacturing parameters and performance parameters of each embodiment and comparative example are shown in Tables 1 to 3.

[0120] Table 1

[0121]

[0122]

[0123]

[0124]

[0125] Table 3

[0126]

[0127]

[0128] The surface of the copper-based material is provided with a first surface treatment layer and a second surface treatment layer, and the components of the first surface treatment layer and the second surface treatment layer affect the adhesion and heat resistance of the laminate. From Synthesis Examples 1 to 5, Examples 1 to 35, and Comparative Examples 1 to 7, it can be seen that when the surface of the copper-based material is provided with a first surface treatment layer formed by a first agent comprising a copolymer A of a styrene-butadiene-acrylic copolymer and a silane compound having a vinyl group and water, and a second surface treatment layer formed by a second agent comprising a metal compound B and a compound D, the resulting laminate has good initial adhesion and adhesion after the float solder test, and good heat resistance, thereby improving the adhesion and heat resistance of the laminate.

[0129] The composition of the second surface treatment layer and the BM / DM and CM / DM values ​​affect the adhesion and heat resistance of the laminate. As can be seen from Examples 1 to 5, when the second agent includes Metal Compound B, Compound C, and Compound D, and the BM / DM and CM / DM values ​​are within the ranges of this application, the laminate formed by the second surface treatment layer has good initial adhesion, good adhesion after the solder float test, and good heat resistance, indicating that it is beneficial for improving the adhesion and heat resistance of the laminate.

[0130] The composition and EM / AM ratio of the first surface treatment layer affect the adhesion and heat resistance of the laminate. As can be seen from Examples 1, 6, and 9, when the first agent comprises copolymer A and metal compound E, and the EM / AM ratio is within the range of this application, the laminate formed by the first surface treatment layer has good initial adhesion, good adhesion after the solder float test, and good heat resistance, indicating that it is beneficial for improving the adhesion and heat resistance of the laminate.

[0131] It can be seen from Example 1, Example 10 to Example 11 that when the first agent contains copolymer A and metal compound E, and the second agent contains metal compound B, compound C, and compound D, and the values ​​of BM / DM, CM / DM, and EM / AM are within the range of this application, the obtained laminate has good initial adhesion and adhesion after the float solder test, and good heat resistance, indicating that it is beneficial to improve the adhesion and heat resistance of the laminate.

[0132] The types of copolymer A, metal compound E, metal compound B, compound C, and compound D affect the adhesion and heat resistance of the laminate. As can be seen from Examples 11 to 23, when the types of copolymer A, metal compound E, metal compound B, compound C, and compound D are within the range of this application, the resulting laminate exhibits good initial adhesion, good adhesion after the solder float test, and good heat resistance, indicating that this is beneficial for improving the adhesion and heat resistance of the laminate.

[0133] The pH of the first and second agents affects the adhesion and heat resistance of the laminate. As can be seen from Examples 11 and 24 to 27, when the pH of the first and second agents is within the ranges of this application, the resulting laminate exhibits good initial adhesion, good adhesion after the solder float test, and good heat resistance, demonstrating improved adhesion and heat resistance of the laminate.

[0134] The single-sided adhesion weight of the first and second surface-treated layers affects the adhesion and heat resistance of the laminate. As can be seen from Examples 11, 28, and 31, when the single-sided adhesion weights of the first and second surface-treated layers are within the ranges of this application, the resulting laminate exhibits good initial adhesion, adhesion after the solder float test, and good heat resistance, demonstrating improved adhesion and heat resistance of the laminate.

[0135] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, or article comprising a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, or article.

[0136] Each embodiment in this specification is described in a related manner. The same or similar parts between the embodiments can be referred to each other. Each embodiment focuses on the differences from other embodiments.

[0137] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A copper material having a first surface treatment layer on or on the surface of the copper material, and a second surface treatment layer provided between the copper material and the first surface treatment layer; The first surface treatment layer is a layer formed of a first agent containing a styrene-butadiene-acrylic acid copolymer and a copolymer A having a vinyl silane compound, a hydrolyzate thereof, or a polycondensate thereof and water; The second surface treatment layer is a layer formed of a second agent containing a metal compound B and a compound D. The metal element of the metal compound B is at least one selected from zirconium, titanium, and trivalent chromium. The compound D contains vanadium.

2. The copper-based material according to claim 1, wherein The copolymer A comprises a structure shown in formula (I): In the formula (I), R1 and R2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, R3 represents a hydrogen atom or a methyl group, M, X, Y and Z are the average values ​​of the number of repeating units, X is an integer from 1 to 100, M / X is from 0.01 to 10, Y / X is from 0.01 to 10, and Z / X is from 0.01 to 20.

3. The copper-based material according to claim 1 or 2, wherein: The second agent further comprises compound C, wherein the compound C comprises fluorine element.

4. The copper-based material according to claim 3, wherein: In the second dose, at least one of the following conditions is met: (I) the ratio of the metal element conversion mass BMg of the metal compound B to the vanadium element conversion mass DM g of the compound D satisfies: BM / DM is 500 to 1200; (II) The ratio of the fluorine element converted mass CMg of the compound C to the DMg satisfies: CM / DM is 500 to 3200.

5. The copper-based material according to claim 1 or 2, wherein: The first agent further comprises a metal compound E, wherein the metal element of the metal compound E is selected from at least one of zirconium, titanium and trivalent chromium.

6. The copper-based material according to claim 5, wherein: In the first dose, at least one of the following conditions is met: (III) the ratio of the solid content mass AMg of the copolymer A to the metal element converted mass EMg of the metal compound E satisfies: EM / AM is 0.01 to 50; (IV) The pH of the first agent is 1 to 6.

7. A method for producing the copper-based material according to any one of claims 1 to 6, comprising: Step a of forming a second surface treatment layer on the surface of a copper-based material, wherein step a comprises: a step of contacting a second agent containing the metal compound B and the compound D with the copper-based material and a drying step after the contacting step; The step b of forming the first surface treatment layer includes a first contact step of the copolymer A, its hydrolyzate, or its polycondensate with water and a drying step after the contact step.

8. The manufacturing method according to claim 7, wherein: The step a includes making the second surface treatment layer 2 mg / m 2 Up to 500 mg / m 2 A contacting step and a drying step at 100° C. to 180° C. after the contacting step; The step b includes: making the first surface treatment layer 2mg / m 2 Up to 500 mg / m 2 contact process.

9. A laminate comprising the copper-based material according to any one of claims 1 to 6 or the copper-based material obtained by the manufacturing method according to claim 7 or 8, wherein the first surface treatment layer of the copper-based material comprises a resin film layer, and the resin film layer comprises a hydrocarbon resin.

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