A copper foil surface coupling agent treatment method, treatment device and copper foil

Abstract

The application discloses a copper foil surface coupling agent treatment method, a treatment device and a copper foil. The treatment method comprises first coupling agent treatment, the first coupling agent is a hydrophilic coupling agent or a hydrophobic coupling agent; second coupling agent treatment, the second coupling agent is a hydrophilic coupling agent; the treatment device comprises at least one treatment component; the treatment component comprises coupling agent treatment mechanism one, a transition mechanism and coupling agent treatment mechanism two; the coupling agent treatment mechanism one comprises a rotating coating part and a coupling agent storage tank, the coupling agent storage tank is used for storing the first coupling agent, and the rotating coating part is used for coating the first coupling agent in the coupling agent storage tank on the roughened surface of the copper foil; the coupling agent treatment mechanism two comprises a spraying part, and the spraying part is used for spraying the second coupling agent on the roughened surface of the copper foil. The copper foil surface is treated by adopting a plurality of surface coupling agents, so that the binding force between the copper foil and the low-polarity high-frequency high-speed resin glass fiber cloth can be effectively improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of metal surface treatment, and particularly relates to a copper foil surface coupling agent treatment method, a treatment device and a copper foil. BACKGROUND

[0002] Copper Clad Laminate (CCL) is a kind of plate-shaped material which is made by impregnating electronic glass fiber cloth or other reinforcing materials with resin, covering one side or both sides with copper foil and hot pressing. Various different forms and different functions of printed circuit boards (PCB) are all made by selectively processing, etching, drilling and plating copper on the copper clad laminate to make different printed circuits to support and connect each other and insulate each other for electronic components.

[0003] With the advent of the 5G era, the demand for high frequency and high speed of communication equipment is increasingly prominent. The high frequency and high speed PCB used by these devices relies more and more on its substrate material side to overcome the difficulty of reducing signal transmission loss. 5G communication high frequency and high speed products require smaller resin Dk / Df of copper clad laminate, and the traditional FR4 epoxy resin system can only meet the Mid Loss demand. For the demand of Low Loss and above, the resin system of copper clad laminate gradually approaches low Df PPO / PPE (polyphenyl ether), BMI (bismaleimide), PTFE (polytetrafluoroethylene), PCH (butadiene homopolymer, styrene-butadiene copolymer, styrene-butadiene-divinylbenzene copolymer, etc. Hydrocarbon material) and other material systems. The mixed system composed of several different resins has the comprehensive advantages of cost, processability and reliability, and has become the mainstream choice of some manufacturers. However, due to the reduced polarity of the mixed resin system required by high frequency and high speed, the adhesion between the resin glass cloth made of such mixed resin and the copper foil is greatly weakened. In the process of manufacturing and application, the copper clad laminate made of such materials is prone to delamination and other abnormal phenomena, which needs to be improved by improving the adhesion between the copper foil and the resin glass cloth.

[0004] One side of the copper foil of the copper clad laminate is a bright or non-roughened surface, which does not combine with the resin glass cloth, and the other side is a roughened or fuzzy surface, which combines with the resin glass cloth. When the copper foil of the copper clad laminate combines with the resin glass cloth, the adhesion between the copper foil and the resin glass cloth is mainly composed of two forces, one is the mechanical anchoring effect provided by the rough profile of the copper foil surface, and the other is the chemical bonding effect between the copper foil and the resin. For high frequency and high speed PCB, the roughness of the copper foil is greatly reduced, and the mechanical anchoring effect is reduced. In order to meet the requirement of interfacial adhesion, the chemical bonding effect must be enhanced, and the dependence on roughness must be reduced.

[0005] Chemical bonding of inorganic / organic interface is usually achieved by coupling agent, different coupling agents have different active groups, thus having excellent binding force for specific materials. Therefore, developing suitable coupling agent surface treatment method, enhancing the binding force of copper foil and PPO, PTFE, hydrocarbon resin, modified epoxy resin and mixed resin made of such resin for high frequency high speed copper clad plate, is crucial for the production and application of high frequency high speed PCB. SUMMARY

[0006] The problem to be solved by the present application is to provide a copper foil surface coupling agent treatment method, treatment device and copper foil, which can effectively improve the binding force between copper foil and low polarity high frequency high speed resin glass cloth by treating the surface of copper foil with multiple surface coupling agents.

[0007] The technical scheme provided by the present application to solve the above problem is a copper foil surface coupling agent treatment method, the treatment method comprising:

[0008] The first coupling agent treatment, the first coupling agent is a hydrophilic coupling agent or a hydrophobic coupling agent, which can infiltrate the surface of copper foil, and is particularly suitable for coupling reaction with low polarity resin;

[0009] The second coupling agent treatment, the second coupling agent is a hydrophilic coupling agent, which has high affinity with the surface of copper foil, and is particularly suitable for coupling reaction with high polarity resin.

[0010] Preferably, the volume concentration of the first coupling agent is 0.05%-4%, and the first coupling agent is one or two of vinyl trimethoxysilane, vinyl triethoxysilane, vinyl-3-(2-methoxyethoxy) silane and oligomeric vinyl silane.

[0011] Preferably, the volume solubility of the second coupling agent is 0.2%-10%, and the second coupling agent is one of 3-glycidyl ether propyl trimethoxysilane, 2-(3,4-epoxy cyclohexane) ethyl trimethoxysilane and gamma-methacryloyloxy propyl trimethoxysilane.

[0012] Preferably, the treatment method further comprises third coupling agent treatment, the third coupling agent adopts amino silane coupling agent; the volume solubility of the third coupling agent is 0.1%-2%, and the third coupling agent is one or a combination of two of N-beta-(aminoethyl)-gamma-aminopropyl methyl dimethoxysilane, bis-(gamma-triethoxysilyl propyl) amine and gamma-aminopropyl triethoxysilane.

[0013] Preferably, the processing method further comprises a fourth coupling agent treatment, the fourth coupling agent being an aqueous solution of an epoxy silane coupling agent; the fourth coupling agent having a volume solubility of 0.2% to 10%, and the fourth coupling agent being one of 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and gamma-methacryloyloxypropyltrimethoxysilane.

[0014] The application further discloses a copper foil surface coupling agent processing device, which comprises at least one processing component.

[0015] The processing component comprises a coupling agent processing mechanism I, a transition mechanism, and a coupling agent processing mechanism II, and the copper foil sequentially passes through the coupling agent processing mechanism I, the transition mechanism, and the coupling agent processing mechanism II.

[0016] The coupling agent processing mechanism I comprises a rotating coating part and a coupling agent storage tank, the coupling agent storage tank is used for storing a first coupling agent, and the rotating coating part is used for coating the first coupling agent in the coupling agent storage tank onto the roughened surface of the copper foil.

[0017] The coupling agent processing mechanism II comprises a spraying part, and the spraying part is used for spraying a second coupling agent onto the roughened surface of the copper foil.

[0018] The transition mechanism comprises a bright surface transition roller, a deionized water spraying rod and a matte surface transition roller II, the roller surface of the bright surface transition roller is in contact with the bright surface of the copper foil, the deionized water spraying rod is arranged above the copper foil 2 between the bright surface transition roller and the matte surface transition roller I 4, the deionized water spraying rod is used for spraying deionized water, and the matte surface transition roller II is arranged obliquely above the bright surface transition roller and the roller surface is in contact with the roughened surface of the copper foil.

[0019] Preferably, the rotating coating part comprises a matte surface transition roller I and a pressing roller, the matte surface transition roller I has a part in the coupling agent storage tank, the roller surface of the matte surface transition roller I carries the coupling agent solution and is in contact with the roughened surface of the copper foil in the process of rotation, and the pressing roller is arranged above the matte surface transition roller I and is used for uniformly and sufficiently infiltrating the coupling agent solution carried by the matte surface transition roller I into the roughened copper tooth gap of the whole width of the copper foil.

[0020] Preferably, the spraying part comprises a coupling agent spraying rod and a coupling agent collecting tank, the coupling agent spraying rod is arranged below the roughened surface of the copper foil, and the coupling agent collecting tank is located directly below the bright surface transition roller and is used for collecting the coupling agent solution flowing along the surface of the copper foil.

[0021] Preferably, the processing assembly further comprises a hot air knife group one and a hot air knife group two, which are respectively arranged at the two sides of the bright surface transition roller and at the lower end of the copper foil, and are used for blowing dry the coupling agent on the copper foil passing through the hot air knife group one and the hot air knife group two.

[0022] The application further discloses a copper foil treated by the copper foil surface coupling agent treatment method.

[0023] Compared with the prior art, the application has the advantages that the coupling agent is used to treat the surface of the copper foil, and the bonding force between the copper foil and the low-polarity high-frequency high-speed resin glass cloth can be effectively improved. BRIEF DESCRIPTION OF DRAWINGS

[0024] The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and serve to explain the principles of the application, and do not limit the application in any manner.

[0025] Figure 1 is a schematic diagram of a copper foil surface coupling agent treatment device of the application Figure One ;

[0026] Figure 2 is a schematic diagram of a copper foil surface coupling agent treatment device of the application Figure Two .

[0027] FIG. 1 is a schematic diagram of a copper foil surface coupling agent treatment device of the application. DETAILED DESCRIPTION

[0028] The embodiments of the application will be described in detail with reference to the drawings and examples, so that the application can be fully understood and implemented.

[0029] In the description of the present application, it should be noted that for the orientation words, such as the terms "center", "transverse", "longitudinal", "length", "width", "thickness", "upper", "lower", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate the orientation and positional relationship based on the orientation or positional relationship shown in the drawings, which is only for the convenience of describing the present application and simplifying the description, and does not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and cannot be understood as limiting the specific protection scope of the present application.

[0030] In addition, the terms "first", "second" are only for the purpose of description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features. Therefore, the "first" and "second" features defined can explicitly or implicitly include one or more of the features, and in the description of the present application, the meaning of "several" is two or more, unless otherwise explicitly specified and limited.

[0031] In the present application, unless otherwise explicitly specified and limited, the terms "assembly", "connection", "connection" should be broadly understood, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected; it can be directly connected, or connected through an intermediate medium; it can be connected internally between two elements. For those skilled in the art, the specific meaning of the above-mentioned terms in the present application can be understood according to the specific circumstances.

[0032] It should be understood that the terms "include" and "contain" as used in the present specification and the appended claims indicate the presence of the described features, whole, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, whole, steps, operations, elements, components and / or sets thereof.

[0033] It should also be understood that the terms used in the specification of the embodiments of the present application herein are only for the purpose of describing specific embodiments and do not intend to limit the embodiments of the present application. As used in the specification and claims of the present application, unless the context clearly indicates otherwise, the singular forms "a", "an" and "the" are intended to include the plural forms.

[0034] Example 1

[0035] The copper foil in the present embodiment is an RTF1 grade electrolytic copper foil with a nominal thickness of 18 μm (roughness Rz of 3.0-3.5 μm).

[0036] The resin system is a copper-clad plate of epoxy resin or PPO, and the copper foil thereof is treated by the following treatment method, which comprises:

[0037] A first coupling agent treatment using a vinyl silane coupling agent aqueous solution; the first coupling agent volume concentration is 0.05%-4%, the first coupling agent treatment is one or two of vinyl trimethoxysilane, vinyl triethoxysilane, vinyl-3-2-methoxyethoxysilane, oligomer vinyl silane.

[0038] A second coupling agent treatment using an epoxy silane coupling agent aqueous solution; the second coupling agent volume solubility is 0.2%-10%, the second coupling agent is one of 3-glycidyloxypropyltrimethoxysilane, 2-3, 4-epoxycyclohexyl ethyl trimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane.

[0039] Example 2

[0040] The copper foil in this embodiment is an RTF1 grade electrolytic copper foil with a nominal thickness of 18 μm (roughness Rz is 3.0-3.5 μm).

[0041] The resin system is a copper-clad plate of (epoxy resin, PPO mixed system) or (epoxy resin, PPO resin, BMI resin mixed system), and the copper foil thereof is treated by the following method, which comprises:

[0042] A first coupling agent treatment using a vinyl silane coupling agent aqueous solution; the first coupling agent volume concentration is 0.05%-4%, the first coupling agent treatment is one or two of vinyl trimethoxysilane, vinyl triethoxysilane, vinyl-3-2-methoxyethoxysilane, oligomer vinyl silane.

[0043] A second coupling agent treatment using an epoxy silane coupling agent aqueous solution; the second coupling agent volume solubility is 0.2%-10%, the second coupling agent is one of 3-glycidyloxypropyltrimethoxysilane, 2-3, 4-epoxycyclohexyl ethyl trimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane.

[0044] A third coupling agent treatment using an amino silane coupling agent; the third coupling agent volume solubility is 0.1%-2%, the third coupling agent is one or a combination of two of N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, bis-(γ-triethoxysilylpropyl) amine, γ-aminopropyl triethoxysilane.

[0045] The fourth coupling agent treatment uses an aqueous solution of an epoxy silane coupling agent; the fourth coupling agent has a volume solubility of 0.2% to 10%, and the fourth coupling agent is one of 3-glycidyloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and gamma-methacryloyloxypropyltrimethoxysilane.

[0046] Table 1

[0047]

[0048] Table 2

[0049]

[0050] As can be seen from Table 1 and Table 2, the copper-clad plates made by using the RTF1 grade electrolytic copper foil with a nominal thickness of 18 μm and four different resin systems have a peel strength that is significantly stronger than the peel strength of the copper-clad plates made by using the treatment method of Comparative Examples 1 to 3.

[0051] Example 3

[0052] The present embodiment discloses a copper foil surface coupling agent treatment device, the device comprising: at least one treatment assembly;

[0053] The treatment assembly comprises a coupling agent treatment mechanism one, a transition mechanism, and a coupling agent treatment mechanism two, and the copper foil 2 passes through the coupling agent treatment mechanism one, the transition mechanism, and the coupling agent treatment mechanism two in sequence;

[0054] The coupling agent treatment mechanism one comprises a rotating coating part and a coupling agent storage tank 5, the coupling agent storage tank 5 is used for storing a first coupling agent, the rotating coating part is used for coating the first coupling agent in the coupling agent storage tank 5 onto the roughened surface of the copper foil 2, one end of the coupling agent storage tank is connected to a liquid inlet pipe, and one end is connected to a liquid outlet pipe, and the first coupling agent solution in the coupling agent storage tank is constantly flowing and updating;

[0055] The coupling agent treatment mechanism two comprises a spraying part, and the spraying part is used for spraying a second coupling agent onto the roughened surface of the copper foil 2;

[0056] The transition mechanism comprises a bright surface transition roller 9, a deionized water spraying rod 8, and a matte surface transition roller two 1, the roller surface of the bright surface transition roller 9 is in contact with the bright surface of the copper foil 2, the deionized water spraying rod 8 is arranged above the copper foil 2 between the bright surface transition roller 9 and the matte surface transition roller one 4, the deionized water spraying rod 8 is used for spraying deionized water to form a water film to protect the copper foil 2 from being contaminated and lubricate the bright surface transition roller 9, and the matte surface transition roller two 1 is arranged obliquely above the bright surface transition roller 9 and the roller surface is in contact with the roughened surface of the copper foil 2.

[0057] In the embodiment, the rotating coating component includes a rough surface transition roller 4 and a pressing roller 3. The rough surface transition roller 4 is partially located in a coupling agent storage tank 5. During rotation, the coupling agent solution carried by the roller surface of the rough surface transition roller 4 is in contact with the roughened surface of the copper foil 2. The pressing roller 3 is arranged above the rough surface transition roller 4. The pressing roller 3 is used to uniformly and sufficiently infiltrate the coupling agent solution carried by the rough surface transition roller 4 into the roughened copper tooth gaps of the whole width of the copper foil 2.

[0058] In the embodiment, further, the spraying component includes a coupling agent spraying rod 12 and a coupling agent collecting tank 10. The coupling agent spraying rod 12 is arranged below the roughened surface of the copper foil 2. The coupling agent collecting tank 10 is located directly below the bright surface transition roller 9. The coupling agent collecting tank 10 is used to collect the coupling agent solution flowing down along the surface of the copper foil 2.

[0059] The processing assembly further includes a hot air knife group one 7 and a hot air knife group two 13. The hot air knife group one 7 and the hot air knife group two 13 are respectively arranged at the lower end of the copper foil 2 on both sides of the bright surface transition roller 9. The hot air knife group one 7 and the hot air knife group two 13 are used to blow dry the coupling agent on the copper foil 2 passing through the hot air knife group one 7 and the hot air knife group two 13. It should be noted that the hot air knife group one 7 includes one group, two groups or three groups of air knives, and the hot air knife group two 13 includes two groups or three groups of air knives. In this way, the second coupling agent can be blown dry, and the coupling agent solution flowing down along the foil surface of the subsequent coupling agent processing device can also be blown dry.

[0060] Due to the use of the roller surface rotating coating mode, the amount of coupling agent solution accumulated on the surface of the copper foil before the pressing roller is small, and the amount of coupling agent solution flowing down along the foil surface is also small. The coupling agent solution can be quickly dried by the hot air knife of the previous coupling agent processing device, so as not to contaminate the second coupling agent solution in the previous coupling agent processing device.

[0061] After being extruded by the pressing roller, the amount of the first coupling agent solution on the roughened surface of the copper foil is reduced, and the first coupling agent solution can be easily blown dry after being blown by the hot air of the hot air knife group, so as not to affect the second coupling agent processing.

[0062] The second coupling agent processing is a spraying treatment, and the second coupling agent processing is blown dry after being blown by the hot air of the hot air knife group.

[0063] In the above scheme, it is to be noted that the coupling agent solution in the coupling agent storage tank 5 is continuously fed and discharged through the liquid inlet and return pipe 6 to maintain the volume and concentration of the coupling agent solution in the coupling agent storage tank 5 stable; the coupling agent solution sprayed by the coupling agent spraying rod 12 flows down along the surface of the copper foil and then enters the coupling agent liquid collecting tank 10, which is recycled through the liquid return pipe 11 on the coupling agent liquid collecting tank 10. Among them, the length of the coupling agent storage tank 5 is longer than the rough surface transition roller one 4, and both ends are located outside the rough surface transition roller one 4. This structure can make the rough surface transition roller one 4 adhere to a sufficient amount of coupling agent solution, and under the extrusion of the pressing roller 3, the coupling agent is uniformly coated to the roughened copper tooth gap of the whole width of the copper foil 2; the length of the coupling agent liquid collecting tank 10 is shorter than the bright surface transition roller 9, and both ends are located inside the bright surface transition roller 9. This structure reduces the deionized water on the copper foil bright surface entering the coupling agent liquid collecting tank 10, avoiding the dilution of the coupling agent solution.

[0064] It is to be noted that the processing assembly in the device can have multiple groups. When applied to embodiment 1, 1 group is used, as shown in Figure 1 When applied to embodiment 2, 2 groups are used (the coupling agent storage tank in the second group contains a third coupling agent, and the spraying part in the second group is used to spray a fourth coupling agent), as shown in Figure 2 The first and second, third and fourth, to the Nth and N+1 coupling agent processing can be achieved, thereby achieving better results.

[0065] Embodiment 4

[0066] The embodiment discloses a copper foil, which is prepared by the copper foil surface coupling agent treatment method according to the embodiment 1 or 2.

[0067] The above only describes the best embodiments of the present application, but cannot be understood as a limitation on the claims. The present application is not limited to the above embodiments, and the specific structure can be changed. Any changes made within the protection scope of the independent claims of the present application are within the protection scope of the present application.

Claims

1. A method for treating the surface of copper foil with a coupling agent, characterized in that, The processing method includes: First coupling agent treatment; The second coupling agent is a hydrophilic coupling agent. The volume concentration of the first coupling agent is 0.05%-4%, and the first coupling agent is one or two of vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-3-(2-methoxyethoxy)silane, and low-polyvinylsilane. The volume solubility of the second coupling agent is 0.2%-10%, and the second coupling agent is one of 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane. The treatment method further includes a third coupling agent treatment, wherein the third coupling agent is an aminosilane coupling agent; the volume solubility of the third coupling agent is 0.1%-2%, and the third coupling agent is one or a combination of two of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, bis-(γ-triethoxysilylpropyl)amine, and γ-aminopropyltriethoxysilane; The treatment method further includes a fourth coupling agent treatment, wherein the fourth coupling agent is an aqueous solution of an epoxy silane coupling agent; the volume solubility of the fourth coupling agent is 0.2%-10%, and the fourth coupling agent is one of 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

2. A copper foil, characterized in that: The copper foil is prepared by a copper foil surface coupling agent treatment method as described in claim 1.

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