阅读说明：本技术 一种抗剥离电路板用铜箔及其制备方法 (Anti-stripping copper foil for circuit board and preparation method thereof ) 是由 王罗海 张春雨 乔印虎 彭永友 陈又斌 国文年 汪全军 于 2019-11-15 设计创作，主要内容包括：本发明提供一种抗剥离电路板用铜箔及其制备方法,涉及电路板铜箔加工技术领域。所述铜箔为先采用复合添加剂A混合制备基础铜箔,后将基础铜箔采用复合处理剂B处理表面得到,其中复合添加剂A由以下原料制成：聚乙二醇、胶原蛋白、2-巯基苯并咪唑、硫脲、钨酸钠；所述复合处理剂B由以下原料制成：γ-甲基丙烯酰氧基丙基三甲氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、甲基丙烯酸缩水甘油酯、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷。本发明克服了现有技术的不足,有效保证所制得铜箔具有优良的抗拉强度与延展性的同时,有效提升铜箔的抗剥离强度,增强铜箔的稳定性,提升其综合性能,适宜推广生产。(The invention provides a copper foil for an anti-stripping circuit board and a preparation method thereof, and relates to the technical field of circuit board copper foil processing, wherein the copper foil is obtained by firstly mixing a composite additive A to prepare a basic copper foil and then treating the surface of the basic copper foil by a composite treating agent B, wherein the composite additive A is prepared from the following raw materials of polyethylene glycol, collagen, 2-mercaptobenzimidazole, thiourea and sodium tungstate, and the composite treating agent B is prepared from the following raw materials of gamma-methacryloxypropyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, glycidyl methacrylate and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane.)

1. The copper foil for the anti-stripping circuit board is characterized by being prepared by firstly mixing a composite additive A to prepare a base copper foil, and then treating the surface of the base copper foil with a composite treating agent B, wherein the composite additive A is prepared from the following raw materials, by weight, 6-8 parts of polyethylene glycol, 2-3 parts of collagen, 3-4 parts of 2-mercaptobenzimidazole, 1-3 parts of thiourea and 2-4 parts of sodium tungstate, and the composite treating agent B is prepared from the following raw materials, by weight, 6-8 parts of gamma-methacryloxypropyltrimethoxysilane, 2-4 parts of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 1-1.4 parts of glycidyl methacrylate and 3-4 parts of N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane.

2. A preparation method of a copper foil for a peeling-resistant circuit board is characterized by comprising the following steps: the preparation method of the copper foil for the anti-stripping circuit board comprises the following steps:

(1) preparation of the composite additive A: adding polyethylene glycol into deionized water with 3 volume parts, keeping the temperature of water bath at 50-55 ℃, stirring uniformly, adding collagen, 2-mercaptobenzimidazole, thiourea and sodium tungstate, mixing uniformly at 40-50 ℃, keeping the temperature for 3-5h, and obtaining a composite additive A for later use;

(2) the preparation of the composite treating agent B comprises the steps of mixing gamma-methacryloxypropyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, glycidyl methacrylate and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane into 100 volume parts of warm water, uniformly stirring at high speed, and standing at normal temperature to obtain the composite treating agent B for later use;

(3) preparing an electrolyte: heating and dissolving a high-purity copper wire in a copper dissolving tank to generate a copper sulfate electrolyte for later use;

(4) adding of the composite additive A: filtering the electrolyte, adding the electrolyte into a high-level tank, dropwise adding the composite additive A, uniformly mixing, and feeding the mixture into a foil forming machine for electrolytic foil forming to obtain a rough copper foil for later use;

(5) primary roughening treatment of the surface of the copper foil: placing the crude copper foil in electrolyte with current density of 20-25A/dm²Processing for 3-4s to obtain a pretreated copper foil for later use;

(6) and (3) high-temperature oxidation treatment of the surface of the copper foil: placing the pretreated copper foil in a high-temperature oxidation furnace at 80-100 ℃, and carrying out high-temperature oxidation for 30-35min in an oxygen-enriched environment to obtain a surface oxidized copper foil for later use;

(7) and (3) secondary roughening treatment of the surface of the copper foil: pickling the surface oxidized copper foil, and then continuously adding the pickled surface oxidized copper foil into electrolyte with the current density of 25-30A/dm²Processing for 3-4s to obtain secondary roughened copper foil for later use;

(8) treating with a composite treating agent B: and spraying the composite treating agent B on the surface of the secondary roughened copper foil in a room temperature environment, and then placing the secondary roughened copper foil in a drying oven to dry for 15-20min at the temperature of 120-.

3. The method for preparing a copper foil for a delamination-resistant circuit board according to claim 2, wherein: in the step (1), in the process of uniformly mixing the solution at the temperature of 40-50 ℃, the heat preservation process of the solution is vibration heat preservation.

4. The method for preparing a copper foil for a delamination-resistant circuit board according to claim 2, wherein: the temperature of the warm water in the step (2) is 45-50 ℃.

5. The method for preparing a copper foil for a delamination-resistant circuit board according to claim 2, wherein: the total addition amount of the composite additive A is 0.3-0.5mg of the composite additive A dropwise added into each liter of electrolyte.

6. The method for preparing a copper foil for a delamination-resistant circuit board according to claim 2, wherein: the concentration of titanium ions in the electrolyte is 0.15%, and the concentration of copper ions in the electrolyte is 0.12%.

7. The method for preparing a copper foil for a delamination-resistant circuit board according to claim 2, wherein: and (7) pickling the surface copper oxide foil, repeatedly washing with clean water, and then roughening for the second time.

Technical Field

The invention relates to the technical field of circuit board copper foil processing, in particular to a copper foil for an anti-stripping circuit board and a preparation method thereof.

Background

Electronic circuit boards, which are used in electronic components to form connections of predetermined circuits between electronic parts, function as relay transmission, are key electronic interconnections of electronic products.

In order to meet the use requirements of conventional circuit boards and promote the development of science and technology, the requirements on copper foil are higher and higher, the general high-quality copper foil needs to meet the performances of tensile strength and ductility, oxidation resistance, corrosion resistance, resistance and the like at normal temperature and high temperature, is environment-friendly and the like, and also needs the copper foil to have lower surface roughness, so that the dielectric loss of a circuit is reduced when the copper foil is used for high-speed transmission. On the other hand, the copper foil with lower thickness is used for printed circuits, which is beneficial to manufacturing more fine circuits.

However, due to the environmental, cost and technical limitations of domestic manufacturing, the lower surface roughness of the copper foil in the preparation process of the copper foil generally causes the reduction of the peel strength of the copper foil and influences the practical use of the copper foil, so that the improvement of the peel strength of the copper foil on the premise of ensuring the technical requirements of the copper foil on the tensile strength and ductility at normal temperature and high temperature, oxidation resistance, corrosion resistance and the like is a great research direction for the production of the copper foil at the present stage.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides the copper foil for the anti-peeling circuit board and the preparation method thereof, which effectively ensure that the prepared copper foil has excellent tensile strength and ductility, effectively improve the anti-peeling strength of the copper foil, enhance the stability of the copper foil, improve the comprehensive performance of the copper foil and are suitable for popularization and production.

In order to achieve the above purpose, the technical scheme of the invention is realized by the following technical scheme:

the copper foil for the anti-stripping circuit board is obtained by firstly mixing a composite additive A to prepare a base copper foil, and then treating the surface of the base copper foil with a composite treating agent B, wherein the composite additive A is prepared from 6-8 parts by weight of polyethylene glycol, 2-3 parts by weight of collagen, 3-4 parts by weight of 2-mercaptobenzimidazole, 1-3 parts by weight of thiourea and 2-4 parts by weight of sodium tungstate, and the composite treating agent B is prepared from 6-8 parts by weight of gamma-methacryloxypropyltrimethoxysilane, 2-4 parts by weight of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 1-1.4 parts by weight of glycidyl methacrylate and 3-4 parts by weight of N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane.

The preparation method of the copper foil for the anti-stripping circuit board comprises the following steps:

(1) preparation of the composite additive A: adding polyethylene glycol into deionized water with 3 volume parts, keeping the temperature of water bath at 50-55 ℃, stirring uniformly, adding collagen, 2-mercaptobenzimidazole, thiourea and sodium tungstate, mixing uniformly at 40-50 ℃, keeping the temperature for 3-5h, and obtaining a composite additive A for later use;

(2) the preparation of the composite treating agent B comprises the steps of mixing gamma-methacryloxypropyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, glycidyl methacrylate and N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane into 100 volume parts of warm water, uniformly stirring at high speed, and standing at normal temperature to obtain the composite treating agent B for later use;

(3) preparing an electrolyte: heating and dissolving a high-purity copper wire in a copper dissolving tank to generate a copper sulfate electrolyte for later use;

(4) adding of the composite additive A: filtering the electrolyte, adding the electrolyte into a high-level tank, dropwise adding the composite additive A, uniformly mixing, and feeding the mixture into a foil forming machine for electrolytic foil forming to obtain a rough copper foil for later use;

(5) surface of copper foil for the first timeRoughening treatment: placing the crude copper foil in electrolyte with current density of 20-25A/dm²Processing for 3-4s to obtain a pretreated copper foil for later use;

(6) and (3) high-temperature oxidation treatment of the surface of the copper foil: placing the pretreated copper foil in a high-temperature oxidation furnace at 80-100 ℃, and carrying out high-temperature oxidation for 30-35min in an oxygen-enriched environment to obtain a surface oxidized copper foil for later use;

(7) and (3) secondary roughening treatment of the surface of the copper foil: pickling the surface copper oxide foil, then continuously adding the pickled surface copper oxide foil into electrolyte, and treating for 3-4s by adopting the current density of 25-30A/dm < 2 > to obtain secondary roughened copper foil for later use;

(8) treating with a composite treating agent B: and spraying the composite treating agent B on the surface of the secondary roughened copper foil in a room temperature environment, and then placing the secondary roughened copper foil in a drying oven to dry for 15-20min at the temperature of 120-.

Preferably, in the step (1), in the process of heat preservation and mixing at 40-50 ℃, the heat preservation process of the solution is vibration heat preservation.

Preferably, the temperature of the warm water in the step (2) is 45-50 ℃.

Preferably, the total addition amount of the composite additive A is 0.3-0.5mg of the composite additive A dropwise added in each liter of electrolyte.

Preferably, the electrolyte has a titanium ion concentration of 0.15% and a copper ion concentration of 0.12%.

Preferably, in the step (7), the surface copper oxide foil is subjected to acid washing, is repeatedly rinsed with clean water, and is then subjected to secondary roughening.

The invention provides a copper foil for an anti-stripping circuit board and a preparation method thereof, and compared with the prior art, the copper foil has the advantages that:

(1) according to the invention, the composite additive A is added into the electrolytic copper solution, wherein the addition of the collagen, the 2-mercaptobenzimidazole, the thiourea and the sodium tungstate can effectively improve the toughness and the ductility of the copper foil and enhance the stability of the prepared copper foil.

(2) According to the invention, the treated copper foil is coated and dried by using the composite treating agent B, wherein the gamma-methacryloxypropyltrimethoxysilane, the 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, the glycidyl methacrylate and the N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane are mixed to tightly bond the surface of the copper foil, so that the stripping resistance of the later-period coating resin of the copper foil is effectively improved, and the using effect of the later-period coating resin is enhanced.

(3) According to the invention, the copper foil is subjected to secondary roughening treatment, and after the primary roughening treatment, the copper foil is subjected to surface high-temperature oxidation and then acid washing, so that the surface roughness of the copper foil can be effectively reduced, the adhesion of the composite treating agent B coated in a later period can be ensured, meanwhile, the toughness of the copper foil is prevented from being reduced by roughening, and the use stability of the copper foil is improved.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.