CN113831852A

CN113831852A - Glue-coated copper foil and preparation method and application thereof

Info

Publication number: CN113831852A
Application number: CN202111079340.4A
Authority: CN
Inventors: 刘飞; 何岳山; 杨柳; 练超; 李东伟; 王粮萍
Original assignee: Shenzhen Newfield New Material Technology Co ltd
Current assignee: Shenzhen Newfield New Material Technology Co ltd
Priority date: 2021-09-15
Filing date: 2021-09-15
Publication date: 2021-12-24

Abstract

The invention provides a gummed copper foil and a preparation method and application thereof. The glue coated copper foil comprises a copper foil, a resin layer and a protective film which are sequentially stacked; the resin layer is made of a resin composition; the resin composition comprises the following raw material components in parts by weight: 5-20 parts of liquid epoxy resin, 20-30 parts of phenoxy resin, 10-20 parts of solid epoxy resin, 8-20 parts of curing agent, 2-5 parts of imidazole curing accelerator and 40-70 parts of filler. The preparation method comprises the following steps: (1) coating the resin composition on the rough surface of the copper foil, and drying to obtain the copper foil with the resin layer; (2) and attaching a protective film to one surface of the resin layer, which is far away from the copper foil, so as to obtain the adhesive coated copper foil. The gummed copper foil provided by the invention has better high temperature resistance and better insulativity, and the resin layer has better fluidity and bonding strength and is suitable for preparing a PCB (printed circuit board).

Description

Glue-coated copper foil and preparation method and application thereof

Technical Field

The invention belongs to the technical field of copper clad laminates, and particularly relates to a glue-coated copper foil and a preparation method and application thereof.

Background

The metal Clad Laminate is a plate-like material prepared by immersing an electronic glass fiber cloth or other reinforcing material in a resin solution, coating a metal foil on one or both surfaces thereof, and hot-pressing, and is called a metal Clad Laminate, which is simply referred to as a metal Clad plate, such as a Copper Clad Laminate or a Copper Clad Laminate (CCL). Metal-clad plates such as copper-clad plates are substrate materials for manufacturing Printed Circuit boards (PCBs for short), and PCBs are one of important components in the electronic industry. Almost every kind of electronic equipment, as small as electronic watches, calculators, as large as computers, communication electronics, military weaponry systems, requires printed boards for electrical interconnection as long as there are electronic components such as integrated circuits. The metal clad laminate is provided on the entire printed circuit board and mainly performs three functions of conduction, insulation and support.

With the development of miniaturization and thinning of electronic technology, the PCB is required to have a finer line width and a thinner thickness of the whole board. Most of insulating materials used in the prior art of PCBs are glass fiber cloth prepregs, for example, CN108164928A discloses a glass fiber cloth-based prepreg, a preparation method thereof, a laminated board and a printed circuit board. The fiberglass cloth-based prepreg comprises a fiberglass cloth reinforcing material and a thermosetting resin composition attached to the fiberglass cloth reinforcing material after impregnation and drying, wherein the fiberglass cloth reinforcing material is coated with an inorganic filler, and the inorganic filler is one or more inorganic fillers in the group consisting of: silica, titania and alumina. Due to the thickness problem of the glass fiber cloth, the PCB prepared by using the glass fiber cloth prepreg provided by the technical scheme is thick, and does not conform to the thinning development direction of electronic products. If the thin glass cloth is used for preparing the glass fiber cloth prepreg, the thickness of the prepared glass fiber cloth prepreg is small, but the prepreg resin content is low, and the use requirement is difficult to meet in a scene needing circuit filling. And the insulating material contains glass fiber cloth, so that the yield of the board is reduced in the laser drilling process of a PCB manufacturer, meanwhile, the unit price of the thin glass cloth is high, the processing yield is difficult to control, and the consistent requirement of pursuing high cost performance of the PCB manufacturer is not met.

To solve this problem, the use of a pure glue film instead of a fiberglass cloth prepreg has become a hot spot of research. Considering that the PCB needs to use copper foil as a conductor layer, the pure glue film and the copper foil are further combined together to manufacture the glue coated copper foil. Thus, the PCB pressing and laminating process is simpler.

CN107760241A discloses an adhesive, a preparation method of the adhesive and a coated copper foil prepared by applying the adhesive. The adhesive comprises the following raw materials in parts by weight: 40-50 parts of bisphenol A type macromolecular epoxy resin, 35-40 parts of high-bromine epoxy resin, 10-20 parts of bisphenol F type epoxy resin, 5-10 parts of bisphenol A type low-molecular epoxy resin, 3-8 parts of cross-linked elastomer resin, 15-25 parts of curing agent, 0.02-0.1 part of catalyst, 30-50 parts of first solvent, 50-100 parts of second solvent and 5-10 parts of inorganic filler; the curing agent comprises diaminodiphenylmethane and diaminodiphenylsulfone. And coating a resin layer with the thickness of 30-100 mu m on the roughened surface of the coated copper foil by using an adhesive to prepare the coated copper foil. The adhesive prepared by the technical scheme has the characteristics of low cost, good flexibility and high copper foil peeling strength.

CN103059789A discloses a preparation process of a gummed copper foil adhesive with high peeling resistance and high dip soldering resistance. The preparation process comprises the following steps: a. 5-30 parts by mass of epoxy resin and 1-20 parts by mass of heterocyclic epoxy resin curing agent are mixed for 3-5 hours at 30-60 ℃ and uniformly mixed; b. and (b) blending the uniformly dispersed mixture in the step a with 50-300 parts by mass of thermosetting phenolic resin and 50-350 parts by mass of polyvinyl acetal resin at 30-60 ℃ for 5-12 hours for compounding, and taking 600-1000 parts of toluene as a solvent. According to the technical scheme, the proper heterocyclic epoxy resin curing agent and the epoxy resin are used for compounding and modifying, so that the problem of dissolution and dispersion of resins with different solubilities in methanol is solved, and the cost for manufacturing the copper foil glue is reduced; meanwhile, the introduction of the heterocyclic epoxy resin improves the peeling strength and dip soldering resistance of the glued copper foil.

In the prior art, the gummed copper foil for the PCB is formed by coating a rough surface of a copper foil with resin and baking at high temperature, a resin layer reaches a certain pre-estimated degree, and the fluidity of the resin is poor, so that how to prepare the gummed copper foil with a resin layer having good fluidity, high temperature resistance and good insulating property becomes a technical problem to be solved urgently at present.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a gummed copper foil and a preparation method and application thereof. According to the invention, through the design of raw material components of the resin layer in the coated copper foil, and further through the use of liquid epoxy resin, imidazole curing accelerator and specific curing agent, the prepared resin layer has good fluidity; by adopting the phenoxy resin, the resin layer has higher bonding strength, and the glued copper foil further has better high-temperature resistance and lower transverse glue overflow amount, so that the glued copper foil is suitable for preparing a PCB (printed circuit board).

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a glued copper foil, which comprises a copper foil, a resin layer and a protective film which are sequentially stacked;

the resin layer is made of a resin composition;

the resin composition comprises the following raw material components in parts by weight: 5-20 parts of liquid epoxy resin, 20-30 parts of phenoxy resin, 10-20 parts of solid epoxy resin, 8-20 parts of curing agent, 2-5 parts of imidazole curing accelerator and 40-70 parts of filler;

the curing agent is selected from any one of phenolic resin, active ester or cyanate or the combination of at least two of the phenolic resin, the active ester and the cyanate.

According to the invention, through the design of raw material components of the resin layer in the coated copper foil, the resin layer prepared by using the liquid epoxy resin, the imidazole curing accelerator and the specific curing agent has better fluidity; by adopting the phenoxy resin, the resin layer has higher bonding strength, and the glued copper foil further has better high-temperature resistance and lower transverse glue overflow amount, so that the glued copper foil is suitable for preparing a PCB (printed circuit board).

According to the invention, by using the liquid epoxy resin and the phenoxy resin and controlling the contents of the liquid epoxy resin and the phenoxy resin within a specific range, the prepared adhesive coated copper foil has better high temperature resistance, and the resin layer has better fluidity, higher bonding strength and lower transverse adhesive overflow amount, so that the PCB is conveniently obtained by pressing. If the content of the liquid epoxy resin is too much and the content of the phenoxy resin is too little, the prepared resin layer has good fluidity, but the bonding strength between the resin layer and the copper foil is poor, and the transverse glue overflow amount is large in the process of preparing the PCB by pressing, so that the resin layer is not suitable for preparing the PCB; if the content of the liquid epoxy resin is too low and the content of the phenoxy resin is too high, the prepared resin layer has poor fluidity and is difficult to press to obtain the PCB.

In the invention, the specific curing agent is used, so that the polymerization reaction degree of the resin composition at room temperature is lower, and the resin composition has better fluidity; meanwhile, by using the specific curing accelerator, the reaction degree of the resin composition is lower in the process of preparing the resin layer, and the obtained resin layer with better fluidity is convenient for pressing to obtain the PCB. If an amine curing agent or other curing accelerators are adopted, the resin composition can generate a large degree of polymerization reaction at room temperature, and in the process of preparing the resin layer at high temperature, the resin composition further generates polymerization reaction, so that the prepared resin layer has poor flowability and is difficult to press to obtain the PCB.

In the present invention, the weight parts of the liquid epoxy resin may be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or the like.

The parts by weight of the phenoxy resin can be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts and the like.

The solid epoxy resin may be present in an amount of 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or the like.

The curing agent may be present in an amount of 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, or the like, by weight.

The parts by weight of the imidazole curing accelerator can be 2 parts, 2.2 parts, 2.5 parts, 2.7 parts, 3 parts, 3.3 parts, 3.6 parts, 4 parts, 4.2 parts, 4.6 parts or 5 parts and the like.

The weight portion of the filler may be 40 parts, 42 parts, 46 parts, 50 parts, 52 parts, 55 parts, 57 parts, 60 parts, 63 parts, 65 parts, 68 parts, 70 parts, or the like.

The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.

In a preferred embodiment of the present invention, the number average molecular weight of the liquid epoxy resin is 120 to 500, and may be, for example, 120, 150, 200, 250, 300, 350, 400, 450, or 500.

The phenoxy resin preferably has a number average molecular weight of 4 to 6 million, and may be, for example, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, or 6 million.

Preferably, the glass transition temperature of the solid epoxy resin is 170-250 ℃, and may be 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃ or the like, for example.

Preferably, NH is present in the solid epoxy resin₄ ⁺The content of (B) is less than or equal to 10ppm (for example, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, etc.), Na⁺The content of (B) is 10ppm or less (for example, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm or 10ppm or the like), and the content of Cl element is 800ppm or less (for example, 10ppm, 50ppm, 100ppm, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm or 800ppm or the like).

It should be noted that, in order to further control the purity of the solid epoxy resin, Cl in the solid epoxy resin is present^-The mass content of (B) is not more than 300ppm, and may be, for example, 10ppm, 20ppm, 50ppm, 100ppm, 150ppm, 200ppm, 250ppm or 300 ppm.

In the present invention, there is no particular limitation on the specific kind of the solid epoxy resin as long as the above conditions are satisfied, and examples include, but are not limited to: SQCN704H from Shandong Shengquan or N-690, N-695, HP4700, HP4710, and HP9500 from Japan DIC.

In a preferred embodiment of the present invention, the curing agent has a viscosity of 80 to 600cps at 23 ± 2 ℃, for example, 80cps, 100cps, 150cps, 200cps, 250cps, 300cps, 350cps, 400cps, 450cps, 500cps, 550cps, 600cps, or the like.

Preferably, Na is contained in the curing agent⁺The content of (B) is 10ppm or less (for example, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm or 10ppm or the like), and the content of Cl element is 400ppm or less (for example, 10ppm, 20ppm, 50ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm or 400ppm or the like).

Preferably, the imidazole-based curing accelerator is selected from any one of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-methylimidazole-isocyanurate, 2, 4-diamino-6 [2 '-methylimidazole- (1') ] ethyl-S-triazine isocyanurate adduct, 2-phenyl-4, 5-dimethylolimidazole or 2-phenyl-4-methyl-5-hydroxymethylimidazole or a combination of at least two thereof.

It should be noted that 2-methylimidazole-isocyanurate is 2MZ-OK produced by the chemical synthesis of Japan, and 2, 4-diamino-6 [2 '-methylimidazole- (1') ] ethyl-S-triazine isocyanurate is 2MA-OK produced by the chemical synthesis of Japan.

Preferably, the filler is selected from silica and/or modified silica.

Preferably, NH is present in said filler₄ ⁺The content of (B) is less than or equal to 10ppm (for example, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, etc.), Na⁺The content of (B) is 10ppm or less (for example, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm or 10ppm or the like), and the content of Cl element is 100ppm or less (for example, 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm or 100ppm or the like).

In the present invention, the purity of the solid epoxy resin (i.e., NH in the solid epoxy resin) is controlled₄ ⁺Mass content of (1), Na⁺Mass content of (b) and mass content of Cl element), purity of the curing agent and purity of the filler, thereby controlling NH in the resin composition₄ ⁺Mass content of (1), Na⁺The prepared resin layer of the gummed copper foil has better insulating property. If the purity of the solid epoxy resin, the purity of the curing agent or the purity of the filler is low, NH in the resin composition is caused₄ ⁺Mass content of (1), Na⁺The mass content of (a) and the mass content of the Cl element are high, the insulation property of the finally obtained resin layer is poor.

In a preferred embodiment of the present invention, the resin composition further comprises 1 to 5 parts of a flame retardant, which may be, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts.

Preferably, the flame retardant is selected from any one of or a combination of at least two of DOPO-HQ, DOPO-NQ, flame retardant SPB-100 or flame retardant DPDP.

It should be noted that DOPO-HQ has the chemical name of 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO-NQ has the chemical name of 10- (1, 4-dihydroxynaphthyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, and DPDP flame retardant has the chemical name of diphenylisodecyl phosphate.

The resin composition further comprises 100 to 150 parts of a solvent, and the solvent may be, for example, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, 125 parts, 130 parts, 135 parts, 140 parts, 145 parts, 150 parts, or the like.

Preferably, the solvent is selected from any one of methanol, ethanol, toluene, xylene, acetone, butanone, cyclohexanone, ethylene glycol monomethyl ether or dimethylformamide, or a combination of at least two thereof.

Preferably, the raw materials for preparing the resin composition further comprise 1-3 parts of an auxiliary agent, which can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts or 3 parts, for example.

Preferably, the auxiliary agent is selected from any one of or a combination of at least two of a leveling agent, an antifoaming agent or a coupling agent.

If the filler is silicon dioxide, 0.5-1 part of coupling agent is required to be contained in the auxiliary agent; when the filler is modified silica, the kind of the assistant is not particularly limited.

In the present invention, the leveling agent is not particularly limited, and exemplary include, but are not limited to: the leveling agent is selected from any one or a combination of at least two of BYK-306, BYK-310, BYK-330, BYK-S706, BYK-333, BYK-390, BYK-392 or FC-4430; the defoaming agent is any one or a combination of at least two of DP-60 defoaming agent, DP-61 defoaming agent, DP-62 defoaming agent, DP-63 defoaming agent produced by Guangdong Tianfeng defoaming company, or BYK-530 and BYK-520 produced by Germany Bikk company.

Preferably, the defoaming agent is selected from any one or a combination of at least two of DP-60, DP-61, DP-62 and DP-63 of Tianfeng defoaming agent company or BYK530 and BYK520 produced by Germany Bick company.

Preferably, the coupling agent is selected from any one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- (N-cyclohexylamino) -propyltrimethoxysilane, N- (N-butyl) -3-aminopropyltriethoxysilane, N- (N-butyl) -3-aminopropyltrimethoxysilane, bis (3-triethoxysilylpropyl) amine or bis (3-trimethoxysilylpropyl) amine or a combination of at least two thereof.

As a preferred embodiment of the present invention, the method for preparing the resin composition comprises the steps of:

uniformly mixing liquid epoxy resin, phenoxy resin, epoxy resin, a curing agent, an imidazole curing accelerator, a filler, a flame retardant, a solvent and an optional auxiliary agent to obtain the resin composition.

In order to mix the components uniformly and as quickly as possible, the solid raw material components in the raw materials for preparing the resin composition may be mixed with a part of the solvent in advance, and the mixing method of the present invention is not particularly limited, and may be, for example: respectively mixing and stirring the solid raw material components and part of the solvent for 0.5-4 h at the temperature of 25-100 ℃ and the rotating speed of 90-300 rpm to respectively obtain mixed liquor of corresponding components.

Meanwhile, if the filler is modified silica, the modified silica and part of the solvent are mixed and stirred for 10-60 min at the temperature of 25-35 ℃ and the rotating speed of 300-2000 rpm to obtain a modified silica mixed solution; if the filler is silica, the filler needs to be modified by using a coupling agent in advance, and the process of modifying the filler in the present invention is not limited in any way, and may be, for example: under the conditions of 25-35 ℃ and the rotating speed of 300-2000 rpm, mixing and stirring the coupling agent and part of the solvent for 10-60 min, adding silicon dioxide, heating to 25-80 ℃, stirring and mixing for 20-60 min to obtain a modified silicon dioxide mixed solution, and then uniformly mixing the modified silicon dioxide mixed solution and other raw material components of the resin composition to obtain the resin composition.

In addition, in order to disperse the modified silica more uniformly in the resin composition, the modified silica mixed solution and the liquid epoxy resin may be mixed in advance, and the mixing method is not particularly limited in this application, and for example, the modified silica mixed solution may be ground for 10 to 120min by using a sand mill at 15 to 60 ℃ and at a rotation speed of 1000 to 5000 rpm; meanwhile, in order to provide the resin composition with better fluidity, the curing agent and the imidazole-based curing accelerator may be added later in the process of preparing the resin composition by mixing.

In a preferred embodiment of the present invention, the temperature of the mixing is 15 to 30 ℃ and may be, for example, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃.

Preferably, the mixing time is 40-240 min, such as 40min, 60min, 80min, 100min, 120min, 140min, 160min, 180min, 200min, 220min or 240 min.

Preferably, the method of mixing is stirring.

Preferably, the rotation speed of the stirring is 90-300 rpm, for example, 90rpm, 100rpm, 120rpm, 140rpm, 160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm or 300rpm, and the like can be used.

Preferably, the mixing step further comprises a post-treatment step.

Preferably, the post-treatment method comprises filtering and impurity removal.

Preferably, the filtration method is to filter the mixed solution sequentially through 300-mesh, 500-mesh and 1000-mesh filter screens.

Preferably, the impurity removal method is to remove impurities by using a 12000GS magnetic rod.

It should be noted that the manufacturer of the 12000GS magnetic rod is the manufacturer of the Jinchuang magnetic company, Foshan, model FB12000GS 25 × 200H M8 × 20-1.

As a preferable technical scheme of the invention, the copper foil is a carrier copper foil, a rolled copper foil or an electrolytic copper foil.

The copper foil preferably has a thickness of 2 to 35 μm, and may be, for example, 2 μm, 3 μm, 4 μm, 5 μm, 7 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, or 35 μm.

The thickness of the resin layer is preferably 10 to 150. mu.m, and may be, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, or the like.

Preferably, the thickness of the protective film is 12 to 50 μm, and may be, for example, 12 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm.

Preferably, the protective film is a PP film or a PET film.

In a second aspect, the present invention provides a method for preparing the adhesive-coated copper foil according to the first aspect, characterized in that the method comprises the steps of:

(1) coating the resin composition on the rough surface of the copper foil, and drying to obtain the copper foil with the resin layer;

(2) and attaching a protective film to one surface of the resin layer, which is far away from the copper foil, so as to obtain the adhesive coated copper foil.

As a preferred embodiment of the present invention, the drying temperature in the step (1) is 70 to 120 ℃, and may be, for example, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃.

Preferably, the drying time in step (1) is 3-15 min, such as 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15 min.

Preferably, the temperature for bonding in step (2) is 40 to 100 ℃, and may be, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃.

The pressure for bonding in the step (2) is preferably 2 to 8MPa, and may be, for example, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa or 8 MPa.

In a third aspect, the present invention provides a use of the rubberized copper foil according to the first aspect of the figure in the manufacture of a PCB circuit board.

Compared with the prior art, the invention has the following beneficial effects:

(1) according to the invention, through the design of raw material components of the resin layer in the adhesive coated copper foil, the resin layer has better fluidity through the use of liquid epoxy resin, imidazole curing accelerator and specific curing agent, and the viscosity of the resin layer is lower than 60-87 Poise; the prepared resin layer and the copper foil have high bonding strength of 0.9-1.44N/mm by using the phenoxy resin, and the glued copper foil has good high-temperature resistance and low transverse glue overflow amount;

(2) according to the invention, through the matching use of the components in the raw materials for preparing the resin layer and the specific preparation method, the prepared resin composition has low impurity content and NH₄ ⁺Mass content of (1), Na⁺The mass content of the resin layer and the mass content of the Cl element are respectively 7-9 ppm, 5-6 ppm and 200-270 ppm, so that the prepared resin layer has good insulativity, can withstand 200h insulativity test, and is suitable for preparing PCB (printed circuit board).

Detailed Description

For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Some of the component sources in the examples and comparative examples are as follows:

liquid epoxy resin: 128E (Macrochang), 1750 (Mitsubishi chemical), ZX1059 (New day iron), 2021P (Daxylon);

phenoxy resin: FX280 (new day iron), FX293 (new day iron), YX8100 (mitsubishi chemical corporation), TER240C30 (guangdong congress);

solid epoxy resin: SQCN704H (santa yunnanensis), HP7200H (japan DIC), HP4700 (japan DIC), HP4710 (japan DIC);

phenolic resin: SH-5085 (Shandong Shengquan Co.), SH-5100 (Shandong Shengquan Co.);

active ester: TEH8803 (guangdong co.);

cyanate ester: CE01PS (yangzhou tianqi corporation);

modified silicon dioxide: SQ023 (Suzhou brocade Co., Ltd.), SC2050-MB (Yadama Co., Japan);

carrier copper foil: MT18SD-H, MT18EX, Mitsui metals, Japan;

rolling the copper foil: RCF-TNBG, Futian metals, Suzhou;

electrolytic copper foil: JCF-FCF-R, Jones Yetz foil;

and (3) PP film: ZYGQ36U, orthowave dongguan;

PET film: DFTR11W0-36SH6, Sichuan Dong material Co.

Example 1

The embodiment provides a glued copper foil and a preparation method thereof, wherein the glued copper foil comprises a carrier copper foil, a resin layer and a PET (polyethylene terephthalate) film which are sequentially overlapped;

the thickness of the carrier copper foil (MT18SD-H) is 2 μm, the thickness of the resin layer is 40 μm, and the thickness of the PET film is 38 μm;

the resin layer is made of a resin composition;

the resin composition comprises the following raw material components in parts by weight: 15 parts of liquid epoxy resin (128E), 25 parts of phenoxy resin (FX280), 15 parts of solid epoxy resin (SQCN704H), 15 parts of phenolic resin (SH-5085), 4 parts of 1-cyanoethyl-2-ethyl-4-methylimidazole, 50 parts of modified silica (SQ023), 1002 parts of flame retardant SPB, 120 parts of acetone, 3101 parts of BYK-3101 parts and 1 part of DP-60 defoaming agent.

The preparation method of the resin composition comprises the following steps:

(A) respectively mixing and stirring phenoxy resin (FX280), solid epoxy resin (SQCN704H), phenolic resin (SH-5085), 1-cyanoethyl-2-ethyl-4-methylimidazole and flame retardant SPB-100 with part of acetone for 2 hours at the temperature of 30 ℃ and the rotating speed of 100rpm to respectively obtain mixed liquor of corresponding components;

mixing and stirring modified silicon dioxide (SQ023) and acetone (20 parts) for 50min at the temperature of 30 ℃ and the rotating speed of 1000rpm to obtain modified silicon dioxide mixed solution;

wherein the total of the parts by weight of the solvent used in the step (A) is 120 parts;

(B) grinding and dispersing the modified silica mixed solution and liquid epoxy resin (128E) for 60min by using a sand mill (Dongguan Shang Mitsubishi machinery company, model No. NT-V10L) at the temperature of 60 ℃ and the rotation speed of 1000rpm to obtain a mixed solution A, sequentially adding a phenoxy resin mixed solution, a solid epoxy resin mixed solution, a phenolic resin mixed solution, a flame retardant mixed solution, a 1-cyanoethyl-2-ethyl-4-methylimidazole mixed solution, BYK-310 and a DP-60 defoaming agent into the mixed solution A at the temperature of 20 ℃ and the rotation speed of 150rpm, stirring for 150min to obtain a mixed solution B, sequentially passing the mixed solution B through filter screens of 300 meshes, 500 meshes and 1000 meshes to obtain a filtrate, and then removing impurities from the filtrate by using a 12000 magnetic GS rod to obtain the resin composition.

The preparation method of the adhesive coated copper foil comprises the following steps:

(1) coating the resin composition on the rough surface of the carrier copper foil, and drying at 100 ℃ for 8min to obtain the carrier copper foil with the resin layer;

(2) and (3) attaching the PET film to the surface of the resin layer far away from the carrier copper foil under the conditions of 70 ℃ and 5MPa to obtain the adhesive coated copper foil.

Example 2

the thickness of the carrier copper foil (MT18EX) is 5 μm, the thickness of the resin layer is 10 μm, and the thickness of the PET film is 12 μm;

the resin layer is made of a resin composition;

the resin composition comprises the following raw material components in parts by weight: 10 parts of liquid epoxy resin (1750, Mitsubishi chemical company), 20 parts of phenoxy resin (FX293), 10 parts of solid epoxy resin (HP7200H), 20 parts of active ester (TEH8803), 2 parts of 1-cyanoethyl-2-ethyl-4-methylimidazole, 70 parts of modified silicon dioxide (SC2050-MB), 1001 parts of flame retardant SPB-1001, 150 parts of butanone, BYK-3100.5 parts and 0.5 part of DP-60 defoaming agent.

The preparation method of the resin composition comprises the following steps:

(A) respectively mixing and stirring phenoxy resin (FX293), solid epoxy resin (HP7200H), active ester (TEH8803), 1-cyanoethyl-2-ethyl-4-methylimidazole and flame retardant SPB-100 with partial butanone for 2 hours at the temperature of 30 ℃ and the rotating speed of 100rpm to respectively obtain mixed liquor of corresponding components;

mixing and stirring modified silicon dioxide (SC2050-MB) and butanone (25 parts) for 50min at the temperature of 30 ℃ and the rotating speed of 1000rpm to obtain a modified silicon dioxide mixed solution;

wherein the total of the parts by weight of the solvent used in the step (A) is 150 parts;

(B) grinding and dispersing the modified silicon dioxide mixed solution and liquid epoxy resin (1750, Mitsubishi chemical company) for 60min by using a sand mill at the temperature of 60 ℃ and the rotation speed of 1000rpm to obtain a mixed solution A, sequentially adding a phenoxy resin mixed solution, a solid epoxy resin mixed solution, a phenolic resin mixed solution, a flame retardant SPB-100 mixed solution, a 1-cyanoethyl-2-ethyl-4-methylimidazole mixed solution, BYK-310 and a DP-60 defoaming agent into the mixed solution A at the temperature of 15 ℃ and the rotation speed of 300rpm, stirring for 40min to obtain a mixed solution B, sequentially passing the mixed solution B through 300-mesh, 500-mesh and 1000-mesh filter screens to obtain a filtrate, and removing impurities from the filtrate by using a 12000GS magnetic rod to obtain the resin composition.

(1) coating the resin composition on the rough surface of the carrier copper foil, and drying at 70 ℃ for 15min to obtain the carrier copper foil with the resin layer;

(2) and adhering the PET film to the surface of the resin layer far away from the carrier copper foil under the conditions of 40 ℃ and the pressure of 8MPa to obtain the adhesive coated copper foil.

Example 3

The embodiment provides a glued copper foil and a preparation method thereof, wherein the glued copper foil comprises a rolled copper foil, a resin layer and a PBT film which are sequentially stacked;

the thickness of the rolled copper foil is 12 micrometers, the thickness of the resin layer is 150 micrometers, and the thickness of the PET film is 50 micrometers;

the resin layer is made of a resin composition;

the resin composition comprises the following raw material components in parts by weight: 20 parts of liquid epoxy resin (ZX1059), 30 parts of phenoxy resin (YX8100), 20 parts of solid epoxy resin (HP4700), 8 parts of phenolic resin (SH-5100), 5 parts of 2-phenyl-4, 5-dimethylolimidazole, 40 parts of modified silicon dioxide (SC2050-MB), 5 parts of DOPO-NQ, 125 parts of cyclohexanone, BYK-3301 and BYK-5301 parts;

the preparation method of the resin composition comprises the following steps:

(A) respectively mixing phenoxy resin (YX8100), solid epoxy resin (HP4700), phenolic resin (SH-5100), 2-phenyl-4, 5-dimethylolimidazole and DOPO-NQ with partial cyclohexanone and stirring for 2h at the temperature of 30 ℃ and the rotating speed of 100rpm to respectively obtain mixed liquor of corresponding components;

mixing and stirring modified silicon dioxide (SC2050-MB) and cyclohexanone (15 parts) for 50min at the temperature of 30 ℃ and the rotating speed of 1000rpm to obtain modified silicon dioxide mixed solution;

wherein, the sum of the parts by weight of the solvents used in the step (A) is 125 parts;

(B) grinding and dispersing the modified silicon dioxide mixed solution and liquid epoxy resin (ZX1059) for 60min by using a sand mill at the temperature of 60 ℃ and the rotation speed of 1000rpm to obtain a mixed solution A, sequentially adding a phenoxy resin mixed solution, a solid epoxy resin mixed solution, a phenolic resin mixed solution, a DOPO-NQ mixed solution, a 2-phenyl-4, 5-dimethylol imidazole mixed solution, BYK-330 and BYK-530 into the mixed solution A at the temperature of 30 ℃ and the rotation speed of 90rpm, stirring for 240min to obtain a mixed solution B, sequentially passing the mixed solution B through 300-mesh, 500-mesh and 1000-mesh filter screens to obtain a filtrate, and removing impurities from the filtrate by using a 12000GS magnetic rod to obtain the resin composition.

(1) coating the resin composition on the rough surface of the rolled copper foil, and drying at 120 ℃ for 3min to obtain the rolled copper foil with the resin layer;

(2) and (3) attaching the PET film to one surface of the resin layer far away from the rolled copper foil under the conditions of 100 ℃ and the pressure of 2MPa to obtain the adhesive coated copper foil.

Example 4

The embodiment provides a glued copper foil and a preparation method thereof, wherein the glued copper foil comprises an electrolytic copper foil, a resin layer and a PP film which are sequentially overlapped;

the thickness of the electrolytic copper foil is 35 mu m, the thickness of the resin layer is 60 mu m, and the thickness of the PP film is 18 mu m;

the resin layer is made of a resin composition;

the resin composition comprises the following raw material components in parts by weight: 5 parts of liquid epoxy resin (2021P), 22 parts of phenoxy resin (TER240C30), 18 parts of solid epoxy resin (HP4710), 10 parts of cyanate ester (CE01PS), 3 parts of 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 60 parts of modified silicon dioxide (SQ023), 4 parts of flame retardant DPDP, 100 parts of cyclohexanone, 1 part of flatting agent (FC-4430), 1 part of defoaming agent (DP-62) and KH-5601.

The preparation method of the resin composition comprises the following steps:

(A) respectively mixing phenoxy resin (TER240C30), solid epoxy resin (HP4710), cyanate ester (CE01PS), 2-phenyl-4-methyl-5-hydroxymethyl imidazole and flame retardant DPDP with part of cyclohexanone and stirring for 2h at the temperature of 30 ℃ and the rotating speed of 100rpm to respectively obtain mixed liquor of corresponding components;

mixing KH-560 and cyclohexanone (25 parts) at 30 deg.C and 1000rpm, stirring for 40min, adding silica modified silica (SQ023), heating to 70 deg.C, stirring and mixing for 50min to obtain modified silica mixed solution;

wherein the total of the parts by weight of the solvent used in the step (A) is 100 parts;

(B) grinding and dispersing the modified silicon dioxide mixed solution and liquid epoxy resin (2021P) for 60min by using a sand mill at the temperature of 60 ℃ and the rotation speed of 1000rpm to obtain a mixed solution A, sequentially adding a phenoxy resin mixed solution, a solid epoxy resin mixed solution, a phenolic resin mixed solution, a flame retardant DPDP mixed solution, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, a leveling agent (FC-4430) and a defoaming agent (DP-62) into the mixed solution A at the temperature of 25 ℃ and the rotation speed of 220rpm, stirring for 180min to obtain a mixed solution B, sequentially passing the mixed solution B through filter screens of 300 meshes, 500 meshes and 1000 meshes to obtain a filtrate, and removing impurities from the filtrate by using a 12000GS magnetic rod to obtain the resin composition.

(1) coating the resin composition on the rough surface of the electrolytic copper foil, and drying at 90 ℃ for 10min to obtain the electrolytic copper foil with the resin layer;

(2) and adhering a PP film to one surface of the resin layer far away from the electrolytic copper foil under the conditions of 80 ℃ and 4MPa of pressure to obtain the glued copper foil.

Example 5

This example provides a rubberized copper foil and a method for manufacturing the same, which are different from example 1 in that the solid epoxy resin (SQCN704H) is replaced with the solid epoxy resin HP7200H (produced by DIC corporation), and other conditions are the same as example 1.

Example 6

This example provides a sized copper foil and a method for preparing the same, which are different from example 1 in that the phenolic resin (SH-5085) is replaced with a phenolic resin TKM (manufactured by rui qi chemical company), and the other conditions are the same as example 1.

Example 7

This example provides a rubberized copper foil and a method for preparing the same, which are different from example 1 in that modified silica (SQ023) is replaced with modified silica SJ-301 (triax chemical engineering), and other conditions are the same as example 1.

Example 8

This example provides a glue application report and a method for preparing the same, which is different from example 1 in that the resin composition was prepared without removing impurities using 12000GS magnetic bar, and the other conditions were the same as example 1.

Example 9

This example provides a gummed copper foil and a preparation method thereof, which are different from example 1 only in that the resin composition contains 20 parts by weight of liquid epoxy resin and 20 parts by weight of phenoxy resin, and other conditions are the same as example 1.

Example 10

This example provides a gummed copper foil and a preparation method thereof, which are different from example 1 only in that the resin composition contains 10 parts by weight of liquid epoxy resin and 30 parts by weight of phenoxy resin, and other conditions are the same as example 1.

Comparative example 1

This comparative example provides a gummed copper foil and a preparation method thereof, which are different from example 1 only in that 25 parts by weight of liquid epoxy resin and 15 parts by weight of phenoxy resin are contained in the resin composition, and other conditions are the same as example 1.

Comparative example 2

This comparative example provides a gummed copper foil and a method for preparing the same, which are different from example 1 only in that the resin composition does not contain a liquid epoxy resin, the part by weight of phenoxy resin is 40 parts, and other conditions are the same as example 1.

Comparative example 3

This comparative example provides a rubberized copper foil and a method for manufacturing the same, which are different from example 1 only in that the phenolic resin is replaced with triethylamine, and other conditions are the same as example 1.

Comparative example 4

This comparative example provides a gummed copper foil and a method for preparing the same, differing from example 1 only in that the imidazole-based curing accelerator is replaced with 2-methylimidazole, and the other conditions are the same as in example 1.

The performance of the gummed copper foils or resin compositions provided in the above examples and comparative examples was tested by the following methods:

NH in the resin layer₄ ⁺Mass content of (1), Na⁺Mass content of (a) and mass content of Cl element: an ion chromatograph ICS-5000+ is used for testing according to GB/T15454-1995;

viscosity: the flowability of the resin layers provided in the above examples and comparative examples was measured using a Brookfield Bodyware high temperature rheometer (model: CAP-2000+) at a test temperature of 150 ℃, a rotor model of 5# and a rotation speed of 50 r/min;

high temperature resistance: IPC-TM-6502.6.8 standard;

insulating property: the Insulation property of the resin layer was tested according to "GX 13 Insulation Reliability/b-HAST (130 ℃, 85% RH, 3.3V)" wherein the thickness of the resin layer was 20 μm. When the testing time exceeds 200h, if the resin layer still has insulation, the testing is not carried out any more, and the record is more than 200h, and if the resin layer fails in the testing process and does not have insulation, the testing time is recorded;

bonding strength: IPC-TM-650-2.4.8 standard.

The test standard results of the performance of the gummed copper foils provided in the above examples and comparative examples are shown in table 1:

TABLE 1

According to the invention, through the design of raw material components of the resin layer in the glued copper foil, and further through the use of liquid epoxy resin, imidazole curing accelerator and specific curing agent, the prepared resin layer has good fluidity, the viscosity of the resin layer is lower than 60-87 Poise, and through the use of phenoxy resin, the prepared resin layer has high bonding strength with the copper foil, the bonding strength is 0.9-1.44N/mm, and meanwhile, the glued copper foil has good high temperature resistance and low transverse glue overflow amount. In addition, the resin composition prepared by the invention has low impurity content and NH content by matching the components in the raw materials for preparing the resin layer and a specific preparation method₄ ⁺Mass content of (1), Na⁺The mass content of the resin layer and the mass content of the Cl element are respectively 7-9 ppm, 5-6 ppm and 200-270 ppm, so that the prepared resin layer has good insulativity, can withstand 200h insulativity test, and is suitable for preparing PCB (printed circuit board).

If the purity of the solid epoxy resin, the purity of the curing agent or the purity of the filler is lower than in example 1 (examples 5 to 7), NH in the resin composition is caused₄ ⁺Mass content of (1), Na⁺The mass content of (a) and the mass content of the Cl element are high, the insulation property of the finally obtained resin layer is poor; if the impurity removal treatment is not performed (example 8), the insulating property of the finally obtained resin layer is poor.

Compared with the embodiment 1, if the content of the liquid epoxy resin is too much and the content of the phenoxy resin is too little (comparative example 1), the prepared adhesive coated copper foil has poor high temperature resistance, and the transverse glue overflow amount is large in the process of pressing and preparing the PCB, so that the adhesive coated copper foil is not suitable for preparing the PCB; if the content of the liquid epoxy resin is too small and the content of the phenoxy resin is too large (comparative example 2), the resin layer for preparing the adhesive coated copper foil has high viscosity and poor fluidity, and the PCB is difficult to obtain by pressing.

Compared with example 1, if the resin layer is prepared by using the amine curing agent (comparative example 3) or the resin layer is prepared by using other curing accelerators (comparative example 4), the resin layer for preparing the gummed copper foil has high viscosity, poor fluidity and poor high temperature resistance, and is not suitable for preparing a PCB (printed circuit board).

In conclusion, the resin layer has better fluidity through the design of the raw material components of the resin layer in the adhesive coated copper foil, and the use of liquid epoxy resin, imidazole curing accelerator and specific curing agent; the resin layer has higher bonding strength by using the phenoxy resin, and the glued copper foil further has better high-temperature resistance and lower transverse glue overflow amount; meanwhile, through the matching use of all components in the raw materials for preparing the resin layer and the specific preparation method, the prepared resin layer has better insulativity and is suitable for preparing the PCB.

The applicant states that the present invention is illustrated by the detailed process flow of the present invention through the above examples, but the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. The glued copper foil is characterized by comprising a copper foil, a resin layer and a protective film which are sequentially stacked;

the resin layer is made of a resin composition;

2. The rubberized copper foil according to claim 1, wherein the liquid epoxy resin has a number average molecular weight of 120 to 500;

preferably, the number average molecular weight of the phenoxy resin is 4 to 6 ten thousand;

preferably, the glass transition temperature of the solid epoxy resin is 170-250 ℃;

preferably, NH is present in the solid epoxy resin₄ ⁺The mass content of the sodium-containing material is less than or equal to 10ppm, Na⁺The mass content of the element(s) is less than or equal to 10ppm, and the mass content of the element Cl is less than or equal to 800 ppm.

3. The rubberized copper foil according to claim 1 or 2, wherein the curing agent has a viscosity of 80 to 600cps at 23 ± 2 ℃;

preferably, Na is contained in the curing agent⁺The mass content of the element is less than or equal to 10ppm, and the mass content of the element Cl is less than or equal to 400 ppm;

preferably, the imidazole-based curing accelerator is selected from any one or a combination of at least two of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-methylimidazole-isocyanurate, 2, 4-diamino-6 [2 '-methylimidazole- (1') ] ethyl-S-triazine isocyanurate adduct, 2-phenyl-4, 5-dimethylolimidazole or 2-phenyl-4-methyl-5-hydroxymethylimidazole;

preferably, the filler is selected from silica and/or modified silica;

preferably, NH is present in said filler₄ ⁺The mass content of the sodium-containing material is less than or equal to 10ppm, Na⁺The mass content of the element(s) is less than or equal to 10ppm, and the mass content of the element Cl is less than or equal to 100 ppm.

4. The rubberized copper foil according to any one of claims 1 to 3, further comprising 1 to 5 parts of a flame retardant;

preferably, the flame retardant is selected from any one of or a combination of at least two of DOPO-HQ, DOPO-NQ, flame retardant SPB-100 or flame retardant DPDP;

the resin composition also comprises 100-150 parts of a solvent;

preferably, the solvent is selected from any one of methanol, ethanol, toluene, xylene, acetone, butanone, cyclohexanone, ethylene glycol monomethyl ether or dimethylformamide or a combination of at least two of the above;

preferably, the raw materials for preparing the resin composition also comprise 1-3 parts of an auxiliary agent;

preferably, the auxiliary agent is selected from any one or a combination of at least two of a leveling agent, a defoaming agent or a coupling agent;

5. The subbing copper foil according to any one of claims 1 to 4, wherein the resin composition is prepared by a method comprising the steps of:

6. The rubberized copper foil according to claim 5, wherein the temperature of mixing is 15 to 30 ℃;

preferably, the mixing time is 40-240 min;

preferably, the method of mixing is stirring;

preferably, the rotating speed of the stirring is 90-300 rpm;

preferably, the method further comprises a post-treatment step after the mixing;

preferably, the post-treatment method comprises filtering and impurity removal;

preferably, the filtering method is that the mixed liquid is filtered by filter screens of 300 meshes, 500 meshes and 1000 meshes in sequence;

7. The rubberized copper foil according to any one of claims 1 to 6, wherein the copper foil is a carrier copper foil, a rolled copper foil, or an electrolytic copper foil;

preferably, the thickness of the copper foil is 2-35 μm;

preferably, the thickness of the resin layer is 10-150 μm;

preferably, the thickness of the protective film is 12-50 μm;

preferably, the protective film is a PP film or a PET film.

8. A method of producing a rubberized copper foil according to any one of claims 1 to 7, comprising the steps of:

9. The preparation method according to claim 8, wherein the drying temperature in the step (1) is 70-120 ℃;

preferably, the drying time in the step (1) is 3-15 min;

preferably, the temperature of the attaching in the step (2) is 40-100 ℃;

preferably, the pressure of the bonding in the step (2) is 2-8 MPa.

10. Use of a rubberized copper foil according to any one of claims 1 to 7 for the preparation of a PCB circuit board.