CN117987056A - Adhesive with uniform glue overflow and preparation method thereof - Google Patents

Adhesive with uniform glue overflow and preparation method thereof Download PDF

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Publication number
CN117987056A
CN117987056A CN202311849479.1A CN202311849479A CN117987056A CN 117987056 A CN117987056 A CN 117987056A CN 202311849479 A CN202311849479 A CN 202311849479A CN 117987056 A CN117987056 A CN 117987056A
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epoxy resin
adhesive
rubber
preparation liquid
stirring
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何益良
黄俊明
李泽南
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Guangdong Geteng Technology Co ltd
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Guangdong Geteng Technology Co ltd
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Priority to CN202311849479.1A priority Critical patent/CN117987056A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The application relates to the technical field of adhesives. The application discloses an adhesive with uniform glue overflow and a preparation method thereof. The adhesive comprises the following raw materials in parts by weight: epoxy resin, thermoplastic resin, rubber, filler, curing agent, leveling agent, antioxidant, flame retardant and catalyst. The preparation method comprises the following steps: weighing raw materials; preparing a rubber preparation liquid; stirring and mixing part of the rubber preparation liquid with the filler to prepare mother liquid 1; the other part of the rubber preparation liquid is stirred and mixed with a flame retardant to prepare mother liquid 2; preparing an epoxy resin preparation liquid and a thermoplastic resin preparation liquid; and (3) stirring and mixing the mother solution 1, the mother solution 2, the epoxy resin preparation solution and the thermoplastic resin preparation solution, adding a curing agent, an antioxidant, a catalyst and a leveling agent, and stirring to obtain the adhesive. The application also discloses application of the adhesive in a cover film for a flexible printed circuit board. The adhesive prepared by the application can well improve the glue overflow condition of the covering film, and the glue overflow is uniform.

Description

Adhesive with uniform glue overflow and preparation method thereof
Technical Field
The application relates to the technical field of adhesives, in particular to an adhesive with uniform glue overflow and a preparation method thereof.
Background
With the continuous development of 5G technology, flexible printed circuit boards (FPCs, flexible Printed Circuit) have been widely used in the fields of communications, digital display, aerospace, new energy sources, and the like, due to their high wiring density, light weight, thin thickness, and the like.
The covering film is used as a surface protection layer of the FPC, can prevent the subsequent surface treatment of the circuit from being polluted and damaged by dust, temperature and humidity and corrosive substances, has insulation and welding resistance effects, has certain flexibility and reinforcing effects, can reduce the influence of stress of the FPC in the bending process, and improves the bending resistance of the FPC. At present, the cover film with the largest FPC use amount is formed by coating an adhesive with a certain thickness on one side of an insulating substrate such as a polyimide film (PI film) or a polyester film (PET film) and the like, and baking and half-curing the adhesive. The common adhesive is epoxy system adhesive, acrylate system adhesive, polyester system adhesive, polyimide system adhesive and the like.
The coating film with larger dosage in the market is an epoxy adhesive PI film base coating film prepared by coating an epoxy system adhesive on a polyimide film. The epoxy adhesive covering film has excellent performances and high overall cost performance, but has the problems of uneven adhesive overflow, unstable adhesive overflow, adhesive spraying, adhesive running and the like in the lamination process. The FPC is pressed and covered with the membrane under high temperature and high pressure, if the glue overflow amount of the covered membrane is too large, the overflowed glue can have residual glue on the bonding pad and the circuit, the use area is reduced, and the glue layer is thinned; if the glue overflow amount is too small, air bubbles and cavities can appear during lamination, and the peeling strength is reduced.
Therefore, there is a need to develop an adhesive which can improve the glue overflow condition of the cover film, has uniform glue overflow, and good peel strength and heat resistance, and the cover film manufactured by the adhesive has small glue overflow amount, stability, smooth edge of the overflow glue, and no saw-tooth glue overflow, glue spraying and other conditions.
Disclosure of Invention
In order to solve at least one of the technical problems, an adhesive which can improve the glue overflow condition of a covering film, has uniform glue overflow and good peeling strength and heat resistance is developed.
On one hand, the adhesive with uniform glue overflow provided by the application comprises the following raw materials in parts by weight: 25-45 parts of epoxy resin, 5-15 parts of thermoplastic resin, 15-30 parts of rubber, 20-35 parts of filler, 1-5 parts of curing agent, 0.1-0.5 part of leveling agent, 0.2-0.5 part of antioxidant, 10-20 parts of flame retardant and 0.1-0.6 part of catalyst.
By adopting the technical scheme, the prepared adhesive is uniform and stable in glue overflow, excellent in peeling strength and heat resistance, small and stable in glue overflow amount of the cover film manufactured by the adhesive, smooth in glue overflow edge, free from saw-tooth glue overflow, glue spraying and the like.
In the application, the epoxy resin has excellent cohesiveness, insulativity and heat resistance, and is beneficial to improving the peeling strength and heat resistance of the adhesive. The thermoplastic resin has elasticity, flexibility and impact resistance, and helps to improve the fluidity of the adhesive. The rubber has high elasticity and good flexibility, and is beneficial to improving the toughness of the adhesive. The filler can improve the viscosity and the adhesion of the adhesive, and is helpful for improving the peeling strength and the heat resistance of the adhesive.
Optionally, the raw materials comprise, by weight: 30-40 parts of epoxy resin, 8-12 parts of thermoplastic resin, 20-25 parts of rubber, 25-32 parts of filler, 1-3 parts of curing agent, 0.1-0.3 part of leveling agent, 0.3-0.4 part of antioxidant, 12-18 parts of flame retardant and 0.2-0.4 part of catalyst.
Optionally, the raw materials comprise, by weight: 35 parts of epoxy resin, 10 parts of thermoplastic resin, 22 parts of rubber, 30 parts of filler, 2 parts of curing agent, 0.2 part of leveling agent, 0.35 part of antioxidant, 15 parts of flame retardant and 0.3 part of catalyst.
Optionally, the epoxy resin is selected from at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenyl type epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl novolac type epoxy resin, bisphenol a novolac type epoxy resin, polyphenylene ether modified epoxy resin, alicyclic type epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, and multifunctional epoxy resin.
By adopting the technical scheme, the adhesive can be prepared from various epoxy resins, has better reliability and stability, and has stable performance and quality.
Alternatively, the multifunctional epoxy resin includes glycidylamine type epoxy resin, glycidylester type epoxy resin.
Optionally, the epoxy resin is solid bisphenol A type epoxy resin NPES-901 type and liquid phosphorus-containing epoxy resin DC-G2630-K70 type, and the weight ratio of the solid bisphenol A type epoxy resin NPES-901 type to the liquid phosphorus-containing epoxy resin DC-G2630-K70 type is 1:2.
Optionally, the thermoplastic resin is selected from at least one of polyester resin, phenoxy resin, acrylic resin, and polyimide resin;
the rubber is at least one selected from acrylic rubber, nitrile rubber, silicon rubber, polyurethane rubber and fluororubber;
The filler is selected from one of silicon dioxide, aluminum oxide and aluminum hydroxide.
By adopting the technical scheme, the adhesive with excellent performance can be prepared by selecting proper thermoplastic resin, rubber and filler, so that the covering film with excellent performance is prepared.
Optionally, the thermoplastic resin is phenoxy resin JER-1256.
Optionally, the rubber is carboxylated nitrile rubber 1072CG type.
Optionally, the filler is electronic grade superfine aluminum hydroxide KH-101LC type.
Optionally, the weight ratio of the epoxy resin to the thermoplastic resin is 2.5-8: 1.
By adopting the technical scheme, the epoxy resin and the thermoplastic resin adopt a specific weight ratio, so that better balance between hardness and toughness can be obtained, and the epoxy resin has excellent heat resistance and high strength, and simultaneously, good processability and flexibility are provided. If the proportion of the epoxy resin is too high, the toughness of the adhesive is poor, and the curing speed is too high, so that the operation is not facilitated; if the proportion of the thermoplastic resin is too high, the hardness is low, and the heat resistance is impaired.
Optionally, the weight of the filler is 20-30% of the weight of the raw material.
By adopting the technical scheme, the filler ratio in the application can ensure that the adhesive has good viscosity and fluidity and excellent heat resistance.
Optionally, the curing agent is at least one selected from the group consisting of an amine curing agent, an imidazole curing agent, a phenol curing agent, and an anhydride curing agent;
the leveling agent is at least one selected from polyether leveling agents, organic silicon leveling agents, polyvinyl alcohol leveling agents and polyether modified polysiloxane leveling agents;
The antioxidant is at least one selected from benzotriazole antioxidants, hindered amine antioxidants, carbodiimide antioxidants and bisphenol antioxidants;
the flame retardant is at least one selected from nitrogen-containing flame retardant, phosphorus-containing flame retardant and halogen-free flame retardant;
The catalyst is at least one selected from amine catalysts, phenol catalysts, imidazole catalysts and organotin catalysts.
By adopting the technical scheme, the curing agent selected by the application can promote the curing process of the adhesive; the leveling agent is helpful for improving the surface flatness of the adhesive; the antioxidant is beneficial to improving the oxidation resistance of the adhesive and prolonging the storage period; the flame retardant is helpful for improving the flame retardant property of the adhesive; the catalyst helps to accelerate the reaction process of the adhesive.
Alternatively, the curing agent is of the 4,4' -diaminodiphenyl sulfone (DDS) type.
Optionally, the leveling agent is a polyether modified polysiloxane copolymer BYK306 type.
Optionally, the antioxidant is bisphenol type antioxidant EVERNOX type 1010.
Optionally, the flame retardant is a halogen-free flame retardant Exolit OP935 type.
Optionally, the catalyst is imidazole type accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (2E 4 ME-CN).
In a second aspect, the present application provides a method for preparing the adhesive with uniform glue overflow, comprising the following steps:
S1, weighing raw materials with the formula amount;
S2, stirring and pre-dissolving the rubber and the solvent to prepare a rubber preparation liquid; according to the weight ratio of the filler to the flame retardant, the rubber preparation liquid is divided into a rubber preparation liquid 1 and a rubber preparation liquid 2, wherein the rubber preparation liquid 1 and the filler are stirred and mixed, and a mother liquid 1 is prepared after grinding by a grinder;
S3, stirring and mixing the rubber preparation liquid 2 and the flame retardant, and grinding by a grinder to obtain a mother liquid 2;
s4, stirring and pre-dissolving the epoxy resin and the solvent to prepare an epoxy resin preparation liquid; stirring and pre-dissolving thermoplastic resin and a solvent to prepare thermoplastic resin preparation liquid;
and S5, stirring and mixing the mother liquor 1, the mother liquor 2, the epoxy resin preparation liquid and the thermoplastic resin preparation liquid, sequentially adding a curing agent, an antioxidant, a catalyst and a leveling agent, and stirring to obtain the adhesive.
By adopting the technical scheme, the preparation method provided by the application has the advantages that the process is simple, the operation is easy, the components are dispersed more uniformly by step mixing, and the performance of the adhesive is improved. In the production process, part of raw materials are pre-dissolved, so that the production time is shortened, and the production efficiency is improved.
Optionally, the solvent is selected from at least one of butanone, toluene, cyclohexane, and cyclohexanone.
Optionally, the solvent is butanone.
Optionally, in the step S2, the weight ratio of the rubber to the solvent in the rubber preparation solution is 1:4, a step of; in the step S4, the weight ratio of epoxy resin to solvent in the epoxy resin preparation solution is 3:2, the weight ratio of thermoplastic resin to solvent in the thermoplastic resin preparation liquid is 7:3.
Optionally, in the step S4, the solid epoxy resin and the solvent are stirred and pre-dissolved, and the liquid epoxy resin is added and stirred and mixed to prepare the epoxy resin preparation liquid.
In a third aspect, the application provides an application of the adhesive with uniform glue overflow in a cover film for a flexible printed circuit board.
By adopting the technical scheme, the raw material components of the adhesive are reasonably selected and compounded, and the adhesive is prepared by adopting a specific proportion, so that the adhesive is used for preparing a flexible printed circuit board cover film, the adhesive overflow is uniform and stable, the adhesive overflow amount is small, the adhesive overflow edge is smooth, the conditions of saw-tooth adhesive overflow, adhesive spraying and the like do not occur, and the overall performance of the circuit board is improved.
In summary, the present invention includes at least one of the following beneficial technical effects:
1. The adhesive prepared by adopting specific raw materials and proportions has excellent peeling strength and heat resistance, and the coating film prepared by the adhesive has good flexibility and uniform and stable glue overflow.
2. The preparation method adopted by the application has simple process and easy operation, and the components are dispersed more uniformly by step mixing, thereby being beneficial to improving the performance of the adhesive.
3. The adhesive is used for preparing the covering film of the flexible printed circuit board, the adhesive is uniform and stable, the adhesive overflow amount is small, the adhesive overflow edge is smooth, the saw-tooth-shaped adhesive overflow, adhesive spraying and the like are avoided, and the overall performance of the flexible printed circuit board is improved.
Drawings
FIG. 1 is a graph showing the appearance of overflow of a cover film prepared from the adhesive prepared in example 1;
FIG. 2 is a graph showing the appearance of overflow of a cover film prepared from the adhesive prepared in comparative example 1.
Detailed Description
The application is described in further detail below with reference to the drawings and examples.
The application designs an adhesive with uniform glue overflow, which comprises the following raw materials in parts by weight: 25-45 parts of epoxy resin, 5-15 parts of thermoplastic resin, 15-30 parts of rubber, 20-35 parts of filler, 1-5 parts of curing agent, 0.1-0.5 part of leveling agent, 0.2-0.5 part of antioxidant, 10-20 parts of flame retardant and 0.1-0.6 part of catalyst.
The adhesive with uniform glue overflow is prepared by the following method, and comprises the following steps:
S1, weighing raw materials with the formula amount;
S2, stirring and pre-dissolving the rubber and the solvent to prepare a rubber preparation liquid; according to the weight ratio of the filler to the flame retardant, the rubber preparation liquid is divided into a rubber preparation liquid 1 and a rubber preparation liquid 2, wherein the rubber preparation liquid 1 and the filler are stirred and mixed, and a mother liquid 1 is prepared after grinding by a grinder;
S3, stirring and mixing the rubber preparation liquid 2 and the flame retardant, and grinding by a grinder to obtain a mother liquid 2;
s4, stirring and pre-dissolving the epoxy resin and the solvent to prepare an epoxy resin preparation liquid; stirring and pre-dissolving thermoplastic resin and a solvent to prepare thermoplastic resin preparation liquid;
and S5, stirring and mixing the mother liquor 1, the mother liquor 2, the epoxy resin preparation liquid and the thermoplastic resin preparation liquid, sequentially adding a curing agent, an antioxidant, a catalyst and a leveling agent, and stirring to obtain the adhesive.
The adhesive with uniform glue overflow can be applied to a cover film for a flexible printed circuit board.
The inventor designs the technical scheme of the application aiming at the problem that the existing epoxy adhesive covering film has uneven adhesive overflow and unstable adhesive overflow in the lamination process.
Firstly, the adhesive with uniform glue overflow is provided, and the components comprise: epoxy resin, thermoplastic resin, rubber, filler, curing agent, leveling agent, antioxidant, flame retardant and catalyst. The prepared adhesive can improve the glue overflow condition of the cover film, and has the advantages of uniform glue overflow, good peeling strength and heat resistance, small glue overflow amount of the cover film manufactured by the adhesive, stability, smooth edge of the overflow glue, no saw-tooth overflow glue, no glue spraying and the like.
Secondly, the preparation method of the adhesive is simple in process and easy to operate, and the components are dispersed more uniformly by step mixing, so that the performance of the adhesive is improved.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Examples 1 to 4
Example 1
The embodiment provides an adhesive with uniform glue overflow, which comprises the following raw materials in parts by weight: 35 parts of epoxy resin, 5 parts of thermoplastic resin, 22 parts of rubber, 20 parts of filler, 2 parts of curing agent, 0.2 part of leveling agent, 0.35 part of antioxidant, 15 parts of flame retardant and 0.3 part of catalyst.
S1, weighing raw materials with the formula amount;
s2, the weight ratio is 1:4, stirring and pre-dissolving the rubber and the solvent to prepare a rubber preparation liquid; according to the weight ratio of the filler to the flame retardant, dividing the rubber preparation liquid into a rubber preparation liquid 1 and a rubber preparation liquid 2, stirring and mixing the rubber preparation liquid 1 and the filler, and grinding by a grinder to obtain a mother liquid 1;
s3, stirring and mixing the rubber preparation liquid 2 and the flame retardant, and grinding the mixture by a grinder to obtain a mother liquid 2;
S4, the weight ratio is 3:2, stirring and pre-dissolving the solid epoxy resin and the solvent, adding the liquid epoxy resin, and stirring and mixing to prepare an epoxy resin preparation liquid; the weight ratio is 7:3, stirring and pre-dissolving the thermoplastic resin and the solvent to prepare thermoplastic resin preparation liquid;
and S5, stirring and mixing the mother liquor 1, the mother liquor 2, the epoxy resin preparation liquid and the thermoplastic resin preparation liquid, sequentially adding a curing agent, an antioxidant, a catalyst and a leveling agent, and stirring to obtain the adhesive.
Wherein the rubber is carboxyl nitrile rubber 1072CG; the solvent is butanone; the filler is aluminum hydroxide KH-101LC; the flame retardant is Exolit OP-935; the solid epoxy resin is NPES-901 epoxy resin; the liquid epoxy resin is DC-G2630-K70; the thermoplastic resin is JER and 1256; the curing agent is 4,4' -diaminodiphenyl sulfone (DDS); the antioxidant is EVERNOX1010,1010 antioxidant; the catalyst is 1-cyanoethyl-2-ethyl-4-methylimidazole; the leveling agent is BYK306 leveling agent.
The raw material selections in examples 2 to 4 were the same as in example 1.
Example 2
The embodiment provides an adhesive with uniform glue overflow, which comprises the following raw materials in parts by weight: 35 parts of epoxy resin, 10 parts of thermoplastic resin, 22 parts of rubber, 20 parts of filler, 2 parts of curing agent, 0.2 part of leveling agent, 0.35 part of antioxidant, 15 parts of flame retardant and 0.3 part of catalyst.
S1, weighing raw materials with the formula amount;
s2, the weight ratio is 1:4, stirring and pre-dissolving the rubber and the solvent to prepare a rubber preparation liquid; according to the weight ratio of the filler to the flame retardant, dividing the rubber preparation liquid into a rubber preparation liquid 1 and a rubber preparation liquid 2, stirring and mixing the rubber preparation liquid 1 and the filler, and grinding by a grinder to obtain a mother liquid 1;
s3, stirring and mixing the rubber preparation liquid 2 and the flame retardant, and grinding the mixture by a grinder to obtain a mother liquid 2;
S4, the weight ratio is 3:2, stirring and pre-dissolving the solid epoxy resin and the solvent, adding the liquid epoxy resin, and stirring and mixing to prepare an epoxy resin preparation liquid; the weight ratio is 7:3, stirring and pre-dissolving the thermoplastic resin and the solvent to prepare thermoplastic resin preparation liquid;
and S5, stirring and mixing the mother liquor 1, the mother liquor 2, the epoxy resin preparation liquid and the thermoplastic resin preparation liquid, sequentially adding a curing agent, an antioxidant, a catalyst and a leveling agent, and stirring to obtain the adhesive.
Example 3
The embodiment provides an adhesive with uniform glue overflow, which comprises the following raw materials in parts by weight: 35 parts of epoxy resin, 5 parts of thermoplastic resin, 22 parts of rubber, 25 parts of filler, 2 parts of curing agent, 0.2 part of leveling agent, 0.35 part of antioxidant, 15 parts of flame retardant and 0.3 part of catalyst.
S1, weighing raw materials with the formula amount;
s2, the weight ratio is 1:4, stirring and pre-dissolving the rubber and the solvent to prepare a rubber preparation liquid; according to the weight ratio of the filler to the flame retardant, dividing the rubber preparation liquid into a rubber preparation liquid 1 and a rubber preparation liquid 2, stirring and mixing the rubber preparation liquid 1 and the filler, and grinding by a grinder to obtain a mother liquid 1;
s3, stirring and mixing the rubber preparation liquid 2 and the flame retardant, and grinding the mixture by a grinder to obtain a mother liquid 2;
S4, the weight ratio is 3:2, stirring and pre-dissolving the solid epoxy resin and the solvent, adding the liquid epoxy resin, and stirring and mixing to prepare an epoxy resin preparation liquid; the weight ratio is 7:3, stirring and pre-dissolving the thermoplastic resin and the solvent to prepare thermoplastic resin preparation liquid;
and S5, stirring and mixing the mother liquor 1, the mother liquor 2, the epoxy resin preparation liquid and the thermoplastic resin preparation liquid, sequentially adding a curing agent, an antioxidant, a catalyst and a leveling agent, and stirring to obtain the adhesive.
Example 4
The embodiment provides an adhesive with uniform glue overflow, which comprises the following raw materials in parts by weight: 35 parts of epoxy resin, 5 parts of thermoplastic resin, 22 parts of rubber, 30 parts of filler, 2 parts of curing agent, 0.2 part of leveling agent, 0.35 part of antioxidant, 15 parts of flame retardant and 0.3 part of catalyst.
S1, weighing raw materials with the formula amount;
s2, the weight ratio is 1:4, stirring and pre-dissolving the rubber and the solvent to prepare a rubber preparation liquid; according to the weight ratio of the filler to the flame retardant, dividing the rubber preparation liquid into a rubber preparation liquid 1 and a rubber preparation liquid 2, stirring and mixing the rubber preparation liquid 1 and the filler, and grinding by a grinder to obtain a mother liquid 1;
s3, stirring and mixing the rubber preparation liquid 2 and the flame retardant, and grinding the mixture by a grinder to obtain a mother liquid 2;
S4, the weight ratio is 3:2, stirring and pre-dissolving the solid epoxy resin and the solvent, adding the liquid epoxy resin, and stirring and mixing to prepare an epoxy resin preparation liquid; the weight ratio is 7:3, stirring and pre-dissolving the thermoplastic resin and the solvent to prepare thermoplastic resin preparation liquid;
and S5, stirring and mixing the mother liquor 1, the mother liquor 2, the epoxy resin preparation liquid and the thermoplastic resin preparation liquid, sequentially adding a curing agent, an antioxidant, a catalyst and a leveling agent, and stirring to obtain the adhesive.
Comparative example 1
The raw material selection of comparative example 1 was the same as in example 1.
The raw materials of the comparative example 1 comprise the following components in parts by weight: 35 parts of epoxy resin, 22 parts of rubber, 20 parts of filler, 2 parts of curing agent, 0.2 part of leveling agent, 0.35 part of antioxidant, 15 parts of flame retardant and 0.3 part of catalyst.
S1, weighing raw materials with the formula amount;
s2, the weight ratio is 1:4, stirring and pre-dissolving the rubber and the solvent to prepare a rubber preparation liquid; according to the weight ratio of the filler to the flame retardant, dividing the rubber preparation liquid into a rubber preparation liquid 1 and a rubber preparation liquid 2, stirring and mixing the rubber preparation liquid 1 and the filler, and grinding by a grinder to obtain a mother liquid 1;
s3, stirring and mixing the rubber preparation liquid 2 and the flame retardant, and grinding the mixture by a grinder to obtain a mother liquid 2;
s4, the weight ratio is 3:2, stirring and pre-dissolving the solid epoxy resin and the solvent, adding the liquid epoxy resin, and stirring and mixing to prepare an epoxy resin preparation liquid;
and S5, stirring and mixing the mother solution 1, the mother solution 2 and the epoxy resin preparation liquid, sequentially adding a curing agent, an antioxidant, a catalyst and a leveling agent, and stirring to obtain the adhesive.
Experimental detection
The adhesives prepared in examples 1 to 4 and comparative example 1 were prepared as follows to prepare cover films and performance test was performed according to the following test methods.
The adhesives prepared in examples 1 to 4 and comparative example 1 were uniformly coated on Polyimide (PI) films having a thickness of 12.5 μm by a coater, respectively, and the thickness of the polyimide films was 20 μm, and the resultant films were baked at 160 c for 3.0min, cooled to room temperature, and the cut release papers were attached to the adhesive surfaces, and attached by a film press to prepare a cover film. And (3) putting the covering film into a baking oven to bake at a low temperature of 60 ℃ for 4 hours, taking out a covering film sample after baking, and performing performance test.
1. And (3) glue overflow test: cutting the baked covering film sample into test pieces (15 cm multiplied by 3 cm), punching a circular hole by a punching machine, bonding the covering film adhesive surface with the copper foil surface of the single panel, placing the single panel into a quick press for preheating for 10s, and then performing hot pressing for 80s, wherein the hot pressing temperature is 180 ℃, and the pressure is 120bar. And measuring the length of the covering film along the punching circumference by adopting a microscope to obtain the result of the glue overflow quantity, and observing the shape of the glue overflow.
2. Peel strength test: and (3) attaching the baked covering film sample adhesive surface with the copper foil surface of the single panel, placing the single panel into a quick press for preheating for 10 seconds, then forming hot press for 80 seconds, wherein the hot press temperature is 180 ℃, the pressure is 120bar, placing the single panel into an oven, curing for 1 hour at 160 ℃, taking out and cooling the single panel, cutting test pieces (three pieces, 1cm multiplied by 18 cm) according to requirements, testing the 90-degree peel strength value by adopting a tensile machine, and taking an average value.
3. Heat resistance test: the cover film sample treatment process was the same as the peel strength test, the test piece (three pieces, 3 cm. Times.3 cm) was cut as required, the test piece was immersed in a tin oven at 288℃for 10 seconds, and then the appearance of the test piece was observed, and the operation was repeated 3 times. If the test pieces were all free of foaming and delamination in appearance, the samples were judged to pass the heat resistant temperature test.
The cover films prepared by using the adhesives prepared in examples 1 to 4 and comparative example 1 were tested for the amount of overflow, the shape of overflow, the peel strength and the heat resistance, and the test results are shown in table 1.
TABLE 1
From the test results in Table 1, it is clear that the cover films prepared by using the adhesives prepared in examples 1 to 4 have small overflow amount, uniform and stable overflow, smooth overflow edge, and excellent peel strength and heat resistance. As shown in fig. 1, the covering film prepared by the adhesive prepared in example 1 has uniform and stable glue overflow and smooth edge of the glue overflow.
Example 2 differs from example 1 in that the weight ratio of epoxy resin to thermoplastic resin is different, and the weight ratio of epoxy resin to thermoplastic resin of example 2 is 3.5: in the step 1, the covering film prepared by the prepared adhesive has the glue overflow amount smaller than that of the embodiment 1 and the peeling strength larger than that of the embodiment 1.
The difference between example 3 and example 4 and example 1 is that the amount of filler is different, and as the amount of filler is increased in examples 3 and 4, the amount of glue overflow of the cover film prepared by the prepared adhesive is obviously reduced.
Comparative example 1 was free of thermoplastic resin, and the adhesive prepared with the adhesive had a rough edge of the cover film, a large amount of overflow, as shown in fig. 2, and low peel strength.
According to the invention, the raw material components of the adhesive are reasonably selected and compounded, and the adhesive obtained according to the raw material component proportion and the preparation method of the invention is used for preparing the covering film, and the performance test shows that the adhesive can effectively reduce the adhesive overflow amount, the situations of adhesive spraying, saw-tooth adhesive overflow and the like are avoided, the adhesive overflow is uniform and stable, and the cured adhesive has excellent heat resistance and peeling strength.
The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.

Claims (10)

1. The adhesive with uniform glue overflow is characterized by comprising the following raw materials in parts by weight: 25-45 parts of epoxy resin, 5-15 parts of thermoplastic resin, 15-30 parts of rubber, 20-35 parts of filler, 1-5 parts of curing agent, 0.1-0.5 part of leveling agent, 0.2-0.5 part of antioxidant, 10-20 parts of flame retardant and 0.1-0.6 part of catalyst.
2. The adhesive of claim 1, wherein the epoxy resin is at least one selected from the group consisting of bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenyl type epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl novolac type epoxy resin, bisphenol a novolac type epoxy resin, polyphenylene ether modified epoxy resin, alicyclic type epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, and multifunctional epoxy resin.
3. The adhesive of uniform flash according to claim 1, wherein said thermoplastic resin is selected from at least one of polyester resin, phenoxy resin, acrylic resin and polyimide resin;
the rubber is at least one selected from acrylic rubber, nitrile rubber, silicon rubber, polyurethane rubber and fluororubber;
The filler is selected from one of silicon dioxide, aluminum oxide and aluminum hydroxide.
4. The adhesive with uniform glue overflow according to claim 1, wherein the weight ratio of the epoxy resin to the thermoplastic resin is 2.5-8: 1.
5. The adhesive with uniform glue overflow according to claim 1, wherein the weight of the filler is 20-30% of the weight of the raw material.
6. The adhesive with uniform flash according to claim 1, wherein the curing agent is at least one selected from the group consisting of amine curing agents, imidazole curing agents, phenol curing agents and anhydride curing agents;
the leveling agent is at least one selected from polyether leveling agents, organic silicon leveling agents, polyvinyl alcohol leveling agents and polyether modified polysiloxane leveling agents;
The antioxidant is at least one selected from benzotriazole antioxidants, hindered amine antioxidants, carbodiimide antioxidants and bisphenol antioxidants;
the flame retardant is at least one selected from nitrogen-containing flame retardant, phosphorus-containing flame retardant and halogen-free flame retardant;
The catalyst is at least one selected from amine catalysts, phenol catalysts, imidazole catalysts and organotin catalysts.
7. A method for preparing the adhesive with uniform glue overflow as defined in claim 1, which is characterized by comprising the following steps:
S1, weighing raw materials with the formula amount;
S2, stirring and pre-dissolving the rubber and the solvent to prepare a rubber preparation liquid; according to the weight ratio of the filler to the flame retardant, the rubber preparation liquid is divided into a rubber preparation liquid 1 and a rubber preparation liquid 2, wherein the rubber preparation liquid 1 and the filler are stirred and mixed, and a mother liquid 1 is prepared after grinding by a grinder;
S3, stirring and mixing the rubber preparation liquid 2 and the flame retardant, and grinding by a grinder to obtain a mother liquid 2;
s4, stirring and pre-dissolving the epoxy resin and the solvent to prepare an epoxy resin preparation liquid; stirring and pre-dissolving thermoplastic resin and a solvent to prepare thermoplastic resin preparation liquid;
and S5, stirring and mixing the mother liquor 1, the mother liquor 2, the epoxy resin preparation liquid and the thermoplastic resin preparation liquid, sequentially adding a curing agent, an antioxidant, a catalyst and a leveling agent, and stirring to obtain the adhesive.
8. The method for preparing a glue overflow uniform adhesive according to claim 7, wherein the solvent is at least one selected from butanone, toluene, cyclohexane and cyclohexanone.
9. The method for preparing the adhesive with uniform overflow according to claim 7, wherein in the step S2, the weight ratio of the rubber to the solvent in the rubber preparation solution is 1:4, a step of; in the step S4, the weight ratio of epoxy resin to solvent in the epoxy resin preparation solution is 3:2, the weight ratio of thermoplastic resin to solvent in the thermoplastic resin preparation liquid is 7:3.
10. Use of the glue-spilled uniform adhesive of claim 1 in a cover film for a flexible printed circuit board.
CN202311849479.1A 2023-12-29 2023-12-29 Adhesive with uniform glue overflow and preparation method thereof Pending CN117987056A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311849479.1A CN117987056A (en) 2023-12-29 2023-12-29 Adhesive with uniform glue overflow and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311849479.1A CN117987056A (en) 2023-12-29 2023-12-29 Adhesive with uniform glue overflow and preparation method thereof

Publications (1)

Publication Number Publication Date
CN117987056A true CN117987056A (en) 2024-05-07

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Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311849479.1A Pending CN117987056A (en) 2023-12-29 2023-12-29 Adhesive with uniform glue overflow and preparation method thereof

Country Status (1)

Country Link
CN (1) CN117987056A (en)

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