阅读说明：本技术 一种环氧复合物胶粘剂和覆盖膜及制备方法 (Epoxy compound adhesive, covering film and preparation method ) 是由 牛新星 周祺昌 于 2021-11-18 设计创作，主要内容包括：本发明公开了一种环氧复合物胶粘剂和覆盖膜及制备方法,涉及胶粘剂领域。胶粘剂主要包括丙烯酸酯类弹性体：2wt％-10wt％；聚乙烯醇缩丁醛：8wt％-15wt％；双酚A环氧树脂：5wt％-15wt％；酚氧树脂：3wt％-10wt％；芳香胺类固化剂：0.5wt％-5wt％；咪唑类促进剂：0.05wt％-2wt％；氮磷系阻燃剂：5wt％-15wt％等。本申请通过配方中各组分的协同作用,同时对关键组分聚乙烯醇缩丁醛、丙烯酸酯类弹性体、氮磷系阻燃剂和芳香胺类固化剂的含量控制,从而最终合成具有高Tg、高剥离强度的环氧复合物胶粘剂,可以应用于高温运行环境的电子产品以满足性能需求。(The invention discloses an epoxy compound adhesive, a covering film and a preparation method thereof, and relates to the field of adhesives. The adhesive mainly comprises an acrylate elastomer: 2-10 wt%; polyvinyl butyral: 8-15 wt%; bisphenol a epoxy resin: 5-15 wt%; phenoxy resin: 3 to 10 weight percent; aromatic amine curing agent: 0.5 wt% -5 wt%; imidazole accelerator: 0.05 wt% -2 wt%; nitrogen-phosphorus flame retardant: 5 wt% -15 wt%, etc. According to the application, through the synergistic effect of all components in the formula, the content of key components including polyvinyl butyral, an acrylate elastomer, a nitrogen-phosphorus flame retardant and an aromatic amine curing agent is controlled, so that the epoxy compound adhesive with high Tg and high peel strength is finally synthesized, and the epoxy compound adhesive can be applied to electronic products in a high-temperature operation environment to meet performance requirements.)

1. The epoxy compound adhesive is characterized by comprising the following raw material components:

acrylic elastomer: 2-10 wt%;

polyvinyl butyral: 8-15 wt%;

bisphenol a epoxy resin: 5-15 wt%;

phenoxy resin: 3 to 10 weight percent;

aromatic amine curing agent: 0.5 wt% -5 wt%;

imidazole accelerator: 0.05 wt% -2 wt%;

nitrogen-phosphorus flame retardant: 5-15 wt%;

inorganic filler: 5-10 wt%;

solvent: and (4) the balance.

2. The epoxy composite adhesive as claimed in claim 1, wherein the mass ratio of the acrylate elastomer to the nitrogen-phosphorus flame retardant is 2: 3.

3. the epoxy composite adhesive according to claim 1, wherein the aromatic amine curing agent is added in an amount of 0.5 wt% to 1 wt%.

4. The epoxy composite adhesive according to claim 1, wherein the aromatic amine-based curing agent is diaminodiphenyl sulfone and/or diaminodiphenyl methane.

5. The epoxy composite adhesive of claim 1, wherein the phenoxy resin comprises one or more of DIC4816 resin, DOW92566 resin, and JER1256 resin.

6. The epoxy composite adhesive of claim 1, wherein the imidazole-based accelerator is one or more of aromatic polyamine adduct, 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole.

7. The epoxy composite adhesive according to claim 1, wherein the nitrogen-phosphorus flame retardant is one or more of OP-935 flame retardant, FP-110 flame retardant, SPB-100 flame retardant and triazine flame retardant.

8. The epoxy composite adhesive as claimed in claim 1, wherein the inorganic filler is one or more of aluminum hydroxide, magnesium hydroxide, alumina, silica, titanium dioxide and talc, and the solvent is one or more of butanone, toluene, N-dimethylformamide and propylene glycol methyl ether.

9. A method for preparing an epoxy composite adhesive, for use in preparing an epoxy composite adhesive as claimed in any one of claims 1 to 8, comprising the steps of: mixing acrylate elastomer, polyvinyl butyral, bisphenol A epoxy resin, phenoxy resin, aromatic amine curing agent, imidazole accelerator, nitrogen-phosphorus flame retardant, inorganic filler and solvent to obtain the adhesive.

10. The coverlay film is characterized in that the epoxy composite adhesive as claimed in any one of claims 11 to 8 is used, and comprises a polyimide insulating film, an epoxy composite adhesive layer coated on the polyimide insulating film and release paper attached to the epoxy composite adhesive layer.

Technical Field

The invention relates to the field of adhesives, in particular to an epoxy compound adhesive, a covering film and a preparation method thereof.

Background

Nowadays, the technological level is rapidly developed, electronic equipment is rapidly developed towards miniaturization and light weight while improving functions and performances, and the electronic equipment is used as a base material of flexible circuit board FPC industry, flexible copper clad laminate and cover film are produced as required, and the using amount is increased more and more.

Due to the improvement of information transmission speed and the increase of heat productivity, the working temperature born by the circuit board is higher and higher, the commonly used covering film is formed by solidifying an adhesive material toughened by nitrile rubber for ensuring flexibility, the Tg temperature of the covering film is not high, the material is difficult to keep the flexibility and the use reliability of the product at high temperature, and particularly, the material is a terminal product which works in high-temperature environments such as vehicles, LDE lamps and the like and has large heat productivity due to high-speed rotation. It is urgently needed to develop a bonding material with high Tg property to meet the performance requirement of electronic equipment products under high-temperature operation conditions.

Disclosure of Invention

The invention provides an epoxy compound adhesive, a covering film and a preparation method thereof, which aim to solve the technical problem of poor Tg (glass transition temperature) performance of the existing bonding material.

In order to solve the technical problems, the invention provides an epoxy compound adhesive, which comprises the following raw material components:

acrylic elastomer: 2-10 wt%;

polyvinyl butyral: 8-15 wt%;

bisphenol a epoxy resin: 5-15 wt%;

phenoxy resin: 3 to 10 weight percent;

aromatic amine curing agent: 0.5 wt% -5 wt%;

imidazole accelerator: 0.05 wt% -2 wt%;

nitrogen-phosphorus flame retardant: 5-15 wt%;

inorganic filler: 5-10 wt%;

solvent: and (4) the balance.

By adopting the scheme, the polyvinyl butyral has higher glass transition temperature, and the content of key components of the polyvinyl butyral, the acrylate elastomer, the nitrogen-phosphorus flame retardant and the aromatic amine curing agent is purposefully controlled through the synergistic effect of the components in the formula, so that the epoxy compound adhesive with high Tg and high peel strength is finally synthesized, the comprehensive performance is better, and the epoxy compound adhesive can be applied to electronic products in high-temperature operation environments to meet the performance requirements.

Preferably, the mass ratio of the acrylate elastomer to the nitrogen-phosphorus flame retardant is 2: 3.

by adopting the scheme, the mass ratio of the acrylate elastomer to the nitrogen-phosphorus flame retardant is controlled to be 2: 3, the glass transition temperature of the adhesive can be reduced, so that the obtained covering film has a high Tg temperature.

Preferably, the addition amount of the aromatic amine curing agent is 0.5 wt% to 1 wt%.

By adopting the scheme, the addition amount of the aromatic amine curing agent is controlled, so that the performance of the adhesive can be integrally improved, and the formed covering film has higher peel strength and Tg temperature.

Preferably, the aromatic amine curing agent is diaminodiphenyl sulfone and/or diaminodiphenyl methane.

Preferably, the phenoxy resin comprises one or more of DIC4816 resin, DOW92566 resin and JER1256 resin.

Preferably, the imidazole accelerator is one or more of aromatic polyamine adduct, 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole.

Preferably, the nitrogen-phosphorus flame retardant is one or more of OP-935 flame retardant, FP-110 flame retardant, SPB-100 flame retardant and triazine flame retardant.

Preferably, the inorganic filler is one or more of aluminum hydroxide, magnesium hydroxide, alumina, silica, titanium dioxide and talcum powder, and the solvent is one or more of butanone, toluene, N-dimethylformamide and propylene glycol methyl ether.

In order to solve the above technical problems, the second object of the present invention is to provide a method for preparing an epoxy composite adhesive, comprising the following steps: mixing acrylate elastomer, polyvinyl butyral, bisphenol A epoxy resin, phenoxy resin, aromatic amine curing agent, imidazole accelerator, nitrogen-phosphorus flame retardant, inorganic filler and solvent to obtain the adhesive.

In order to solve the above technical problems, a third object of the present invention is to provide a coverlay film using the above epoxy composite adhesive, including a polyimide insulating film, an epoxy composite adhesive layer coated on the polyimide insulating film, and a release paper attached to the epoxy composite adhesive layer.

Preferably, the thickness of the polyimide insulating film is 7.5-100 μm, the thickness of the release paper is 50-150 μm, and the thickness of the epoxy compound adhesive layer is 5-45 μm.

Preferably, the thickness of the epoxy compound adhesive layer is 10 μm to 35 μm.

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

the added polyvinyl butyral has higher glass transition temperature, and the content of key components of the polyvinyl butyral, the acrylate elastomer, the nitrogen-phosphorus flame retardant and the aromatic amine curing agent is purposefully controlled through the synergistic effect of all the components in the formula, so that the epoxy compound adhesive with high Tg and high peel strength is finally synthesized, and the epoxy compound adhesive can be applied to electronic products in a high-temperature operation environment to meet the performance requirements.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

TABLE 1-Source and type of raw materials used in this embodiment

The application provides an epoxy compound adhesive, which comprises the following raw material components: acrylic elastomer: 2-10 wt%, polyvinyl butyral: 8-15 wt%, bisphenol A epoxy resin: 5-15 wt%, phenoxy resin: 3-10 wt%, aromatic amine curing agent: 0.5 wt% -5 wt%, imidazole accelerator: 0.05 wt% -2 wt%, nitrogen phosphorus fire retardant: 5-15 wt%, inorganic filler: 5-10 wt%, solvent: and (4) the balance.

In one embodiment, the acrylic elastomer is an acrylate rubber.

In one embodiment, the mass ratio of the acrylate rubber to the nitrogen-phosphorus flame retardant is as follows.

In one embodiment, the nitrogen-phosphorus flame retardant isAt least one of OP flame retardant, FP-110 flame retardant, SPB-100 flame retardant and triazine flame retardant.

In one of the embodiments, the first and second electrodes are,the OP flame retardant is OP-935 flame retardant.

In one embodiment, the triazine flame retardant is an SR-245 flame retardant.

In one embodiment, the aromatic amine-based curing agent is added in an amount of 0.5 wt% to 1 wt%.

In one embodiment thereof, the phenoxy resin comprises a DIC4816 treeAt least one of resin, DOW92566 resin and JER1256 resin, the structural formula of the phenoxy resin is:wherein X is

In one embodiment thereof, the aromatic amine-based curing agent refers to diaminodiphenyl sulfone and/or diaminodiphenyl methane.

In one embodiment thereof, the imidazole-based accelerator is at least one of an aromatic polyamine adduct, 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole.

In one embodiment, the inorganic filler is at least one of aluminum hydroxide, magnesium hydroxide, alumina, silica, titanium dioxide, talc.

In one embodiment, the solvent is one of butanone, toluene, N-dimethylformamide, and propylene glycol methyl ether.

The application also provides a cover film, including the polyimide insulation film, the polyimide insulation film surface adopts above-mentioned epoxy compound adhesive coating to form epoxy compound adhesive layer, and epoxy compound adhesive layer one side facing away from the polyimide insulation film is pasted and is applied release paper.

In one embodiment, the polyimide insulating film has a thickness of 7.5 to 100 μm, the release paper has a thickness of 50 to 150 μm, and the epoxy composite adhesive layer has a thickness of 5 to 45 μm.

In one embodiment, the thickness of the epoxy composite adhesive layer is preferably 10 μm to 35 μm.

The following detailed description is given in conjunction with specific preparation examples and examples to illustrate the practical effects of the epoxy composite adhesive of the present application by comparison.

Preparation example 1

An epoxy compound adhesive comprises the following raw material components: 4 wt% of acrylate rubber, 8 wt% of polyvinyl butyral, 10 wt% of bisphenol A epoxy resin, 3 wt% of phenoxy resin, 2.4 wt% of diamino diphenyl sulfone, 0.05 wt% of 2-ethyl-4-methylimidazole, 6 wt% of 0P935 flame retardant, 6 wt% of aluminum hydroxide and 60.55 wt% of butanone; wherein the phenoxy resin is particularly DOW92566 resin, and the adhesive is prepared by mixing the components.

Preparation example two

An epoxy compound adhesive comprises the following raw material components: 5 wt% of acrylate rubber, 10 wt% of polyvinyl butyral, 15 wt% of bisphenol A epoxy resin, 5 wt% of phenoxy resin, 0.5 wt% of diaminodiphenyl sulfone, 2 wt% of 1-cyanoethyl-2-methylimidazole, 5 wt% of FP-110 flame retardant, 5 wt% of titanium dioxide and 52.5 wt% of toluene; wherein the phenoxy resin is specifically DIC4816 resin, and the adhesive is prepared by mixing the components.

Preparation example three

An epoxy compound adhesive comprises the following raw material components: 10 wt% of acrylate rubber, 15 wt% of polyvinyl butyral, 5 wt% of bisphenol A epoxy resin, 10 wt% of phenoxy resin, 5 wt% of diaminodiphenylmethane, 1 wt% of 2-methylimidazole, 15 wt% of SPB-100 flame retardant, 10 wt% of talcum powder and 29 wt% of propylene glycol methyl ether; wherein the phenoxy resin is specifically JER1256 resin, and the adhesive is prepared by mixing the components.

Preparation example four

The epoxy compound adhesive has the same steps, reagents and technological parameters as those in the first preparation example, except that diamino diphenyl sulfone in 0.5 wt% and butanone in 62.45 wt%.

Preparation example five

The epoxy compound adhesive has the same steps, reagents and technological parameters as those in the first preparation example, except that diamino diphenyl sulfone in 1 wt% and butanone in 61.95 wt%.

Preparation example six

The epoxy compound adhesive has the same steps, reagents and technological parameters as those in the first preparation example, except that diamino diphenyl sulfone in 1.3 wt% and butanone in 61.65 wt%.

Preparation example seven

The epoxy compound adhesive comprises the following steps, reagents used in the steps and process parameters are the same as those in preparation example one, and the difference is that the mass ratio of the acrylate rubber to the 0P935 flame retardant is 2: 3, the addition amount of the acrylate rubber is 6 weight percent, the addition amount of the 0P935 flame retardant is 9 weight percent, and the addition amount of the butanone is 55.55 weight percent.

Preparation example eight

The epoxy compound adhesive comprises the following steps, reagents used in the steps and process parameters are the same as those in preparation example one, and the difference is that the mass ratio of the acrylate rubber to the 0P935 flame retardant is 1: 1, the addition amount of the acrylate rubber is 8 wt%, the addition amount of the 0P935 flame retardant is 8 wt%, and the addition amount of the butanone is 54.55 wt%.

Example one

A cover film comprises a polyimide insulating film, wherein the surface of the polyimide insulating film is coated with the epoxy compound adhesive obtained in the first preparation example to form an epoxy compound adhesive layer, release paper is attached to the side, opposite to the polyimide insulating film, of the epoxy compound adhesive layer, the thickness of the polyimide insulating film is about 45 microns, the thickness of the release paper is about 60 microns, and the thickness of the epoxy compound adhesive layer is about 30 microns.

Example two

The covering film has the same steps, reagents and technological parameters as those in the first step, and the epoxy composite adhesive obtained in the second step is used to replace the epoxy composite adhesive.

EXAMPLE III

The covering film has the same steps, reagents and technological parameters as those in the first step, and the epoxy composite adhesive obtained in the third step is used to replace the epoxy composite adhesive.

Example four

The covering film has the same steps, reagents and technological parameters as those in the first step, except that the epoxy composite adhesive obtained in the first preparation example is replaced with the epoxy composite adhesive obtained in the fourth preparation example.

EXAMPLE five

The covering film has the same steps, reagents and technological parameters as those in the first step, except that the epoxy composite adhesive obtained in the first preparation example is replaced with the epoxy composite adhesive obtained in the fifth preparation example.

EXAMPLE six

The covering film has the same steps, reagents and technological parameters as those in the first step, and the epoxy composite adhesive obtained in the second step is replaced with the epoxy composite adhesive obtained in the first step.

EXAMPLE seven

The covering film has the same steps, reagents and technological parameters as those in the first step, except that the epoxy composite adhesive obtained in the first step is replaced with the epoxy composite adhesive obtained in the seventh step.

Example eight

The covering film has the same steps, reagents and technological parameters as those in the first step, except that the epoxy composite adhesive obtained in the first preparation example is replaced with the epoxy composite adhesive obtained in the eighth preparation example.

Comparative preparation example 1

An epoxy compound adhesive comprises the following raw material components: 15 wt% of acrylate rubber, 3 wt% of polyvinyl butyral, 8 wt% of bisphenol A epoxy resin, 6 wt% of phenoxy resin, 1.3 wt% of diamino diphenyl sulfone, 0.05 wt% of 2-ethyl-4-methylimidazole, 3 wt% of 0P935 flame retardant, 6 wt% of aluminum hydroxide and 57.65 wt% of butanone; wherein the phenoxy resin is specifically DOW92566 resin.

Comparative preparation example 2

An epoxy compound adhesive comprises the following raw material components: 2 wt% of acrylate rubber, 15 wt% of polyvinyl butyral, 8 wt% of bisphenol A epoxy resin, 6 wt% of phenoxy resin, 7 wt% of diaminodiphenyl sulfone, 1 wt% of 2-ethyl-4-methylimidazole, 2 wt% of 0P935 flame retardant, 6 wt% of aluminum hydroxide and 53 wt% of butanone; wherein the phenoxy resin is specifically DOW92566 resin.

Comparative preparation example C

The epoxy compound adhesive has the same steps, reagents and technological parameters as those in the first preparation example, except that diamino diphenyl sulfone is replaced with dicyclopentadienyl phenolic resin.

Comparative example 1

The covering film comprises the same steps, reagents and process parameters as those used in the first step, except that the epoxy composite adhesive obtained in the first preparation example is replaced by the epoxy composite adhesive obtained in the first comparative preparation example.

Comparative example No. two

The covering film comprises the same steps and reagents and process parameters as those used in the first step, except that the epoxy composite adhesive obtained in the first preparation example is replaced by the epoxy composite adhesive obtained in the second preparation example.

Comparative example No. three

The covering film comprises the same steps, reagents and process parameters as those used in the first step, and is different from the first step in that the epoxy composite adhesive obtained in the first preparation example is replaced by the epoxy composite adhesive obtained in the third preparation example.

Performance test

1. Peel strength: the cover films obtained in examples 1 to 8 and comparative examples 1 to 3 were tested by IPC-TM-6502.4.9, and the results are shown in tables 2 to 3.

2. Flame retardancy the test results of the coverlay films obtained in examples 1 to 8 and comparative examples 1 to 3 were measured according to the UL-94 vertical burning method and are shown in tables 2 to 3.

3. Dip solderability (300 ℃ 10 s): the cover films obtained in examples 1 to 8 and comparative examples 1 to 3 were tested by IPC-TM-6502.4.13, and the results are shown in tables 2 to 3.

4. Folding resistance: the coverlay films obtained in examples 1 to 8 and comparative examples 1 to 3 were tested by the method according to JIS-6471 under the test conditions of 500g/O.38R and the test piece specification of 12.5. mu. mPI/13 μm coating/18 μm rolled copper foil, and the test results are shown in tables 2 to 3.

5. Dimensional stability: the cover films obtained in examples 1 to 8 and comparative examples 1 to 3 were tested by IPC-TM-6502.2.4, and the results are shown in tables 2 to 3.

6. And (3) Tg detection: the covering films obtained in examples 1 to 8 and comparative examples 1 to 3 were subjected to a Tg test using a DMA apparatus, and the results of the test are shown in tables 2 to 3.

7. Softness: the cover films obtained in examples 1 to 8 and comparative examples 1 to 3 were tested using a softness tester (Toyo Seiki Seisaku-sho, model GS-2), and the test results are shown in tables 2 to 3.

TABLE 2 results of Performance test of examples 1 to 5

TABLE 3-Performance test results of examples 6 to 8 and comparative examples 1 to 3

According to the detection results of the example 1 and the comparative examples 1 to 2 in the tables 2 to 3, the polyvinyl butyral has a higher glass transition temperature, and the content of key components of the polyvinyl butyral, the acrylate rubber, the 0P935 flame retardant and the diaminodiphenyl sulfone is controlled through the synergistic effect of the components in the formula, so that the epoxy compound adhesive covering film with high Tg is finally synthesized, and the application requirement of electronic products in a high-temperature operation environment is met.

Combining the test results of examples 1-3 and comparative example 3 in tables 2-3, it can be seen that the addition of diaminodiphenyl sulfone in the formulation can increase the Tg of the cover film, improve the peel strength of the cover film, and improve the overall performance of the adhesive.

The results of the tests of examples 1 and 4 to 6 in tables 2 to 3 show that the performance of the adhesive can be improved by controlling the amount of diaminodiphenyl sulfone added, and the formed cover film has high peel strength and Tg temperature.

By combining the detection results of examples 1 and 7 to 8 in tables 2 to 3, it can be seen that the mass ratio of the acrylate rubber to the 0P935 flame retardant is controlled to be 2: 3, the glass transition temperature of the adhesive can be reduced, so that the obtained covering film has a high Tg temperature.

The above-mentioned embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, and it should be understood that the above-mentioned embodiments are only examples of the present invention and are not intended to limit the scope of the present invention. It should be understood that any modifications, equivalents, improvements and the like, which come within the spirit and principle of the invention, may occur to those skilled in the art and are intended to be included within the scope of the invention.