CN114736624A - A kind of silicon-free high temperature resistant protective film and preparation method thereof - Google Patents

Abstract

The invention discloses a silicon-free high temperature resistant protective adhesive film, which comprises a base material layer, an adhesive layer and a silicon-free release film layer in sequence from top to bottom; the base material layer is a polybenzimidazole film layer; The adhesive layer is made of the following components in parts by weight: 30-40 parts of hyperbranched polybenzimidazoles whose end groups are amino groups, 5-10 parts of acetylated modified polyphenylene sulfide, 2,000 parts, 2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane 2-4 parts, titanate coupling agent 1-2 parts, acetic acid 1-2 parts, molecular sieve 3-5 parts, solvent 60-80 parts . The invention also discloses a preparation method of the silicon-free high temperature resistant protective adhesive film. The silicon-free high temperature resistant protective adhesive film disclosed by the invention has good high temperature resistance, good thermal stability and mechanical and mechanical properties, high roller peeling strength, and can effectively avoid silicon transfer.

Description

A kind of silicon-free high temperature resistant protective film and preparation method thereof

technical field

The invention relates to the technical field of adhesives, in particular to a silicon-free high temperature resistant protective adhesive film and a preparation method thereof.

Background technique

In recent years, the high-frequency and high-speed wireless communication industry represented by 5G mobile phones is promoting the rapid development of radio frequency circuits in the direction of flexibility, miniaturization, thinning, high performance and multi-functionality. The demand for flexible circuit boards has suddenly risen. The performance requirements of the protective film for masking in the flexible circuit board manufacturing process are also getting higher and higher. The ideal protective film used in the flexible circuit board manufacturing process needs to have the characteristics of good initial adhesion, high adhesion in long-term high-temperature process and acid-base process, and long service life.

The traditional protective adhesive film needs the protection of the release film on the side of the adhesive layer away from the substrate layer. The surface of the common release film on the market is often coated with silicone oil or silicon-containing release agent. This kind of protective film is easy to cause silicon transfer, which will cause damage to the surface of the adhesive, and the use of some adhesive products and silicon-sensitive electronic materials will be affected, which is not conducive to long-term use. On the other hand, the production and use of silicone oil and silicon-containing release agents have great environmental pollution, and are very harmful to human health and the environment, and are not suitable for long-term large-area contact. It is in this situation that the silicone-free protective film came into being, and its advent has attracted great attention in the industry. However, the silicone-free protective film on the market is more or less expensive, the production process conditions are harsh, the adhesion between the silicone-free release agent and the film body is insufficient, and the high temperature resistance and thermal stability are poor. , the mechanical properties and roller peel strength need to be further improved, and the service life needs to be further extended.

In order to solve the above problems, Chinese invention patent application CN113831851A discloses a cover film and a preparation method thereof, including a polyimide film and an adhesive film compounded on the polyimide film; the adhesive film is composed of the following components by weight The mixture is made of: high temperature oil absorbing filler: 25-35 parts; rubber: 25-30 parts; modified epoxy resin: 20-25 parts; curing agent: 5-10 parts; surface treatment agent: 0.1-0.2 parts . The film surface of the cover film of the invention is smooth, the viscosity is low at room temperature, and it is difficult for the cover film to cover the circuit board to move and align. Protecting the surface of the film is equivalent to saving the cost of the release film and the production steps of compounding the release film on the adhesive film, which is equivalent to saving the production cost. However, the film performance stability and mechanical properties need to be further improved.

Therefore, the development of a silicon-free high-temperature resistant protective film with good high temperature resistance, good thermal stability and mechanical properties, high roller peel strength, and can effectively avoid silicon transfer and its preparation method meet the market demand and have a wide range of market value. And application prospects, it is of great significance to promote the development of the field of protective film.

SUMMARY OF THE INVENTION

The main purpose of the present invention is to provide a silicon-free high temperature resistant protective film with good high temperature resistance, good thermal stability and mechanical properties, high roller peeling strength, and can effectively avoid silicon transfer and a preparation method thereof.

In order to achieve the above purpose, the present invention provides a silicon-free high temperature resistant protective adhesive film, which is characterized in that it includes a base material layer, an adhesive layer and a silicon-free release film layer in sequence from top to bottom; the base material layer is Polybenzimidazole film layer; the adhesive layer is made of the following components by weight: 30-40 parts of hyperbranched polybenzimidazole whose end groups are amino groups, acetylated modified polyphenylene sulfide 5-10 parts of ether, 2-4 parts of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 1-2 parts of titanate coupling agent, 1-2 parts of acetic acid, molecular sieve 3- 5 parts, 60-80 parts of solvent.

Preferably, the source of the hyperbranched polybenzimidazole whose end group is an amino group has no special requirements. In one embodiment of the present invention, the hyperbranched polybenzimidazole whose end group is an amino group is obtained according to Chinese Invention Patent 2015101111019.4 prepared by the method of Example 3.

Preferably, there is no special requirement for the source of the acetylated modified polyphenylene sulfide. In one embodiment of the present invention, the acetylated modified polyphenylene sulfide is the method of Example 1 in Chinese Invention Patent 201110347014.7 production.

Preferably, the titanate coupling agent is at least one of titanate coupling agent NXH-501 and titanate coupling agent 201.

Preferably, the molecular sieve is at least one of type 3A molecular sieve, type 4A molecular sieve, and type 5A molecular sieve.

Preferably, the solvent is any one of N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

Preferably, the silicon-free release film layer is made of any one of silicon-free release film RF3220 and PET non-silicon release film GT-989.

Another object of the present invention is to provide a method for preparing the silicon-free high temperature resistant protective adhesive film, which is characterized in that it includes the following steps: first, corona pretreatment is performed on the lower surface of the base material layer; After the components of the layer are mixed evenly, it is coated on the lower surface of the base material layer, and then pasted with the silicon-free release film layer.

Due to the application of the above-mentioned technical solutions, the present invention has the following beneficial effects:

(1) The preparation method of the silicon-free high temperature resistant protective film disclosed in the present invention has the advantages of simple process, convenient operation, little dependence on equipment, high preparation efficiency and finished product qualification rate, and is suitable for continuous large-scale production.

(2) The silicon-free high-temperature protective adhesive film disclosed in the present invention includes a substrate layer, an adhesive layer and a silicon-free release film layer in order from top to bottom; through this structure, dust can be avoided from sticking to the adhesive film. At the same time, it avoids silicon transfer and environmental problems caused by silicon, and can also ensure stable peelability and no adhesive residue; The hyperbranched polybenzimidazoles in which the component group is amino group all contain polybenzimidazole structures, and have better compatibility between them, making the bonding more tight and not easy to delaminate.

(3) In the silicon-free high temperature resistant protective adhesive film disclosed in the present invention, the adhesive layer is made of the following components in parts by weight: 30-40 parts of hyperbranched polybenzimidazole whose end groups are amino groups , 10-20 parts of acetylated modified polyphenylene sulfide, 2-4 parts of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 1-2 parts of titanate coupling agent, acetic acid 1-2 parts, molecular sieves 3-5 parts, solvent 60-80 parts. When in use, it is cured at 70-100°C, and the curing principle is hyperbranched polybenzimidazole with amino end groups and amino groups on 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane It can undergo imidization reaction with the carbonyl group on acetylated modified polyphenylene sulfide to form an interpenetrating network structure, which effectively improves the physical properties of the adhesive film, so that it has sufficient high temperature resistance, good mechanical properties and long service life. ; After bonding with the adherend, it has good stability over time.

(4) In the silicone-free high-temperature protective adhesive film disclosed in the present invention, the adhesive layer acts together through the mutual cooperation of various components, and simultaneously introduces polybenzimidazole, polyphenylene sulfide and containing polybenzimidazole into the adhesive film. The fluorobenzene structure effectively improves the high temperature resistance and heat resistance stability; the introduction of the hyperbranched structure improves the compatibility between the components, and the synergistic effect of each component can ensure its good adhesion.

Detailed ways

The following description serves to disclose the invention to enable those skilled in the art to practice the invention. The preferred embodiments described below are given by way of example only, and other obvious modifications will occur to those skilled in the art.

The hyperbranched polybenzimidazoles whose end groups are amino groups in the embodiments of the present invention are prepared according to the method of Example 3 in Chinese Invention Patent 2015101111019.4; the acetylated modified polyphenylene sulfide is prepared according to Chinese Invention Patent 201110347014.7 prepared by the method of Example 1. The molecular sieves used in the various embodiments of the present invention are ground into powder with a particle size of 1000 meshes before use.

Example 1

A silicon-free high temperature resistant protective adhesive film comprises a base material layer, an adhesive layer and a silicon-free release film layer in sequence from top to bottom; the base material layer is a polybenzimidazole film layer; the adhesive The layer is made of the following components in parts by weight: 30 parts of hyperbranched polybenzimidazoles whose end groups are amino groups, 5 parts of acetylated modified polyphenylene sulfide, 2,2-bis(3-amino- 4-hydroxyphenyl) hexafluoropropane 2 parts, titanate coupling agent 1 part, acetic acid 1 part, molecular sieve 3 parts, solvent 60 parts.

The titanate coupling agent is titanate coupling agent NXH-501; the molecular sieve is type 3A molecular sieve; the solvent is N,N-dimethylformamide; the silicon-free release film layer is Made of silicon-free release film RF3220.

A preparation method of the silicon-free high temperature resistant protective adhesive film, comprising the following steps: firstly performing corona pretreatment on the lower surface of a base material layer; then mixing the components of the adhesive layer evenly, and then coating it on the base material The lower surface of the layer is then pasted with the silicon-free release film layer, and after winding and curing, a silicon-free high temperature resistant protective film is made.

Example 2

A silicon-free high temperature resistant protective adhesive film comprises a base material layer, an adhesive layer and a silicon-free release film layer in sequence from top to bottom; the base material layer is a polybenzimidazole film layer; the adhesive The layer is made of the following components in parts by weight: 33 parts of hyperbranched polybenzimidazoles whose end groups are amino groups, 6 parts of acetylated modified polyphenylene sulfide, 2,2-bis(3-amino- 2.5 parts of 4-hydroxyphenyl) hexafluoropropane, 1.2 parts of titanate coupling agent, 1.3 parts of acetic acid, 3.5 parts of molecular sieves, and 65 parts of solvent.

The titanate coupling agent is titanate coupling agent 201; the molecular sieve is type 4A molecular sieve; the solvent is N,N-dimethylacetamide; the silicon-free release film layer is made of Any of silicon release film RF3220 and PET non-silicon release film GT-989.

Another object of the present invention is to provide a method for preparing the silicon-free high temperature resistant protective adhesive film, which is characterized in that it includes the following steps: first, corona pretreatment is performed on the lower surface of the base material layer; After the components of the layer are mixed evenly, it is coated on the lower surface of the base material layer, and then pasted with the silicon-free release film layer.

Example 3

A silicon-free high temperature resistant protective adhesive film comprises a base material layer, an adhesive layer and a silicon-free release film layer in sequence from top to bottom; the base material layer is a polybenzimidazole film layer; the adhesive The layer is made of the following components in parts by weight: 35 parts of hyperbranched polybenzimidazole with amino end groups, 7.5 parts of acetylated modified polyphenylene sulfide, 2,2-bis(3-amino- 4-hydroxyphenyl) hexafluoropropane 3 parts, titanate coupling agent 1.5 parts, acetic acid 1.5 parts, molecular sieve 4 parts, solvent 70 parts.

The titanate coupling agent is titanate coupling agent NXH-501; the molecular sieve is type 5A molecular sieve; the solvent is N-methylpyrrolidone; the silicon-free release film layer is made of PET non-silicon The release film is made of GT-989.

A preparation method of the silicon-free high temperature resistant protective adhesive film, comprising the following steps: firstly performing corona pretreatment on the lower surface of a base material layer; then mixing the components of the adhesive layer evenly, and then coating it on the base material The lower surface of the layer is then pasted with the silicon-free release film layer, and after winding and curing, a silicon-free high temperature resistant protective film is made.

Example 4

A silicon-free high temperature resistant protective adhesive film comprises a base material layer, an adhesive layer and a silicon-free release film layer in sequence from top to bottom; the base material layer is a polybenzimidazole film layer; the adhesive The layer is made of the following components in parts by weight: 38 parts of hyperbranched polybenzimidazoles whose end groups are amino groups, 9 parts of acetylated modified polyphenylene sulfide, 2,2-bis(3-amino- 4-hydroxyphenyl) hexafluoropropane 3.5 parts, titanate coupling agent 1.8 parts, acetic acid 1.8 parts, molecular sieve 4.5 parts, solvent 75 parts.

The titanate coupling agent is a mixture formed by mixing titanate coupling agent NXH-501 and titanate coupling agent 201 in a mass ratio of 3:5; the molecular sieve is 3A type molecular sieve, 4A type molecular sieve, 5A type molecular sieve Type molecular sieves are mixed in a mass ratio of 1:1:3; the solvent is N-methylpyrrolidone; the silicon-free release film layer is made of silicon-free release film RF3220.

A preparation method of the silicon-free high temperature resistant protective adhesive film, comprising the following steps: firstly performing corona pretreatment on the lower surface of a base material layer; then mixing the components of the adhesive layer evenly, and then coating it on the base material The lower surface of the layer is then pasted with the silicon-free release film layer, and after winding and curing, a silicon-free high temperature resistant protective film is made.

Example 5

A silicon-free high temperature resistant protective adhesive film comprises a base material layer, an adhesive layer and a silicon-free release film layer in sequence from top to bottom; the base material layer is a polybenzimidazole film layer; the adhesive The layer is made of the following components in parts by weight: 40 parts of hyperbranched polybenzimidazoles whose end groups are amino groups, 10 parts of acetylated modified polyphenylene sulfide, 2,2-bis(3-amino- 4-hydroxyphenyl) hexafluoropropane 4 parts, titanate coupling agent 2 parts, acetic acid 2 parts, molecular sieve 5 parts, solvent 80 parts.

The titanate coupling agent is titanate coupling agent NXH-501; the molecular sieve is 4A type molecular sieve; the solvent is N-methylpyrrolidone; the silicon-free release film layer is made of PET non-silicon The release film is made of GT-989.

A preparation method of the silicon-free high temperature resistant protective adhesive film, comprising the following steps: firstly performing corona pretreatment on the lower surface of a base material layer; then mixing the components of the adhesive layer evenly, and then coating it on the base material The lower surface of the layer is then pasted with the silicon-free release film layer, and after winding and curing, a silicon-free high temperature resistant protective film is made.

Comparative Example 1

The present invention provides a silicon-free high temperature resistant protective film, the formula and preparation method of which are similar to those in Example 1, except that 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane is not added.

Comparative Example 2

The present invention provides a silicon-free high temperature resistant protective film, the formula and preparation method of which are similar to those in Example 1, except that polyphenylene sulfide is used instead of acetylated modified polyphenylene sulfide. The data of the polyphenylene sulfide The molecular weight is 40,000, and M _w /M _n =1.29.

In order to further illustrate the beneficial technical effects of the silicon-free high temperature resistant protective film made by each embodiment of the present invention, the relevant performance tests were carried out on the silicon-free high temperature resistant protective film made from Examples 1-5 and Comparative Examples 1-2, The test results are shown in Table 1. The test method is as follows: After curing the protective film in each example at 80 ° C for 2 hours, the performance test was carried out. Condition test; honeycomb drum is composed of metal honeycomb core and 0.5mm thick 2024T3 aluminum panel in accordance with BMS4-40-N specification; tensile shear strength at 25℃ is tested according to GB/T 7124-1986, high temperature tensile strength The shear strength is tested according to GJB444-1988; the tensile shear test piece is the aluminum alloy LY12CZ test piece treated by chemical oxidation; the thermal aging test is that after each product is placed at 280 ℃ for 1200h, it is cooled to 25 ℃, Measured by comparing the retention rate of tensile shear strength with the initial value of tensile shear strength at 25°C, the larger the value, the better the heat aging resistance.

Table 1

As can be seen from Table 1, the silicone-free high temperature resistant protective film disclosed in the embodiment of the present invention has more excellent high temperature resistance and heat aging resistance compared with the products of the comparative example, and the peel strength is larger, which is the result of each component The results of synergy; the addition of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane and acetylated modified polyphenylene sulfide are all beneficial to improve the above properties.

The foregoing has shown and described the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited by the above-mentioned embodiments. The above-mentioned embodiments and descriptions describe only the principles of the present invention. Without departing from the spirit and scope of the present invention, there are various Variations and improvements are intended to fall within the scope of the claimed invention. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims (8)

1. A silicon-free high-temperature-resistant protective adhesive film is characterized by sequentially comprising a base material layer, an adhesive layer and a silicon-free release film layer from top to bottom; the substrate layer is a polybenzimidazole film layer; the adhesive layer is prepared from the following components in parts by weight: 30-40 parts of hyperbranched polybenzimidazole with an amino end group, 5-10 parts of acetylated modified polyphenylene sulfide, 2-4 parts of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1-2 parts of titanate coupling agent, 1-2 parts of acetic acid, 3-5 parts of molecular sieve and 60-80 parts of solvent.

2. The silicon-free high temperature resistant protective adhesive film according to claim 1, wherein the hyperbranched polybenzimidazole with an amino group as an end group is prepared by the method of embodiment 3 in the Chinese patent 2015101111019.4.

3. The silicon-free high temperature resistant protective adhesive film according to claim 1, wherein the acetylated modified polyphenylene sulfide is prepared by the method of example 1 in the chinese patent 201110347014.7.

4. The silicon-free high temperature resistant protective adhesive film as claimed in claim 1, wherein the titanate coupling agent is at least one of a titanate coupling agent NXH-501 and a titanate coupling agent 201.

5. The silicon-free high temperature resistant glue film according to claim 1, wherein the molecular sieve is at least one of a 3A type molecular sieve, a 4A type molecular sieve and a 5A type molecular sieve.

6. The silicon-free high temperature resistant protective adhesive film according to claim 1, wherein the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

7. The non-silicon high temperature resistant adhesive protective film according to claim 1, wherein the non-silicon release film layer is made of any one of a non-silicon release film RF3220 and a PET non-silicon release film GT-989.

8. The method for preparing the silicon-free high-temperature-resistant protective adhesive film according to any one of claims 1 to 7, comprising the following steps: firstly, performing corona pretreatment on the lower surface of a base material layer; and then uniformly mixing all components of the adhesive layer, coating the adhesive layer on the lower surface of the substrate layer, laminating the adhesive layer and the silicon-free release film layer, rolling and curing to prepare the silicon-free high-temperature-resistant protective adhesive film.