阅读说明：本技术 一种挠性印刷电路板基材用双向拉伸聚酰亚胺薄膜及制备方法 (Biaxially oriented polyimide film for flexible printed circuit board base material and preparation method thereof ) 是由 孙大山 曲延涛 张范 曹广文 于 2019-11-30 设计创作，主要内容包括：本发明属于有机高分子材料制备技术领域,尤其为一种挠性印刷电路板基材用双向拉伸聚酰亚胺薄膜及制备方法,其方法包括：S1：原料准备：按以下重量份称取材料：芳香族二元胺1.5～1.8份、刚性芳香族二酐1.3～1.5份、芳香族二酐0.8～1.2份、对氨基苯基三甲氧基硅烷4～8份、芳香族四羧酸6～10份、六氟二酐6～9份、芳香族四羧酸二烷酯5～10份、二氨基二苯醚2～3份、均苯四甲酸酐2～6份和二甲基乙酰胺42～46份；S2：聚合：将称量得到的材料在低压、惰性气体保护条件下进行高温混合。本发明设计合理,能够制得兼具导电性和磁性的聚酰亚胺复合薄膜,以获得符合挠性印刷电路板基材使用要求的专用双向拉伸聚酰亚胺薄膜材料。(The invention belongs to the technical field of organic polymer material preparation, and particularly relates to a biaxially oriented polyimide film for a flexible printed circuit board substrate and a preparation method thereof, wherein the method comprises the following steps: s1: preparing raw materials: weighing the following materials in parts by weight: 1.5-1.8 parts of aromatic diamine, 1.3-1.5 parts of rigid aromatic dianhydride, 0.8-1.2 parts of aromatic dianhydride, 4-8 parts of p-aminophenyl trimethoxy silane, 6-10 parts of aromatic tetracarboxylic acid, 6-9 parts of hexafluoro dianhydride, 5-10 parts of dialkyl aromatic tetracarboxylic acid ester, 2-3 parts of diaminodiphenyl ether, 2-6 parts of pyromellitic anhydride and 42-46 parts of dimethylacetamide; s2: polymerization: and (3) mixing the weighed materials at high temperature under the conditions of low pressure and inert gas protection. The invention has reasonable design, and can prepare the polyimide composite film with both conductivity and magnetism so as to obtain the special biaxially oriented polyimide film material which meets the use requirement of the flexible printed circuit board substrate.)

1. The biaxially oriented polyimide film for the flexible printed circuit board base material is characterized by comprising the following raw materials in parts by weight: 1.5-1.8 parts of aromatic diamine, 1.3-1.5 parts of rigid aromatic dianhydride, 0.8-1.2 parts of aromatic dianhydride, 4-8 parts of p-aminophenyltrimethoxysilane, 6-10 parts of aromatic tetracarboxylic acid, 6-9 parts of hexafluoro dianhydride, 5-10 parts of dialkyl aromatic tetracarboxylic acid ester, 2-3 parts of diaminodiphenyl ether, 2-6 parts of pyromellitic anhydride and 42-46 parts of dimethylacetamide.

2. The biaxially oriented polyimide film for the flexible printed circuit board base material according to claim 1, which is characterized by comprising the following raw materials in parts by weight: 1.6-1.7 parts of aromatic diamine, 1.35-1.45 parts of rigid aromatic dianhydride, 0.9-1.1 parts of aromatic dianhydride, 5-7 parts of p-aminophenyltrimethoxysilane, 7-9 parts of aromatic tetracarboxylic acid, 7-8 parts of hexafluoro dianhydride, 6-9 parts of dialkyl aromatic tetracarboxylic acid ester, 2.3-2.7 parts of diaminodiphenyl ether, 3-5 parts of pyromellitic anhydride and 43-45 parts of dimethylacetamide.

3. The biaxially oriented polyimide film for the flexible printed circuit board base material according to claim 1, which is characterized by comprising the following raw materials in parts by weight: 1.5 parts of aromatic diamine, 1.4 parts of rigid aromatic dianhydride, 1 part of aromatic dianhydride, 6 parts of p-aminophenyltrimethoxysilane, 8 parts of aromatic tetracarboxylic acid, 7.5 parts of hexafluorodianhydride, 8 parts of dialkyl aromatic tetracarboxylic acid ester, 2.5 parts of diaminodiphenyl ether, 4 parts of pyromellitic anhydride and 44 parts of dimethylacetamide.

4. A preparation method of a biaxially oriented polyimide film for a flexible printed circuit board substrate is characterized by comprising the following steps:

s1: preparing raw materials: weighing the following raw materials in parts by weight: 1.5-1.8 parts of aromatic diamine, 1.3-1.5 parts of rigid aromatic dianhydride, 0.8-1.2 parts of aromatic dianhydride, 4-8 parts of p-aminophenyl trimethoxy silane, 6-10 parts of aromatic tetracarboxylic acid, 6-9 parts of hexafluoro dianhydride, 5-10 parts of dialkyl aromatic tetracarboxylic acid ester, 2-3 parts of diaminodiphenyl ether, 2-6 parts of pyromellitic anhydride and 42-46 parts of dimethylacetamide for later use;

s2: polymerization: mixing the aromatic diamine, rigid aromatic dianhydride, p-aminophenyltrimethoxysilane, aromatic tetracarboxylic acid, hexafluoro dianhydride, dialkyl ester of aromatic tetracarboxylic acid, diaminodiphenyl ether, pyromellitic dianhydride and dimethylacetamide weighed in the step S1 at high temperature under the protection of low pressure and inert gas to obtain a polymerization solution for later use;

s3: defoaming: defoaming and equalizing the polymerization solution in S2 under low-pressure and high-temperature conditions to obtain a polyimide stock solution for later use:

s4: coating and film forming: after preheating and dedusting treatment is carried out on the supporting surface, the polyimide stock solution in the S3 is coated on the surface of the supporting surface under the high-temperature condition, so as to obtain an original film;

s5: and (3) bidirectional stretching: putting the original film in S4 into a stretcher for stretching twice, and then carrying out stepped heating treatment and removing moisture to obtain a film;

s6: trimming: and (4) cutting off the edge of 5-10 cm of the film in the step (S5), and then heating in a water bath to obtain a polyimide stock solution finished product.

5. The biaxially oriented polyimide film for flexible printed circuit board substrates and the preparation method thereof according to claim 4, wherein in S2, the raw materials are mixed under the conditions of 100kPa to 200kPa and 145 ℃ to 195 ℃, and the mixing and stirring speed is 25 to 35 rpm.

6. The biaxially oriented polyimide film for flexible printed circuit board substrates and the preparation method thereof according to claim 4, wherein in S2, the inert gas is selected from one of helium and nitrogen.

7. The biaxially oriented polyimide film for a flexible printed circuit board substrate according to claim 4, wherein in S3, the polymerization solution is subjected to a defoaming step at 0 to 25kPa at 190 to 220 ℃.

8. The biaxially oriented polyimide film for a flexible printed circuit board substrate and the preparation method thereof according to claim 4, wherein in S4, the preheating temperature of the supporting surface is 370-395 ℃, and the coating thickness of the polyimide stock solution is 30-70 μm.

9. The biaxially oriented polyimide film for flexible printed circuit board substrates and the preparation method thereof according to claim 4, wherein in step S5, the original film is stretched twice in mutually perpendicular directions by a stretcher, and the stepwise heating temperatures are respectively: 270-290 ℃ for 25-35 min, 290-390 ℃ for 10-25 min, 470-590 ℃ for 5-10 min.

10. The biaxially oriented polyimide film for flexible printed circuit board substrates and the preparation method thereof according to claim 4, wherein in S6, the water bath conditions are as follows: 110 to 130kPa, 102 to 105 ℃.

Technical Field

The invention relates to the technical field of organic polymer material preparation, in particular to a biaxially oriented polyimide film for a flexible printed circuit board substrate and a preparation method thereof.

Background

At present, most manufacturers for producing biaxially oriented polyimide films in China adopt a very original process technology, and adopt a solvent method of two raw materials, namely pyromellitic dianhydride and diaminodiphenyl ether are subjected to condensation polymerization in a very strong solvent dimethylacetamide to form a film in a parallel flow manner, and then imidization is carried out, for example, Chinese patent application No. 201110248294.6 discloses a biaxially oriented polyimide film for a flexible printed circuit board base material and a preparation method thereof, wherein the method mainly comprises the following steps of 1 polymerization, preparation of polyimide stock solution according to the following mixture ratio, namely 1-5% of p-phenylenediamine, 2-8% of biphenyltetracarboxylic dianhydride, 5-10% of diaminodiphenyl ether, 8-15% of pyromellitic dianhydride, 62-84% of dimethylacetamide, 2 tape casting to form a film, 3 longitudinal drawing, a drawing ratio of 1: 1.02 ~ 1.15, 4 transverse drawing and imidization, a drawing ratio of 1: 1.05 ~ 1.2.2, 5 edge cutting and rolling, 6 post-treatment, and 7 slitting and packaging.

However, the above design has disadvantages, and the polyimide film prepared by the method for preparing a polyimide film designed in the above patent is not perfect in conductivity and magnetism, and cannot be well adapted to the development and performance requirements of a circuit board, and needs to be improved, so we propose a biaxially oriented polyimide film for a flexible printed circuit board substrate and a preparation method thereof to solve the above problems.

Disclosure of Invention

The invention aims to solve the defects of the prior art and provides a biaxially oriented polyimide film for a flexible printed circuit board substrate and a preparation method thereof.

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

a biaxially oriented polyimide film for a flexible printed circuit board base material comprises the following raw materials in parts by weight: 1.5-1.8 parts of aromatic diamine, 1.3-1.5 parts of rigid aromatic dianhydride, 0.8-1.2 parts of aromatic dianhydride, 4-8 parts of p-aminophenyltrimethoxysilane, 6-10 parts of aromatic tetracarboxylic acid, 6-9 parts of hexafluoro dianhydride, 5-10 parts of dialkyl aromatic tetracarboxylic acid ester, 2-3 parts of diaminodiphenyl ether, 2-6 parts of pyromellitic anhydride and 42-46 parts of dimethylacetamide.

Preferably, the biaxially oriented polyimide film for the flexible printed circuit board substrate comprises the following raw materials in parts by weight: 1.6-1.7 parts of aromatic diamine, 1.35-1.45 parts of rigid aromatic dianhydride, 0.9-1.1 parts of aromatic dianhydride, 5-7 parts of p-aminophenyltrimethoxysilane, 7-9 parts of aromatic tetracarboxylic acid, 7-8 parts of hexafluoro dianhydride, 6-9 parts of dialkyl aromatic tetracarboxylic acid ester, 2.3-2.7 parts of diaminodiphenyl ether, 3-5 parts of pyromellitic anhydride and 43-45 parts of dimethylacetamide.

Preferably, the biaxially oriented polyimide film for the flexible printed circuit board substrate comprises the following raw materials in parts by weight: 1.5 parts of aromatic diamine, 1.4 parts of rigid aromatic dianhydride, 1 part of aromatic dianhydride, 6 parts of p-aminophenyltrimethoxysilane, 8 parts of aromatic tetracarboxylic acid, 7.5 parts of hexafluorodianhydride, 8 parts of dialkyl aromatic tetracarboxylic acid ester, 2.5 parts of diaminodiphenyl ether, 4 parts of pyromellitic anhydride and 44 parts of dimethylacetamide.

The invention also provides a preparation method of the biaxially oriented polyimide film for the flexible printed circuit board substrate, which comprises the following steps:

s1: preparing raw materials: weighing the following raw materials in parts by weight: 1.5-1.8 parts of aromatic diamine, 1.3-1.5 parts of rigid aromatic dianhydride, 0.8-1.2 parts of aromatic dianhydride, 4-8 parts of p-aminophenyl trimethoxy silane, 6-10 parts of aromatic tetracarboxylic acid, 6-9 parts of hexafluoro dianhydride, 5-10 parts of dialkyl aromatic tetracarboxylic acid ester, 2-3 parts of diaminodiphenyl ether, 2-6 parts of pyromellitic anhydride and 42-46 parts of dimethylacetamide for later use;

s2: polymerization: mixing the aromatic diamine, rigid aromatic dianhydride, p-aminophenyltrimethoxysilane, aromatic tetracarboxylic acid, hexafluoro dianhydride, dialkyl ester of aromatic tetracarboxylic acid, diaminodiphenyl ether, pyromellitic dianhydride and dimethylacetamide weighed in the step S1 at high temperature under the protection of low pressure and inert gas to obtain a polymerization solution for later use;

s3: defoaming: defoaming and equalizing the polymerization solution in S2 under low-pressure and high-temperature conditions to obtain a polyimide stock solution for later use:

s4: coating and film forming: after preheating and dedusting treatment is carried out on the supporting surface, the polyimide stock solution in the S3 is coated on the surface of the supporting surface under the high-temperature condition, so as to obtain an original film;

s5: and (3) bidirectional stretching: putting the original film in S4 into a stretcher for stretching twice, and then carrying out stepped heating treatment and removing moisture to obtain a film;

s6: trimming: and (4) cutting off the edge of 5-10 cm of the film in the step (S5), and then heating in a water bath to obtain a polyimide stock solution finished product.

Preferably, in the S2, the raw materials are mixed under the conditions of 100kPa to 200kPa and 145 ℃ to 195 ℃, and the mixing and stirring speed is 25 to 35 r/min.

Preferably, in S2, the inert gas is selected from helium and nitrogen.

Preferably, in S3, the polymerization solution is subjected to a degassing step under a condition of 0 to 25kPa at 190 to 220 ℃.

Preferably, in S4, the preheating temperature of the supporting surface is 370-395 ℃, and the coating thickness of the polyimide stock solution is 30-70 μm.

Preferably, in S5, the original film is stretched twice in mutually perpendicular directions by the stretcher, and the stepwise heating temperatures are: 270-290 ℃ for 25-35 min, 290-390 ℃ for 10-25 min, 470-590 ℃ for 5-10 min.

Preferably, in S6, the water bath conditions are: 110 to 130kPa, 102 to 105 ℃.

The invention relates to a biaxially oriented polyimide film for flexible printed circuit board base material and a preparation method thereof.A polycondensation type polyimide synthesis reaction is carried out in a high-boiling-point aprotic solvent which is prepared by mixing aromatic diamine, rigid aromatic dianhydride, p-aminophenyl trimethoxy silane, aromatic tetracarboxylic acid, hexafluoro dianhydride, dialkyl ester of aromatic tetracarboxylic acid and diaminodiphenyl ether material for reaction to generate a fluorine-containing biphenyl type polyamic acid solution;

the invention relates to a biaxially oriented polyimide film for a flexible printed circuit board substrate and a preparation method thereof.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.