TW201930469A - Polyamide acid composition, polyamide composition, polyamide film and method for making the polyamide film - Google Patents

Abstract

A polyamide acid composition comprising a polyamide acid, a titanium black, and a dispersant. The polyamide acid composition comprises: 100 parts by weight of the polyimide acid, 5~50 parts by weight of the titanium black, and 0.5~4 parts by weight of the dispersant. A polyamide composition making by the polyamide acid composition, a polyamide film making by the polyamide acid composition, and a method for making the polyamide film are also provided.

Description

Polyacrylic acid composition, polyimide composition, polyimide film and preparation method thereof

The invention relates to a polyfluorinated acid composition, a polyfluorinated imine composition prepared by using the polyfluorinated acid composition, a polyfluorinated imine film prepared by using the polyfluorinated acid composition, and the polyfluorinated polyfluorinated acid. Method for making imine film.

Polyimide film is formed by coating polyamidic acid film with high temperature ring closure. In the conventional technology, a black dye or a black pigment is generally added to the polyamic acid to improve the blackness and hiding power of the polyimide film to obtain a black polyimide film. When a white pattern is required to be formed on the surface of the black polyimide film, a white pattern is obtained by printing a white ink on the surface of the black polyimide film by a screen printing process.

However, when a black polyimide film prepared by adding a black dye is added, when printing a white ink, the black dye in the black polyimide film may be dissolved out and penetrate into the white ink, causing discoloration problems. In addition, the above-mentioned black polyimide film also has problems of fading or discoloration at high temperatures.

Carbon black has good hiding power and low price, and is often used as a black pigment to make black polyimide films. However, carbon black itself has electrical conductivity, which will cause the resistance value of the resulting black polyimide film to decrease.

In addition, a white pattern obtained by printing a white ink on the surface of the black polyimide film through a screen printing process protrudes on the surface of the black polyimide film, making the surface of the black polyimide film uneven.

In view of this, it is necessary to provide a new polyamic acid composition to solve the above problems.

It is also necessary to provide a polyfluorene imine composition prepared by using the polyphosphonium acid composition.

In addition, it is necessary to provide a polyfluorene imide film prepared by using the polyphosphonium acid composition.

In addition, it is necessary to provide a manufacturing method using the polyfluoreneimide film.

A polyamic acid composition comprising polyamic acid, titanium black, and a dispersant. In the polyamino acid composition, the content of the polyamino acid is 100 parts by weight, and the content of the titanium black is 5 to 40 parts by weight, and the content of the dispersant ranges from 0.5 to 4 parts by weight.

A polyimide composition is obtained by subjecting the polyamidate composition to a heat treatment to subject the polyamidate composition in the polyamidate composition to imidization.

A polyimide film is obtained by applying a heat treatment to the polyamidic acid composition, and then performing polyimidation of the polyamidic acid in the polyamidic acid composition.

A method for manufacturing a polyimide film includes the following steps:

Step S1: providing a substrate;

Step S2: Provide a polyamic acid composition, and coat the polyamino acid composition on the surface of the substrate. The polyamino acid composition includes polyamic acid, titanium black, and a dispersant. In the fluoric acid composition, the content of the polyamidic acid is in the range of 100 parts by weight, the content of the titanium black is in the range of 5 to 40 parts by weight, and the content of the dispersant is in the range of 0.5 to 4 parts by weight;

Step S3: heat treatment to imidize the polyfluorene phosphonium in the polyphosphonic acid composition.

The polyfluorinated acid composition of the present invention includes titanium black, and the polyfluorinated imide film prepared from the fluorinated acid composition is black and has high surface resistivity, volume resistivity, and light transmittance. When it is necessary to form a white pattern on the polyimide film, YAG laser is performed on the polyimide film, and a pattern is engraved on the polyimide film to make the titanium black in the polyimide film. By oxidizing to titanium white, a white pattern can be obtained. Since the white pattern is directly converted from the polyimide film, the surface of the white pattern is flush with the surface of the polyimide film.

In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, but not all of them.

Based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.

All technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field of the invention. The terms used herein in the description of the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the present invention.

A preferred embodiment of the present invention provides a polyfluorene acid composition, which is used to make a polyfluorine film 100 (see FIG. 1). The polyamic acid composition includes polyamino acid (PAA), titanium black, and a dispersant.

In the polyamic acid composition, the content of the polyamic acid is 100 parts by weight, the content of the titanium black is 5 to 40 parts by weight, and the content of the dispersant is 0.5 to 4 parts by weight. Serving.

It is well known that titanium black is a non-conductive black powder pigment. The blackness of titanium black is very good, and it can be used for temperature-resistant coatings. It has the characteristics of high temperature resistance, environmental protection, non-toxic and edible. Low-priced titanium oxide and titanium oxynitride are collectively referred to as titanium black. Titanium black can be oxidized to titanium white when exposed to high temperature or laser light. Titanium white is an inert white pigment with a chemical composition of titanium dioxide.

The dispersant is selected from one or two of an inorganic dispersant and an organic dispersant. The inorganic dispersant includes, but is not limited to, one or two of a silicate-based dispersant and an alkali metal phosphate-based dispersant. The silicate-based dispersant may be water glass, and the alkali metal phosphate-based dispersant includes, but is not limited to, one or more of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate. The organic dispersant includes, but is not limited to, one of triethylhexyl phosphoric acid, sodium lauryl sulfate, methylpentanol, cellulose derivative, polypropylene amidamine, Gur gum, and fatty acid polyethylene glycol ester. Or several. The dispersant can disperse solid particles of inorganic and organic pigments which are difficult to dissolve in the liquid, and can also prevent the solid particles from settling and agglomerating to form a stable suspension. The dispersant can shorten the dispersing time, improve gloss, improve tinting power and hiding power, improve color spreadability and hueability, prevent floating and blooming, prevent flocculation and sedimentation.

The method for preparing the polyamic acid composition may be: adding polyamic acid, titanium black, and a dispersant into a reaction bottle according to a predetermined ratio, stirring at a high speed for a period of time, and grinding and dispersing with a three-roll mill. Let stand for a while to defoam. Then vacuum defoam and let stand for a while.

The present invention also provides a polyimide composition. The polyimide composition is obtained by subjecting the polyimide composition to a heat treatment to subject the polyimide to a polyimide to form a polyimide. The titanium black is dispersed in polyimide. In other words, the polyimide composition includes polyimide, titanium black and a dispersant dispersed in the polyimide. The method of the imidization is not particularly limited, and for example, heat treatment is suitably used.

Please refer to FIG. 1. The present invention also provides a polyimide film 100. The polyimide film 100 is formed by applying a polyamic acid composition and then performing a heat treatment to form the polyimide acid. Obtained from polyimide. The polyfluorene film 100 has titanium black. The polyimide film 100 is black. The polyfluorene film 100 has high surface resistivity, volume resistivity, and light transmittance.

Please refer to FIG. 2, when it is necessary to form a white pattern 101 on the polyimide film 100, perform YAG laser irradiation on the polyimide film 100 to engrav a pattern on the polyimide film 100, By oxidizing the titanium black in the polyimide film 100 to titanium white, a white pattern 101 can be obtained. Since the white pattern 101 is directly converted from the polyimide film 100, the surface of the white pattern 101 is flush with the surface of the polyimide film 100.

Please refer to FIG. 1, a method for manufacturing a polyimide film 100, which includes the following steps:

Step S1: Provide a substrate 10.

The substrate 10 may be a release paper, a resin substrate, a metal substrate, or the like.

Step S2: providing the polyamidic acid composition, and coating the polyamidic acid composition on the surface of the substrate 10.

Step S3: baking, removing most of the solvent to form a non-stick film surface, and then placing it in a high-temperature oven at a first heating rate from room temperature to a first temperature T _{1 and} then holding it for a period of time t ₁ , Then, the temperature is raised to a second temperature T ₂ at a second heating rate and the temperature is maintained for a period of time t ₂ to polyimide the polyamidate in the polyamidate composition to obtain a polyimide film. 100.

In at least one embodiment, the baking temperature during baking is 180 ° C, the first heating rate is 10 ° C / min, the second heating rate is 10 ° C / min, and the first temperature T1 is 200 ℃, the second temperature T2 is 300 ℃ ~ 400 ℃, the time t ₁ of 1 hour, the time t ₂ of 2 hours.

Hereinafter, the present invention will be specifically described by using examples.

Polyamines used in the following examples and comparative examples were prepared by the following method: 167.0 g of N-methylpyrrolidone, 5.53 g of p-phenylenediamine, and 4.33 g of 4 were sequentially added to a 500 mL reaction bottle. , 4'-diaminodiphenyl ether, 0.63g of 3,5-diamino-1,2,4-triazole, pass nitrogen and stir at high speed until completely dissolved, and then add 23.18g of 3,3 ' , 4,4'-benzophenonetetracarboxylic dianhydride, and then stirred for 12 hours to obtain polyamidic acid.

Example 1

Add 500 g of polyamic acid, 5 g of titanium black, and 0.5 g of dispersant to a 500 mL reaction bottle. After stirring at high speed for 60 minutes, use a three-roll mill to grind and disperse it (after 2 loops), and then leave to stand for 1 day. Then, it was defoamed under vacuum for 2 hours to obtain a polyamidic acid composition.

Example 2

Into a 500mL reaction bottle, add 100g of polyamic acid, 20g of titanium black, and 2g of dispersant. After stirring at high speed for 60 minutes, use a three-roll mill to grind and disperse (after 2 cycles), and leave to stand for 1 day. After being degassed under vacuum for 2 hours, a polyamic acid composition was prepared.

Example 3

In a 500mL reaction bottle, add 100g of polyamidic acid, 40g of titanium black, and 4g of dispersant. After stirring at high speed for 60 minutes, use a three-roll mill to grind and disperse it (after 2 cycles), and then leave it to stand for 1 day. After being degassed under vacuum for 2 hours, a polyamic acid composition was prepared.

Comparative Example 1

Add 500g of polyamidoic acid, 2g of carbon black, and 0.2g of dispersant to a 500mL reaction bottle, stir at high speed for 60min, and then grind and disperse it with a three-roll mill (after 2 loops), and then leave to stand for 1 day. Then, it was defoamed under vacuum for 2 hours to obtain a polyamidic acid composition.

Comparative Example 2

In a 500 mL reaction bottle, add 100 g of polyamic acid, 20 g of carbon black, and 0.2 g of a dispersant, and stir at high speed for 60 minutes. Then use a three-roll mill to grind and disperse it (after 2 loops), and leave it to stand for 1 day Then, it was defoamed under vacuum for 2 hours to obtain a polyamidic acid composition.

Comparative Example 3

In a 500mL reaction bottle, add 100g of polyamic acid and 80g of commercially available high-resistance carbon slurry (pigment loading = 25%), stir at high speed for 60min, leave it to stand for 1 day, and then degas in a vacuum for 2 hours. That is, a polyamic acid composition is obtained.

The polyamic acid compositions in Examples 1 to 3 and Comparative Examples 1 to 3 were coated on a substrate, and then baked at 180 ° C for 20 minutes, and most of the solvents were removed to form a non-stick film surface Then put it in a high-temperature oven at a heating rate of 10 ° C / min from room temperature to 200 ° C and then keep it at a constant temperature for 1 hour, and then at 10 ° C / min to 300 ~ 400 ° C and then keep it at a constant temperature for 2 hours. After polyimide acid was imidized, the temperature was lowered to 50 ° C. and then taken out to obtain a polyimide film having a thickness of 25 μm.

The surface resistivity and volume resistivity tests were performed on the polyimide films prepared from the polyamidic acid compositions of Examples 1 to 3 and Comparative Examples 1 to 3, and the test results are shown in Table 1.

Table I:

As can be seen from Table 1, the polyimide films prepared by the polyamidic acid compositions of Examples 1 to 3 are compared with the polyimide films prepared by the polyamidic acid compositions of Comparative Examples 1 to 3. Has higher surface resistivity and volume resistivity.

The polyfluorinated acid composition of the present invention includes titanium black, and the polyfluorinated imide film 100 prepared from the fluorinated acid composition is black and has high surface resistivity, volume resistivity, and light transmittance. When it is necessary to form a white pattern 101 on the polyimide film 100, a YAG laser is performed on the polyimide film 100, and a pattern is engraved on the polyimide film 100 to make the polyimide The titanium black in the film 100 is oxidized to titanium white, and a white pattern 101 can be obtained. Since the white pattern 101 is directly converted from the polyimide film 100, the surface of the white pattern 101 is flush with the surface of the polyimide film 100.

In addition, the above are only preferred embodiments of the present invention, and are not a limitation on the present invention in any form. Although the present invention has disclosed the preferred embodiments as above, it is not intended to limit the present invention and anyone familiar with the profession Without departing from the scope of the technical solution of the present invention, those skilled in the art can use the disclosed technical content to make a few changes or modify equivalent implementations of equivalent changes. Anyone who does not depart from the technical solution of the present invention, according to the present invention Any simple modifications, equivalent changes, and modifications made to the above embodiments by the technical essence of the invention still fall within the scope of the technical solution of the present invention.

100‧‧‧Polyimide film

101‧‧‧ white pattern

10‧‧‧ Substrate

FIG. 1 is a schematic cross-sectional view of a polyfluoreneimide film according to a preferred embodiment of the present invention.

2 is a schematic cross-sectional view of a polyimide film having a white pattern according to a preferred embodiment of the present invention.

Claims (10)

A polyamic acid composition, which is improved in that the polyamino acid composition includes polyamino acid, titanium black, and a dispersant, and the polyamino acid content in the polyamino acid composition ranges from 100 The content of the titanium black ranges from 5 to 40 parts by weight, and the content of the dispersant ranges from 0.5 to 4 parts by weight. The polyamidic acid composition according to item 1 of the scope of patent application, wherein the dispersant is selected from one or two of an inorganic dispersant and an organic dispersant. The polyamidic acid composition according to item 2 of the scope of the patent application, wherein the inorganic dispersant includes one or more of water glass, sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate. The organic dispersant includes one or more of triethylhexylphosphoric acid, sodium lauryl sulfate, methylpentanol, cellulose derivatives, polypropylene amidamine, Gur gum, and fatty acid polyethylene glycol esters. . A polyimide composition, which is improved in that the polyimide composition is subjected to a heat treatment to the polyimide composition according to any one of the claims 1 to 3 in the patent application scope to make the polyimide The polyamidic acid in the composition is obtained by imidating. The polyfluorene imine composition according to item 4 of the scope of application for a patent, wherein the polyfluorene imine composition includes a polyfluorene imine and titanium black dispersed in the polyfluorene imine. A polyimide film is an improvement in that the polyimide film is heat-treated after coating the polyimide composition according to any one of the claims 1 to 3 of the application patent scope to make the polyimide The polyamidic acid in the composition is obtained by imidating. A method for manufacturing a polyimide film includes the following steps: step S1: providing a substrate; step S2: providing a polyamic acid composition, and coating the polyamino acid composition on the substrate On the surface, the polyamic acid composition includes polyamic acid, titanium black, and a dispersant. In the polyamic acid composition, the content of the polyamic acid is 100 parts by weight, and the content of the titanium black is 5 to 40 parts by weight, the content of the dispersant is in the range of 0.5 to 4 parts by weight; Step S3: heat treatment, so that the polyfluorene sulfonium is imidized in the polyfluorinated acid composition. According to the method for manufacturing a polyimide film according to item 7 of the scope of the patent application, wherein the heat treatment is baking, removing most of the solvent to form a non-stick film surface, and then putting it in an oven to The first heating rate is maintained at a constant temperature for a period of time from room temperature to a first temperature, and then maintained at a second temperature for a period of time at a second heating rate. The method for manufacturing a polyimide film according to item 8 of the scope of the patent application, wherein the first temperature increasing rate is 10 ° C / min, the second temperature increasing rate is 10 ° C / min, and the first temperature The temperature is 200 ° C., the second temperature is 300 ° C. to 400 ° C., the time of constant temperature after heating up to the first temperature is 1 hour, and the time of constant temperature after heating up to the second temperature is 2 hours. The method for manufacturing a polyfluoreneimide film according to item 7 of the scope of the patent application, wherein the dispersant includes water glass, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexyl phosphate, ten One or more of sodium dialkyl sulfate, methylpentanol, cellulose derivative, polypropylene amidamine, Gur gum, and fatty acid polyethylene glycol ester.