阅读说明：本技术 聚酰胺酰亚胺膜的制备方法及由其制备的聚酰胺酰亚胺膜 (Method for producing polyamideimide film and polyamideimide film produced thereby ) 是由 李吉男 金纪勋 崔祯烈 于 2018-11-28 设计创作，主要内容包括：本发明提供聚酰胺酰亚胺膜的制备方法,该方法包括：步骤(a),将分散在水中的至少一种二胺单体和至少一种酸酐单体的分散液放入压力容器中,在5℃至400℃的温度及加压条件下进行反应,对反应得到的产物进行过滤并干燥以获得聚酰胺酰亚胺粉末；步骤(b),将所述聚酰胺酰亚胺粉末和炭黑颗粒放入有机溶剂中混合后进行研磨,得到聚酰胺酰亚胺涂料组合物；步骤(c),将所述聚酰胺酰亚胺涂料组合物柔性地涂敷在保护膜上；以及步骤(d),在180℃以下的温度下,干燥及固化经涂敷的所述涂料组合物,在保护膜上形成聚酰胺酰亚胺薄膜,相对于100重量份的所述聚酰胺酰亚胺粉末,所述炭黑颗粒的含量为5重量份至20重量份,所述聚酰胺酰亚胺薄膜的厚度为10μm以下。(The present invention provides a method for producing a polyamideimide film, which comprises: a step (a) of placing a dispersion of at least one diamine monomer and at least one acid anhydride monomer dispersed in water in a pressure vessel, reacting at a temperature of 5 ℃ to 400 ℃ under pressure, filtering and drying the product obtained by the reaction to obtain polyamide imide powder; step (b), putting the polyamide imide powder and the carbon black particles into an organic solvent, mixing and grinding to obtain a polyamide imide coating composition; a step (c) of flexibly coating the polyamideimide coating composition on a protective film; and a step (d) of drying and curing the coated coating composition at a temperature of 180 ℃ or less to form a polyamideimide film on the protective film, wherein the content of the carbon black particles is 5 to 20 parts by weight with respect to 100 parts by weight of the polyamideimide powder, and the thickness of the polyamideimide film is 10 μm or less.)

1. A method for producing a polyamideimide film, wherein,

the method comprises the following steps:

a step (a) of placing a dispersion of at least one diamine monomer and at least one acid anhydride monomer dispersed in water in a pressure vessel, reacting at a temperature of 150 ℃ to 250 ℃ and a pressure of 5bar to 20bar, filtering and drying a product obtained by the reaction to obtain polyamideimide powder;

step (b), putting the polyamide imide powder and the carbon black particles into an organic solvent, mixing and grinding to obtain a polyamide imide coating composition;

a step (c) of flexibly coating the polyamideimide coating composition on a protective film; and

a step (d) of drying and curing the coated coating composition at a temperature of 180 ℃ or less to form a polyamideimide thin film on the protective film,

the content of the carbon black particles is 5 to 20 parts by weight with respect to 100 parts by weight of the polyamideimide powder,

the thickness of the polyamide-imide film is 10 [ mu ] m or less.

2. The method according to claim 1, wherein, in the step (b), the organic solvent is an organic solvent having a boiling point range of 100 ℃ to 180 ℃.

3. The method according to claim 2, wherein the organic solvent is one selected from the group consisting of N, N '-dimethylformamide and N, N' -dimethylacetamide.

4. The method according to claim 1, wherein in the step (d), the residual solvent content in the polyamideimide film is 10% or less by performing drying and curing.

5. The process of claim 1, wherein the anhydride monomer comprises trimellitic anhydride.

6. The method of claim 1, wherein the diamine monomer comprises one or more selected from the group consisting of oxydianiline, methylenedianiline, and p-phenylenediamine.

7. The method according to claim 1, wherein the average particle diameter of the carbon black particles contained in the coating composition is in the range of 0.1 μm to 1 μm.

8. The method of claim 1, wherein the protective film has a glass transition temperature of 100 ℃ to 140 ℃.

9. The method of claim 1, wherein the protective film is a polyethylene terephthalate film.

10. The process of claim 1, wherein the reaction in step (a) is carried out at a temperature in the range of 160 ℃ to 240 ℃.

11. The method of claim 1, wherein the reaction in step (a) is carried out for 4 hours to 2 days.

12. The method of claim 1, wherein the polyamideimide film has a thickness in the range of 1 μ ι η to 5 μ ι η.

13. The method according to claim 1, wherein the polyamideimide film has a light transmittance in the visible light region of 1.1% or less and a tensile strength of 9kg/cm³The above.

14. A polyamideimide film produced by the production method according to any one of claims 1 to 13, comprising a polyamideimide thin film formed on a protective film.

15. A cover layer comprising the polyamideimide film according to claim 14.

16. An electronic device comprising the cover layer of claim 15.

Technical Field

The invention relates to a preparation method of a polyamide-imide membrane and the polyamide-imide membrane prepared by the same.

Background

Generally, a Polyimide (PI) resin refers to a highly heat-resistant resin prepared by solution-polymerizing an aromatic dianhydride with an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, dehydrating by ring closure at a high temperature, and imidizing.

Such polyimide has excellent properties such as high heat resistance that can withstand a temperature of 400 ℃ or higher, electrical insulation, radiation resistance, chemical resistance, and the like, and is used for high-tech materials and insulating coating agents in the fields of electronics, semiconductors, displays, automobiles, aviation, and aerospace materials.

However, polyimide itself is not easily soluble in a solvent, and its use in a wide range of fields such as difficulty in thermoforming is somewhat limited.

Therefore, most of polyimides are prepared by a curing imidization process after processing and high-temperature heat treatment of polyamic acid (polyamic acid) as a precursor, and typical products produced in this manner are polyimide films.

Such a polyimide film is widely used as a barrier (barrier) film for protecting a flexible circuit board, an electronic component, a lead frame of an integrated circuit package, and the like, and particularly, recently, as an insulation layer is thinned with the lightweight and thin simplification of an electronic component, a demand for using a black polyimide film as a coverlay (coverlay) is sharply increasing due to demands for safety, shielding, a light shielding function, and a visual effect.

Conventional black polyimide films are generally prepared by a Solution Casting (Solution Casting) method, which is a method in which a polyamic acid Solution is polymerized from a dianhydride and a diamine, and the resulting polyamic acid Solution is mixed with carbon black, such as silica, TiO₂Such quenched particles, and an acid anhydride and a tertiary amine for imidization as a catalyst are mixed to form a film. Specifically, a polyamic acid solution mixed with the catalyst and the like is coated (Casting) on a support (end Belt), dried in a specific temperature range, and then a self-supporting gel film in a semi-dry state is peeled off from the support, and transferred to an oven at a high temperature and dried, and subjected to an imidization process at a high temperature to prepare a black polyimide film.

However, in the above-described production method, since the specific gravity difference between the quenched particles and the polyamic acid to be mixed is large, the mechanical properties and the electrical properties of the black polyimide film produced are deteriorated due to precipitation or aggregation of the quenched particles in the imidization step after the polyamic acid is applied. However, when the amount of addition of the quenched particles is reduced to solve this problem, there is a limit that a desired level of shielding property cannot be achieved.

In particular, in the case of preparing a black polyimide film having a thickness of 10 μm or less on a protective film, there is a problem that commercial production cannot be performed, for example, physical properties of the film are seriously deteriorated according to the added quenching particles, so that breakage may occur.

On the other hand, as described above, in the case of a black polyimide film having a thickness of 10 μm or less, the film can be prepared by attaching a protective film to one side or both sides in the production process for protecting the outer surface of the film, and this process is increased to lower the productivity, and there is a problem that wrinkles or damages are generated on the polyimide film in the process of attaching the protective film.

In order to solve the above problems, in some prior arts, a polyamic acid is coated on a protective film and then imidized to prepare a polyimide film or a polyimide powder in a state where the polyimide film is coated on the protective film, and then a coating composition in which the polyimide powder is dissolved in an organic solvent is prepared and coated on the protective film, and then dried and cured to prepare a film in a form where the polyimide film is coated on the protective film.

However, since the protective film used for producing the above-described thin film mainly uses a material having a glass transition temperature of 150 ℃, the high-temperature imidization process is limited when using polyamic acid.

In addition, in the method of applying the coating composition in which the polyimide powder is dissolved to the protective film, there is a problem that the protective film is deformed at the temperature of drying and curing. On the contrary, when drying and lowering the temperature are performed to prevent deformation of the protective film, a polar organic solvent (boiling point of 200 ℃ or higher) mainly used in this method remains in the film, and there is a possibility that a problem of lowering mechanical properties or the like may occur.

Therefore, there is an urgent need for a film preparation method that can achieve thinning without damaging a polyimide film or a protective film while maintaining the barrier ratio and mechanical properties of a conventional black polyimide film, and a film prepared by the method.

Disclosure of Invention

Technical problem to be solved by the invention

The invention aims to provide a preparation method of a polyamide-imide film and the polyamide-imide film prepared by the method.

According to an aspect of the present invention, the method for preparing the polyamideimide film comprises the steps of: a polyamideimide powder prepared by aqueous polymerization and carbon black are ground to prepare a coating composition, which is coated on a protective film and dried and cured to form a polyamideimide film. Therefore, a thinned polyamideimide film can be formed without requiring an imidization process at a high temperature and without lowering mechanical properties and a shielding rate.

According to another aspect of the present invention, since drying and curing are performed at a relatively low temperature, the protective film having a low glass transition temperature is not damaged, and a polyamideimide film having a small residual solvent content in the film can be manufactured, as compared to a manufacturing method including a solvent polymerization method using a conventional high-boiling organic solvent.

It is therefore a primary object of the present invention to provide embodiments thereof.

Means for solving the problems

The invention provides a preparation method of a polyamide-imide film, which comprises the following steps: a step (a) of placing a dispersion of at least one diamine monomer and at least one acid anhydride monomer dispersed in water in a pressure vessel, reacting at a temperature of 150 ℃ to 250 ℃ and a pressure of 5bar to 20bar, filtering and drying a product obtained by the reaction to obtain polyamideimide powder; step (b), putting the polyamide imide powder and the carbon black particles into an organic solvent, mixing and grinding to obtain a polyamide imide coating composition; a step (c) of flexibly coating the polyamideimide coating composition on a protective film; and a step (d) of drying and curing the coated coating composition at a temperature of 180 ℃ or less to form a polyamideimide film on the protective film, wherein the content of the carbon black particles is 5 to 20 parts by weight with respect to 100 parts by weight of the polyamideimide powder, and the thickness of the polyamideimide film is 10 μm or less.

In the present invention, the method for preparing a polyamideimide film comprises the steps of: a polyamideimide powder prepared by aqueous polymerization and carbon black were ground to prepare a coating composition, which was coated on a protective film and dried and cured to form a polyamideimide film, thereby finding that the polyamideimide film can be formed without lowering mechanical properties and a shielding rate.

Accordingly, details for achieving the above-described preparation method are described herein.

Before this, terms or words used herein and in the scope of the claimed invention should not be construed as being limited to general or dictionary meanings, but interpreted as meanings and concepts conforming to the technical spirit of the present invention on the basis of the principle that the inventor can appropriately define the concept of terms in order to explain his invention in the best way.

Therefore, the structure of the embodiment described herein is only one of the most preferable embodiments of the present invention and does not represent all the technical spirit of the present invention, and therefore, it should be understood that various equivalents and modifications capable of substituting them may exist at the time of the present application.

As used herein, the singular forms "a", "an" and "the" include plural forms unless the context clearly dictates otherwise. The terms "comprising," "including," or "having," and the like, as used herein, are intended to specify the presence of stated features, integers, steps, elements, or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, elements, or groups thereof.

In this context, "anhydride" is intended to include precursors or derivatives thereof, which may not technically be anhydrides, but which may also be reacted with diamines, which may then be converted to polyamideimides.

In this context, "diamine" is intended to include precursors or derivatives thereof, which may not technically be a diamine but which may also be reacted with an anhydride and which may then be converted to a polyamideimide.

When an amount, concentration, or other value or parameter is given herein as either a range, preferred range or an upper preferred value, and a lower preferred value, unless a range is specifically disclosed, it is to be understood that all ranges that can be formed from any upper limit or preferred value in any pair, and any lower limit or preferred value of a range, are specifically disclosed.

When a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

It is intended that the scope of the invention not be limited to the particular values mentioned in defining the range.

Method for producing polyamideimide film

The method for producing a polyamideimide film of the present invention is characterized by comprising: a step (a) of placing a dispersion of at least one diamine monomer and at least one acid anhydride monomer dispersed in water in a pressure vessel, reacting at a temperature of 150 ℃ to 250 ℃ and a pressure of 5bar to 20bar, filtering and drying a product obtained by the reaction to obtain polyamideimide powder; step (b), putting the polyamide imide powder and the carbon black particles into an organic solvent, mixing and grinding to obtain a polyamide imide coating composition; a step (c) of flexibly coating the polyamideimide coating composition on a protective film; and a step (d) of drying and curing the coated coating composition at a temperature of 180 ℃ or less to form a polyamideimide film on the protective film, wherein the content of the carbon black particles is 5 to 20 parts by weight with respect to 100 parts by weight of the polyamideimide powder, and the thickness of the polyamideimide film is 10 μm or less.

The polyamideimide film may have a light transmittance of 1.1% or less in a visible light range and a tensile strength of 9kg/cm³The above.

In the present invention, the protective film may have a polyamideimide thin film formed thereon, and may be a material capable of protecting the polyamideimide thin film included in a film used as a thin film flexible insulating material having, for example, an electromagnetic shielding film (EMI), a cover layer, etc. for preparing a flexible printed circuit board.

Specifically, the protective film is a material having a glass transition temperature of 100 ℃ to 140 ℃, for example, a Polyethylene terephthalate (PET) film, but is not limited thereto.

In addition, the thickness of the protective film may be 25 to 100 μm, preferably 30 to 50 μm, in terms of mechanical strength, workability, productivity, and the like.

On the other hand, as described above, when a conventional polyamide-amic acid Solution or polyamic acid Solution is polymerized in an organic solvent to prepare a film and the film is prepared by a Solution Casting (Solution Casting) method, the temperature for imidization is relatively high, and thus there is a problem in that the protective film is damaged during the formation of a polyamideimide film thereon.

In contrast, the production method according to the present invention can solve the problems as described above by including the steps of grinding the polyamideimide powder produced by aqueous polymerization and carbon black to prepare a coating composition, coating it on a protective film, and drying and curing to form a polyamideimide film.

That is, in the production method according to the present invention, instead of polymerizing a polyamide-amic acid solution in an organic solvent, by mixing and grinding carbon black and a low-boiling organic solvent after producing a polyamideimide powder by aqueous polymerization, a carbon black content capable of ensuring a desired degree of barrier properties can be contained in a film, and drying and curing can be performed at a relatively low temperature to prevent damage to a protective film due to high temperature.

On the other hand, in the step (b), the boiling point of the organic solvent may be in the range of 100 ℃ to 180 ℃.

The organic solvent having a boiling point satisfying the above range and capable of dissolving the polyamide imide powder may be, for example, one selected from dimethylformamide, dimethylacetamide, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether propionate, dipropylene glycol dimethyl ether, cyclohexanone, and Propylene Glycol Monomethyl Ether Acetate (PGMEA).

In the present invention, preferably, the organic solvent may be one selected from the group consisting of N, N '-Dimethylformamide (DMF) and N, N' -dimethylacetamide (DMAc).

Such an organic solvent has a boiling point similar to the glass transition temperature of the protective film, and therefore, the content of the residual solvent can be reduced without deformation of the protective film at the drying and curing temperature of the present invention.

That is, in the step (d), the residual solvent content in the polyamideimide film can be made 10% or less, more specifically, 5% or less, by drying and curing.

On the other hand, the thickness of the polyamideimide film may be 10 μm or less, and specifically, may be in the range of 1 μm to 5 μm. When the thickness of the polyamideimide film is less than the above range, the rigidity of the prepared polyamideimide film is lowered and a desired degree of light transmittance cannot be achieved.

On the other hand, if the thickness of the polyamideimide film is more than the above range, the object of thinning the insulating layer according to the thinning and simplification of the electronic component, which is sought by the present invention, cannot be achieved, which is not preferable.

The anhydride monomer may be any anhydride monomer derived from a carboxylic acid and having at least one anhydride group.

Specifically, the acid anhydride monomer includes, but is not limited to, maleic anhydride, phthalic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, methyl naphthoate anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, tetrahydrotrimellitic anhydride, hexahydrotrimellitic anhydride, dodecylsuccinic anhydride, and mixtures thereof, but is not limited thereto.

In the present invention, particularly preferably, the acid anhydride usable as the acid anhydride monomer may be trimellitic anhydride (TMA), and a mixture of two or more acid anhydride monomers containing the same may be used.

The diamine monomer is an aromatic diamine and can be classified as follows.

1) Diamines having a structurally one benzene ring, diamines having a relatively rigid structure, for example, 1, 4-diaminobenzene (or p-phenylenediamine, PDA), 1, 3-diaminobenzene, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 3, 5-diaminobenzoic acid (or DABA);

2) diamines having two benzene rings in the structure, for example, diaminodiphenyl ethers such as 4,4 '-diaminodiphenyl ether (or oxydianiline, ODA), 3,4' -diaminodiphenyl ether and the like, 4 '-diaminodiphenylmethane (methylenediamine), 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 3' -dicarboxyl-4, 4 '-diaminodiphenylmethane, 3',5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane, mixtures thereof, and the like, Bis (4-aminophenyl) sulfide, 4 '-diaminobenzanilide, 3' -dichlorobenzidine, 3 '-dimethylbenzidine (or o-toluidine), 2' -dimethylbenzidine (or m-toluidine), 3 '-dimethoxybenzidine, 2' -dimethoxybenzidine, 3 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl sulfide, 3,4 '-diaminodiphenyl sulfide, 4' -diaminodiphenyl sulfide, 3 '-diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfone, 3' -diaminobenzophenone, 3 '-diaminodiphenyl ketone, 3' -diaminodiphenyl ketone, and mixtures thereof, 4,4 '-diaminobenzophenone, 3,3' -diamino-4, 4 '-dichlorobenzophenone, 3,3' -diamino-4, 4 '-dimethoxybenzophenone, 3,3' -diaminodiphenylmethane, 3,4 '-diaminodiphenylmethane, 4' -diaminodiphenylmethane, 2-bis (3-aminophenyl) propane, 2-bis (4-aminophenyl) propane, 2-bis (3-aminophenyl) -1,1,1,1,3,3, 3-hexafluoropropane, 2-bis (4-aminophenyl) -1,1,1,3,3, 3-hexafluoropropane, 3,3 '-diaminodiphenyl sulfoxide, 3,4' -diaminodiphenyl sulfoxide, sodium chloride, 4,4' -diaminodiphenyl sulfoxide, etc.;

3) diamines having three benzene rings in the structure, for example, 1, 3-bis (3-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 1, 4-bis (3-aminophenyl) benzene, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene (or TPE-Q), 1, 4-bis (4-aminophenoxy) benzene (or TPE-Q), 1, 3-bis (3-aminophenoxy) -4-trifluoromethylbenzene, 3' -diamino-4- (4-phenyl) phenoxybenzophenone, 3' -diamino-4, 4' -bis (4-phenylphenoxy) benzophenone, 1, 3-bis (3-aminophenyl sulfide) benzene, 1, 3-bis (4-aminophenyl sulfide) benzene, 1, 4-bis (4-aminophenyl sulfide) benzene, 1, 3-bis (3-aminophenyl sulfone) benzene, 1, 3-bis (4-aminophenyl sulfone) benzene, 1, 4-bis (4-aminophenyl sulfone) benzene, 1, 3-bis [2- (4-aminophenyl) isopropyl ] benzene, 1, 4-bis [2- (3-aminophenyl) isopropyl ] benzene, 1, 4-bis [2- (4-aminophenyl) isopropyl ] benzene, etc.;

4) diamines having four benzene rings in the structure, for example, 3,3 '-bis (3-aminophenoxy) biphenyl, 3,3' -bis (4-aminophenoxy) biphenyl, 4 '-bis (3-aminophenoxy) biphenyl, 4' -bis (4-aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl ] ether, bis [3- (4-aminophenoxy) phenyl ] ether, bis [4- (3-aminophenoxy) phenyl ] ether, bis (4- (4-aminophenoxy) phenyl) ether, bis (3- (3-aminophenoxy) phenyl) ketone, bis (3- (4-aminophenoxy) phenyl ] ketone, bis [4- (3-aminophenoxy) phenyl ] ketone, bis (4-aminophenoxy) phenyl) ketone, bis (4-aminophenoxy) phenyl ] ketone, bis (4, Bis [4- (4-aminophenoxy) phenyl ] ketone, bis [3- (3-aminophenoxy) phenyl ] sulfide, bis [3- (4-aminophenoxy) phenyl ] sulfide, bis [4- (3-aminophenoxy) phenyl ] sulfide, bis [4- (4-aminophenoxy) phenyl ] sulfide, bis [3- (3-aminophenoxy) phenyl ] sulfone, bis (3- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl ] sulfone, bis [3- (3-aminophenoxy) phenyl ] methane, bis [3- (4-aminophenoxy) phenyl ] methane, bis [4- (3-aminophenoxy) phenyl ] methanephosphine bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] methane Oxy) phenyl ] methane, 2-bis [3- (3-aminophenoxy) phenyl ] propane, 2-bis [3- (4-aminophenoxy) phenyl ] propane, 2-bis (4- (3-aminophenoxy) phenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane (BAPP), 2-bis [3- (3-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane, 2-bis [3- (4-aminophenoxy silicon) phenyl ] -1,1,1,3,3, 3-hexafluoropropane, 2-bis (4- (3-aminophenoxy) phenyl) -1,1,1,3,3, 3-hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane and the like. May be used alone or in combination of two or more thereof as required.

In the present invention, particularly preferably, the diamine that may be used as the diamine monomer may be at least one selected from the group consisting of Oxydianiline (ODA), Methylenedianiline (MDA), and p-phenylenediamine (PPD).

On the other hand, as described above, the content of the carbon black particles is 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the polyamideimide powder. In addition, it is preferable that the average particle diameter of the carbon black particles contained in the coating composition is in the range of 0.1 μm to 1 μm.

When the content or average particle diameter of the carbon black particles is less than the range, it is difficult to ensure a desired degree of shielding property because light transmittance increases.

In contrast, when the carbon black particle content or the average particle diameter is larger than the range, the degree of dispersion is reduced when mixed with an organic solvent during the production process, and carbon black protrudes from the surface of the film to cause poor appearance, mechanical properties may be reduced, for example, since the tensile strength of the film may be reduced, and thus it is not preferable.

On the other hand, as described above, it is preferable that the reaction in the step (a) is performed at a temperature of 150 ℃ to 250 ℃, in detail, at a temperature of 160 ℃ to 240 ℃.

When the reaction temperature is more than the range, the reactant of the diamine monomer or the acid anhydride monomer used may be coagulated or decomposed, and on the contrary, when the reaction temperature is less than the range, the reaction rate may be lowered and imidization may not be sufficiently performed, so that a polyamideimide powder cannot be practically produced.

In addition, in the process (a), the reaction may be carried out under pressure conditions ranging from 3bar to 200bar, preferably, from 5bar to 20bar for 4 hours to 2 days, more preferably, from 5 hours to 1 day.

When the pressure condition is more than the range, the reaction vessel may be damaged in use for pressurization, and on the contrary, when the pressurization condition is less than the range, the reaction itself does not proceed, and thus it is not preferable.

In addition, when the reaction time is more than the range, the produced polymer resin may be hydrolyzed, and when the reaction time is less than the range, the reaction itself does not proceed, and thus is not preferable.

In the present invention, the pressurizing method is not particularly limited, and for example, a method of forming a water vapor pressure in a pressure vessel or injecting an inert gas into a pressure vessel, or a method of compressing a pressure vessel may be used, and the pressurizing method may be selected from one or more methods.

On the other hand, in the "coating composition preparation step", a filler may be added in order to improve various properties of the film or film, such as slidability, thermal conductivity, electrical conductivity, corona resistance, circuit hardness, and the like. The filler to be added is not particularly limited, but preferable examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like.

The particle size of the filler is not particularly limited and may be determined according to the characteristics of the film or membrane to be modified and the kind of the filler to be added. In general, the average particle diameter is from 0.05 μm to 10 μm, preferably from 0.1 μm to 5 μm, more preferably from 0.1 μm to 3 μm, and particularly preferably from 0.1 μm to 2 μm.

When the particle diameter is less than this range, it is difficult to exhibit the modifying effect, and when the particle diameter is more than this range, there is a possibility that the surface characteristics are impaired or the mechanical properties are greatly lowered.

The amount of the filler to be added is not particularly limited, and may be determined according to the properties of the film or membrane to be modified, the particle diameter of the filler, and the like. In general, the filler is added in an amount of 0.01 to 20 parts by weight, preferably 0.01 to 10 parts by weight, and more preferably 0.02 to 3 parts by weight, relative to 100 parts by weight of the polyamideimide powder.

When the amount of the filler added is less than this range, the modifying effect by the filler is hardly exhibited, and when the particle diameter is more than this range, there is a possibility that the mechanical properties of the film or film are largely deteriorated. The method of adding the seasoning is not particularly limited, and any known method may be used.

Polyamide-imide film

The present invention also provides a polyamideimide film prepared by the preparation method, which includes a polyamideimide thin film formed on a protective film.

As described above, with the polyamideimide film according to the present invention, the thickness of the polyamideimide film may be 10 μm or less, the light transmittance of the polyamideimide film in the visible light region may be 1.1% or less, and the tensile strength may be 9kg/cm³The above.

Therefore, when the polyamideimide film is applied to a cover layer, an insulating film, a semiconductor, or the like, the product is made thinner, the product can be improved in aesthetic property, and the internal shape and a charging member can be blocked from the external view, thereby being useful in safety.

The present invention may also provide a cover layer (cover) including the polyamideimide film, and may provide an electronic device including the cover layer.

For reference, the polyamideimide film of the present invention includes a protective film and a polyamideimide thin film, and thus, when a cover layer is prepared using the polyamideimide film, the protective film may be removed.

Detailed Description

Hereinafter, the operation and effect of the present invention will be described in more detail by way of specific examples of the invention. However, these embodiments are merely presented as examples of the present invention, and the scope of the invention claimed by the present invention is not determined thereby.

Preparation examples 1 to 1: preparation of polyamideimide powder by aqueous polymerization

22.34g of TMA as an acid anhydride monomer and 23.17g of ODA as a diamine monomer were dispersed in 200mL of distilled water. The dispersion was transferred to a 500ml pressure vessel having a stirrer and a temperature controller, the temperature was adjusted to 185 ℃, and then stirred under a pressure of 10bar for 10 hours, to prepare a polyamideimide powder.

Preparation examples 1 to 2: preparation of polyamideimide powder by aqueous polymerization

22.34g TMA as anhydride monomer and 23.06g MDA as diamine monomer were dispersed in 200mL distilled water. The dispersion was transferred to a 500ml pressure vessel having a stirrer and a temperature controller, the temperature was adjusted to 200 ℃, and then stirred under a pressure of 15bar for 8 hours to prepare a polyamideimide powder.

Comparative preparation example 1-1: preparation of polyamic acid solution by solution polymerization

After 200g of NMP was placed in a 500ml reactor equipped with a stirrer and a nitrogen gas injection/discharge tube and the temperature of the reactor was set to 30 ℃, 19.71g of TMA as an acid anhydride monomer and 25.68g of MDI as a diamine monomer were charged into the reactor and complete dissolution was confirmed. Subsequently, the temperature was raised to 90 ℃ under a nitrogen atmosphere, and while heating, 120 minutes of stirring was carried out, and then the temperature was raised to 160 ℃ to carry out further reaction and imidization. When the bubbles in the solution were reduced, the solution was cooled to prepare a polyamide-amic acid solution.

Comparative preparation examples 1 to 2: preparation of polyamic acid solution by solution polymerization

While injecting nitrogen, 200g of DMF was charged into a 500ml reactor having a stirrer and a nitrogen injection/discharge pipe, the temperature of the reactor was set to 20 ℃, 21.73g of ODA was charged into the reactor as a diamine monomer, after dissolution, 23.64g of PMDA as a dianhydride monomer was added, and stirring was performed for 120 minutes under a nitrogen atmosphere, to prepare a polyamic acid solution.

Preparation example 2-1: preparation of Polyamide-imide coating compositions

After 10g of the polyamideimide powder prepared in the preparation example 1 and 0.8g of carbon black were added to 90g of DMF as an organic solvent and mixed, a coating composition having an average particle diameter of 0.5 μm and containing 8 parts by weight of carbon black particles per 100 parts by weight of the polyamideimide powder was prepared using a grinder.

Preparation examples 2 to 2: preparation of Polyamide-imide coating compositions

A polyamideimide coating composition was prepared in the same manner as in preparation example 2-1, except that 1g of carbon black was added so that 10 parts by weight of carbon black particles were contained with respect to 100 parts by weight of polyamideimide powder.

Preparation examples 2 to 3: preparation of Polyamide-imide coating compositions

A polyamideimide coating composition was prepared in the same manner as in preparation example 2-1, except that 1.5g of carbon black was added so that 15 parts by weight of carbon black particles were contained with respect to 100 parts by weight of polyamideimide powder.

Preparation examples 2 to 4: preparation of Polyamide-imide coating compositions

A polyamideimide coating composition was prepared using the same preparation method as in preparation example 2-1, except that DMAc was used instead of DMF as an organic solvent, as shown in table 1 below.

Preparation examples 2 to 5: preparation of Polyamide-imide coating compositions

A polyamideimide coating composition was prepared using the same preparation method as in preparation example 2-1, except that the polyamideimide powder of preparation example 1-2 was used.

Comparative preparation example 2-1: preparation of Polyamide-imide coating compositions

After 0.74g of carbon black was added to 50g of the polyamidoamide acid solution prepared in the comparative preparation example 1-1 to perform mixing, a coating composition having an average particle diameter of 0.5 μm and containing 8 parts by weight of carbon black particles per 100 parts by weight of the polyamidoamide acid resin was prepared using a grinder.

Comparative preparation example 2-2: preparation of polyimide precursor composition

After 50g of the polyamide-amic acid solution prepared in comparative preparation example 1-2 and 0.74g of carbon black were added to mix, a precursor composition having an average particle size of 0.5 μm and containing 8 parts by weight of carbon black particles per 100 parts by weight of the polyamic acid resin was prepared using a grinder.

Comparative preparation examples 2 to 3: preparation of Polyamide-imide coating compositions

A polyamideimide coating composition was prepared using the same preparation method as in preparation example 2-1, except that 3g of carbon black was added so that 30 parts by weight of carbon black particles were contained with respect to 100 parts by weight of polyamideimide powder.

Comparative preparation examples 2 to 4: preparation of Polyamide-imide coating compositions

A polyamideimide coating composition was prepared using the same preparation method as in preparation example 2-1, except that NMP was used instead of DMF as an organic solvent, as shown in table 1 below.

Example 1

The polyamideimide coating composition prepared in the preparation example 2-1 was flexibly coated at a thickness of 5 d on a protective film (PET film) having a surface pad shape and a thickness of 50 d, and dried and cured at a temperature of 150 c to prepare a polyamideimide film having a polyamideimide thin film having a thickness of 5 d formed on the protective film. The thickness of the prepared polyamideimide Film was measured using an Electric Film thickness meter (Electric Film thickness tester) available from Riben-Aishi (Anritsu) Co.

Example 2

A polyamideimide film was prepared using the same preparation method as example 1, except that the polyamideimide coating composition prepared in the preparation examples 2-2 was used.

Example 3

A polyamideimide film was prepared using the same preparation method as example 1, except that the polyamideimide coating compositions prepared in the preparation examples 2 to 3 were used.

Example 4

A polyamideimide film was prepared using the same preparation method as example 1, except that the polyamideimide coating compositions prepared in the preparation examples 2 to 4 were used.

Example 5

A polyamideimide film was prepared using the same preparation method as example 1, except that the polyamideimide coating compositions prepared in the preparation examples 2 to 5 were used.

Example 6

As shown in table 1 below, a polyamideimide film was prepared using the same preparation method as example 1, except that the temperature for drying and curing was changed to 130 ℃.

Example 7

As shown in table 1 below, a polyamideimide film was prepared using the same preparation method as example 1, except that the temperature for drying and curing was changed to 180 ℃.

Comparative example 1

A polyamideimide film was prepared using the same preparation method as example 1, except that the polyamideimide coating composition prepared in the comparative preparation example 2-1 was used.

Comparative example 2

Bubbles were removed from the polyimide precursor composition prepared in the comparative preparation example 2-2 by high-speed rotation at 1500rpm or more. Then, the degassed polyimide precursor composition was coated on a glass substrate using a spin coater. Thereafter, the film was dried at a temperature of 120 ℃ for 30 minutes under a nitrogen atmosphere to prepare a gel film, the gel film was heated to 450 ℃ at a rate of 2 ℃/minute, and heat-treated at 450 ℃ for 60 minutes, and then cooled to 30 ℃ at a rate of 2 ℃/minute, thereby obtaining a polyimide film. Thereafter, the polyimide film was peeled off from the glass substrate by immersion (tapping) in distilled water. The polyimide film was adhered to a protective film (PET film) having a surface pad shape and a thickness of 50 μm, thereby preparing a polyimide film having a thickness of 5 μm formed on the protective film.

Comparative example 3

A polyamideimide film was prepared using the same preparation method as example 1, except that the polyamideimide coating compositions prepared in the comparative preparation examples 2 to 3 were used.

Comparative example 4

A polyamideimide film was prepared using the same preparation method as example 1, except that the polyamideimide coating compositions prepared in the comparative preparation examples 2 to 4 were used.

Comparative example 5

As shown in table 1 below, a polyamideimide film was prepared using the same preparation method as example 1, except that the temperature for drying and curing was changed to 200 ℃.

Comparative example 6

A polyamideimide film was prepared using the same preparation method as example 1, except that the polyamideimide coating compositions prepared in the comparative preparation examples 2 to 4 were used and the drying and curing temperature was changed to 200 c as shown in the following table 1.

TABLE 1

Experimental example 1: evaluation of light transmittance

The polyamideimide films or polyimide films respectively prepared in examples 1 to 7 and comparative examples 1 to 6 were cut into 50mm × 50mm to prepare test pieces. Subsequently, with respect to the film obtained by peeling the polyamideimide film or the polyimide film from the protective film, the light transmittance in the visible light region was measured by the ASTM D1003 method of the American society for materials and tests using a light transmittance measuring instrument (model: ColorQuesetXE, manufactured by Hunter Lab, Inc., USA), and the test results thereof are shown in FIG. 2 below.

TABLE 2

Experimental example 2: evaluation of tensile Strength

Test pieces were prepared by cutting the polyamideimide films or polyimide films prepared in examples 1 to 7 and comparative examples 1 to 6, respectively, into 50mm × 50 mm. Subsequently, as for a film obtained by peeling a polyamide imide film or a polyimide film from a protective film, tensile strength was measured by a method proposed in KS6518 of korean industrial standards, and the experimental results thereof are shown in fig. 3 below.

TABLE 3

Experimental example 3: evaluation of residual solvent

With respect to the polyamideimide films or polyimide films respectively prepared in examples 1 to 7 and comparative examples 1 to 6, residual solvent contents were measured with respect to films obtained by peeling the polyamideimide films or polyimide films from the protective films, and the experimental results thereof are shown in table 4 below.

Specifically, about 10mg of a sample was collected by a TGA apparatus for measuring the solvent remaining in the film, and the sample was heated from room temperature to 100 ℃ at a rate of 20 degrees/minute for 1 minute, and then heated to 200 ℃ for 30 minutes. After 1 minute at 100 ℃, the weight change was recorded.

TABLE 4

	Residual solvent content (%)
		Example 1	5
Example 2	4
		Example 3	3
Example 4	7
		Example 5	5
Example 6	9
		Example 7	1
Comparative example 1	15
		Comparative example 2	17
Comparative example 3	2
		Comparative example 4	15
Comparative example 5	0.8
		Comparative example 6	2

First, referring to tables 2 and 3, it was confirmed that the polyamide-imide films of examples 1 to 7 satisfy the requirements of light transmittance of 1.1% or less in the visible light region and tensile strength of 9kg/cm³The above.

On the contrary, in the case of the polyamideimide film of comparative example 1 prepared by solution polymerization, the polyimide film of comparative example 2 prepared by polyamic acid solution, and the polyamideimide film of comparative example 4 using NMP as an organic solvent, it was confirmed that the light transmittance in the visible light region was not superior to that of the examples.

In addition, in the case of the polyamideimide film of comparative example 3 in which the content of carbon black is greater than the range of the present invention, the light transmittance in the visible light region is 0.3% or less, which is an excellent level, but the tensile strength is low as compared with the examples, and the tensile strength of the polyamideimide film or polyimide film of comparative examples 1, 2 and 4 is also not superior to the examples.

On the other hand, referring to fig. 4, in the case of the polyamideimide films of examples 1 to 7, the residual solvent content was 9% or less, which is a very excellent level, but the residual solvent content of comparative examples 1, 2 and 4 was 15% or more. For reference, in the case of comparative examples 5 and 6 in which the temperature of drying and curing was 200 ℃, although the content of the residual solvent was 2% or less, which is an excellent level, no excellent product was prepared because wrinkles were generated on the finally prepared polyamideimide film due to the deformation of the protective film, and thus the light transmittance and the tensile strength could not be measured.

While the present invention has been described with reference to the embodiments, those skilled in the art can make various applications and modifications based on the above description without departing from the scope of the present invention.

Industrial availability

The production method according to the present invention includes the steps of producing a polyamideimide powder by aqueous-based polymerization instead of solution polymerization and grinding the polyamideimide powder with carbon black to produce a coating composition, so that it is possible to achieve thinning while exhibiting a desired level of low shielding rate.

In addition, in the preparation method according to the present invention, the coating composition is dried and cured at a temperature of 180 ℃ or less using a low-boiling organic solvent, and thus deterioration of mechanical properties of the polyamideimide thin film due to a high residual solvent content can be prevented without damaging the protective film.

Therefore, preferably, the polyimide film according to the present invention can be used as a cover sheet for portable electronic devices and communication devices.