KR20200038156A - Manufacturing Method of Polyamideimide Film and Polyamideimide Film Manufactured Thereby - Google Patents

Abstract

The present invention provides a method of preparing a polyamide-imide film, comprising the steps of: (a) placing, in a pressure vessel, a dispersion solution obtained by dispersing at least one diamine monomer and at least one anhydride monomer in water and inducing a reaction therein at 5-400°C under a pressure, and filtering and drying the reaction product obtained from the reaction, to obtain polyamide-imide particles; (b) mixing the polyamide-imide particles and carbon black particles in an organic solvent and milling the mixture to obtain a polyamide-imide coating composition; (c) cast-coating the polyamide-imide coating composition onto a protection film; and (d) drying and curing the coated coating composition at a temperature of 180°C or less, thereby forming a polyamide-imide thin film on the protection film, wherein the carbon black particle content is 5-20 parts by weight with respect to 100 parts by weight of the polyamide-imide particles, and the polyamide-imide thin film has a thickness of 10 μm or less.

Description

Manufacturing method of polyamideimide film and polyamideimide film produced therefrom {Manufacturing Method of Polyamideimide Film and Polyamideimide Film Manufactured Thereby}

The present invention relates to a method for producing a polyamideimide film and a polyamideimide film produced therefrom.

In general, polyimide (PI) resin refers to a high heat-resistant resin produced by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to produce a polyamic acid derivative, followed by dehydration at high temperature by dehydration.

These polyimides have excellent properties such as high heat resistance, electrical insulation, radiation resistance, and chemical resistance to withstand high temperatures of 400 ° C or higher, and high-tech materials and insulation coatings in the fields of electric and electronic, semiconductor, display, automotive, aerospace, and space materials Used for etc.

However, the polyimide itself is insoluble in solvents, and there are certain limitations to its use in a wide range of fields, such as difficulties in warm forming.

Accordingly, most of the polyimide is produced by processing and high temperature heat treatment of a precursor polyamic acid, followed by a curing imidization process, and a representative product produced in this way is a polyimide film.

These polyimide films are widely used as barrier films to protect flexible circuit boards, electronic components, and lead frames of integrated circuit packages, and in particular, with the thinning of the insulating layer due to the thinning of electronic components, Due to the demands for security, shielding, shading, and visual effects, the demand for using black polyimide film as a coverlay is rapidly increasing.

Conventional black polyimide films generally polymerize a polyamic acid solution from dianhydride and diamine, and quench particles such as carbon black and silica or TiO ₂ in the prepared polyamic acid solution, and anhydride and tertiary amines for imidization. It is produced by the solution casting method to form a film by mixing as a catalyst. Specifically, the polyamic acid solution mixed with the catalyst is applied to a support (endless belt), dried in a constant temperature range, and a self-supporting gel film in a semi-dry state is peeled from the support to obtain a high temperature, dry oven. After transferring to a high-temperature imidization process to prepare a black polyimide film.

However, in such a manufacturing method, since the difference in specific gravity between the matting particles to be mixed and the polyamic acid is large, the mechanical properties of the black polyimide film produced by sedimentation or aggregation of the matting particles during the imidization process after applying the polyamic acid, There was a problem in that the electrical properties were deteriorated, and in order to solve this, when reducing the amount of matting particles added, a desired level of shielding was not realized.

In particular, in the case of manufacturing a black polyimide thin film having a thickness of 10 µm or less on a protective film, there is a problem in that commercial production is impossible, such as the degree of deterioration in physical properties of the film depending on the matting particles to be added, resulting in fracture.

On the other hand, in the case of a black polyimide thin film having a thickness of 10 μm or less as described above, it may be manufactured by attaching a protective film to one side or both sides during production in order to protect the outer surface of the film, and the addition of such a process decreases productivity, In the process of attaching the protective film, there was a problem that wrinkles or damage occurred in the polyimide thin film.

In order to solve the above problems, in some prior arts, a polyimide thin film is produced by coating a polyimide thin film on a protective film by imidizing it after coating a polyamic acid on a protective film, or preparing a polyimide powder. Then, a method of manufacturing a coating composition in which a polyimide thin film is coated on a protective film has been attempted by preparing a coating composition dissolved in an organic solvent, applying it on a protective film, drying and curing it.

However, since the protective film used to manufacture the film of such a thin film is mainly used for a material having a glass transition temperature of 150 ° C., there is a limit to performing a high temperature imidization process in the case of a method using polyamic acid. have.

In addition, in the case of a method of coating a coating composition on which a polyimide powder is dissolved on a protective film, there is a problem that deformation occurs in the protective film even at a temperature for drying and curing. Conversely, when drying and lowering the temperature to prevent deformation in the protective film, a polar organic solvent (boiling point of 200 ° C. or higher), which is mainly used in this method, may remain in the film, thereby deteriorating mechanical properties and the like.

Therefore, it is possible to thin the film while maintaining the shielding rate and mechanical properties of the conventional black polyimide film, and there is a high need for a method for producing a film without damage to the polyimide thin film or a protective film and a film produced therefrom. This is true.

An object of the present invention is to provide a method for producing a polyamideimide film and a polyamideimide film prepared therefrom.

According to an aspect of the present invention, in a method for producing a polyamideimide film, a polyamideimide powder and carbon black produced through water-based polymerization are milled to prepare a coating composition, which is coated on a protective film, dried, and cured to produce poly By including the step of forming an amidimide thin film, a high temperature imidization process is not required, and a thin polyamideimide thin film can be formed without deteriorating mechanical properties and shielding rate.

According to another aspect of the present invention, drying and curing proceed at a relatively low temperature, so that there is no damage to the protective film having a low glass transition temperature, and a manufacturing method including a solvent polymerization method using a conventional high boiling point organic solvent Compared, a polyamideimide film having less residual solvent content in the film can be produced.

Accordingly, the present invention has a practical purpose to provide a specific embodiment thereof.

The present invention is obtained by reacting (a) at least one diamine monomer and at least one anhydride monomer dispersed in water in a pressure vessel and reacting at a temperature of 150 to 250 ° C and a pressurized condition of 5 to 20 bar. Filtering and drying the reaction product to obtain a polyamideimide powder;

(b) mixing the polyamideimide powder and carbon black particles in an organic solvent and milling to obtain a polyamideimide coating composition;

(c) flexible coating the polyamideimide coating composition on a protective film; And

(d) drying and curing the applied coating composition at a temperature of 180 ° C. 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 compared to 100 parts by weight of the polyamideimide powder,

Provided is a method for producing a polyamideimide film, wherein the thickness of the polyamideimide thin film is 10 μm or less.

In the present invention, a polyamideimide film is prepared by milling a polyamideimide powder and carbon black produced through water-based polymerization in a method for producing a polyamideimide film, and coated, dried and cured on a protective film to form a polyamideimide thin film. By including the steps, it was found that a polyamideimide thin film can be formed without deteriorating mechanical properties and shielding rate.

Therefore, specific details for its implementation will be described herein.

Prior to this, the terms or words used in the present specification and claims should not be construed as being limited to ordinary or lexical meanings, and the inventor appropriately explains the concept of terms to explain his or her invention in the best way. Based on the principle that it can be defined, it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.

Therefore, the configuration of the embodiments described herein is only one of the most preferred embodiments of the present invention and does not represent all of the technical spirit of the present invention, and various equivalents and modifications that can replace them at the time of this application It should be understood that examples may exist.

In the present specification, a singular expression includes a plural expression unless the context clearly indicates otherwise. In this specification, the terms "include", "have" or "have" are intended to indicate the presence of implemented features, numbers, steps, elements or combinations thereof, one or more other features or It should be understood that the existence or addition possibilities of numbers, steps, elements, or combinations thereof are not excluded in advance.

As used herein, “anhydride” is intended to include its precursors or derivatives, which may not technically be anhydrides, but can nevertheless react with diamines, after which the polyamide is Can be converted to mid.

“Diamine” as used herein is intended to include precursors or derivatives thereof, which may not technically be diamines, but can nevertheless react with anhydrides and then be converted to polyamideimides.

Where an amount, concentration, or other value or parameter herein is given as an enumeration of a range, a preferred range, or a preferred upper and lower limits, any upper limit of any pair of any pair, regardless of whether the ranges are disclosed separately or It should be understood to specifically disclose all ranges formed of preferred values and any lower range limits or desirable values.

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

It is intended that the scope of the invention not be limited to the specific values recited when defining a range.

<Method for producing polyamideimide film>

In the polyamideimide film production method according to the present invention, (a) a dispersion in which one or more diamine monomers and one or more anhydride monomers are dispersed in water is placed in a pressure vessel, and a temperature of 150 to 250 ° C. and a temperature of 5 to 20 filtering and drying the reaction product obtained by reacting under the pressure of bar to obtain a polyamideimide powder;

(b) mixing the polyamideimide powder and carbon black particles in an organic solvent and milling to obtain a polyamideimide coating composition;

(c) flexible coating the polyamideimide coating composition on a protective film; And

(d) drying and curing the applied coating composition at a temperature of 180 ° C. 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 compared to 100 parts by weight of the polyamideimide powder,

The thickness of the polyamideimide thin film is 10 μm or less.

In addition, the polyamideimide thin film has a light transmittance of 1.1% or less in the visible light region and a tensile strength of 9 kg / cm ³ or more. Can be

In the present invention, a polyamideimide thin film may be formed as a protective film, and a polyamideimide thin film included in a film used as a thin film flexible insulating material such as an electromagnetic wave shielding film (EMI) for manufacturing a flexible printed circuit board and a coverlay may be protected. It can be a material that can be done.

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

In addition, the thickness of the protective film may be usually 25 to 100 μm in terms of mechanical strength, handling properties, productivity, etc., and specifically 30 to 50 μm is preferable.

On the other hand, as described above, the conventional polyamide amic acid solution or polyamic acid solution is prepared by polymerizing in an organic solvent, and in the case of a method of filming it by a solution casting method, the temperature for imidation is relatively high. , In the process of forming the polyamideimide thin film on the protective film, a problem that the protective film is damaged may occur.

On the other hand, in the manufacturing method according to the present invention, a polyamideimide powder and carbon black prepared through water-based polymerization are milled to prepare a coating composition, which is coated on a protective film, dried and cured to form a polyamideimide thin film. By including steps, the above problems can be solved.

That is, the manufacturing method according to the present invention, instead of polymerizing the polyamide amic acid solution in an organic solvent, after preparing the polyamide imide powder by water-based polymerization and mixing and milling in a carbon black and a low boiling point organic solvent, desired degree The carbon black content that can secure the shielding properties of the film may be included in the thin film, and drying and curing may be performed at a relatively low temperature to prevent damage to the protective film due to high temperature.

Meanwhile, in the step (b), the organic solvent may have a boiling point in the range of 100 to 180 ° C.

Such an organic solvent is an organic solvent having a boiling point that satisfies the above range and can be dissolved by a polyamideimide powder, for example, dimethylformamide, dimethylacetamide, diethylene glycol methylethyl ether, diethylene glycol dimethyl ether, diethylene Glycol diethyl ether, dipropylene glycol dimethyl ether, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, propylene glycol methyl ether propionate, dipropyrene glycol dimethyl ether, cyclohexanone and propylene glycol It may be one selected from monomethyl ether acetate (PGMEA).

The organic solvent that can be particularly preferably used as the organic solvent in the present invention may be one selected from N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc).

Since the organic solvent has a boiling point similar to that of the glass transition temperature of the protective film, it is possible to lower the content of the residual solvent without deformation of the protective film even at the drying and curing temperatures of the present invention.

That is, drying and curing in step (d) may be performed such that the residual solvent content in the polyamideimide thin film is 10% or less, and more specifically 5% or less.

Meanwhile, the thickness of the polyamideimide thin film may be 10 μm or less, and in detail, may range from 1 to 5 μm. When the thickness of the polyamideimide thin film is less than the above range, the stiffness of the polyamideimide thin film to be produced decreases, and light transmittance below a desired degree cannot be achieved, which is not preferable.

On the other hand, when the thickness of the polyamideimide thin film exceeds the above range, it is not preferable because the object of the present invention, which aims to thin the insulating layer due to the light and small size of the electronic component, cannot be achieved.

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

Specifically, the anhydride monomers include maleic anhydride, phthalic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, methyl dianhydride, methyl hexahydrophthalic acid Anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, tetrahydrotrimellitic anhydride, hexahydro trimellitic anhydride , Dodecenyl succinic anhydride and mixtures thereof.

An anhydride that can be particularly preferably used as the anhydride monomer in the present invention may be trimellitic anhydride (TMA), and a mixture of two or more anhydride monomers including the same may be used.

The said diamine monomer is an aromatic diamine, and is classified, for example, as follows.

1) 1,4-diaminobenzene (or paraphenylenediamine, PDA), 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzo Diamines having one benzene ring in the structure, such as diacid (or DABA), etc., which have a relatively rigid structure in diamine;

2) Diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether (or oxidianiline, ODA), 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenylmethane (Methylenediamine), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl ) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane , 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis (4-aminophenyl) sulfide, 4,4'-diaminobenzanilide, 3,3' -Dichlorobenzidine, 3,3'-dimethylbenzidine (or o-tolidine), 2,2'-dimethylbenzidine (or m-tolidine), 3,3'-dimethoxybenzidine, 2,2'-dimethoxy Benzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfide, 3,4 ' -Diaminodiphenylsulfide, 4,4'-diami Diphenylsulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4 '-Diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodi Phenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4- Aminophenyl) propane, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1, 1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylsulfoxide, 3,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide Diamine having two benzene rings in structure, such as a side;

3) 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-amino Phenyl) 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, 3,3'-diamino-4- (4-phenyl) phenoxybenzophenone, 3 , 3'-diamino-4,4'-di (4-phenylphenoxy) benzophenone, 1,3-bis (3-aminophenylsulfide) benzene, 1,3-bis (4-aminophenylsulfide) Benzene, 1,4-bis (4-aminophenylsulfide) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis ( 4-aminophenylsulfone) 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. Diamine;

4) 3,3'-bis (3-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-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 Si) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ketone, 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-ami) Phenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) Phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 2,2-bis [3- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- ( 4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4 -Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1, 3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, etc., A diamine having four benzene rings in structure. These can be used alone or in combination of two or more as desired.

The diamine that can be particularly preferably used as the diamine monomer in the present invention may be one or more selected from the group consisting of oxydianiline (ODA), methylenedianiline (MDA) and paraphenylenediamine (PPD).

On the other hand, as described above, the content of the carbon black particles may be 5 to 20 parts by weight compared to 100 parts by weight of the polyamideimide powder. In addition, the carbon black particles contained in the coating composition preferably has an average particle diameter in the range of 0.1 to 1 μm.

When the content of the carbon black particles or the average particle diameter is less than the above range, it is not preferable because the light transmittance becomes high and it is difficult to secure a desired degree of shielding property.

Conversely, when the content or average particle diameter of the carbon black particles exceeds the above range, the dispersion degree is lowered when mixing with an organic solvent in the manufacturing process, and the carbon black protrudes from the surface of the thin film, which may cause poor appearance and mechanical It is not preferable because the physical properties may decrease, for example, the tensile strength of the thin film.

On the other hand, as described above, in the process (a), the reaction is preferably performed at a temperature of 150 ° C to 250 ° C, and in detail, it is preferably 160 to 240 ° C.

When the reaction temperature exceeds the above range, the reactants of the diamine monomer or anhydride monomer used may aggregate or decompose, and, conversely, when the reaction temperature is below the above range, the reaction rate is lowered and sufficient It is virtually impossible to produce the polyamideimide powder because dehydration does not proceed.

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

When the pressurization condition exceeds the above range, the reaction vessel may be damaged in the process for pressurization. Conversely, when the pressurization condition is below the above range, the reaction itself does not proceed, so it is not preferable.

In addition, when the reaction time exceeds the above range, a problem in that the polymer resin to be produced may be hydrolyzed, and when the reaction time is below the above range, the reaction itself does not proceed, which is not preferable.

In the present invention, the pressurization method is not particularly limited, for example, water vapor pressure is formed inside the pressure vessel, inert gas is injected into the pressure vessel, or one or more methods selected from the method of compressing the pressure vessel. Can be configured.

Meanwhile, a filler may be added to the "coating composition manufacturing process" for the purpose of improving various properties of a thin film or film such as sliding property, thermal conductivity, conductivity, corona resistance, and loop hardness. The filler to be added is not particularly limited, and preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.

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

When the particle diameter is less than this range, a modification effect is unlikely to appear, and if it exceeds this range, surface properties may be significantly impaired, or mechanical properties may be significantly deteriorated.

In addition, the addition amount of the filler is not particularly limited, and may be determined by thin film or film properties to be modified, particle size of the filler, and the like. Generally, the amount of the filler added is 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 based on 100 parts by weight of the polyamideimide powder.

If the amount of the filler added is less than this range, the modification effect by the filler is unlikely to appear, and if it exceeds this range, there is a possibility that the mechanical properties of the thin film or film are significantly impaired. The method for adding the filler is not particularly limited, and any known method can be used.

<Polyamideimide film>

The present invention is also a polyamideimide film produced by the above production method,

It is possible to provide a polyamideimide film comprising a polyamideimide thin film formed on a protective film.

As described above, in the polyamideimide film according to the present invention, the thickness of the polyamideimide thin film may be 10 μm or less, and the polyamideimide thin film has a light transmittance of 1.1% or less in the visible light region and a tensile strength of 9 kg / cm ^{3 or} more.

Therefore, when the polyamideimide film is applied to a coverlay, an insulating film, a semiconductor, etc., it can not only make the product slimmer, but also improve the aesthetic properties, and the internal shape and charging parts can be blocked from the external field of view. It is useful for security.

The present invention can also provide a coverlay comprising the polyamideimide film, and an electronic device including the coverlay.

For reference, the polyamideimide film of the present invention includes a protective film and a polyamideimide thin film. When the coverlay is prepared using the polyamideimide film, the protective film may be removed.

The manufacturing method according to the present invention comprises the steps of preparing a polyamideimide powder by aqueous polymerization rather than solution polymerization, and milling it with carbon black to prepare a coating composition, thereby exhibiting a desired low shielding rate and thinning. Can be implemented.

In addition, the manufacturing method according to the present invention uses a low-boiling point organic solvent to dry and cure the coating composition at a temperature of 180 ° C. or less, so that there is no damage to the protective film and deterioration of mechanical properties of the polyamideimide thin film due to high residual solvent content Can be prevented.

Accordingly, the polyideimide film according to the present invention has an advantage that can be preferably used as a coverlay in portable electronic devices and communication devices.

Hereinafter, the operation and effects of the invention will be described in more detail through specific examples of the invention. However, these examples are only presented as examples of the invention, and the scope of the invention is not thereby determined.

Production Example 1-1: Preparation of polyamideimide powder by water-based polymerization

22.23 g of TMA as an anhydride monomer and 23.17 g of ODA as a diamine monomer were dispersed in 200 mL of distilled water. After the dispersion was transferred to a 500 mL pressure vessel equipped with a stirrer and a temperature controller, the temperature was adjusted to 185 ° C. and then stirred at a pressure of 10 bar for 10 hours to prepare a polyamideimide powder.

Production Example 1-2: Preparation of polyamideimide powder by water-based polymerization

22.34 g of TMA as an anhydride monomer and 23.06 g of MDA as a diamine monomer were dispersed in 200 mL of distilled water. After transferring the dispersion to a 500 mL pressure vessel equipped with a stirrer and a temperature controller, the temperature was adjusted to 200 ° C., and then stirred at a pressure of 15 bar for 8 hours to prepare a polyamideimide powder.

Comparative Production Example 1-1: Preparation of polyamide amic acid solution by solution polymerization

After injecting nitrogen into a 500 ml reactor equipped with a stirrer and a nitrogen injection / discharge tube, 200 g of NMP was added and the temperature of the reactor was set to 30 ° C., followed by 19.71 g of TMA as an anhydride monomer and 25.68 g of a diamine monomer. It was confirmed that MDI was completely dissolved. Subsequently, the temperature was raised to 90 ° C under a nitrogen atmosphere and stirred for 120 minutes while heating, and then the temperature was raised to 160 ° C to further react and imidize. When the generation of bubbles in the solution was reduced, the solution was cooled to prepare a polyamide amic acid solution.

Comparative Preparation Example 1-2: Preparation of polyamic acid solution by solution polymerization

After injecting nitrogen into a 500 ml reactor equipped with a stirrer and a nitrogen injection / discharge tube, 200 g of DMF was added, the temperature of the reactor was set to 20 ° C., and then 21.73 g of ODA was added as a diamine monomer to dissolve and then dianhydride. As a monomer, 23.64 g of PMDA was added and stirred under a nitrogen atmosphere for 120 minutes to prepare a polyamic acid solution.

Preparation Example 2-1: Preparation of polyamideimide coating composition

After adding and mixing 10 g of polyamideimide powder prepared in Preparation Example 1 and 0.8 g of carbon black with respect to DMF 90 g as an organic solvent, the average particle size was 0.5 μm using a milling machine, and 100 parts by weight of polyamideimide powder A coating composition including 8 parts by weight of carbon black particles was prepared.

Preparation Example 2-2: Preparation of polyamideimide coating composition

A polyamideimide coating composition was prepared in the same manner as in Production Example 2-1, except that 1 g of carbon black was added to contain 10 parts by weight of carbon black particles relative to 100 parts by weight of polyamideimide powder.

Preparation Example 2-3: Preparation of polyamideimide coating composition

A polyamideimide coating composition was prepared in the same manner as in Production Example 2-1, except that 1.5 g of carbon black was added to contain 15 parts by weight of carbon black particles relative to 100 parts by weight of polyamideimide powder.

Preparation Example 2-4: Preparation of polyamideimide coating composition

As shown in Table 1, a polyamideimide coating composition was prepared in the same manner as in Preparation Example 2-1, except that DMAc was used instead of DMF as the organic solvent.

Preparation Example 2-5: Preparation of polyamideimide coating composition

A polyamideimide coating composition was prepared in the same manner as in Production Example 2-1, except that the polyamideimide powder of Preparation Example 1-2 was used.

Comparative Preparation Example 2-1: Preparation of polyamideimide coating composition

After adding and mixing 0.74 g of carbon black with respect to 50 g of the polyamide amic acid solution prepared in Comparative Preparation Example 1-1, the average particle diameter was 0.5 μm using a milling machine, and 8 parts by weight compared to 100 parts by weight of the polyamide amic acid resin A coating composition comprising parts by weight of carbon black particles was prepared.

Comparative Preparation Example 2-2: Preparation of polyimide precursor composition

50 g of the polyamic acid solution prepared in Comparative Production Example 1-2 and 0.74 g of carbon black were added and mixed, and then the average particle diameter was 0.5 μm using a milling machine, and 8 parts by weight of carbon black particles compared to 100 parts by weight of the polyamic acid resin. A precursor composition was prepared.

Comparative Preparation Example 2-3: Preparation of polyamideimide coating composition

A polyamideimide coating composition was prepared in the same manner as in Production Example 2-1, except that 3 g of carbon black was added to contain 30 parts by weight of carbon black particles compared to 100 parts by weight of polyamideimide powder by adding 3 g of carbon black. It was prepared.

Comparative Preparation Example 2-4: Preparation of polyamideimide coating composition

As shown in Table 1, a polyamideimide coating composition was prepared in the same manner as in Preparation Example 2-1, except that NMP was used instead of DMF as the organic solvent.

<Example 1>

The polyamide-imide coating composition prepared in Preparation Example 2-1 was softly applied onto a protective film (PET film) having a surface mat shape of 5 μm in thickness and 50 μm in thickness, dried and cured at a temperature of 150 ° C. A polyamideimide film having a polyamideimide thin film having a thickness of 5 μm was formed on the protective film. The thickness of the prepared polyamideimide film was measured using an Anritsu company's electric film thickness tester.

<Example 2>

A polyamideimide film was prepared in the same manner as in Example 1, except that the polyamideimide coating composition prepared in Preparation Example 2-2 was used.

<Example 3>

A polyamideimide film was prepared in the same manner as in Example 1, except that the polyamideimide coating composition prepared in Preparation Example 2-3 was used.

<Example 4>

A polyamideimide film was prepared in the same manner as in Example 1, except that the polyamideimide coating composition prepared in Preparation Example 2-4 was used.

<Example 5>

A polyamideimide film was prepared in the same manner as in Example 1, except that the polyamideimide coating composition prepared in Preparation Example 2-5 was used.

<Example 6>

A polyamideimide film was prepared in the same manner as in Example 1, except that the drying and curing temperatures were changed to 130 ° C as shown in Table 1 below.

<Example 7>

A polyamideimide film was prepared in the same manner as in Example 1, except that the drying and curing temperatures were changed to 180 ° C as shown in Table 1 below.

<Comparative Example 1>

A polyamideimide film was prepared in the same manner as in Example 1, except that the polyamideimide coating composition prepared in Comparative Production Example 2-1 was used.

<Comparative Example 2>

In the polyimide precursor composition prepared in Comparative Preparation Example 2-2, air bubbles were removed through high-speed rotation of 1,500 rpm or more. Thereafter, the defoamed polyimide precursor composition was applied to the glass substrate using a spin coater. Then, under a nitrogen atmosphere and dried at a temperature of 120 ° C. for 30 minutes, a gel film was prepared. Cooling at a rate of 2 ° C / min yielded a polyimide film. Thereafter, the polyimide thin film was peeled off the glass substrate by dipping in distilled water. The polyimide thin film was adhered onto a protective film (PET film) having a surface mat shape of 50 µm thick to prepare a polyimide film having a 5 µm thick polyimide thin film formed on the protective film.

<Comparative Example 3>

A polyamideimide film was prepared in the same manner as in Example 1, except that the polyamideimide coating composition prepared in Comparative Preparation Example 2-3 was used.

<Comparative Example 4>

A polyamideimide film was prepared in the same manner as in Example 1, except that the polyamideimide coating composition prepared in Comparative Production Example 2-4 was used.

<Comparative Example 5>

A polyamideimide film was prepared in the same manner as in Example 1, except that the drying and curing temperatures were changed to 200 ° C as shown in Table 1 below.

<Comparative Example 6>

The polyamideimide film was prepared in the same manner as in Example 1, except that the polyamideimide coating composition prepared in Comparative Preparation Example 2-4 was used and the drying and curing temperatures were changed to 200 ° C as shown in Table 1 below. It was prepared.

Monomer type Organic solvent type Carbon black particle content
(Parts by weight) Drying and curing temperature
(℃) Example 1 TMA; ODA DMF 8 150 ℃ Example 2 TMA; ODA DMF 10 150 ℃ Example 3 TMA; ODA DMF 15 150 ℃ Example 4 TMA; ODA DMAc 8 150 ℃ Example 5 TMA; MDA DMF 8 150 ℃ Example 6 TMA; ODA DMF 8 130 ℃ Example 7 TMA; ODA DMF 8 180 ℃ Comparative Example 1 TMA; ODA NMP 8 150 ℃ Comparative Example 2 PMDA; ODA NMP 8 150 ℃ Comparative Example 3 TMA; ODA DMF 30 150 ℃ Comparative Example 4 TMA; ODA NMP 8 150 ℃ Comparative Example 5 TMA; ODA DMF 8 200 ℃ Comparative Example 6 TMA; ODA NMP 8 200 ℃

Experimental Example 1: Light transmittance evaluation

The polyamideimide film or polyimide film prepared in Examples 1 to 7 and Comparative Examples 1 to 6 were cut to 50 mm X 50 mm to prepare specimens. Subsequently, the light transmittance of the thin film obtained by peeling the polyamideimide thin film or the polyimide thin film from the protective film was measured using the light transmittance measuring device (model name: ColorQuesetXE, manufacturer: HunterLab) in the visible light region by ASTM D1003 method, Table 2 shows the results of the experiment.

Light transmittance
(%) Example 1 One Example 2 0.9 Example 3 0.7 Example 4 One Example 5 0.9 Example 6 1.1 Example 7 0.9 Comparative Example 1 1.2 Comparative Example 2 1.3 Comparative Example 3 0.3 Comparative Example 4 1.2 Comparative Example 5 Measurement not possible
(Film wrinkle) Comparative Example 6 Measurement not possible
(Film wrinkle)

Experimental Example 2: Evaluation of tensile strength

Example 1 to Example 7, Comparative Examples 1 to Comparative Example 6, respectively, the polyamideimide film or polyimide film prepared were cut to 50 mm × 50 mm to prepare specimens. Subsequently, the tensile strength was measured by the method presented in KS6518 for the thin film obtained by peeling the polyamideimide thin film or the polyimide thin film from the protective film, and the results are shown in Table 3 below.

The tensile strength
(kg / cm ³ ) Example 1 14 Example 2 12 Example 3 9 Example 4 13 Example 5 13 Example 6 10 Example 7 15 Comparative Example 1 7 Comparative Example 2 4 Comparative Example 3 3 Comparative Example 4 6 Comparative Example 5 Measurement not possible
(Film wrinkle) Comparative Example 6 Measurement not possible
(Film wrinkle)

Experimental Example 3: Evaluation of residual solvent

Regarding the polyamideimide film or polyimide film prepared in Examples 1 to 7 and Comparative Examples 1 to 6, respectively, the polyamideimide thin film or the polyimide thin film obtained by peeling the polyamideimide thin film from the protective film remains The solvent content was measured, and the results are shown in Table 4 below.

Specifically, for the measurement of the residual solvent in the thin film, a sample of about 10 mg was collected using TGA equipment, and the temperature was raised to 100 ° C at a rate of 20 degrees / minute at room temperature, maintained for 1 minute, then heated to 200 ° C and maintained for 30 minutes. do. After the weight change was maintained at 100 ° C. for 1 minute, the weight change was recorded.

Residual solvent content
(%) Example 1 5 Example 2 4 Example 3 3 Example 4 7 Example 5 5 Example 6 9 Example 7 One 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, in the case of the polyamideimide thin films of Examples 1 to 7, the light transmittance in the visible light region is 1.1% or less, and the tensile strength satisfies 9 kg / cm ³ or more. You can confirm that.

On the other hand, in the case of the polyamideimide thin film of Comparative Example 1 prepared by solution polymerization, the polyimide thin film of Comparative Example 2 prepared through a polyamic acid solution and the polyamideimide thin film of Comparative Example 4 using NMP as an organic solvent, It can be seen that the light transmittance in the visible light region was not superior to the embodiments.

In addition, in the case of the polyamideimide thin film of Comparative Example 3 in which the content of carbon black exceeds the range of the present invention, the light transmittance in the visible light region is excellent at 0.3% or less, but it exhibits a lower tensile strength than the examples. In addition, it can be seen that the polyamideimide thin film or the polyimide thin film of Comparative Examples 1, 2 and 4 also has less tensile strength than the examples.

On the other hand, referring to Table 4, in the case of the polyamideimide thin films of Examples 1 to 7, the residual solvent content is very good as 9% or less, but Comparative Examples 1, 2, and 4 have a residual solvent content of 15% or more. Can be confirmed. For reference, in the case of Comparative Examples 5 and 6 having a drying and curing temperature of 200 ° C., the residual solvent content was excellent at 2% or less, but deformation occurred in the protective film, resulting in wrinkles in the resulting polyamideimide thin film. Bars and good products were not manufactured, and thus it was impossible to measure light transmittance and tensile strength.

Although described above with reference to the embodiments of the present invention, those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

Claims (16)

(a) The dispersion obtained by dispersing one or more diamine monomers and one or more anhydride monomers in water is placed in a pressure vessel, and the reaction product obtained by reacting at a temperature of 150 to 250 ° C and a pressurized condition of 5 to 20 bar is filtered. And drying to obtain a polyamideimide powder;
(b) mixing the polyamideimide powder and carbon black particles in an organic solvent and milling to obtain a polyamideimide coating composition;
(c) flexible coating the polyamideimide coating composition on a protective film; And
(d) drying and curing the applied coating composition at a temperature of 180 ° C. 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 compared to 100 parts by weight of the polyamideimide powder,
A method for producing a polyamideimide film, wherein the thickness of the polyamideimide thin film is 10 μm or less. According to claim 1,
The method of manufacturing a polyamideimide film, wherein the organic solvent in step (b) is an organic solvent having a boiling point in the range of 100 to 180 ° C. According to claim 2,
The organic solvent is a method selected from N, N'-dimethylformamide (DMF) and N, N'-dimethylacetamide (DMAc), a method for producing a polyamideimide film. According to claim 1,
The drying and curing in the step (d) is carried out so that the residual solvent content in the polyamideimide thin film is 10% or less, a method for producing a polyamideimide film. According to claim 1,
The anhydride monomer comprises a trimellitic anhydride (TMA), a method for producing a polyamideimide film. According to claim 1,
The diamine monomer is oxydianiline (ODA), methylene dianiline (MDA) and paraphenylenediamine (PPD) at least one selected from the group consisting of, polyamideimide film production method. According to claim 1,
The carbon black particles contained in the coating composition has an average particle diameter in the range of 0.1 to 1 μm, a method for producing a polyamideimide film. According to claim 1,
The protective film has a glass transition temperature of 100 to 140 ℃, a method for producing a polyamideimide film. According to claim 1,
The protective film is a method for producing a polyamideimide film, which is a PET (Polyethylene terephthalate) film. According to claim 1,
In the process (a), the reaction is carried out at a temperature range of 160 to 240 ° C., a method for producing a polyamideimide film. According to claim 1,
The reaction in the process (a) is carried out for 4 hours to 2 days, a method for producing a polyamideimide film. According to claim 1,
The method for producing a polyamideimide film, wherein the thickness of the polyamideimide thin film ranges from 1 to 5 μm. According to claim 1,
The polyamideimide thin film has a light transmittance in the visible light region of 1.1% or less, and a tensile strength of 9 kg / cm ³ or more, a method for producing a polyamideimide film. A polyamideimide film produced by the production method according to any one of claims 1 to 13,
A polyamideimide film comprising a thin film of polyamideimide formed on a protective film. A coverlay comprising the polyamideimide film according to claim 14. An electronic device comprising the coverlay according to claim 15.