KR20200090043A - Preparing method of polyamideimide block copolymer, polyamideimide block copolymer and polymer resin film using the same - Google Patents

Abstract

The present invention relates to: a method for producing a polyamideimide block copolymer, in which an aromatic dicarboxylic acid or a derivative thereof, which is a reactant, is added in a slurry state in a step of synthesizing an amide repeating unit; a polyamideimide block copolymer; and a polymer resin film using the same. The polyamideimide block copolymer is colorless and transparent, and has excellent mechanical properties.

Description

Manufacturing method of polyamideimide block copolymer, polyamideimide block copolymer and polymer resin film using the same{PREPARING METHOD OF POLYAMIDEIMIDE BLOCK COPOLYMER, POLYAMIDEIMIDE BLOCK COPOLYMER AND POLYMER RESIN FILM USING THE SAME}

The present invention relates to a polyamideimide block copolymer, a polyamideimide block copolymer, and a polymer resin film using the polyamideimide block copolymer having colorless and transparent, excellent mechanical properties, high elasticity and heat resistance.

Aromatic polyamide-imide resin is a polymer having mostly an amorphous structure, and exhibits excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to its rigid chain structure. These polyamide-imide resins are widely used as materials for electric/electronic, aerospace, aviation, and automobiles.

However, despite the excellent heat resistance, the wholly aromatic polyamide-imide resin is mostly insoluble and insoluble, and thus, molding and workability are deteriorated, and thus, it is difficult to use conventional processing equipment for processing of the resin.

Accordingly, various studies have been conducted to improve melt moldability while minimizing degradation in mechanical properties at high temperatures and excellent heat resistance of polyamide-imide resins, for example, to improve the flexibility of chains in polyamide-imide resins. In order to increase, a method of introducing -O-, -S- groups, etc., a method of introducing meta-substituents or bulky molecular structures has been proposed. The polyamide-imide resin according to the above proposals is difficult to exhibit sufficient heat resistance by a curved structure or an aliphatic cyclic compound, and the film produced using it still has limitations showing poor mechanical properties.

In addition, when the polyamide-imide resin is used as a flexible display material, it is required to have excellent optical properties in addition to thermal properties and mechanical properties, and there is a problem that it is difficult to satisfy these properties to the required level at the same time.

The present invention is to provide a method for producing a polyamideimide block copolymer having colorless and transparent, excellent mechanical properties, and high elasticity and heat resistance.

In addition, the present invention is to provide a polyamideimide block copolymer having colorless and transparent, excellent mechanical properties, high elasticity and heat resistance, and a polymer resin film using the same.

In the present specification, a first step of reacting an aromatic diamine compound with an aromatic tetracarboxylic acid or anhydride thereof; And a second step of reacting the resultant of the first step with an aromatic dicarboxylic acid or derivative thereof, and a second step of reacting the aromatic diamine.

In addition, in the present specification, an imide block including a first repeating unit represented by Formula 1 below; And an amide block comprising any one selected from the group consisting of a second repeating unit represented by the following formula (2) and a third repeating unit represented by the following formula (3); and the second repeating unit: A polyamideimide block copolymer having a molar ratio of 1: 10 to 1: 1 and having an elastic modulus of 4.90 GPa or more measured based on a specimen having a thickness of 50 ± 2 μm according to a measurement method of ASTM D 882 may be provided.

[Formula 1]

In Chemical Formula 1, R ¹ is the same in each repeating unit or different from each other, and each independently a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S (=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤=10), -(CF ₂ ) _q -(here 1=q=10),- C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a divalent aromatic organic group having 6 to 30 carbon atoms; R ² is the same or different from each repeating unit, and each independently -H, -F, -Cl, -Br, -I, -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, -COCH ₃ , -CO ₂ C ₂ H ₅ , a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms ; n1 and m1 are each independently an integer from 0 to 3; Y ¹ is the same or different in each repeating unit, and each independently includes a divalent aromatic organic group having 6 to 30 carbon atoms containing at least one trifluoromethyl group (-CF ₃ ); The aromatic organic group may be present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic groups are a single bond, a fluorenylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si( CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤=10), -(CF ₂ ) _q -(here 1=q≤=10), -C(CH ₃ ) ₂ -,- C(CF ₃ ) ₂ -, or -C(=O)NH-. E ¹ is each independently a single bond or -NH-;

[Formula 2]

[Formula 3]

In the formula 2 and formula 3, Y ² and Y ^{2 'is} a bivalent group having 6 to 30 carbon atoms including a methyl group (-CF ₃₎ base of one or more trifluoromethyl, the same or different from each other in each repeating unit, are each independently Aromatic organic groups; The aromatic organic group may be present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic groups are single bonds, fluorenylene groups, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si( CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤=≤10), -(CF ₂ ) _q -(here 1=q≤=≤10), -C(CH ₃ ) _2- , -C(CF ₃ ) ₂ -, or -C(=O)NH-; E is ^{2, E 2 ', E 3} , E 3', E 4 and E ^{4 'is} a single bond or -NH-, each independently.

In addition, in the present specification, a polymer resin film containing the polyamideimide block copolymer may be provided.

Hereinafter, a method for producing a polyamideimide block copolymer, a polyamideimide block copolymer, and a polymer resin film using the same will be described in detail.

Unless expressly stated in this specification, the terminology is only for referring to a specific embodiment, and is not intended to limit the present invention.

Singular forms used herein include plural forms unless the phrases clearly indicate the opposite.

As used herein, the meaning of'include' embodies a specific characteristic, region, integer, step, action, element, and/or component, and other specific characteristic, region, integer, step, action, element, component, and/or group. It does not exclude the existence or addition of.

In addition, in this specification, terms including an ordinal number such as'first' and'second' are used for the purpose of distinguishing one component from other components, and are not limited by the ordinal number. For example, within the scope of the present invention, the first component may also be referred to as the second component, and similarly, the second component may be referred to as the first component.

In this specification, the weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, detectors and analytical columns, such as a commonly known analytical device and a differential index detector, can be used, and the temperature is usually applied. Conditions, solvents and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 65°C, a dimethylformamide solvent (N,N-Dimethylformamide), and a flow rate of 1 mL/min.

In the present specification, a direct bond or a single bond means that there is no atom or atomic group at the corresponding position, and is connected by a bond line.

1. Manufacturing method of polyamideimide block copolymer

According to an embodiment of the present invention, a first step of reacting an aromatic diamine compound with an aromatic tetracarboxylic acid or anhydride thereof; And a second step of reacting the resultant of the first step with an aromatic dicarboxylic acid or derivative thereof, and a second step of reacting the aromatic diamine.

As a result of continuous research by the present inventors, in the second step of the amide repeating unit synthesis step of the polyamideimide block copolymer, when the reactant aromatic dicarboxylic acid or its derivative is added in a slurry state, the aromatic dicarboxylic acid or its By minimizing the decomposition of the derivatives by the water dissolved in the solvent, it was confirmed through experiments that a colorless, transparent, and excellent mechanical property and a polyamideimide block copolymer having high elasticity and heat resistance could be provided. .

On the other hand, in the past, the aromatic dicarboxylic acid or its derivative and aromatic diamine, which are monomers used for synthesizing the amide repeating unit, are sufficiently dissolved in a solvent, and then put into the solvent. During the dissolving process, the monomer is decomposed by moisture dissolved in the solvent, resulting in polyamideimide. There was a limitation in that the physical properties of the block copolymer were significantly reduced.

Specifically, the polyamideimide block copolymer obtained by the method for preparing the polyamideimide block copolymer of the above embodiment may have a relatively high number average molecular weight and a low polydispersity index (PDI). Accordingly, the polymer resin film containing the polyamideimide block copolymer may have excellent transparency while realizing excellent mechanical properties through such high molecular weight and low polydispersity index.

The method for producing the above-described polyamideimide block copolymer will be described in more detail.

(1) Step 1

In the first step, the aromatic diamine compound and the aromatic tetracarboxylic acid or anhydride thereof can be reacted. Through the reaction of the first step, a repeating unit or precursor thereof constituting the imide block of the polyamideimide block copolymer may be synthesized. As the polyamideimide block copolymer contains an imide block, the amide bond contained in the imide repeating unit forms a hydrogen bond with the amide bond contained in the amide repeating unit to align the polymer chains, thereby providing a colorless, transparent and excellent mechanical The properties of physical properties and high elasticity can be realized.

The aromatic diamine compound may use an aromatic diamine containing an electron withdrawing functional group, and by introducing a strong electron withdrawing group such as a trifluoromethyl (-CF3) group to limit the movement of π electrons present in the imide chain, By inhibiting the formation of the charge transfer complex (CTC) of the π electrons, the polyamideimide resin is colorless and transparent, and can realize excellent mechanical properties and high elastic properties.

Specific examples of the aromatic diamine compound are 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine (2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine), 2, 2'-dimethyl-4,4'-diaminobenzidine, 4,4'-diaminodiphenyl sulfone, 4 ,4'-(9-fluorenylidene)dianiline(4,4'-(9-fluorenylidene)dianiline), bis(4-(4-aminophenoxy)phenyl) sulfone (bis(4-(4- aminophenoxy)phenyl)sulfone), 2,2',5,5'-tetrachlorobenzidine (2,2',5,5'-tetrachlorobenzidine), 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, m-phenylenediamine, p-phenylenediamine, 4,4'-oxydianiline (4 ,4'-oxydianiline), 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis[4-(4- Aminophenoxy)phenyl]propane(2,2-bis[4-(4-aminophenoxy)phenyl]propane), 1,3-bis(4-aminophenoxy)benzene(1,3-bis(4-aminophenoxy) benzene), and 4,4'-diaminobenzanilide (4,4'-diaminobenzanilide). More preferably, the aromatic diamine monomer is 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine (2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine, TFDB ) Or 2,2'-dimethyl-4,4'-diaminobenzidine.

The aromatic tetracarboxylic acid or anhydride thereof includes aromatic tetracarboxylic dianhydride containing an unsubstituted aromatic functional group having 6 to 30 carbon atoms and aromatic tetracar containing an aromatic functional group having 6 to 30 carbon atoms substituted with an electron withdrawing functional group. Carboxylic acid dianhydrides.

Specific examples of the aromatic tetracarboxylic dianhydride containing an unsubstituted aromatic functional group having 6 to 30 carbon atoms are 3,3',4,4'-(biphenylcarboxylic)diphthalic anhydride (3,3' ,4,4'-biphenyltetracarboxylic dianhydride (BPDA).

In addition, specific examples of the aromatic tetracarboxylic dianhydride containing an aromatic functional group having 6 to 30 carbon atoms substituted with the electron withdrawing functional group is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (4, And 4'-(hexafluoroisopropylidene) diphthalic anhydride; 6FDA).

The aromatic tetracarboxylic dianhydride containing an unsubstituted aromatic functional group having 6 to 30 carbon atoms: 10 to 1 to an aromatic tetracarboxylic dianhydride containing an aromatic functional group having 6 to 30 carbon atoms substituted with an electron withdrawing functional group 1: 1, or 5: 1 to 1.1:1, or 3: 1 to 1.1:1, or 2: 1 to 1.2:1, or 1.5: 1 to 1.3:1, may be included in a molar ratio.

The aromatic tetracarboxylic dianhydride containing the unsubstituted aromatic functional group having 6 to 30 carbon atoms with respect to 1 mol of the aromatic tetracarboxylic dianhydride containing the aromatic functional group having 6 to 30 carbon atoms substituted with the electron withdrawing functional group If the molar ratio is excessively increased to more than 10 moles, yellowness and hazeness may increase. Moreover, with respect to 1 mol of the aromatic tetracarboxylic dianhydride containing the aromatic functional group having 6 to 30 carbon atoms substituted with the electron withdrawing functional group, the aromatic tetracarboxylic acid containing the unsubstituted aromatic functional group having 6 to 30 carbon atoms When the molar ratio of the dianhydride is excessively reduced to less than 1 mole, the elastic modulus of the synthesized polyamideimide block copolymer may decrease.

The aromatic diamine compound and aromatic tetracarboxylic acid or anhydride thereof may be dissolved in an organic solvent. That is, in the course of the reaction of the first step, the aromatic diamine compound and the aromatic tetracarboxylic acid or anhydride thereof may be introduced into the reactor in a state dissolved in an organic solvent to initiate a reaction.

Specific examples of the organic solvent are dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone , Dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide , 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexa Paddy, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate , Ethylene glycol monopropyl ether, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and the like. These may be used alone or in combination.

The aromatic diamine compound and the aromatic tetracarboxylic acid or anhydride thereof may be reacted at a molar ratio of 1:0.95 to 1:1.05. When the aromatic diamine compound and the aromatic tetracarboxylic acid or anhydride thereof are reacted in a molar ratio of 1:0.95 to 1:1.05, the degree of polymerization of the imide block synthesized therefrom is 50 or more, or 90 or more. The polymer resin film using the polyamide-imide block copolymer thus prepared may have a lower yellow index, and may also have a relatively high molecular weight and a low level of polydispersity index (PDI). , It is also colorless and transparent, but may have higher elasticity.

(2) Stage 2

In the second step, the product of the first step, a slurry containing an aromatic dicarboxylic acid or a derivative thereof, and an aromatic diamine may be reacted. Through the reaction of the second step, a repeating unit or precursor thereof constituting the amide block of the polyamideimide block copolymer may be synthesized. As the polyamideimide block copolymer includes an amide block, mechanical properties are improved and optical properties and elastic properties can be improved.

In addition, since the second step has a characteristic in order to proceed after the reaction of the first step, the polyamideimide obtained by performing the reaction in the order of proceeding to the second step after the first step is imide Block and amide blocks may be block copolymers, respectively.

The product of the first step may be a reaction product between an aromatic diamine compound and an aromatic tetracarboxylic acid or anhydride thereof, that is, a polyamic acid compound or a polyimide compound. More specifically, the result of the first step may be a polyamic acid solution or a polyimide solution in which the polyamic acid compound or polyimide compound is dissolved in an organic solvent.

The polyamic acid is meant to include both amic acid or polyamic acid, and polyimide may be used to mean both imide or polyimide.

On the other hand, in the course of the reaction of the second step, the slurry containing the aromatic dicarboxylic acid or its derivative may be introduced into the reactor to proceed with the reaction. The slurry may mean an aromatic dicarboxylic acid or a derivative thereof, specifically, a mixed solution in which the particles of the aromatic dicarboxylic acid or a derivative thereof are dispersed in an organic solvent. That is, the slurry may further include an organic solvent. The organic solvent may include the contents described above in the first step.

The aromatic dicarboxylic acid or derivative particles thereof means an insoluble substance that is not soluble in the organic solvent, such as a solid powder or a complex thereof. Accordingly, in the slurry, the aromatic dicarboxylic acid or derivative particles thereof may not be dissolved in an organic solvent and may exist in a dispersed state.

The viscosity of the slurry containing the aromatic dicarboxylic acid or derivative thereof may be 2 cP to 30 cP, or 2 cP to 10 cP, or 5 cP to 10 cP, or 5 cP to 6 cP. The viscosity of the slurry can be measured with a Haake rheometer, and specifically, the viscosity can be measured at a shear of 1.2/s. If the viscosity of the slurry is too low, there is an excessive amount of monomers decomposed by moisture, and the polymerization degree decreases. If the viscosity is too high, the polymerization time becomes too long and the non-uniformity of the resin may increase. As such, by using the slurry containing the aromatic dicarboxylic acid or its derivatives, the aromatic dicarboxylic acid or its derivatives are minimized to be decomposed by moisture dissolved in a solvent, thereby providing colorless, transparent, excellent mechanical properties, high elasticity and heat resistance It is possible to provide a polyamideimide block copolymer having

Examples of the method for preparing the slurry are not particularly limited. For example, the aromatic dicarboxylic acid or a derivative thereof and an organic solvent are 50° C. or less, or 0° C. or more and 50° C. or less, or 5° C. or more and 50° C. or less, or It can be produced by mixing at a temperature of 10°C or more and 50°C or less, or 20°C or more and 30°C or less. When the mixing temperature of the aromatic dicarboxylic acid or a derivative thereof and the organic solvent is increased to more than 50°C, specifically 55°C or more, the slurry is prepared as a solution is prepared by starting to dissolve the aromatic dicarboxylic acid or its derivative in an organic solvent. It becomes difficult. In addition, when the mixing temperature of the aromatic dicarboxylic acid or a derivative thereof and the organic solvent increases to 70° C. or higher, the yellow index increases due to the modification of the monomeric aromatic dicarboxylic acid or its derivative by moisture dissolved in the solvent during the dissolution process. For example, the physical properties of the polyamideimide block copolymer may be poor.

In addition, the process of mixing the aromatic dicarboxylic acid or a derivative thereof and an organic solvent at a temperature of 50° C. or less can be performed within 1 minute, or 10 seconds to 50 seconds, or 20 seconds to 40 seconds. When the mixing time of the aromatic dicarboxylic acid or its derivative and the organic solvent is excessively increased by more than 1 minute, the aromatic dicarboxylic acid or its derivative is dissolved in an organic solvent and decomposed by moisture dissolved in the solvent. Can occur.

Mixing between the aromatic dicarboxylic acid or a derivative thereof and an organic solvent is a conventional mixing method, specifically a homogenizer, a mixing device such as a bead mill, a ball mill, a basket mill, an attrition mill, a universal stirrer, a clear mixer or a TK mixer It can be performed using. Meanwhile, the total solid content of the slurry may be 10 wt% or more and 30 wt% or less, or 10 wt% or more and 25 wt% or less. The solid content is a percentage of the weight of the monomer as a solid content relative to the total weight of the slurry. When the content of the organic solvent is excessively increased to decrease the solid content to less than 10% by weight, the aromatic dicarboxylic acid or its derivative is organic. As it is dissolved in a solvent, a problem that may be decomposed by moisture dissolved in the solvent may occur.

The aromatic diamine can be dissolved in an organic solvent. That is, in the course of proceeding the reaction of the second step, the aromatic diamine compound may be introduced into the reactor in a state dissolved in an organic solvent to initiate a reaction.

In the aromatic dicarboxylic acid or a derivative thereof, the derivative refers to a compound produced by performing substitution, omission, polymerization, and crosslinking reaction from the aromatic dicarboxylic acid, and the aromatic dicarboxylic acid or a derivative thereof is specifically represented by the following formula (A) Can be.

[Formula A]

In the above formula (A), Ar is an arylene group having 6 to 20 carbon atoms, and X ₁ and X ₂ are each independently a hydroxyl group or halogen. In the present specification, the arylene group is a divalent functional group derived from arene, and the description of the aryl group described above may be applied except that they are divalent functional groups. For example, it may be a phenylene group, biphenylene group, terphenylene group, naphthalene group, fluorenyl group, pyrenyl group, phenanthrenyl group, perylene group, tetrasenyl group, anthracenyl group, and the like. The arylene group may be substituted or unsubstituted. Further, examples of the halogen include fluorine, chlorine, bromine or iodine.

More specifically, the aromatic dicarboxylic acid or a derivative thereof may include an isophthalic acid derivative compound and a biphenyl dicarboxylic acid derivative compound. The derivative of isophthalic acid may be isophthaloyl chloride, and the derivative of biphenyl dicarboxylic acid may be 4,4'-biphenyldicarbonyl chloride.

Due to the linear molecular structure of the biphenyl dicarboxylic acid derivative compound, chain packing and alignment in the polymer can be maintained constant, and surface hardness and mechanical properties of the polymer resin film can be improved.

The isophthalic acid derivative compound has a characteristic of interfering with chain packing and alignment in the polymer due to the curved molecular structure, and increases the amorphous region in the polyamideimide block copolymer, thereby increasing the optical properties of the polymer resin film. And it can improve the break strength.

The isophthalic acid derivative compound: the biphenyl dicarboxylic acid derivative compound is 1: 10 to 1: 1, or 1: 10 to 1: 2, or 1: 5 to 1: 1, or 1: 5 to 1: 2, or 1 : 4 to 1: 2 may be included in a molar ratio.

By satisfying the molar ratio, it is possible to simultaneously improve the thermal properties, mechanical properties, and optical properties of the polyamideimide block copolymer, and dimensional stability against water absorption can be relatively improved. If the molar ratio is outside the above-described range, problems such as increased haze or yellowing may occur.

In addition, when preparing the polyamideimide block copolymer, preferably, the result of the first step: the molar ratio of the sum of the aromatic dicarboxylic acid or a derivative thereof and the aromatic diamine may be 3:7 to 6:4. By satisfying the molar ratio, mechanical properties, thermal properties, and optical properties of the polymer resin film obtained from the polyamideimide block copolymer can all be improved to a high level.

Meanwhile, after the second step, the step of chemically imidizing or thermally imidizing the product of the first step may be further included. More specifically, with respect to the result of the first step, chemical imidization reaction is induced by adding a compound such as acetic anhydride or pyridine, or amic acid is obtained by Azeotropic Distillation (azeotropic distillation). The step of inducing a thermal imidization reaction may be performed. The step of thermal imidization may be performed at a temperature of 100°C or higher, or a temperature of 100°C to 350°C, or a temperature of 150°C to 250°C.

In addition, as is commonly known, low-temperature solution polymerization, interfacial polymerization, melt polymerization, solid phase polymerization, and the like may be used to prepare the polyamideimide block copolymer.

2. Polyamideimide block copolymer

According to another embodiment of the invention, an imide block comprising a first repeating unit represented by Formula 1; And an amide block comprising any one selected from the group consisting of a second repeating unit represented by Formula 2 and a third repeating unit represented by Formula 3; wherein the second repeating unit: of the third repeating unit The molar ratio is 1: 10 to 1: 1, and the elastic modulus measured based on a specimen having a thickness of 50 ± 2 μm according to the measurement method of ASTM D 882 is 4.90 GPa or more, or 4.90 GPa or more, 10 GPa or less, or 4.90 GPa or more 5.5 Polyamideimide block copolymers of less than GPa, or greater than 4.96 GPa and less than 5.46 GPa can be provided.

The polyamideimide block copolymer of the other embodiment can be obtained by a method for producing a polyamideimide block copolymer of the above embodiment.

As a result of continuous research by the present inventors, when the polyamideimide block copolymer containing the second repeating unit: the third repeating unit in a specific content is used, it is a colorless transparent polymer film having excellent mechanical properties, high elasticity and heat resistance It was confirmed through experiments that it can provide and completed the invention.

The molar ratio of the second repeating unit: the third repeating unit contained in the polyamideimide block copolymer is 1: 10 to 1: 1, or 1: 10 to 1: 2, or 1: 5 to 1: 1, or 1 : 5 to 1: 2, or 1: 4 to 1: 2, it can have a polymer internal structure (feature) that can improve the elasticity while maintaining high mechanical properties, and thus has excellent workability to make the film While easy to form, it is possible to provide a colorless and transparent film having excellent mechanical properties.

In particular, as will be described later, in the process of forming the imide block contained in the polyamideimide block copolymer, the degree of polymerization of the imide block [degree of polymerization] is 50 or more, such as the molar ratio of reactants such as 90 or more. By controlling the reaction conditions, the polyamideimide resin film of the above embodiment may have a lower yellow index.

The polyamideimide block copolymer may have a relatively high molecular weight. Specifically, the polyamideimide block copolymer is 200000 g/mol or more, or 200000 g/mol to 800000 g/mol, or 200000 g/mol to 400000 g/mol, or 220000 g/mol to 350000 g/mol, Or it may have a number average molecular weight of 230000 g / mol to 336000 g / mol.

In addition, the polyamideimide block copolymer is 350000 g/mol or more and 1000000 g/mol or less, or 400000 g/mol to 600000 g/mol, or 410000 g/mol to 560000 g/mol, or 417000 g/mol to 551000 It may have a weight average molecular weight of g / mol.

If the weight average molecular weight of the polyamideimide block copolymer is excessively increased to more than 1000000 g/mol, molding processability may be reduced to the extent that molding into a film is impossible.

Accordingly, the polyamideimide block copolymer may have a polydispersity index (PDI) of 2.0 or less, or 1 to 2, or 1.5 to 1.9, or 1.6 to 1.85.

The above-described polyamideimide block copolymer will be described in more detail.

As described above, in preparing the polyamideimide block copolymer, by introducing a specific structure into the repeating unit included in the amide block, it is possible to simultaneously improve the thermal, mechanical and optical properties of the copolymer. Specifically, the diacyl halide, dicarboxylic acid, and dicarboxylate compounds are limited to a specific structure when the copolymer is prepared, and the molar ratio thereof is limited, thereby providing excellent mechanical properties and heat resistance of the polyamideimide block copolymer. While maintaining the level, it was confirmed that the optical properties of the resin can be improved together.

As described above, the polyamideimide block copolymer may include an imide block comprising a first repeating unit represented by Formula 1 below.

(1) repeat unit derived from imide: first repeat unit

[Formula 1]

In Chemical Formula 1, R ¹ is the same in each repeating unit or different from each other, and each independently a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S (=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤==10), -(CF ₂ ) _q -(where 1=q≤==10 ), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a divalent aromatic organic group having 6 to 30 carbon atoms; R ² is the same or different from each repeating unit, and each independently -H, -F, -Cl, -Br, -I, -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, -COCH ₃ , -CO ₂ C ₂ H ₅ , a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms ; n1 and m1 are each independently an integer from 0 to 3; Y ¹ is the same or different in each repeating unit, and each independently includes a divalent aromatic organic group having 6 to 30 carbon atoms containing at least one trifluoromethyl group (-CF ₃ ); The aromatic organic group may be present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic groups are a single bond, a fluorenylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si( CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤==10), -(CF ₂ ) _q -(here 1=q≤==10), -C(CH ₃ ) _2- , -C(CF ₃ ) ₂ -, or -C(=O)NH-; E ¹ is each independently a single bond or -NH-.

Here, the single bond means a case of chemically bonding to simply connect the groups R ¹ of the next amount in the formula (1).

R ² is the same or different from each repeating unit, and each independently -H, -F, -Cl, -Br, -I, -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, -COCH ₃ , -CO ₂ C ₂ H ₅ , a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms have.

n1 and m1 may be each independently an integer of 0 to 3.

Y ¹ may be the same or different from each other in each repeating unit, and each independently an aliphatic organic group having 3 to 10 carbon atoms.

E ¹ may each independently be a single bond or -NH-.

Here, the single bond means a chemical bond in which the groups on either side of each substituent in the formula (1) are simply connected.

Preferably, the first repeating unit may include a repeating unit represented by Chemical Formula 1-1:

[Formula 1-1]

In Chemical Formula 1-1,

R ¹ , R ² , n1 and m1 are as defined in Chemical Formula 1.

In addition, the polyamideimide block copolymer may include an amide block including any one selected from the group consisting of a second repeating unit represented by the following Chemical Formula 2 and a third repeating unit represented by the following Chemical Formula 3. In the polyamideimide block copolymer, the molar ratio of the following second repeating unit: third repeating unit is 1: 10 to 1: 1, or 1: 10 to 1: 2, or 1: 5 to 1: 1, or 1: It may be 5 to 1: 2, or 1: 4 to 1: 2.

(2) Amide-derived repeating unit: second repeating unit and third repeating unit

[Formula 2]

[Formula 3]

In the formula 2 and formula 3, Y ² and Y ^{2 'is} a bivalent group having 6 to 30 carbon atoms including a methyl group (-CF ₃₎ base of one or more trifluoromethyl, the same or different from each other in each repeating unit, are each independently Aromatic organic groups; The aromatic organic group may be present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic groups are a single bond, a fluorenylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si( CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤==10), -(CF ₂ ) _q -(here 1=q≤==10), -C(CH ₃ ) _2- , -C(CF ₃ ) ₂ -, or -C(=O)NH-; E is ^{2, E 2 ', E 3} , E 3', E 4 and E ^{4 'is} a single bond or -NH-, each independently.

)에 대하여 메타 위치에 위치하며, 제3 반복 단위에서 2개의 -C(=O)-는 A(

)에 대하여 파라 위치에 위치한다.The second repeating unit and the third repeating unit are amide-derived repeating units, and among the formulas 2 and 3, a divalent linking group of the form -C(=O)-AC(=O)- is diacyl halide, dicar It is derived from one or more compounds selected from the group consisting of carboxylic acids and dicarboxylates. In the second repeating unit, two -C(=O)- are A(

) In the meta position, and in the third repeating unit, two -C(=O)- are A(

) In the para position.

Preferably, the second repeating unit may include a repeating unit represented by Chemical Formula 2-1.

[Formula 2-1]

Preferably, the three repeating units may include repeating units represented by the following Chemical Formula 3-1.

[Formula 3-1]

On the other hand, the above-described polyamideimide block copolymer has a molar ratio of the second repeating unit and the third repeating unit of 1: 10 to 1: 1, or 1: 10 to 1: 2, or 1: 5 to 1: 1, Or 1: 5 to 1: 2, or 1: 4 to 1: 2, by satisfying the molar ratio, it is possible to improve the thermal properties, mechanical properties and optical properties of the copolymer at the same time. When the molar ratio of the second repeating unit and the third repeating unit is outside the above-mentioned range, problems such as increased hazes or yellowing may occur.

More specifically, in the polyamideimide block copolymer, preferably, the molar ratio of the imide block: amide block may be 3:7 to 6:4. By simultaneously satisfying the molar ratio and the molar ratio of the above-described second repeating unit and third repeating unit, it is possible to improve all of the mechanical properties, thermal properties and optical properties of the polyamideimide resin film to a high level.

In addition, in the polyamideimide block copolymer, when the molar ratio of the imide block:amide block is 3:7 to 4:6, the molar ratio of the second repeating unit: third repeating unit is 20:80 to 50: It may be 50, or 20:80 to 45:55, and more preferably about 40:60. When the above ranges are simultaneously satisfied, mechanical properties, thermal properties, and optical properties of the polymer resin film obtained from the polyamideimide block copolymer can all be improved to a high level.

The degree of polymerization of the imide block in the polyamideimide block copolymer may be 50 or more, or 90 or more. The degree of polymerization of the imide block can be confirmed through a molar ratio of the reactants forming the imide block.

As is commonly known, the degree of polymerization of the imide block can be confirmed through a molar ratio of reactants forming the imide block.

For example, according to Carothers Equation, the degree of polymerization (DP) of a step-growth polymer can be represented by the following general formula (1).

[Formula 1]

In the general formula 1, Xn is the degree of polymerization, p is the extent of the reaction (extent of reaction). That is, it shows that the degree of polymerization increases and the higher the molecular weight can be obtained as the reaction approaches 100%.

On the other hand, when any one of the monomers participating in the reaction is used in excess, the polymerization degree can be predicted through the following general formula (2).

[Formula 2]

In the general formula 2, Xn is the degree of polymerization, p is the extent of the reaction (extent of reaction), r is the stoichiometric ratio of reactant. For example, when using dianhydride/diamine 0.99/1.01, it can be calculated as r=0.98.

Accordingly, when one monomer is used in excess, it can be assumed that a limited number of monomers are all reacted and p converges to 1, and thus General Formula 2 can be expressed again as the following calculation formula.

[formula]

Through such a calculation formula, in the case of using 0.99/1.01 of acid dianhydride/diamine, the polymerization degree of polymer may be calculated as 99 in the polymerization reaction calculated as r=0.98. In addition, in the case of a polymer in which dianhydride/diamine is polymerized in half, the degree of polymerization may be calculated as 3.

Meanwhile, the polyamideimide block copolymer may further include a fourth repeating unit represented by Chemical Formula 4 in addition to the imide block and amide block:

[Formula 4]

In Formula 4, R ^{1 'are} the same or different from each other in each repeating unit, and each independently represents an aromatic group include divalent organic group having 6 to 30 carbon atoms; The aromatic organic group may be present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic groups are a single bond, a fluorenylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si( CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤==10), -(CF ₂ ) _q -(here 1=q≤==10), -C(CH ₃ ) _2- , -C(CF ₃ ) ₂ -, or -C(=O)NH-.

R ^{2 'are} the same or different from each other in each repeating unit, each independently -H, -F, -Cl, -Br, -I, -CF 3, -CCl 3, -CBr 3, -CI 3, - NO ₂ , -CN, -COCH ₃ , -CO ₂ C ₂ H ₅ , silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, aliphatic organic group having 1 to 10 carbon atoms, or aromatic organic group having 6 to 20 carbon atoms Can.

n3 and m3 may each independently be an integer from 0 to 3.

Y ^{1 'is} the same or different from each other in each repeating unit, are each independently a group of one or more base trifluoromethyl (-CF ₃₎ divalent aromatic organic group having 6 to 30 carbon atoms comprising a single aromatic organic group is the Exists; Two or more aromatic organic groups may be bonded to each other to form a divalent condensed ring; Or two or more aromatic organic groups are a single bond, a fluorenylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si( CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤==10), -(CF ₂ ) _q -(here 1=q≤==10), -C(CH ₃ ) _2- , -C(CF ₃ ) ₂ -, or -C(=O)NH-.

E ^{1 'may} be a single bond or -NH-, each independently.

As described above, the polyamideimide block copolymer including both the imide block and the amide block satisfies the molar ratio of the above-described second repeating unit and third repeating unit to the molar ratio between the imide block and the amide block in a specific range. , It can improve the mechanical properties, thermal properties and optical properties of the copolymer at the same time.

The polyamideimide block copolymer has an elastic modulus of 4.90 GPa or more, or 4.90 GPa or more, 10 GPa or less, or 4.90 GPa or more and 5.5 GPa for specimens having a thickness of 50±2 μm, measured according to the method of ASTM D 882. Or less, or greater than 4.96 GPa and less than 5.46 GPa. When the elastic modulus value of the polyamideimide block copolymer is reduced to less than 4.90 GPa, a level applicable to a display substrate, a protective film for a display, a touch panel, a cover film of a flexible or foldable device It is difficult to secure mechanical properties.

The polyamideimide block copolymer has a yellow index (YI) value measured according to ASTM E313 for a specimen having a thickness of 50±2 μm, 4.0 or less, or 3 or more and 4 or less, or 3.1 or more 3.6 or less. When the yellow index (YI) value measured in accordance with ASTM E313 of the polyamideimide block copolymer increases to more than 4.0, it is difficult to secure a sufficient level of transparency by increasing opacity.

3. Polymer resin film

According to another embodiment of the invention, a polymer resin film including the polyamideimide block copolymer of the other embodiment may be provided.

The polymer resin film may be provided by forming a film from the polyamideimide block copolymer of the other embodiment obtained from the method for producing the polyamideimide block copolymer of the embodiment.

More specifically, The polymer resin film may be prepared by a conventional method such as a dry method or a wet method using the polyamideimide block copolymer. For example, the polymer resin film may be obtained by coating a solution containing the polyamideimide block copolymer on an arbitrary support to form a film, and evaporating the solvent from the film to dry it. If necessary, stretching and heat treatment for the polymer resin film may be performed.

As described above, the polymer resin film may be prepared by preparing and stretching the polyamideimide block copolymer of the other embodiment at a predetermined temperature, for example, at a temperature of 100° C. or higher.

The specific method or condition of the stretching, and the device to be used are not particularly limited. For example, after the primary heat treatment of the polyamideimide block copolymer at a temperature of 150°C to 280°C, a predetermined stretching rate at a temperature of 150°C to 280°C (for example, a stretching rate of about 5% or more) It is possible to provide a stretched polymer resin film by applying a rate of about 0.1%/sec to a stretch.

As described above, the polymer resin film may be colorless and transparent, but may have excellent mechanical properties, high elasticity and heat resistance, and more specifically, the polymer resin film measured based on a thickness of 50±2 μm according to the measurement method of ASTM D 882. The elastic modulus of may be 4.90 GPa or more, or 4.90 GPa or more and 10 GPa or less, or 4.90 GPa or more and less than 5.5 GPa, or 4.96 GPa or more and 5.46 GPa or less. When the elastic modulus value of the polymer resin film is reduced to less than 4.90 GPa, mechanical properties of a level applicable to a display substrate, a protective film for a display, a touch panel, and a cover film of a flexible or foldable device are applied. Difficult to secure

In addition, the polymer resin film has a yellow index value (yellow index, YI) measured in accordance with ASTM E313 for a specimen having a thickness of 50 ± 2 ㎛, 4.0 or less, or 3 or more 4 or less, or 3.1 or more and 3.6 or less Can. When the yellow index value (YI) measured in accordance with ASTM E313 of the polymer resin film increases to more than 4.0, it is difficult to secure a sufficient level of transparency by increasing opacity.

The thickness of the polymer resin film is not particularly limited, but considering the optical properties, mechanical properties, and elastic modulus of the film, the polymer resin film may have a thickness of 10 μm to 100 μm. When the thickness of the polymer resin film increases or decreases by a specific value, physical properties measured in the polymer resin film may also change by a certain value.

Due to the above-described characteristics, the polymer resin film may be applied as a display substrate, a display protective film, a touch panel, a cover film of a flexible or foldable device, and the like.

According to the present invention, it is possible to provide a polyamideimide block copolymer, a polyamideimide block copolymer and a polymer resin film using the same, which are colorless, transparent, and have excellent mechanical properties and high elasticity and heat resistance.

Hereinafter, preferred embodiments are provided to help understanding of the invention. However, the following examples are only for illustrating the invention, and the invention is not limited thereto.

[Production Examples 1 to 2: Preparation of monomer slurry]

Preparation Example 1

Isophthaloyl dichloride (IPC) 18.25 g (0.090 mol), 4,4'-biphenyldicarbonyl chloride (4,4'-Biphenyldicarbonyl Chloride; BPC) in a beaker at room temperature (about 25 °C) 56.66 After adding g (0.262 mol), 600 g of dimethylacetamide (DMAc) was added and mixed for 30 seconds to prepare a slurry in which IPC and BPC were dispersed.

Preparation Example 2

Isophthaloyl dichloride (IPC) 163.63 g (0.806 mol), 4,4'-biphenyldicarbonyl chloride (4,4'-Biphenyldicarbonyl Chloride; BPC) 508.00 in a beaker at room temperature (about 25 °C) After adding g (2.345 mol), 2500 g of dimethylacetamide (DMAc) was added and mixed for 30 seconds to prepare a slurry in which IPC and BPC were dispersed.

[Comparative Production Examples 1 to 2: Preparation of monomer solution]

Comparative Production Example 1

Isophthaloyl dichloride (IPC) 18.25 g (0.090 mol), 4,4'-biphenyldicarbonyl chloride (BPC) 56.66 g (0.262 mol) in a beaker at 55°C ) Was added, and then 600 g of dimethylacetamide (DMAc) was added and mixed for 300 seconds to prepare a solution in which IPC and BPC were completely dissolved.

Comparative Production Example 2

Isophthaloyl dichloride (IPC) 163.63 g (0.806 mol), 4,4'-biphenyldicarbonyl chloride (4,4'-Biphenyldicarbonyl Chloride; BPC) 508.00 g (2.345 mol) in a beaker at 55°C ) Was added, and then 6000 g of dimethylacetamide (DMAc) was added and mixed for 300 seconds to prepare a solution in which IPC and BPC were completely dissolved.

[Examples 1 to 2: Preparation of polyamideimide block copolymer]

Example 1

2,2'-bis(trifluoromethyl)benzidine (TFMB) 93.80 g (3,2'-bis(trifluoromethyl)benzidine in a 3 L round flask equipped with a dean-stark device and condenser 0.293 mol), 3,3',4,4'-(biphenylcarboxylic) diphthalanhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride; BPDA) 50.34 g (0.171 mol), 4, 4'-(hexafluoroisopropylidene) diphthalic anhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride; 6FDA) 51.53 g (0.116 mol) and dimethylacetamide (DMAc) 978.36 g and nitrogen The mixture was stirred in an oil bath at 40° C. for 4 hours under an atmosphere to form a polyamic acid polymer.

To the reaction mixture, 2,2'-bis(trifluoromethyl)benzidine (2,2'-bis(trifluoromethyl)benzidine; TFMB) 91.94 g (0.287 mol), and dimethylacetamide (DMAc) 234.27 g were added. I put it.

Then, the slurry prepared in Preparation Example 1 was added to the reaction mixture, and stirred at 40° C. for 4 hours under a nitrogen atmosphere to form a polyamide polymer.

Thereafter, 299.58 g of acetic anhydride and 232.12 g of pyridine were added to the reaction mixture, and the mixture was stirred at 40° C. for 13 hours to perform a chemical imidization reaction.

After the completion of the reaction, dimethylacetamide was further added to dilute the reaction mixture and precipitate in ethanol to obtain a polyamide-imide block copolymer A-1 comprising the first to fourth repeating units having the following structure.

[First repeating unit]-Imide repeating unit

[2nd repeating unit]-imide repeating unit

[Third repeating unit]-Amide repeating unit

[Fourth repeating unit]-Amide repeating unit

Example 2

840.95 g of 2,2'-bis(trifluoromethyl)benzidine (TFMB) in a 30 L round flask equipped with a dean-stark device and a condenser 2.626 mol), 3,3',4,4'-(biphenylcarboxylic) diphthalanhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride; BPDA) 451.33 g (1.534 mol), 4, 4'-(hexafluoroisopropylidene)diphthalic anhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride; 6FDA) 462.01 g (1.040 mol) and dimethylacetamide (DMAc) 8771.47 g and nitrogen The mixture was stirred in an oil bath at 40° C. for 4 hours under an atmosphere to form a polyamic acid polymer.

To the reaction mixture, 2,2'-bis(trifluoromethyl)benzidine (2,2'-bis(trifluoromethyl)benzidine; TFMB) 792.59 g (2.475 mol), and dimethylacetamide (DMAc) 4979.65 g were added. I put it.

Thereafter, the slurry prepared in Preparation Example 2 was added to the reaction mixture, and stirred at 40° C. for 4 hours under a nitrogen atmosphere to form a polyamide polymer.

Thereafter, 2685.90 g of acetic anhydride and 2081.05 g of pyridine were added to the reaction mixture, and the mixture was stirred at 40° C. for 13 hours to perform a chemical imidization reaction.

After completion of the reaction, dimethylacetamide was further added to dilute the reaction mixture and precipitate in ethanol to obtain a polyamide-imide block copolymer A-2 comprising the first to fourth repeating units of Example 1 above. .

[Comparative Examples 1 to 2: Preparation of polyamideimide block copolymer]

Comparative Example 1

A polyamide-imide block copolymer B-1 was obtained in the same manner as in Example 1, except that the solution prepared in Comparative Preparation Example 1 was used instead of the slurry prepared in Preparation Example 1.

Comparative Example 2

Polyamide-imide block copolymer B-2 was obtained in the same manner as in Example 2, except that the solution prepared in Comparative Preparation Example 2 was used instead of the slurry prepared in Preparation Example 2.

Comparative Example 3

Instead of the slurry prepared in Preparation Example 1, isophthaloyl dichloride (IPC) powder 18.25 g and 4,4'-biphenyldicarbonyl chloride (4,4'-Biphenyldicarbonyl Chloride; BPC) powder 56.66 g A polyamide-imide block copolymer B-3 was obtained in the same manner as in Example 1, except that it was used.

[Test Examples 1 to 2]

Test Example 1

For the slurry obtained in the above Preparation Example, the viscosity was measured and shown in Table 1 below. The viscosity was measured at a Shear of 1.2/s with a Haake rheometer, and the results are shown in Table 1 below.

division Viscosity (cP) Preparation Example 1 5.35 Preparation Example 2 5.97

Test Example 2

For the polyamide-imide block copolymer obtained in Examples and Comparative Examples, or a film prepared therefrom, physical properties were evaluated in the following manner, and the results are shown in Table 2 below.

The specific method of manufacturing the film is as follows. A polyamide-imide block copolymer was dissolved in dimethylacetamide to prepare a solution of about 10 wt%. The solution was cast on a glass plate through a bar coater equipment, and the drying temperature was sequentially controlled at 80°C and 140°C. As a result, a polyamide-imide film having a thickness of 50 μm was prepared.

1. Measurement of weight average molecular weight, number average molecular weight, and polydispersity index (PDI)

The polydispersity index of the polyamide-imide block copolymer obtained in Examples and Comparative Examples is a value obtained by dividing a weight average molecular weight (Mw: Weight Average Molecular Weight) by a number average molecular weight (Mw/ Mn), and the weight average molecular weight and number average molecular weight were measured by GPC (Gel Permeation Chromatograph) [temperature of 65° C., dimethylformamide solvent (N,N-Dimethylformamide) and flow rate of 1 mL/min].

2. Mechanical properties

For the polyamide-imide specimens (thickness 50±2 μm) prepared in Examples and Comparative Examples, elastic modulus (EM, GPa) was measured according to the measurement method of ASTM D 882 using a universal testing machine. .

3. Yellow index measurement

For the polyamide-imide specimens (50±2 μm thick) prepared in Examples and Comparative Examples, the yellowing index was measured according to the measurement method of ASTM D1925 using a UV-2600 UV-Vis Spectrometer (SHIMADZU).

Example 1 Comparative Example 1 Comparative Example 3 Example 2 Comparative Example 2 IPC, BPC input method Production Example 1 Slurry Comparative Production Example 1
solution powder Preparation Example 2
Slurry Comparative Production Example 2
solution Weight average molecular weight (g/mol) 417000 301000 1220000 551000 326000 Number average molecular weight (g/mol) 230000 169000 316000 336000 145000 Polydispersity Index 1.813 1.781 3.87 1.640 2.248 Elastic Modulus (GPa) 4.96 4.75 Measurement impossible 5.46 4.86 Yellow index 3.14 3.71 Measurement impossible 3.57 3.17

As shown in Table 2, the polyamide-imide block copolymer of Example 1 has a higher molecular weight and a polydispersity index than Comparative Example 1 in which only the IPC and BPC input methods are different, and has higher elasticity during film production. It has been confirmed that it has a modulus, a yellowness index is reduced, and has excellent mechanical properties along with colorless and transparent appearance characteristics. On the other hand, in the case of Comparative Example 2, which differed only in Example 1 and the IPC and BPC input methods, as the molecular weight was excessively increased, there was a limitation in that the molding processability was reduced to the extent that molding into a film was impossible.

In addition, it was confirmed that the polyamide-imide block copolymer of Example 2 also has a higher molecular weight than Comparative Example 2 in which only the IPC and BPC input methods were different, and has a higher elastic modulus during film production.

Claims (17)

A first step of reacting an aromatic diamine compound with an aromatic tetracarboxylic acid or anhydride thereof; And
A method for producing a polyamideimide block copolymer comprising a second step of reacting the resultant of the first step with an aromatic dicarboxylic acid or a derivative thereof, and an aromatic diamine.
According to claim 1,
The viscosity of the slurry is 2 cP to 30 cP, a method for producing a polyamideimide block copolymer.
According to claim 1,
The slurry,
A method for producing a polyamideimide block copolymer prepared by mixing the aromatic dicarboxylic acid or a derivative thereof and an organic solvent at a temperature of 50° C. or less.
According to claim 1,
The slurry,
A method for producing a polyamideimide block copolymer prepared by mixing the aromatic dicarboxylic acid or a derivative thereof and an organic solvent within 1 minute.
According to claim 1,
A method for producing a polyamideimide block copolymer having a solid content of 10% by weight or more and 30% by weight or less of the slurry.
According to claim 1,
The aromatic dicarboxylic acid or a derivative thereof is represented by the following formula (A), a method for preparing a polyamideimide block copolymer:
[Formula A]

In the above formula A,
Ar is an arylene group having 6 to 20 carbon atoms,
X ₁ and X ₂ are each independently a hydroxy group or halogen.
According to claim 1,
The aromatic dicarboxylic acid or a derivative thereof comprises an isophthalic acid derivative compound and a biphenyl dicarboxylic acid derivative compound, a method for producing a polyamideimide block copolymer.
The method of claim 7,
Isophthalic acid derivative compound: A method for producing a polyamideimide block copolymer comprising a biphenyl dicarboxylic acid derivative compound in a molar ratio of 1: 10 to 1: 1.
According to claim 1,
In the first step,
A method for producing a polyamideimide block copolymer, wherein an aromatic diamine compound and an aromatic tetracarboxylic acid or anhydride thereof are reacted in a molar ratio of 1:0.95 to 1:1.05.
According to claim 1,
The aromatic tetracarboxylic acid or anhydride thereof,
A polyamide comprising an aromatic tetracarboxylic dianhydride containing an unsubstituted aromatic functional group having 6 to 30 carbon atoms and an aromatic tetracarboxylic dianhydride containing an aromatic functional group having 6 to 30 carbon atoms substituted with electron withdrawing functional groups Method for preparing mid block copolymer.
The method of claim 10,
The aromatic tetracarboxylic dianhydride containing an unsubstituted aromatic functional group having 6 to 30 carbon atoms: 10 to 1 to an aromatic tetracarboxylic dianhydride containing an aromatic functional group having 6 to 30 carbon atoms substituted with an electron withdrawing functional group A method for producing a polyamideimide block copolymer comprising a molar ratio of 1:1.
According to claim 1,
After the second step,
The method of the polyamideimide block copolymer further comprising the step of chemically imidizing or thermally imidating the product of the first step.
An imide block comprising a first repeating unit represented by Formula 1 below; And an amide block comprising any one selected from the group consisting of a second repeating unit represented by Formula 2 and a third repeating unit represented by Formula 3 below:
The molar ratio of the following second repeating unit: third repeating unit is from 1: 10 to 1: 1,
Elastic modulus measured based on a specimen having a thickness of 50 ± 2 μm according to the method of ASTM D 882 is 4.90 GPa or more,
Polyamideimide block copolymer:
[Formula 1]

In Chemical Formula 1,
R ¹ is the same or different from each repeating unit, and each independently a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤=10), -(CF ₂ ) _q -(here 1=q≤=10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or a divalent aromatic organic group having 6 to 30 carbon atoms;
R ² is the same or different from each repeating unit, and each independently -H, -F, -Cl, -Br, -I, -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, -COCH ₃ , -CO ₂ C ₂ H ₅ , a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms ;
n1 and m1 are each independently an integer from 0 to 3;
Y ¹ is the same or different in each repeating unit, and each independently includes a divalent aromatic organic group having 6 to 30 carbon atoms containing at least one trifluoromethyl group (-CF ₃ ); The aromatic organic group may be present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic groups are a single bond, a fluorenylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si( CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤=10), -(CF ₂ ) _q -(here 1=q≤=10), -C(CH ₃ ) ₂ -,- C(CF ₃ ) ₂ -, or -C(=O)NH-.
E ¹ is each independently a single bond or -NH-;
[Formula 2]

[Formula 3]

In Formula 2 and Formula 3,
Y ² and Y ^{2 'are} the same or different from each other in each repeating unit, each independently selected from one or more base trifluoromethyl group (-CF ₃₎ group having 6 to 30 carbon atoms of the divalent aromatic organic group containing gt; The aromatic organic group may be present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic groups are a single bond, a fluorenylene group, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) ₂ -, -Si( CH ₃ ) ₂ -, -(CH ₂ ) _p -(where 1=p≤=10), -(CF ₂ ) _q -(here 1=q≤=10), -C(CH ₃ ) ₂ -,- C(CF ₃ ) ₂ -, or -C(=O)NH-.
E is ^{2, E 2 ', E 3} , E 3', E 4 and E ^{4 'is} a single bond or -NH-, each independently.
The method of claim 13,
A polyamideimide block copolymer having a number average molecular weight of 200000 g/mol or more of the polyamideimide block copolymer.
The method of claim 13,
The polyamideimide block copolymer having a weight average molecular weight of 350000 g/mol or more and 1000000 g/mol or less of the polyamideimide block copolymer.
The method of claim 13,
A polyamideimide block copolymer having a yellow index of 4.0 or less measured based on a specimen having a thickness of 50±2 μm according to the measurement method of ASTM D 1925.
A polymer resin film comprising the polyamideimide block copolymer of claim 13.