TW202003636A - Poly(amide-imide) resin film and method for producing the same - Google Patents

Abstract

The present invention relates to a polyamide-imide resin film, and more particularly, to a polyamide-imide resin film containing a polyamideimide block copolymer of a specific structure and having a low yellowness index, and a method for producing the same. The polyamide-imide resin film comprising: a polyamide-imide block copolymer including an imide block containing a first repeating unit represented by Chemical Formula 1; and an amide block containing any one selected from the group consisting of a second repeating unit represented by Chemical Formula 2 and a third repeating unit represented by Chemical Formula 3. In Chemical Formulae 1 to 3, the definition of each substituents is the same as in the detailed description.

Description

Polyamide-imide resin film

[Cross-reference of related applications] This application claims the rights and interests of Korean Patent Application No. 10-2018-0062983 filed with the Korean Intellectual Property Office on May 31, 2018. The entire contents of the patent application are incorporated by reference In this article.

The present invention relates to a poly(amide-imide) resin film.

Aromatic polyamide-imide resin is a polymer usually having an amorphous structure, and exhibits excellent heat resistance, chemical resistance, electrical characteristics, and dimensional stability due to its rigid chain structure.

Such polyimide resins are widely used as materials for power/electronic parts, aerospace materials, aerospace materials, automotive materials, and the like.

However, regardless of their excellent heat resistance, all aromatic polyamide-imide resins are mostly insoluble and infusible, and have poor moldability. Therefore, there is a problem that it is difficult to use conventional processing equipment to process the resin.

Therefore, various studies have been conducted to improve the melt formability while having excellent heat resistance of the polyamido-imide resin and minimizing the reduction in mechanical properties at high temperatures. For example, in an attempt to increase the flexibility of the chain in the polyamido-imide resin, methods of introducing -O-, -S- groups, etc. and introducing meta substituents or large molecular structures and Analog methods.

Due to the curved structure or the aliphatic cyclic compound, the polyamido-imidimide resin according to the aforementioned proposal has difficulty in exhibiting sufficient heat resistance, and the film manufactured using the polyamido-imide resin still has limitations such as poor mechanical properties.

In addition, when the polyimide-imide resin is used as a flexible display material, in addition to thermal characteristics and mechanical characteristics, it is also necessary to have excellent optical characteristics. There is a problem that it is difficult to satisfy these physical characteristics at the required level at the same time.

[technical problem] The object of the present invention is to provide a polyamine-imide resin film having excellent mechanical properties, high elasticity and heat resistance while being colorless and transparent.

Another object of the present invention is to provide a method for manufacturing a polyamido-imide resin film having excellent mechanical properties, high elasticity, and heat resistance while being colorless and transparent.

其中，在化學式1中， R¹ 在各重複單元中彼此相同或不同，且各自獨立地為單鍵、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)₂ -、-Si(CH₃ )₂ -、-(CH₂ )_p -（其中1=p≤=10）、-(CF₂ )_q -（其中1=q≤=10）、-C(CH₃ )₂ -、-C(CF₃ )₂ -、-C(=O)NH-或具有6至30個碳原子的二價芳族有機基團； R² 在各重複單元中彼此相同或不同，且各自獨立地為-H、-F、-Cl、-Br、-I、-CF₃ 、-CCl₃ 、-CBr₃ 、-CI₃ 、-NO₂ 、-CN、-COCH₃ 、-CO₂ C₂ H₅ 、具有三個具有1至10個碳原子的脂族有機基團的矽烷基、具有1至10個碳原子的脂族有機基團或具有6至20個碳原子的芳族有機基團； n1及m1各自獨立地為0至3之整數； Y¹ 在各重複單元中彼此相同或不同，且各自獨立地包含具有6至30個碳原子的二價芳族有機基團，包含至少一個三氟甲基（-CF₃ ）；且所述芳族有機基團單獨存在；或兩個或大於兩個芳族有機基團彼此鍵結以形成二價稠環；或兩個或大於兩個芳族有機基團由以下鍵聯：單鍵、芴基、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)₂ -、-Si(CH₃ )₂ -、-(CH₂ )_p -（其中1=p≤=10）、-(CF₂ )_q -（其中1=q≤=10）、-C(CH₃ )₂ -、-C(CF₃ )₂ -或-C(=O)NH-； 各E¹ 獨立地為單鍵或-NH-； [化學式2]

[化學式3]

其中，在化學式2及化學式3中， Y² 及Y^2' 在各重複單元中彼此相同或不同，且各自獨立地為具有6至30個碳原子的芳族有機基團，包含至少一個三氟甲基（-CF₃ ）；且所述芳族有機基團單獨存在；或兩個或大於兩個芳族有機基團彼此鍵結以形成二價稠環；或兩個或大於兩個芳族有機基團由以下鍵聯：單鍵、芴基、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)₂ -、-Si(CH₃ )₂ -、-(CH₂ )_p -（其中1=p≤=10）、-(CF₂ )_q -（其中1=q≤=10）、-C(CH₃ )₂ -、-C(CF₃ )₂ -或-C(=O)NH-；以及 E² 、E^2' 、E³ 、E^3' 、E⁴ 以及E^4' 各自獨立地為單鍵或-NH-。[Technical Solution] In one aspect of the present invention, there is provided a polyamido-imidimide resin film, which comprises a polyamido-amidimide block copolymer, and the polyamido-amidimide block The copolymer contains: an amide imide block, which contains the first repeating unit represented by the following chemical formula 1; and an amide block, which contains any one selected from the group consisting of: the second of the following chemical formula 2 The repeating unit and a third repeating unit represented by the following Chemical Formula 3, wherein the molar ratio between the second repeating unit and the third repeating unit is 10:90 to 50:50, and wherein the polyamido-acyl The imine resin film has a yellowness index of 3.80 or less. [Chemical Formula 1]

Among them, in Chemical Formula 1, R ¹ is the same as or different from each other in each repeating unit, and each is 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 repeated in each The units are the same or different from each other, and are 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 , silane group having three aliphatic organic groups having 1 to 10 carbon atoms, aliphatic organic group having 1 to 10 carbon atoms or having 6 to 20 Aromatic organic groups of carbon atoms; n1 and m1 are each independently an integer of 0 to 3; Y ¹ is the same or different from each other in each repeating unit, and each independently contains a divalent having 6 to 30 carbon atoms Aromatic organic groups, including at least one trifluoromethyl group (-CF ₃ ); and the aromatic organic groups exist alone; or two or more aromatic organic groups are bonded to each other to form a divalent condensate Ring; or two or more aromatic organic groups are linked by the following bonds: single bond, fluorenyl, -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 -or -C(=O)NH-; each E ^{1 is} independently a single bond or -NH-; [Chemical Formula 2]

[Chemical Formula 3]

Among them, in Chemical Formula 2 and Chemical Formula 3, Y ² and Y ^2′ are the same or different from each other in each repeating unit, and are each independently an aromatic organic group having 6 to 30 carbon atoms, including at least one trifluoro Methyl (-CF ₃ ); and the aromatic organic groups exist alone; or two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; or two or more aromatic groups Organic groups are linked by the following bonds: single bond, fluorenyl, -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 -or -C(=O)NH-; and E ² , E ^2' , E ³ , E ^3' , E ⁴ and E ^4'are each independently a single bond or -NH-.

In another aspect of the present invention, there is provided a method for manufacturing a polyamido-imide resin film, comprising: making a diamine compound and an aromatic tetracarboxylic acid at a molar ratio of 1:0.98 to 1:1.02 The initial step of the reaction of acid or its anhydride; the synthesis step of the polyamido-imide block copolymer, including the time between the product obtained in the initial step and the mole containing 10:90 to 50:50 A reaction of a mixture of phthalic acid or its derivatives and a derivative of terephthalic acid with an aromatic diamine; and a step of forming a film from a polyamide-imide block copolymer.

Hereinafter, the polyamido-imide resin film and the method for manufacturing the polyamido-imide resin film will be described in detail according to exemplary embodiments of the present invention.

Unless explicitly stated otherwise in this specification, the terms are only used to describe specific embodiments and are not intended to limit the present invention.

As used herein, unless the context clearly indicates otherwise, the singular forms "a" and "said" are intended to include the plural forms as well.

The terms "comprises/comprising" and/or "includes/including" as used herein specify the presence of stated features, regions, integers, steps, operations, elements and/or components, but do not exclude a Or the presence or addition of multiple other features, regions, integers, steps, operations, elements, components, and/or their ethnic groups.

Terms containing serial numbers such as "first" and "second" are used only for the purpose of distinguishing one component from another component, and are not limited by the serial number. For example, the first component may be referred to as the second component, or similarly, the second component may be referred to as the first component without departing from the scope of the present invention.

As used herein, the weight average molecular weight refers to the weight average molecular weight of polystyrene measured by the GPC method. In the process of measuring the weight-average molecular weight of polystyrene measured by the GPC method, a detector and an analytical column, such as commonly known analytical equipment and a differential refractive index detector (refractive) index detector), and commonly used temperature conditions, solvents, and flow rates can be used. Specific examples of measurement conditions may include a temperature of 30°C, chloroform as a solvent, and a flow rate of 1 ml/min (mL/min).

According to an embodiment of the present invention, a polyimide-imide resin film may be provided, which includes a polyimide-imide block copolymer, and the polyimide-imide block copolymer includes: amide The amine block contains the first repeating unit represented by Chemical Formula 1; and the amide block contains any one selected from the group consisting of: the second repeating unit represented by Chemical Formula 2 and the one represented by Chemical Formula 3 The third repeating unit, wherein the molar ratio between the second repeating unit and the third repeating unit is 10:90 to 50:50, and wherein the polyamido-imide resin film has 3.80 or less than 3.80 Yellowness index.

According to another study by the present inventors, it has been found through experiments that when using a polyamido-imino block copolymer containing a first repeating unit in a specific amount: a second repeating unit: a third repeating unit, there is It is possible to provide a polyamide-imide resin film having excellent mechanical properties, high elasticity, and heat resistance while being colorless and transparent, thereby completing the present invention.

When the molar ratio of the second repeating unit: the third repeating unit contained in the polyamide-amide imide block copolymer is 10:90 to 50:50, it is possible to have improved elasticity while maintaining high mechanical properties The internal structure (features) of the polymer. Therefore, it is possible to provide a film which is excellent in processability and easy to form a film, is colorless and transparent, and has excellent mechanical properties.

Specifically, as described below, in the process of forming the amide imide block contained in the polyimide-amide imide block copolymer, the reaction conditions such as the molar ratio of the reactants are adjusted so that the amide When the degree of polymerization of the imine block is 50 or greater than 50 or 90 or greater than 90, the polyimide-imide resin film of the embodiment may have a lower yellowness index, for example, 3.80 or less than 3.80 The yellowness index.

Since the polyamido-imino block copolymer can be prepared by adjusting the reaction conditions (such as the combination of monomers used in the synthesis method as described above), it can have a relatively high weight average molecular weight At the same time, it has a low level of polydispersity index (PDI). In particular, the polyamide-imide block copolymer may have a weight average molecular weight of 100,000 g/mole (g/mol) to 800,000 g/mole and a polydispersity index (PDI) of 1 to 5, And the polyimide-imide resin film of the embodiment can have a high transmittance and a low yellowness index even when the polyimide-imide block copolymer having this weight average molecular weight and polydispersity index is included .

As described above, the polyamido-imide resin film of the embodiment may have excellent mechanical properties, high elasticity, and heat resistance, while being colorless and transparent. More specifically, the elastic modulus of the polyamide-imide resin film measured according to the test method ASTM D 882 based on a thickness of 50±2 micrometers (µm) may be 5.50 GPa or greater than 5.50 GPa , Or 5.50 to 7.00 jipa.

The thickness of the polyimide-imide resin film is not particularly limited, but considering the optical properties, mechanical properties, and elastic modulus of the film, the polyimide-imide resin film may have a thickness of 10 to 100 microns.

The above-mentioned polyamide-imide block copolymer will be described in more detail.

As described above, by introducing a specific structure into the repeating unit contained in the amide block during the manufacture of the polyamido-imide copolymer, the thermal, mechanical, and optical characteristics of the copolymer can be simultaneously improved. In particular, it has been found that by restricting diacyl halide, dicarboxylic acid, and dicarboxylic acid ester compounds to a specific structure and limiting their molar ratio during the manufacture of the copolymer, the optical properties of the resin can be improved Characteristics, while maintaining the mechanical properties and heat resistance of the polyamide-imide copolymer at an excellent level.

其中，在化學式1中， R¹ 在各重複單元中彼此相同或不同，且各自獨立地為單鍵、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)₂ -、-Si(CH₃ )₂ -、-(CH₂ )_p -（其中1=p≤=10）、-(CF₂ )_q -（其中1=q≤=10）、-C(CH₃ )₂ -、-C(CF₃ )₂ -、-C(=O)NH-或具有6至30個碳原子的二價芳族有機基團； R² 在各重複單元中彼此相同或不同，且各自獨立地為-H、-F、-Cl、-Br、-I、-CF₃ 、-CCl₃ 、-CBr₃ 、-CI₃ 、-NO₂ 、-CN、-COCH₃ 、-CO₂ C₂ H₅ 、具有三個具有1至10個碳原子的脂族有機基團的矽烷基、具有1至10個碳原子的脂族有機基團或具有6至20個碳原子的芳族有機基團； n1及m1各自獨立地為0至3之整數； Y¹ 在各重複單元中彼此相同或不同，且各自獨立地包含具有6至30個碳原子的二價芳族有機基團，包含至少一個三氟甲基（-CF₃ ）；且所述芳族有機基團單獨存在；或兩個或大於兩個芳族有機基團彼此鍵結以形成二價稠環；或兩個或大於兩個芳族有機基團由以下鍵聯：單鍵、芴基、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)₂ -、-Si(CH₃ )₂ -、-(CH₂ )_p -（其中1=p≤=10）、-(CF₂ )_q -（其中1=q≤=10）、-C(CH₃ )₂ -、-C(CF₃ )₂ -或-C(=O)NH-；以及 各E¹ 獨立地為單鍵或-NH-。As described above, the polyimide-imide block copolymer may include an imide block, including the first repeating unit represented by the following Chemical Formula 1. ( I ) Repeating unit derived from amide imine : the first repeating unit [Chemical Formula 1]

Among them, in Chemical Formula 1, R ¹ is the same as or different from each other in each repeating unit, and each is 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 repeated in each The units are the same or different from each other, and are 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 , silane group having three aliphatic organic groups having 1 to 10 carbon atoms, aliphatic organic group having 1 to 10 carbon atoms or having 6 to 20 Aromatic organic groups of carbon atoms; n1 and m1 are each independently an integer of 0 to 3; Y ¹ is the same or different from each other in each repeating unit, and each independently contains a divalent having 6 to 30 carbon atoms Aromatic organic groups, including at least one trifluoromethyl group (-CF ₃ ); and the aromatic organic groups exist alone; or two or more aromatic organic groups are bonded to each other to form a divalent condensate Ring; or two or more aromatic organic groups are linked by the following bonds: single bond, fluorenyl, -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 -or -C(=O)NH-; and each E ^{1 is} independently a single bond or -NH-.

Here, the single bond means the case where R ¹ in Chemical Formula 1 is a chemical bond that bonds only groups on both sides.

R ² is the same as or different from each other in each repeating unit, and each may independently be H, -F, -Cl, -Br, -I, -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, -COCH ₃ , -CO ₂ C ₂ H ₅ , silane group having three aliphatic organic groups having 1 to 10 carbon atoms, 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 of 0 to 3.

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

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

Here, a single bond means a case where each substituent in Chemical Formula 1 is a chemical bond that bonds only groups on both sides.

其中，在化學式1-1中， R¹ 、R² 、n1以及m1與化學式1中定義之彼等相同。Preferably, the first repeating unit may include a repeating unit represented by the following Chemical Formula 1-1: [Chemical Formula 1-1]

However, in Chemical Formula 1-1, R ¹ , R ² , n1, and m1 are the same as those defined in Chemical Formula 1.

[化學式3]

其中，在化學式2及化學式3中， Y² 及Y^2' 在各重複單元中彼此相同或不同，且各自獨立地為具有6至30個碳原子的二價芳族有機基團，包含至少一個三氟甲基（-CF₃ ）；且所述芳族有機基團單獨存在；或兩個或大於兩個芳族有機基團彼此鍵結以形成二價稠環；或兩個或大於兩個芳族有機基團由以下鍵聯：單鍵、芴基、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)₂ -、-Si(CH₃ )₂ -、-(CH₂ )_p -（其中1=p≤=10）、-(CF₂ )_q -（其中1=q≤=10）、-C(CH₃ )₂ -、-C(CF₃ )₂ -或-C(=O)NH-；以及 E² 、E^2' 、E³ 、E^3' 、E⁴ 以及E^4' 獨立地為單鍵或-NH-。In addition, the polyamide-amide imide 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 following chemical formula 3 Indicates the third repeating unit. The molar ratio between the second repeating unit and the third repeating unit in the polyamide-amide imide block copolymer may be 10:90 to 50:50. ( Ii ) Repeating units derived from amide : the second repeating unit and the third repeating unit [Chemical Formula 2]

[Chemical Formula 3]

Among them, in Chemical Formula 2 and Chemical Formula 3, Y ² and Y ^2′ are the same or different from each other in each repeating unit, and are each independently a divalent aromatic organic group having 6 to 30 carbon atoms, including at least one Trifluoromethyl (-CF ₃ ); and the aromatic organic group exists alone; or two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; or two or more than two Aromatic organic groups are linked by the following bonds: single bond, fluorenyl, -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} - or -C (= O) NH-; and ^{E 2, E 2 ', E} 3, E 3', E 4 and E ^{4 'are} independently a single bond or -NH-.

）位於間位處，且第三重複單元中之兩個-C(= O)-相對於A（

）位於對位處。The second repeating unit and the third repeating unit are repeating units derived from amide, and in Chemical Formula 2 and Chemical Formula 3, a divalent linking group in the form of -C(=O)-AC(=O)- It is derived from at least one compound selected from the group consisting of diacyl halide, dicarboxylic acid, and dicarboxylic acid ester. Two of the second repeating units -C(=O)-relative to A(

) Is at the meta position, and two of the third repeating units -C(= O)- are relative to A(

) Is located at the counterpoint.

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

Preferably, the third repeating unit may include a repeating unit represented by the following Chemical Formula 3-1. [Chemical Formula 3-1]

On the other hand, in the above-mentioned polyamide-imide block copolymer, the molar ratio between the second repeating unit and the third repeating unit is 10:90 to 50:50, and by satisfying the above molar It can improve the thermal, mechanical and optical properties of the copolymer at the same time. When the molar ratio between the second repeating unit and the third repeating unit is outside the above range, there may be a problem that haze (haziness) increases or yellowing occurs.

More specifically, in the polyimide-imide block copolymer, preferably, the molar ratio of the imide block:amide block may be 3:7 to 6:4. By satisfying the above molar ratio and the molar ratio of the second repeating unit and the third repeating unit at the same time, the mechanical properties, thermal properties, and optical properties of the polyamido-imide resin film can be improved to a high level.

In addition, in the polyimide-imide block copolymer, when the molar ratio of the imide block: amide block is 3:7 to 4:6, the second repeating unit: the third repeating unit The molar ratio may be 20:80 to 50:50 or 30:70 to 45:55, and more preferably about 40:60. When the above ranges are satisfied at the same time, the mechanical properties, thermal properties, and optical properties of the polyamide-imide resin film can be improved to a high level.

In addition, in the above polyimide-imide block copolymer, when the molar ratio of the imide block: amide block is 4.5:5.5 to 4:6, the second repeating unit: the third repeating The molar ratio of the unit may be 20:80 to 40:60. When the above range is satisfied at the same time, the mechanical properties, thermal properties, and optical properties of the polyamide-imide resin film can be improved to a high level.

In the polyimide-imide block copolymer, the degree of polymerization of the imide block may be 50 or greater than 50 or 90 or greater than 90. The degree of polymerization of the imidate block can be confirmed by the molar ratio of the reactant forming the imidate block.

其中，在化學式4中， R^1' 在各重複單元中彼此相同或不同，且各自獨立地為具有6至30個碳原子的二價芳族有機基團；且所述芳族有機基團單獨存在；或兩個或大於兩個芳族有機基團彼此鍵結以形成二價稠環；或兩個或大於兩個芳族有機基團可由以下鍵聯：單鍵、芴基、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)₂ -、-Si(CH₃ )₂ -、-(CH₂ )_p -（其中1=p≤=10）、-(CF₂ )_q -（其中1=q≤=10）、-C(CH₃ )₂ -、-C(CF₃ )₂ -或-C(=O)NH-。 R^2' 在各重複單元中彼此相同或不同，且各自可獨立地為H、-F、-Cl、-Br、-I、-CF₃ 、-CCl₃ 、-CBr₃ 、-CI₃ 、-NO₂ 、-CN、-COCH₃ 、-CO₂ C₂ H₅ 、具有三個具有1至10個碳原子的脂族有機基團的矽烷基、具有1至10個碳原子的脂族有機基團或具有6至20個碳原子的芳族有機基團。 n3及m3可各自獨立地為0至3之整數。 Y^1' 在各重複單元中彼此相同或不同，且各自獨立地為具有6至30個碳原子的二價芳族有機基團，包含至少一個三氟甲基（-CF₃ ）；且所述芳族有機基團單獨存在；或兩個或大於兩個芳族有機基團彼此鍵結以形成二價稠環；或兩個或大於兩個芳族有機基團可由以下鍵聯：單鍵、芴基、-O-、-S-、-C(=O)-、-CH(OH)-、-S(=O)₂ -、-Si(CH₃ )₂ -、-(CH₂ )_p -（其中1=p≤=10）、-(CF₂ )_q -（其中1=q≤=10）、-C(CH₃ )₂ -、-C(CF₃ )₂ -或-C(=O)NH-。 各E^1' 可獨立地為單鍵或-NH-。On the other hand, in addition to the amide imide block and the amide imide block, the polyamide amide-imide block copolymer may further include a fourth repeating unit represented by the following Chemical Formula 4. [Chemical Formula 4]

Wherein, in Chemical Formula 4, R ^{1 'in} each repeating unit the same or different, and are each independently a divalent aromatic organic group having 6 to 30 carbon atoms; and the aromatic organic group alone Exist; or two or more aromatic organic groups are bonded to each other to form a divalent fused ring; or two or more aromatic organic groups can be linked by the following bonds: single bond, fluorenyl, -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 -or -C(=O)NH-. R ^{2 'in} each repeating unit the same or different, and each may independently be H, -F, -Cl, -Br, -I, -CF 3, -CCl 3, -CBr 3, -CI 3, - NO ₂ , -CN, -COCH ₃ , -CO ₂ C ₂ H ₅ , silane group having three aliphatic organic groups having 1 to 10 carbon atoms, aliphatic organic group having 1 to 10 carbon atoms Group or aromatic organic group having 6 to 20 carbon atoms. n3 and m3 can each independently be an integer from 0 to 3. Y ^{1 'in} each repeating unit the same or different, and are each independently a divalent aromatic organic radical having 6-30 carbon atoms, comprising at least one trifluoromethyl group (-CF _3); and the The aromatic organic group exists alone; or two or more aromatic organic groups are bonded to each other to form a divalent fused ring; or two or more aromatic organic groups may be linked by the following bonds: single bond, Fluorenyl, -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 -or -C(= O)NH-. Each of E ^{1 'may} independently be a single bond or -NH-.

As described above, in the polyimide-imide block copolymer containing both the imide block and the amide block, by satisfying the mole between the second repeating unit and the third repeating unit Comparing the molar ratio between the amide imide block and the amide block within a specific range can simultaneously improve the mechanical, thermal and optical properties of the copolymer.

On the other hand, according to another embodiment of the present invention, a method for manufacturing a polyamido-imide resin film may be provided, which includes: combining a diamine compound with a molar ratio of 1:0.98 to 1:1.02 The initial step of the reaction of aromatic tetracarboxylic acid or its anhydride; the synthesis step of polyimide-amide imide block copolymer, which includes making the product and the content of the initial step between 10:90 and 50:50 The reaction of a molar mixture of isophthalic acid or its derivatives and terephthalic acid derivatives with an aromatic diamine; and the step of forming a film from a polyamide-imide block copolymer.

By reacting a diamine compound with an aromatic tetracarboxylic acid or its anhydride at a molar ratio of 1:0.98 to 1:1.02 and the resulting product and isophthalic acid containing a molar ratio of 10:90 to 50:50 Or its derivative: a polyamide-imide block copolymer obtained by the reaction step of a mixture of terephthalic acid derivatives can provide a colorless and transparent polymer with excellent mechanical properties, high elasticity and heat resistance Acetamide-imide resin film.

More specifically, by reacting a diamine compound with an aromatic tetracarboxylic acid or its anhydride at a molar ratio of 1:0.98 to 1:1.02, the degree of polymerization of the amide imide block can be 50 (Unit) or greater than 50, 90 (unit) or greater than 90, and the polyamido-imide resin film produced thereby may have a lower yellowness index (for example, a yellowness index of 3.80 or less than 3.80), It may have a low level of polydispersity index (PDI) while having a relatively high weight average molecular weight, and in addition may have higher elasticity, while being colorless and transparent.

As is generally known, the degree of polymerization of the imidate block can be confirmed by the molar ratio of the reactants forming the imidate block, or the like.

其中，在通式1中，Xn是聚合度，且p意謂反應程度（extend of reaction）。亦即，此表明在反應更接近100%時，聚合度更高，且可獲得更高分子量。For example, according to the Carothers equation, the degree of polymerization (DP) of a step-growth polymer can be expressed by the following general formula 1. [Formula 1]

However, in Formula 1, Xn is the degree of polymerization, and p means the degree of reaction (extend of reaction). That is, this indicates that when the reaction is closer to 100%, the degree of polymerization is higher, and a higher molecular weight can be obtained.

其中，在通式2中，Xn是聚合度，且p意謂反應程度（extend of reaction），且r意謂反應物之化學計量比（stoichiometric ratio of reactant）。舉例而言，當以0.99/1.01之比使用二酐（dianhydride）/二胺（diamine）時，其可經計算為r=0.98。On the other hand, when any of the monomers participating in the reaction is used in excess, the degree of polymerization can be predicted via the following general formula 2. [Formula 2]

Among them, in Formula 2, Xn is the degree of polymerization, and p means the extent of reaction (extend of reaction), and r means the stoichiometric ratio of reactant (stoichiometric ratio of reactant). For example, when dianhydride/diamine is used in a ratio of 0.99/1.01, it can be calculated as r=0.98.

Thus, when one monomer is excessively used, it can be assumed that a limited number of monomers undergo all reactions and p converges to 1, and thus, the general formula 2 can be rewritten as shown in the following calculation equation. [Calculation equation]

Based on such calculation equation, when acid dianhydride/diamine is used in the ratio of 0.99/1.01, the polymerization degree of the polymer can be calculated as 99 in the polymerization reaction calculated as r=0.98 . In addition, in the case of polymer obtained by polymerizing acid dianhydride/diamine at a ratio of 1/2, the degree of polymerization can be calculated to be 3.

On the other hand, specific examples of the diamine compound and the aromatic tetracarboxylic acid or its anhydride are not limited, and a diamine compound capable of forming a repeating unit of Chemical Formula 1 (for example, a diamine containing Y ¹ in Chemical Formula 1 may be used) ) Or an aromatic tetracarboxylic acid or its anhydride (for example, a tetracarboxylic acid or its anhydride containing a chemical structure other than -Y ¹ -E ¹ -in Chemical Formula 1).

On the other hand, the mixture of amide imide blocks formed above and isophthalic acid or its derivatives containing a molar ratio of 10:90 to 50:50: derivatives of terephthalic acid and aromatic Group diamine reaction steps to form polyamide-imide block copolymers.

When the molar ratio of the second repeating unit: the third repeating unit contained in the polyamide-amide imide block copolymer is 10:90 to 50:50, it is possible to have improved elasticity while maintaining high mechanical properties The internal structure (features) of the polymer, and therefore, it is possible to provide a film that is excellent in processability and easy to form a film and is colorless and transparent and has excellent mechanical properties.

On the other hand, the polyamide-imide block copolymer can be synthesized by a method including the steps of: mixing a diamine compound with an aromatic tetracarboxylic acid or its anhydride in a suitable solvent to start the reaction; and then The product obtained in the initial step is reacted with a mixture containing isophthalic acid or its derivative: terephthalic acid derivative in a molar ratio of 10:90 to 50:50 and an aromatic diamine.

The step of synthesizing the polyimide-imide block copolymer may include the step of subjecting the resulting product of the initial step to chemical imidization or thermal imidization. More specifically, a step of inducing a chemical amide imidization reaction by adding a compound such as acetic anhydride or pyridine to the resulting product of the initial step or by azeotropic distillation (azeotropic distillation) or the like to induce the thermal imidization of amide acid. The thermal imidization step may be performed at a temperature of 100°C or higher, or at a temperature of 100°C to 350°C, or at a temperature of 150°C to 250°C.

In addition, as is generally known, low-temperature solution polymerization, interfacial polymerization, melt polymerization, solid-phase polymerization, or the like can be used to manufacture polyamide-amide imide block copolymers.

When manufacturing the polyamide-imide resin film, preferably, the molar ratio of the product of the initial step: the sum of the mixture and the aromatic diamine may be 3:7 to 6:4. By satisfying the above molar ratio, the mechanical properties, thermal properties, and optical properties of the polyamido-imide resin film can be improved to a high level.

The product obtained in the initial step may be the reaction product between the diamine compound and the aromatic tetracarboxylic acid or its anhydride (ie, the amide acid compound or the amide imine compound).

More specifically, in the method for manufacturing a polyamido-imide resin film, the ratio of the mole number of the product obtained in the initial step to the mole number of the sum of the mixture and the aromatic diamine may be 3 :7 to 6:4, and the molar ratio of isophthalic acid or its derivatives: terephthalic acid derivatives can be 30:70 to 45:55.

In addition, in the process for manufacturing the polyamide-imide resin film, the molar ratio of the product of the initial step: the sum of the mixture and the aromatic diamine can be 4.5:5.5 to 6:4, and in between The molar ratio of phthalic acid or its derivative: derivative of terephthalic acid may be 20:80 to 40:60, more preferably about 40:60. When the above ranges are satisfied at the same time, the mechanical properties, thermal properties, and optical properties of the polyamide-imide resin film can be improved to a high level.

The derivative of isophthalic acid may be isophthaloyl chloride, and the derivative of terephthalic acid may be terephthaloyl chloride.

On the other hand, the polyamide-amideimide resin film of the embodiment can be provided by forming a film from the polyamide-amideimide block copolymer formed above. More specifically, the polyamido-imide block copolymer can be manufactured by a conventional method (such as a dry method, a wet method, or the like) using a polyamido-imide block copolymer. For example, a polyimide-based membrane can be obtained by coating a solution containing a copolymer on any carrier to form a membrane, and then evaporating the solvent from the membrane to dry the membrane. If necessary, stretching and heat treatment of the polyimide film can be performed.

As described above, the polyimide-imide resin film can be produced by: at a predetermined temperature (for example, at a temperature of 100° C. or higher), the above-mentioned polyimide-imide The block copolymer is heat-treated to prepare a film, and then the film is stretched.

The specific methods and conditions of stretching and the equipment to be used are not subject to specific restrictions. For example, after subjecting the polyamide-amide imide block copolymer to a preliminary heat treatment at a temperature of 150°C to 280°C, a rate of about 0.1%/sec (%/sec) can be applied at 150°C Stretching is performed at a temperature to 280° C. at a predetermined stretch ratio (for example, a stretch ratio of about 5%) to obtain a stretched polyamide-imide resin film.

[Favourable effect] According to the present invention, it is possible to provide a colorless and transparent polyimide-imide resin film having excellent mechanical properties, high elasticity, and folding strength. The polyamide-imide resin film can be used for the substrate of the display, the protective film of the display, the touch panel, and the covering of flexible devices or foldable devices due to the characteristics described above Membranes and the like.

In the following, preferred examples are presented to help understand the present invention. However, the following examples are given for illustrative purposes only, and the scope of the present invention is not intended to be limited to or by these examples. [ Example 1 to Example 2 and Comparative Example 1 to Comparative Example 2 : Preparation of Polyamide - Imidimide Block Copolymer ] Example 1

Combine 2,2'-bis(trifluoromethyl)benzidine (2,2'-bis(trifluoromethly)benzidine) (3.23 grams (g)), 3,3',4,4'-biphenyltetracarboxylic acid bis Anhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride) (1.74 g), 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride) (1.78 g) and dimethylacetamide (37.48 g) were added to a 500-mL (mL) round-bottom flask equipped with a Dean-Stark equipment and condenser, and The mixture was stirred in an oil bath at a temperature of 40°C for 4 hours under a nitrogen atmosphere to form a polyamide polymer.

After 4 hours, add 2,2'-bis(trifluoromethyl)benzidine (4.77 g), isophthaloyl dichloride (IPC) (0.93 G), 4,4'-biphenyldicarbonyl chloride (4,4'-biphenyldicarbonyl chloride; BPC) (2.93 g) and dimethylacetamide (116.35 g) were added to the reaction mixture, and It was reacted under a nitrogen atmosphere at a temperature of 40°C for 4 hours to form a polyamide polymer. Acetic anhydride (10.22 g) and pyridine (7.92 g) were added to the reaction mixture, and the mixture was stirred at a temperature of 40°C for 12 hours to carry out chemical imidization.

After the reaction is completed, dimethylacetamide is additionally added, and the reaction mixture is diluted and then precipitated in ethanol to obtain polyamido-amide imide containing the first to fourth repeating units of the following structure Segment copolymer A-1 (weight average molecular weight of about 600,000 g/mol).

[第二重複單元]-醯亞胺重複單元

[第三重複單元]-醯胺重複單元

[第四重複單元]-醯胺重複單元

實例 2 以及 比較例 1 至比較例 2 The obtained polyimide-imide block copolymer has a molar ratio of about 40:60 of the first repeating unit and the second repeating unit: the sum of the third repeating unit and the fourth repeating unit (acetylimide block : Amide block), the molar ratio of the first repeating unit: second repeating unit is about 60:40, and the molar ratio of the third repeating unit: fourth repeating unit is about 30:70. [First repeating unit]-amide imine repeating unit

[Second repeating unit]-amide imide repeating unit

[Third repeating unit]-amide repeating unit

[Fourth repeating unit]-amide repeating unit

Example 2 and Comparative Examples 1 to 2

The polyimide-imide copolymer was prepared by adjusting the addition ratio of the individual monomers in Example 1, so as to satisfy the molar ratios shown in Table 1 below. Test case

The polyamide-amide imide copolymer obtained in Examples and Comparative Examples was dissolved in dimethylacetamide to prepare a solution of about 10% by weight (wt%). The solution was cast on a glass plate via a bar coater, and the drying temperature was controlled in order at 80°C and 140°C. Therefore, polyamide-imide films of Examples and Comparative Examples having a thickness of 50 μm were manufactured.

The physical properties of the polymer films prepared using the products obtained in Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 2 below. 1. Measure weight average molecular weight and polydispersity index ( polydispersity index ; PDI )

It is the value (Mw/Mn) of the weight average molecular weight (Mw: weight average molecular weight) of each polymer obtained in the example and the comparative example divided by the number average molecular weight (Mn: number average molecular weight) of the polymer, and By gel permeation chromatography (Gel Permeation Chromatograph; GPC) [65°C temperature, N,N-dimethylformamide (N,N-dimethylformamide) solvent and flow rate of 1 ml/min (flow rate )] to measure the weight average molecular weight and number average molecular weight. 2. Mechanical properties

A universal testing machine (universal testing machine) was used to measure the elastic modulus (EM, GPa) of a film with a thickness of 30±2 microns according to the test method ASTM D 882. 3. Measure the yellowness index

Using the UV-2600 UV-vis spectrometer (SHIMADZU) according to the test method ASTM D1925 to measure the polyamido-imide film samples (thickness 50±2 microns) manufactured in the examples and comparative examples The yellowness index and the results are shown in Table 1 below. [Table 1]

As shown in Table 1 above, it was confirmed that when the yellowness index is low, the polyamido-imide resin films of Examples 1 and 2 have a high elastic modulus, and therefore have excellent mechanical properties and colorless transparency Appearance characteristics.

no

no

Claims (15)

A polyimide-imide resin film, comprising: a polyimide-imide block copolymer, the polyimide-imide block copolymer comprising: an imide block, containing the following chemical formula 1 represents the first repeating unit; and the amide block contains 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, Wherein the molar ratio between the second repeating unit and the third repeating unit is 10:90 to 50:50, and wherein the polyamido-imide resin film has a yellowness of 3.80 or less than 3.80 Index: [Chemical Formula 1]

Among them, in Chemical Formula 1, R ¹ is the same as or different from each other in each repeating unit, and each is 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 Each repeating unit is the same as or different from each other, and each is 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 , silane group having three aliphatic organic groups having 1 to 10 carbon atoms, aliphatic organic group having 1 to 10 carbon atoms or having 6 Aromatic organic groups of up to 20 carbon atoms; n1 and m1 are each independently an integer of 0 to 3; Y ¹ is the same or different from each other in each repeating unit, and each independently contains a group of 6 to 30 carbon atoms A divalent aromatic organic group containing at least one trifluoromethyl group (-CF ₃ ); and the aromatic organic group exists alone; or two or more aromatic organic groups are bonded to each other to form a di Valence fused ring; or two or more aromatic organic groups are linked by the following bonds: single bond, fluorenyl, -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 -or -C(=O)NH-; each E ^{1 is} independently a single bond or -NH-; [Chemical Formula 2]

[Chemical Formula 3]

Among them, in Chemical Formula 2 and Chemical Formula 3, Y ² and Y ^2′ are the same or different from each other in each repeating unit, and are each independently an aromatic organic group having 6 to 30 carbon atoms, including at least one trifluoro Methyl (-CF ₃ ); and the aromatic organic groups exist alone; or two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; or two or more aromatic groups Organic groups are linked by the following bonds: single bond, fluorenyl, -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 -or -C(=O)NH-; and E ² , E ^2' , E ³ , E ^3' , E ⁴ and E ^4'are each independently a single bond or -NH-. The polyimide-amideimide resin film as described in item 1 of the patent application range, wherein the molar ratio of the amideimide block: the amideamide block is 3:7 to 6:4. The polyimide-imide resin film as described in item 1 of the patent application range, wherein the polyimide-imide block copolymer has a weight average molecular weight of 100,000 g/mol to 800,000 g/mol And a polydispersity index (PDI) of 1 to 5. The polyimide-imide resin film as described in item 1 of the patent application scope, wherein the elasticity of the polyimide-imide resin film is measured based on a test method ASTM D 882 based on a thickness of 50±2 microns The modulus is 5.50 MPa or greater. The polyimide-imide resin film as described in item 1 of the patent application scope, wherein the degree of polymerization of the imide block is 50 or more. The polyimide-imide resin film as described in item 1 of the scope of the patent application, wherein the molar ratio of the imide block: the amide block is 3:7 to 4:6, and the The second repeating unit: the molar ratio of the third repeating unit is 30:70 to 45:55. The polyimide-amideimide resin film as described in item 1 of the patent application range, wherein the molar ratio of the amideimide block: amide block is 4.5:5.5 to 6:4, and the Second repeating unit: The molar ratio of the third repeating unit is 20:80 to 40:60. The polyimide-imide resin film as described in item 1 of the patent application range, wherein the polyimide-imide resin film has a thickness of 10 μm to 100 μm. A method for manufacturing polyimide-imide resin film includes: The initial step of reacting the diamine compound with aromatic tetracarboxylic acid or its anhydride at a molar ratio of 1:0.98 to 1:1.02; The synthesis step of the polyamide-imide block copolymer includes: the product obtained in the initial step and isophthalic acid or its derivatives containing a molar ratio of 10:90 to 50:50 and Reaction of a mixture of terephthalic acid derivatives with aromatic diamine; and The step of forming a film from the polyamide-imide block copolymer. The method for manufacturing a polyimide-imide resin film as described in item 9 of the patent application range, wherein the degree of polymerization of the imide block is 50 or more. The method for manufacturing polyimide-imide resin film as described in item 9 of the patent application scope, wherein the degree of polymerization of the imide block is 90 or more. The method for manufacturing a polyamide-imide resin film as described in item 9 of the scope of the patent application, wherein the resulting product of the initial step: the sum of the mixture and the aromatic diamine The molar ratio is 3:7 to 6:4. The method for manufacturing a polyamido-imidimide resin film as described in item 9 of the patent application scope, wherein the number of moles of the resulting product in the initial step: the mixture and the aromatic diamine The molar ratio of the sum of the amines is 3:7 to 6:4; and the molar ratio of the isophthalic acid or its derivative: the derivative of terephthalic acid may be 30:70 to 45: 55. The method for manufacturing a polyamide-imide resin film as described in item 9 of the scope of the patent application, wherein the resulting product of the initial step: the sum of the mixture and the aromatic diamine The molar ratio is 4.5:5.5 to 6:4; and the molar ratio of the isophthalic acid or its derivative: the derivative of terephthalic acid may be 20:80 to 40:60. The method for manufacturing polyamide-imide resin film as described in item 9 of the patent application scope, wherein the derivative of isophthalic acid is isophthaloyl chloride, and the derivative of terephthalic acid The substance is p-phthaloyl chloride.