TW201946955A - Polyamide-imide block copolymer and polyamide-imide resin film comprising the same - Google Patents

Abstract

The present disclosure relates to a polyamide-imide resin film, and more particularly to a polyamide-imide block copolymer in which the content of fluorine element is 10% by weight to 50% by weight, and has a low dimensional change against water, and a polymer resin film including the same.

Description

Polyimide resin film

[Cross Reference to Related Applications]
This application claims Korean Patent Application No. 10-2018-0056588 filed with the Korean Intellectual Property Office on May 17, 2018, and Korean Patent Application filed with the Korean Intellectual Property Office on May 9, 2019 Case No. 10-2019-0054492, the entire disclosure of the Korean patent application is incorporated in this case for reference.

The invention relates to a polyamidamine / imine resin film.

Aromatic polyamidoamine imine resin is a polymer mainly having an amorphous structure, and because of its rigid chain structure, it exhibits excellent heat resistance, chemical resistance, electrical properties, and dimensional stability. Such polyimide resins are widely used as materials for electrical / electronic, aerospace, aviation, automotive, and the like.

However, although the wholly aromatic polyamide-imide resin has excellent heat resistance, most of it is insoluble and infusible, and has poor moldability and handleability. . Therefore, there is a problem that it is difficult to process the resin using conventional processing equipment.

Therefore, various studies have been conducted to improve melt formability while making the polyamidoamine imine resin excellent in heat resistance and minimizing a decrease in mechanical properties at high temperatures. For example, in an attempt to increase the flexibility of a chain in a polyamidamine / imine resin, a method of introducing -O-, -S- groups, etc., introducing a meta-substituent or a macromolecular structure have been proposed. Method, etc. According to the above-mentioned proposed polyamidoamine imine resin, it is difficult to exhibit sufficient heat resistance due to a curved structure or an aliphatic cyclic compound, and a film produced using the polyamidoamine imine resin still has, for example, mechanical properties. Best restrictions.

In addition, when using a polyamidoamine imine resin as a flexible display material, it is necessary to have excellent optical properties in addition to thermal and mechanical properties. The problem is that it is difficult to simultaneously satisfy these physical properties at the required level.

[technical problem]
An object of the present invention is to provide a polyamidoamine imine block copolymer, which has excellent mechanical properties, high elasticity and folding resistance, and is colorless and transparent at the same time. , And also has high dimensional stability against water.

Another object of the present invention is to provide a polymer resin film including the above-mentioned polyamidofluorine imine block copolymer.

[Technical solution]
In one aspect of the present invention, a polyamidoamine imine block copolymer may be provided, in which the content of the fluorine element is 10 to 50% by weight, and The dimensional change measured after immersion in distilled water at room temperature for 20 hours and drying was 12 microns (µm) or less.

In another aspect of the present invention, a polymer resin film including the polyamidamine / imine block copolymer described above can be provided.

Hereinafter, the polyamidoamine imine block copolymer and the polymer resin film according to the specific examples of the present disclosure will be explained in detail.

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

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

When the terms "comprises and computing" and / or "includes and including" are used herein, they are used to indicate the features, regions, integers, steps, operations, elements, and / or components The presence, but not exclusion, of the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and / or groups thereof.

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

As used herein, the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by the GPC method. Detectors and analytical columns (for example, well-known analytical equipment and differential refractive index detectors) can be used to measure the weight average molecular weight in polystyrene as measured by the GPC method. )), And can use commonly used temperature conditions, solvents and flow rates. Specific examples of measurement conditions may include 1) a temperature of 30 ° C, a chloroform solvent and a flow rate of 1 milliliter / minute (mL / min), or 2) a temperature of 65 ° C, dimethyl formaldehyde ( dimethyl formaldehyde (DMF) and a flow rate of 1 ml / min.

According to an embodiment of the present invention, there can be provided a polyamidamine / imine block copolymer, in which the content of the fluorine element is 10 to 50% by weight, and The dimensional change measured after immersion in distilled water at room temperature for 20 hours and after drying was 12 microns or less.

As a result of further continuous research by the present inventors, a polyamidoamine imine block copolymer was synthesized, in which the content of the fluorine element was 10 to 50% by weight, And even after the polyamidofluorene imine block copolymer is exposed to water, the dimensional change is not so high.

Because of its excellent mechanical properties, high elasticity and folding resistance, it is colorless and transparent, and it also has high water-resistant dimensional stability.醯 Imine block copolymers are suitable for products and industries exposed to humid environments, such as display substrates, display protective films, touch panels, flexible or foldable device covers Film, etc.

More specifically, the polyfluoreneimide block copolymer according to an exemplary embodiment has the following characteristics: the content of the fluorine element is 10 to 50% by weight, and even when the polyfluoreneimide block is The dimensional change of the copolymer after exposure to water is also not too high. This polyamidamine / imine block copolymer has the following physical properties. For example, for a sample with a thickness of 50 ± 2 microns, the yellowness index measured based on ASTM D 1925 is 4.5 or less, and measured based on ASTM D 1003. The haze is 1.1% or less, and therefore has colorless and transparent optical properties.

In addition, when a measurement is performed by applying a strain rate of 12.5 millimeters per minute (mm / min) to a sample having a thickness of 50 ± 2 micrometers, the polyamidoimide block according to the exemplary embodiment is measured. The copolymer may have an elastic modulus of 5 billion Pascals (GPa) or more than 5 Gpa or 5 to 10 GPa, and thus has excellent mechanical properties, high elasticity, and folding resistance.

Specifically, the polyamidoamine imine block copolymer may be an aromatic polyamidoamine imine block copolymer containing a functional group containing fluorine.

More specifically, the polyfluorene imine block copolymer may include a fluorene imine block including a fluorene imine repeat unit, the fluorene imine repeat unit containing an aromatic tetravalent functional group; and Amidine block of amidamine repeating unit, said amidamine repeating unit containing an aromatic divalent functional group, wherein said amidamine repeating unit having an aromatic repeating unit and an aromatic repeat containing an aromatic divalent functional group At least one of the units may be substituted with at least one fluorine-containing functional group.

The dimensional change of the polyamidoamine imine block copolymer of this embodiment can be defined by the following Equation 1, and as described above, the dimensional change according to the definition of Equation 1 can be 12 microns or less, or 11 microns Or less than 11 microns or 1 to 11 microns.
[Equation 1]
Dimensional change (micron) = │ L1-L0 │
Wherein, in Equation 1, L0 is obtained by immersing a film sample prepared from the polyamidamine / imine block copolymer with a thickness of 50 μm, a width of 0.5 cm (cm), and a length of 1.5 cm at 25 ° C The length measured after 20 hours in distilled water, and L1 is the length of the film sample measured after measuring L0 while being dried after being exposed to nitrogen for 12 hours.

The above-mentioned polyamidofluorene imine block copolymer will be explained in more detail.

The polyamidofluorine imine block copolymer can introduce a specific structure into the repeating unit contained in the polyamine block, thereby simultaneously improving the thermal, mechanical, and optical properties of the copolymer. Specifically, it has been found that by limiting diacyl halide, dicarboxylic acid, and dicarboxylic acid ester compounds to a specific structure and limiting their molar ratios during the production of the copolymer, the resin can be improved together Optical properties, while maintaining the mechanical properties and heat resistance of polyamidoamine imine copolymers at an excellent level.

More specifically, the polyfluorene imine block copolymer may include: a fluorene imine block including a first repeating unit represented by the following chemical formula 1; and a fluorene block comprising a selected from the following chemical formula 2 Any one of the group consisting of the second repeating unit represented by and the third repeating unit represented by the following Chemical Formula 3.
( I ) hydrazone-derived repeating unit: first repeating unit
[Chemical Formula 1]

Wherein, in Chemical Formula 1,
R ^{1 is the} same 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 C6 to C30 divalent aromatic organic group;
R ^{2 is the} same or different from each other in each repeating unit, and 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, an alkyl group having three silicon C1 to C10 aliphatic organic group, C1 to C10 aliphatic organic group or a C6 to C20 aromatic organic group;
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 includes a C6 to C30 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 divalent condensed ring; or two or more aromatic organic groups are connected through the following groups: 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} independent Ground is a single bond or -NH-.

Here, a single bond refers to a chemical formula ^1, R ¹ is a case where a chemical bond is simply connected 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 , a silyl group having three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group.

n1 and m1 may be 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 a C3 to C10 aliphatic organic group.

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

Here, the single bond refers to a case where the corresponding substituent in Chemical Formula 1 is a chemical bond that simply connects groups on both sides.

Preferably, the first repeating unit may include a repeating unit represented by the following chemical formula 1-1:
[Chemical Formula 1-1]

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

In addition, the polyamidofluorine imine block copolymer may include a polyamine block comprising a second repeat unit selected from the following chemical formula 2 and a third repeat unit represented by the following chemical formula 3 Anyone in the group.

In the polyamidamine / imine block copolymer, the molar ratio of the second repeating unit: the third repeating unit may be 10:90 to 50:50.

Since the molar ratio of the second repeating unit: the third repeating unit contained in the polyamidoamine imine block copolymer is 10:90 to 50:50, it may have the ability to improve elasticity while maintaining high mechanical The internal structure (characteristics) of a polymer of a natural nature, thereby making it possible to provide a polymer material or film that is excellent in handleability and easily forms a film, and is also colorless and transparent and has excellent mechanical properties. In addition, since the above-mentioned molar ratio is satisfied, the dimensional stability at the time of water absorption can be improved relatively significantly while having a fluorine content of the same level as that of a random copolymer.
( Ii ) Amidine-derived repeating units: second repeating unit and 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 C6 to C30 divalent aromatic organic group 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 condensed ring; or two or more aromatic organic groups are connected through the following groups: 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-.

The second repeating unit and the third repeating unit are repeating units derived from amidine, and in Chemical Formula 2 and Chemical Formula 3, the divalent linking group of the form -C (= O) -AC (= O)-is derived from A group of at least one compound selected from the group consisting of a difluorenyl halide, a dicarboxylic acid, and a dicarboxylic acid ester. Two -C (= O)-relative to A ( ) Is in meta position, and two -C (= O)-in the third repeating unit are relative to A ( ) Is in opposition.

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 polyamidamine / imine block copolymer described above, 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 ratio , Can simultaneously improve the thermal, mechanical and optical properties of the copolymer, and can relatively significantly improve the dimensional stability when absorbing water.

When the molar ratio between the second repeating unit and the third repeating unit exceeds the above range, there may be a problem that haziness increases or yellowing occurs.

More specifically, in the polyamidofluorene imine block copolymer, the mole of the fluoreneimine block: aminium block may be preferably 3: 7 to 6: 4. By satisfying the above-mentioned molar ratios and the molar ratios of the second repeating unit and the third repeating unit at the same time, the mechanical properties, thermal properties, and optical properties of the polyimide resin film can be improved to a high level and can be relatively large. Significantly improves dimensional stability when absorbing water.

In addition, in the polyfluorene imine block copolymer, when the molar ratio of the fluorene imine block: fluorene 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 range is satisfied at the same time, the mechanical properties, thermal properties, and optical properties of the polyamidamine / imide resin film can be improved to a high level, and the dimensional stability when water is absorbed can be relatively greatly improved.

In addition, in the polyfluorene imine block copolymer, when the molar ratio of the fluorene imine block: fluorene block is 4.5: 5.5 to 4: 6, the second repeating unit: the third repeating unit The mole ratio can be from 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 polyamidamine / imide resin film can be improved to a high level, and the dimensional stability when water is absorbed can be relatively greatly improved.

On the other hand, in addition to the fluorene imine block and the fluoramine block, the polyfluorene fluorene imine block copolymer may further include a fourth repeating unit represented by the following chemical formula 4:
[Chemical Formula 4]

Among them, in Chemical Formula 4,
R ^{1 ′ in} each repeating unit is the same or different from each other, and each is independently a C6 to C30 divalent aromatic organic group; 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 aromatic organic groups may be connected through the following groups: 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 ′ is the} same 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 , a silyl group having three C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group.

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

Y ^{1 ′ is the} same or different from each other in each repeating unit, and each is independently a C6 to C30 divalent aromatic organic group including at least one trifluoromethyl group (—CF ₃ ); and the aromatic organic group exists alone ; Or 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 may be connected through the following groups: 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 ′} may be independently a single bond or -NH-.

As described above, in the polyamidoimine block copolymer including both the amidoimide block and the amidate block, by satisfying the relationship between the second repeating unit and the third repeating unit within a specific range. The molar ratio and the molar ratio between the fluorene imine block and the fluoramine block can greatly improve the dimensional stability during water absorption and the mechanical, thermal, and optical properties of the copolymer.

The polyamidamine imine block copolymer may have a weight average molecular weight of 10,000 g / mol (g / mol) to 1,000,000 g / mol, preferably 15,000 g / mol to 800,000 g / mol.

On the other hand, the polyamidoamine imine block copolymer can be provided by a preparation method including the steps of: mixing a compound forming a first repeating unit in a suitable solvent to initiate the reaction; and reacting to the above steps A step of adding a compound forming a repeating unit to perform a reaction is added to the mixture; a step of adding a compound forming a third repeating unit to perform a reaction is added to the reaction mixture of the above step; and adding, for example, acetic acid, acetic anhydride ( acetic anhydride, pyridine and other compounds to induce chemical amidine imidation reaction or azeotropic distillation to induce the thermal amidine reaction of amidine acid.

More specifically, the polyamidoamine imine block copolymer can be provided by a synthetic process of the polyamidoamine imine block copolymer including the following steps: a diamine compound and an aromatic tetracarboxylic acid or an anhydride thereof A starting step of the reaction; and a mixture of the product obtained from the starting step with isophthalic acid or a derivative thereof and a terephthalic acid derivative having a molar ratio of 10:90 to 50:50 and an aromatic Diamine reaction step.

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 the repeating unit of the above Chemical Formula 1 (for example, a diamine containing Y ¹ in Chemical Formula 1 may be used) Amine), or an aromatic tetracarboxylic acid or an anhydride thereof (for example, a tetracarboxylic acid or an anhydride thereof having a chemical structure different from -Y ¹ -E ¹ -in Chemical Formula 1).

On the other hand, the polyamidofluorene imine block copolymer can be formed by the following steps: forming the polyamidoamine imine block copolymer with isophthalic acid containing a molar ratio of 10:90 to 50:50 or Its derivatives react with a mixture of terephthalic acid derivatives and aromatic diamines.

The step of synthesizing the polyfluorene-imide block copolymer may include a step of subjecting the resulting product of the initial step to chemical hydration or thermal hydration. More specifically, it is possible to induce a chemical amidine reaction by adding a compound such as acetic anhydride or pyridine to the product obtained in the initial step, or by azeotropic distillation ) To induce the step of hot amidine imidation. The thermal arsine 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, when the polyamidamine / imine block copolymer further includes a fourth repeating unit, the following steps may be performed: a step of mixing a compound forming the first repeating unit in an appropriate solvent to initiate the reaction; A step of adding a compound forming a second repeating unit to the reaction mixture to perform the reaction; a step of adding a compound forming a third repeating unit to the reaction mixture to perform the reaction; a step of adding a fourth repeat to the reaction mixture of the above step A unit compound to perform a reaction step; and adding a compound such as acetic anhydride or pyridine to the product obtained in the above step to induce a chemical amidine reaction or by azeotropic distillation A step of inducing the thermal amidation reaction of amidine.

In addition, as is generally known, low-temperature solution polymerization, interfacial polymerization, melt polymerization, solid phase polymerization, and the like can be used for producing polyamide.醯 Imine block copolymer.

According to another embodiment of the present disclosure, a polymer resin film containing a polyamidamine / imine block copolymer may be provided.

The polymer resin film may have a thickness of 5 to 300 microns or 10 to 100 microns.

The polymer resin film of the examples can be produced by using a polyamidamine / imine copolymer by a conventional method such as a dry method or a wet method. For example, a polyimide-based film can be obtained by coating a solution containing a copolymer on an arbitrary support to form a film, and then evaporating a solvent from the film to dry the film. If necessary, stretching and heat treatment of the polyfluorene-imide-based film may be performed.

As described above, a film can be prepared by heat-treating the above polyamidene / imide block copolymer at a predetermined temperature (for example, at a temperature of 100 ° C or higher) to prepare a film, and then stretch the film. To produce polyimide resin.

The specific method and conditions for stretching and the equipment used are not particularly limited. For example, after subjecting the polyamidofluorene imine block copolymer to a primary heat treatment at a temperature of 150 ° C to 280 ° C, it may be applied at a temperature of 150 ° C to 280 ° C by applying about 0.1% / second (% / sec) is stretched at a predetermined stretch ratio (for example, a stretch ratio of about 5%) to provide a stretched polyamidamineimide resin film.

[Beneficial effect]
According to the present invention, it is possible to provide a polymer resin film including a polyamidoimine block copolymer, which has excellent mechanical properties, high elasticity, and folding resistance, and It is colorless and transparent, and also has high moisture dimensional stability.

The polymer resin film containing a polyamidamine imine block copolymer can be used for a display substrate, a display protective film, a touch panel, a cover film for a flexible or foldable device due to the above-mentioned properties. Wait.

In the following, preferred examples are provided to help understand the present invention. However, the following examples are provided for illustrative purposes only, and the scope of the present invention is not intended to be limited to or limited by these examples.
[ Example 1 and Comparative Example 1 : Preparation of polyamidoamine imine block copolymer ]
Example 1

Add 2,2'-bis (trifluoromethyl) benzidine (2,2'-bis (trifluoromethyl) benzidine, 4,4 '-(hexafluoroisopropyl) diphthalic anhydride (4,4 '-(hexafluoroisopropylidene) diphthalic anhydride) and dimethylacetamide were placed in a round bottom flask equipped with a Dean-Stark device and a condenser, and started at room temperature The reaction was stirred. The reaction mixture was stirred under a nitrogen atmosphere using an oil bath at 0 ° C for 4 hours.

After 4 hours, the reaction product was taken out and returned to room temperature, and 2,2'-bis (trifluoromethyl) benzidine, m-benzene was added thereto. Isophthaloyl chloride (IPC), 4,4'-biphenyldicarbonyl chloride (BPC), and dimethylacetamide. The reaction was initiated at room temperature.

After the polyamic acid polymer was formed by the reaction for 4 hours, acetic anhydride and pyridine were added to the reaction mixture, and the mixture was stirred at 40 ° C. in an oil bath. It took 15 hours to perform a chemical amidine reaction.

After the reaction was completed, the mixture was precipitated with water and ethanol (1: 1 (v / v)) to obtain a first repeating unit, a second repeating unit, and a third repeating unit (weight average molecular weight approximately 200,000 g / mole). Polyfluorene imine-block copolymer A-1. The obtained polyamidamine / imine block copolymer has a first repeating unit: the sum of the second repeating unit and the third repeating unit is 50:50 in a molar ratio (①), and the second repeating unit: the third The repeating unit is a Morse ratio of 20:80 (②).
[First repeating unit] -Amidine repeating unit

[Second repeating unit]-Amidine repeating unit (derived from IPC)

[Third repeating unit]-Amidine repeating unit (derived from BPC)

Examples 2 to 4

A polyamidofluorene imine copolymer was prepared in the same manner as in Example 1 except that the addition ratio of the corresponding monomers was adjusted to satisfy the molar ratio shown in Table 1 below.
Comparative Example 1

Add 2,2'-bis (trifluoromethyl) benzidine (2,2'-bis (trifluoromethyl) benzidine), 4,4 '-(hexafluoroisopropyl) diphthalic anhydride (4, 4 '-(hexafluoroisopropylidene) diphthalic anhydride), 4,4'-biphenyldicarbonyl chloride (BPC), isophthaloyl dichloride, and dimethylacetamide (Dimethylacetamide) (70 ml) was placed in a 250 ml round bottom flask equipped with a Dean-Stark apparatus and a condenser, and the reaction was initiated at room temperature.

To the reaction mixture, acetic anhydride and pyridine were added, and then the mixture was stirred at 40 ° C. for 15 hours in an oil bath to perform chemical hydrazone imidization. reaction.

After the reaction was completed, the mixture was precipitated with water and ethanol to obtain a polyfluorene-based random copolymer including the following repeating units (weight average molecular weight: 400,000 g / mole).
[Table 1]
* Imide: amide (Imide: amide) ① represents the molar ratio of the first repeating unit: the second repeating unit + the third repeating unit.
* Amide (amide) repeating unit ratio ② represents the molar ratio of the second repeating unit (or 2-2 repeating unit): the third repeating unit (or 2-2 repeating unit).
Experimental example

The polyamidoamine imine copolymer obtained in each of the above examples and comparative examples was dissolved in dimethylacetamide to prepare a solution of about 10% by weight. The solution was cast on a glass plate by a bar coater, and the drying temperature was controlled to 120 ° C and 200 ° C in this order. As a result, a polyaminium-imide film having a thickness of 50 micrometers was produced.

The physical properties of the polymer films obtained in the examples and comparative examples were evaluated by the following methods, and the results are shown in Table 2 below.
Experimental Example 1: The yellow index (Yellow Index, YI)

According to the test method ASTM D1925, a COH-400 spectrophotometer (NIPPON DENSHOKU INDUSTRIES) was used to measure the polyimide / imide film samples (thickness: 50) produced in the above examples and comparative examples. ± 2 microns) and the results are shown in Table 2 below.
Experimental Example 2: Haze (Hazeness)

According to the test method ASTM D1003, a sample of the polyamidamine / imide film (thickness of 50) was measured using a COH-400 spectrophotometer (NIPPON DENSHOKU INDUSTRIES). ± 2 microns), and the results are shown in Table 2 below.
Experimental Example 3 : Elastic Modulus ( GPa )

The polymer produced in the above examples and comparative examples was measured using a Zwich / Roell z005 (5kN) under a strain rate of 12.5 millimeters per minute (mm / min). Elastic Modulus (GPa) of the amine imine film sample (thickness 50 ± 2 microns), and the results are shown in Table 2 below.
[Table 2]

As shown in Table 2 above, it has been confirmed that the films produced from the polyamidoamine imine resins of Examples 1 to 4 have a high elastic modulus, and at the same time have a low yellow index and a low haze value. Therefore, it was confirmed that the polyfluorene imine block copolymer of the example has improved optical properties as well as excellent thermal properties and mechanical properties.
Experimental Example 4 : Measurement of fluorine element ( F ) content in polymer resin film

The content of the fluorine element (F) in each of the polymer resin films obtained in Example 1 and Comparative Example 1 was measured by element analysis (EA). Connect and use the AQF-2100H device (manufacturer: Mitsubishi Chemical Analytech) and the ICS-5000 device (manufacturer: Dionex) in each of the examples and comparative examples The obtained polymer film collected 0.01 g (g) and was used as a sample.

The total content of the fluorine element contained in the polymer film obtained in each of the above examples and comparative examples was measured twice and averaged. As a result, it was confirmed that the comparative example was 22.6% by weight (wt%), and the example was 22.1% by weight.
Experimental example 5 : Measurement of water resistance dimensional stability of a polymer resin film

The water resistance of the polymer resin film obtained in each of Example 1 and Comparative Example was measured using TMA / SDTA 840 (Thermomechanical Analysis, manufactured by Mettler Toledo). Dimensional stability.

Samples having a width of 0.5 cm * a length of 1.5 cm were obtained from the polymer films obtained in each of the examples and the comparative examples. This sample was immersed in distilled water at 25 ° C for 20 hours, and then the initial dimensions were measured under conditions of 25 ° C and 0.05 Newton (tensile direction). After flowing nitrogen for 12 hours, the samples were finally dried for 12 hours. The dimensions of the samples were measured to obtain water dimensional stability data. The dimensional change of the polymer film obtained in each of the examples and comparative examples obtained according to the following Equation 1 was 12.7 micrometers for the comparative example, and 10.5 micrometers was confirmed for the example.
[Equation 1]
Dimensional change (micron) = │ L1-L0 │
Wherein, in Equation 1, L0 is immersed in a sample of a film having a thickness of 50 micrometers, a width of 0.5 cm, and a length of 1.5 cm prepared from the polyamidofluorine imine block copolymer in a distilled water of 25 ° C. 20 The length measured in hours (in-plane direction of the film), and L1 is the length of the film sample (the surface of the film) measured after drying after measuring L0 while being exposed to nitrogen for 12 hours while drying In-plane direction).
[table 3]

As shown in Table 3, it was confirmed that the polyamidoamine imine block copolymer obtained in the example has extremely high dimensional stability against water, while having the same properties as the polyamidoamine imine random copolymer of the comparative example. Level of fluorine content.

no

no

Claims (15)

A polyamidofluorine imine block copolymer, wherein the content of fluorine element is 10 to 50% by weight, and the dimensional change measured after being immersed in distilled water at room temperature for 20 hours and dried is 12 microns or less. The polyamidamine / imide block copolymer according to item 1 of the scope of the patent application, wherein the dimensional change of the polyamidamine / imide block copolymer is defined by the following Equation 1: [Equation 1] Dimensional change (micron) = │ L1-L0 │ Where, in Equation 1, L0 is the length measured after immersing a film sample made of the polyamidofluorene imine block copolymer with a thickness of 50 microns, a width of 0.5 cm, and a length of 1.5 cm into distilled water at 25 ° C for 20 hours, And L1 is the length of the film sample measured after drying after measuring L0 while being exposed to nitrogen for 12 hours while drying. The polyamidoamine imine block copolymer according to item 1 of the patent application scope, wherein for a sample of the polyamidoimine block copolymer having a thickness of 50 ± 2 micrometers, based on the amount of ASTM D 1925 The measured yellowness index is 4.5 or less, and the haze measured based on ASTM D 1003 is 1.1% or less. The polyamidamine / imide block copolymer according to item 1 of the patent application scope, wherein the polyamidamine / imide block copolymer is applied by applying a strain rate of 12.5 mm / min to the polyamidamine / imide The modulus of elasticity measured for the sample of the segment copolymer is 5 billion Pascals or more. The polyamidoamine imine block copolymer according to item 1 of the scope of patent application, wherein the polyamidoamine imine block copolymer includes: a polyimide block comprising a iminium repeat unit, and Said fluorene imine repeating unit contains an aromatic tetravalent functional group; and a fluorene imine block including a fluorene repeating unit, said fluorene imine repeating unit containing an aromatic divalent functional group, At least one of the amidine repeat unit having an aromatic repeat unit and the aromatic repeat unit containing an aromatic divalent functional group is substituted with at least one fluorine-containing functional group. The polyamidoimide / imine block copolymer according to item 1 of the scope of the patent application, wherein the polyamidoimide / imine block copolymer includes: a polyimide block, including the A repeating unit; and an amidine 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, [Chemical Formula 1] Among them, in Chemical Formula 1, R ^{1 is the} same 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 C6 to C30 divalent aromatic organic group; R ^{2 is the} same or different from each other in each repeating unit, and are 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 C1 to C10 aliphatic organic groups, a C1 to C10 aliphatic organic group, or a C6 to C20 aromatic organic group; n1 and m1 are each independently an integer of 0 to 3; Y ^{1 in the} unit is the same or different from each other, and each independently includes a C6 to C30 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 divalent condensed ring; or two or more aromatic organic groups are connected through the following groups: single bond, fluorene Group, -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 -,-(CF ₃ ) ₂ -or -C (= O) NH- And 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 a C6 to C30 divalent aromatic 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 divalent condensed ring; or two or more aromatic organic groups are through the following groups Connect: 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-. The polyamidamine / imide block copolymer according to item 6 of the application, wherein the molar ratio of the second repeating unit: the third repeating unit is from 10:90 to 50:50. The polyamidofluorene imine block copolymer according to item 6 of the patent application scope, wherein the molar ratio of the fluoreneimine block: the fluoreneamine block is 3: 7 to 6: 4. The polyamidofluorene imine block copolymer according to item 6 of the scope of patent application, wherein the molar ratio of the fluoreneimine block: the fluoramine block is 3: 7 to 4: 6, and The molar ratio of the second repeating unit: the third repeating unit is 30:70 to 45:55. The polyamidofluorene imine block copolymer according to item 6 of the patent application range, wherein the molar ratio of the fluoreneimine block: the fluoreneamine block is 4.5: 5.5 to 4: 6, and The second repeating unit: the molar ratio of the third repeating unit is 20:80 to 40:60. The polyamidamine / imine block copolymer according to item 6 of the scope of patent application, wherein the first repeating unit includes a repeating unit represented by the following chemical formula 1-1: [Chemical formula 1-1] Among them, in Chemical Formula 1-1, R ¹ , R ² , n1 and m1 are the same as those defined in item 1 of the scope of patent application. The polyamidamine / imine block copolymer according to item 6 of the scope of patent application, wherein the second repeating unit includes a repeating unit represented by the following chemical formula 2-1, and the third repeating unit includes a repeating unit Repeating unit represented by Chemical Formula 3-1: [Chemical Formula 2-1] [Chemical Formula 3-1] . The polyamidamine / imine block copolymer according to item 1 of the patent application range, wherein the polyamidamine / imide block copolymer has a weight average of 10,000 g / mole to 1,000,000 g / mole Molecular weight. A polymer resin film comprising the polyamidamine / imine block copolymer described in item 1 of the patent application scope. The polymer resin film according to item 14 of the scope of patent application, wherein the polymer resin film has a thickness of 5 to 300 microns.