KR20190123631A - Poly(amide-imide), Film including the same, and Electronic device including the same - Google Patents

Abstract

Poly(amide-imide), a film including the same, and an electronic device including the same are provided. According to the present invention, poly(amide-imide) may comprise a polymerization unit represented by chemical formula A; and a polymerization unit represented by chemical formula B.

Description

Polyamide-imide, a film comprising the same, and an electronic device comprising the same {Poly (amide-imide), Film including the same, and Electronic device including the same}

TECHNICAL FIELD The present invention relates to polymers, and in particular, to polyamide-imide for electronic device substrates.

Glass substrates used in conventional flat panel displays have the advantages of high heat resistance, transparency, and barrier properties, but can be broken when dropped, inflexible, and have a heavier weight compared to thinner thicknesses, which can replace conventional glass substrates. Various studies are being conducted on flexible displays.

In order to use a manufacturing process that controls an electrical signal of a pixel in a flexible display, an organic substrate must be able to withstand high process temperatures. Therefore, the organic substrate should have a low coefficient of thermal expansion. In addition, organic substrates are required to satisfy requirements such as chemical resistance, low oxygen and moisture permeability, transparency and low manufacturing cost.

An object of the present invention is to provide a polymer having improved heat resistance and transparency and a substrate of an electronic device using the same.

The problem to be solved by the present invention is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

According to the present invention, polyamide-imide, films using the same, and electronic devices are provided. According to the present invention, the polyamide-imide may be a polymerized unit represented by the following Chemical Formula A; And it may include a polymerization unit represented by the formula (B).

 [Formula A]

In formula (A), L ₁ includes at least one substituted or unsubstituted aromatic compound having 6 to 30 carbon atoms, and X ₁ , X ₂ , and X ₃ are each independently hydrogen, deuterium, or an alkyl group having 1 to 5 carbon atoms. , A halogen substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen substituted alkoxy group having 1 to 5 carbon atoms, and a is an integer of 1 to 1000.

[Formula B]

In formula (B), Ar ₁ and Ar ₂ are each independently an unsubstituted aromatic ring having 6 to 18 carbon atoms, an alkyl, alkoxy, halogenated alkyl, or halogenated alkoxy substituted aromatic ring having 6 to 18 carbon atoms, b is 1 to 1000 Is an integer between.

In some embodiments, in Formula A, L ₁ may be any one selected from compounds represented by Formula A0.

[Formula A0]

,

,

,

,

,

,

In formula (A0), X ₁₀ , X ₂₀ , and X ₃₀ are each independently hydrogen, deuterium, alkyl group having 1 to 5 carbon atoms, halogen substituted alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, and carbon number Any of 1 to 5 halogen substituted alkoxy groups.

According to an embodiment, any _one of X ₁ , X ₂ , and X ₃ in Formula A is independently a halogen substituted alkyl group having 1 to 5 carbon atoms and a halogen substituted alkoxy group having 1 to 5 carbon atoms. Either one of which is X ₁ , X ₂ , and X ₃ may be hydrogen.

According to embodiments, the ratio of the polymerized unit represented by Formula A to the polymerized unit represented by Formula B may be 20:80 to 80:20.

According to embodiments, the polymerization unit represented by Formula A may be represented by the following Formula A1.

 [Formula A1]

According to embodiments, the polymer unit represented by Formula B may be represented by the following Formula B1.

[Formula B1]

According to embodiments, it may have a number average molecular weight of 10,000 to 200,000.

In some embodiments, the polymer unit represented by Formula A may be combined with the polymer unit represented by Formula B.

According to the invention, the film may comprise said poly amide-imide.

According to the present invention, an electronic device comprises: a substrate comprising said polyamide-imide; A first electrode on the substrate; An emission layer on the first electrode; And a second electrode on the light emitting layer.

According to the present invention, the polyamide-imide may be represented by the following formula (1).

 [Formula 1]

In Formula 1, L ₁ includes at least one or more substituted or unsubstituted aromatic compounds having 6 to 30 carbon atoms, and X ₁ , X ₂ , and X ₃ are each independently hydrogen, deuterium, or an alkyl group having 1 to 5 carbon atoms. , A halogen substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen substituted alkoxy group having 1 to 5 carbon atoms, and Ar ₁ and Ar ₂ are each independently 6 to 18 carbon atoms. Unsubstituted aromatic ring or alkyl, alkoxy, halogenated alkyl, or halogenated alkoxy substituted aromatic ring having 6 to 18 carbon atoms, n is an integer from 10 to 2,000, a is an integer from 1 to 1000, b is 1 Is an integer between 1000 and 1000.

According to embodiments, L ₁ in Formula 1 may be any one selected from compounds represented by Formula A0 below.

[Formula A0]

,

,

,

,

,

,

In formula (A0), X ₁₀ , X ₂₀ , and X ₃₀ are each independently hydrogen, deuterium, alkyl group having 1 to 5 carbon atoms, halogen substituted alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, and carbon number Any of 1 to 5 halogen substituted alkoxy groups.

According to embodiments, in Formula 1, the ratio of a to b may be 20:80 to 80:20.

According to the present invention, polyamide-imide can exhibit high permeability and improved heat resistance.

1 is a cross-sectional view showing a film according to the embodiments.
2 is a cross-sectional view illustrating an electronic device according to example embodiments.
3 is a result of Fourier Transform Infrared spectroscopy of the polymer of Comparative Example 1.
4 is an infrared spectroscopic analysis result of the polymer of Comparative Example 2.
5 is an infrared spectroscopic analysis result of the polymer of Experimental Example 3.

In order to fully understand the constitution and effects of the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be embodied in various forms and various changes may be made. Only, the description of the embodiments are provided to make the disclosure of the present invention complete, and to provide a complete scope of the invention to those skilled in the art. Those skilled in the art will understand that the concept of the present invention may be carried out in any suitable environment.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In this specification, the singular also includes the plural unless specifically stated otherwise in the phrase. As used herein, the words "comprises" and / or "comprising" refer to the presence of one or more other components, steps, operations and / or elements. Or does not exclude additions.

In the present specification, the alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. Although carbon number of an alkyl group is not specifically limited, It may be a C1-C5 alkyl group. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, i-butyl group, 2-ethylbutyl group, 3, 3-dimethylbutyl group, n-pentyl group , i-pentyl group, neopentyl group, t-pentyl group, cyclopentyl group and the like, but are not limited thereto.

In the present specification, the carbon number of the alkoxy group is not particularly limited, but may be 1 or more and 5 or less. Alkoxy groups may include alkyl alkoxy groups and aryl alkoxy groups.

In the present specification, examples of the halogen include, but are not limited to, fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

In this specification, "substituted or unsubstituted" is selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group It may mean substituted or unsubstituted with one or more substituents selected. In addition, each of the substituents exemplified above may be substituted or unsubstituted. For example, halogenated alkoxy groups can be interpreted as alkoxy groups. .

Unless otherwise defined in the chemical formula of the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it may mean that a hydrogen atom is bonded at the position.

In this specification, like reference numerals may refer to like elements throughout.

Hereinafter, a polymer according to the concept of the present invention will be described.

According to the present invention, polymers can be used in substrates for electronic devices. The polymer may be a random copolymer. The polymer may comprise poly (amide-imide). According to the embodiments, the polymer may include a polymerization unit represented by Formula A below and a polymerization unit represented by Formula B below. The polymer may have a number average molecular weight of 10,000 to 200,000.

[Formula A]

In formula (A), L ₁ includes at least one substituted or unsubstituted aromatic compound having 6 to 30 carbon atoms, and X ₁ , X ₂ , and X ₃ are each independently hydrogen, deuterium, or an alkyl group having 1 to 5 carbon atoms. , A halogen substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen substituted alkoxy group having 1 to 5 carbon atoms. a can be an integer between 1 and 1000.

According to an embodiment, any _one of X ₁ , X ₂ , and X ₃ in Formula A is each independently selected from a halogen substituted alkyl group having 1 to 5 carbon atoms and a halogen substituted alkoxy group having 1 to 5 carbon atoms Can be. The other one of X ₁ , X ₂ , and X ₃ in Formula A may be hydrogen.

According to an embodiment, in Formula A, L ₁ may be any one selected from compounds represented by Formula A0 below.

[Formula A0]

,

,

,

,

,

,

In formula (A0), X ₁₀ , X ₂₀ , and X ₃₀ are each independently hydrogen, deuterium, alkyl group having 1 to 5 carbon atoms, halogen substituted alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, and carbon number Any of 1 to 5 halogen substituted alkoxy groups.

According to one embodiment, any two of X ₁₀ , X ₂₀ , and X ₃₀ in Formula A0 are each independently selected from a halogen substituted alkyl group having 1 to 5 carbon atoms and a halogen substituted alkoxy group having 1 to 5 carbon atoms , And the other of X ₁₀ , X ₂₀ , and X ₃₀ may be hydrogen or deuterium.

The polymerization unit represented by Formula A may be, for example, represented by Formula A1 below.

[Formula A1]

According to embodiments, the polymer may include a polymer unit represented by the following formula (B).

[Formula B]

In Formula B, Ar ₁ and Ar ₂ may each independently be an unsubstituted aromatic ring having 6 to 18 carbon atoms or an alkyl, alkoxy, halogenated alkyl, or halogenated alkoxy substituted aromatic ring having 6 to 18 carbon atoms. L ₁ may include at least one substituted or unsubstituted aromatic compound having 6 to 30 carbon atoms. b can be an integer between 1 and 1000.

According to an embodiment, in Formula B, L ₁ may be any one selected from the compounds represented by Formula A0.

The polymerization unit represented by the formula (B) may be represented by, for example, the formula (B1) below.

[Formula B1]

According to one embodiment, the ratio of the polymerized unit represented by Formula A to the polymerized unit represented by Formula B in the polymer may be 20:80 to 80:20. For example, the ratio of the total number of polymer units represented by Formula A to the total number of polymer units represented by Formula B in the polymer may be 20:80 to 80:20. The polymerization unit represented by the formula (A) may be combined with the polymerization unit represented by the formula (B).

According to embodiments, the polymer may be represented by the formula (1).

[Formula 1]

In Formula 1, L ₁ includes at least one substituted or unsubstituted aromatic compound having 6 to 30 carbon atoms, and X ₁ , X ₂ , and X ₃ are each independently hydrogen, deuterium, or an alkyl group having 1 to 5 carbon atoms. , A halogen substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen substituted alkoxy group having 1 to 5 carbon atoms, and Ar ₁ and Ar ₂ are each independently 6 to 18 carbon atoms. Unsubstituted aromatic ring or alkyl, alkoxy, halogenated alkyl, or halogenated alkoxy substituted C6-C18 aromatic ring, n is an integer from 10 to 2,000, a is an integer from 1 to 1000, b is from 1 to 1 It can be an integer between 1000.

According to an embodiment, L ₁ in Formula 1 may be any one selected from compounds represented by Formula A0.

According to one embodiment, in Formula 1, a: b may be 20: 80 to 80: 20.

Hereinafter, a method of manufacturing a polymer according to the embodiments will be described.

The polymer may be prepared by a polymerization reaction of the first monomer, the second monomer, and the third monomer. The first monomer may be represented by Formula (2).

[Formula 2]

In formula (2), X ₁ , X ₂ , and X ₃ are each independently hydrogen, deuterium, an alkyl group having 1 to 5 carbon atoms, a halogen substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. It may be any one selected from halogen substituted alkoxy groups of five.

In one embodiment, the first monomer represented by Formula 2 may be represented by the following Formula 2A.

[Formula 2A]

The first monomer represented by Formula 2A is 2,2 '-(2,2'-bis (trifluoromethyl)-[1,1'-biphenyl] -4,4'-diyl) bis (1,3 -Dioxoisoindolin-5-carboxylic acid) (2,2 '-(2,2'-bis (trifluoromethyl)-[1,1'-biphenyl] -4,4'-diyl) bis (1,3-dioxoisoindoline -5-carboxylic acid)).

In one embodiment, the first monomer represented by Formula 2A may be prepared based on Scheme A below.

Scheme A

(AcOH in Scheme A means acetic acid, CH ₃ COOH.)

The second monomer may be represented by the formula (3).

[Formula 3]

In Formula 3, Ar ₁ and Ar ₂ may each independently be an unsubstituted aromatic ring having 6 to 18 carbon atoms, or an alkyl, alkoxy, halogenated alkyl, or halogenated alkoxy substituted aromatic ring having 6 to 18 carbon atoms.

In one embodiment, the first monomer represented by Formula 3 may be represented by the following Formula 3A.

[Formula 3A]

The third monomer represented by Formula 3A is 1,3,5,7-tetraoxo-2,6-diphenyldodecahydropyrrolo [3,4-f] isoindole-4,8-dicarboxylic acid (1, 3,5,7-Tetraoxo-2,6-diphenyldodecahydropyrrolo [3,4-f] isoindole-4,8-dicarboxylic acid).

In one embodiment, the second monomer represented by Formula 3A may be prepared as in Scheme B.

Scheme B

(AcOH in Scheme B means acetic acid, CH ₃ COOH.)

The third monomer may be represented by the formula (4).

[Formula 4]

In Formula 4, L ₁ may include at least one substituted or unsubstituted aromatic compound having 6 to 30 carbon atoms. L0 may be any one of the compounds represented by Formula A0.

In one embodiment, the first monomer represented by Formula 4 may include the following Formula 4A.

[Formula 4A]

The preparation of the polymer can proceed as in Scheme 1.

Scheme 1

In Scheme 1, NMP is N-methylpyrrolidone, Py is pyridine and TPP is triphenylphosphite. L ₁ , X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ , a, b, and n are as defined in Formula 1.

More specific example of Scheme 1 is the same as Scheme 1A below.

Scheme 1A

According to the embodiments, by controlling the molar ratio of the first monomer and the second monomer added, the ratio of the polymer unit represented by the formula (A) and the polymer unit represented by the formula (B) in the polymer can be controlled. For example, the ratio of the polymerized unit represented by the general formula (A) and the polymerized unit represented by the general formula (B) in the polymer may be substantially the same as the molar ratio of the first monomer and the second monomer to be added. Here, the substantially same includes the error range that can occur in the process.

Hereinafter, a film and an electronic device including a polymer according to embodiments of the present invention will be described.

1 is a cross-sectional view showing a film according to the embodiments.

Referring to FIG. 1, the film 100 may include the polymer described above. For example, the polymer may include a polymerized unit represented by Formula A and a polymerized unit represented by Formula B. According to embodiments, the polymer solution may be prepared by dissolving the polymer in a solvent. The polymer can be dissolved in various kinds of solvents. For example methylacetamide, tetrahydrofuran (THF), acetone, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), and / or Cresol may be used as the solvent. Accordingly, the restriction on the selection of the solvent in the manufacturing process of the film 100 can be reduced. By applying the polymer solution onto a temporary substrate (not shown), a preliminary film (not shown) can be produced. A drying process of the preliminary film may be performed to manufacture the film 100. During the drying process of the preliminary film, the solvent in the preliminary film can be removed. The drying process of the preliminary film can be carried out under vacuum conditions. The drying process of the preliminary film may include a first drying process, a second drying process, and a third drying process. The first drying process may be performed at room temperature (eg, 10 ° C. to 30 ° C.). During the first drying process, bubbles in the film 100 may be removed. The second drying process may be performed at higher temperature conditions (eg, greater than 30 ° C. and less than 50 ° C.) than the first drying process. The third drying process may be performed at higher temperature conditions (eg, greater than 50 ° C. and 200 ° C.) than the second drying process. During the second and third drying processes, the solvent in the film 100 may be removed. The temporary substrate can be removed from the film 100.

If the polymer has an extremely low number average molecular weight (eg, a number average molecular weight of less than 10,000), the film 100 may be difficult to manufacture. For example, the preliminary film can be broken. The polymer may have a relatively high molecular weight, including polymerized units represented by formula (A). Accordingly, the film 100 is not broken and can be easily manufactured. The polymerization unit represented by the formula (B) may include an aliphatic ring compound. The polymer may include a polymerized unit represented by Formula B so that the film 100 may have a high transmittance. For example, the film 100 may have a transmittance of 80% or more for light having a wavelength of 550 nm. The film 100 may have a transmittance of 15% or more, specifically 20% or more, for light having a wavelength of 400 nm. The cutoff wavelength of the film 100 may be 370 nm or less. In detail, the breaking wavelength of the film 100 may be, for example, 365 nm to 370 nm.

The film 100 may exhibit heat resistance. For example, the film 100 may have a low coefficient of thermal expansion and a high glass transition temperature (eg, a glass transition temperature of 350 ° C. or higher). According to embodiments, the film 100 may be flexible.

2 is a cross-sectional view illustrating an electronic device according to example embodiments.

Referring to FIG. 2, the electronic device 1 may include a polymer substrate 100 ′, a first electrode 200, a light emitting layer 300, and a second electrode 400. The film 100 described in FIG. 1 may be used as the polymer substrate 100 ′. The polymer substrate 100 ′ may have a high transmittance. For example, the polymer substrate 100 ′ may be transparent. The first electrode 200, the light emitting layer 300, and the second electrode 400 layer are formed on the polymer substrate 100 ′ to manufacture the electronic device 1. For example, the light emitting layer 300 may be an organic light emitting layer, and the electronic device 1 may be an organic light emitting diode.

According to embodiments, since the film 100 is used as the polymer substrate 100 ′, the polymer substrate 100 ′ may have heat resistance. The film 100 may not be damaged in the process of forming the first electrode 200, the process of forming the light emitting layer 300, and the process of forming the second electrode 400.

Hereinafter, the synthesis of the polymer and the production of the organic film will be described with reference to the experimental examples of the present invention.

1. Synthesis of First Monomer Represented by Formula 2A

2,2'-bis (trifluoromethyl) benzidine (0.64 g, 2.0 mmol), trimellitic anhydride (0.77 g, 4.02 mmol), and 15 ml of glacial acetic acid were added to a two-necked round bottom flask to prepare a mixed solution. . The mixture is refluxed at 128 ^° C. for 24 hours and then precipitated in distilled water to give the product. The product is recrystallized in methanol and then filtered and dried to 120 ^° C. in a vacuum oven.

[Nuclear Magnetic Resonance (NMR) Analysis]

The chemical shift value (δ) of the synthesized material measured by ¹ H NMR (400 MHz, DMSO- d ₆ , 25 ° C., ppm) is 13.82 (broad, COOH), 8.45 (dd, J = 7.8, 1.4 Hz, 2H ), 8.35 (dd, J = 1.4, 0.7 Hz, 2H), 8.14 (dd, J = 7.7, 0.7 Hz, 2H), 8.07 (d, J = 2.1 Hz, 2H), 7.88 (dd, J = 8.2, 2.1 Hz, 2H), 7.70 (d, J = 8.4 Hz, 2H).

The chemical shift value (δ) of the synthesized material measured by ¹³ C NMR (100 MHz, DMSO- d ₆ , 25 ° C, ppm) is 166.38 (d, J = 1.7 Hz), 166.21, 137.10, 136.06, 135.88, 135.30 , 132.96, 132.83, 132.48, 130.47, 128.26 (q, J = 31.0 Hz), 124.98, 124.44, 123.95, 123.87 (q, J = 274.4 Hz).

(In the present specification, DMSO means dimethyl sulfoxide)

Therefore, it can be confirmed that the synthesized material is a compound represented by Chemical Formula 2A.

2. Synthesis of Second Monomer Represented by Formula 3A

Cyclohexane-1,2,3,4,5,6-hexacarboxylic acid (1.0 g, 2.88 mmol) and aniline (0.805 g, 8.64 mmol) and 15 ml of glacial acetic acid were added to a two-necked round bottom flask to prepare a mixed solution. do. Mix the mixture for 128 hours^oReflux to C and precipitate in ethyl acetate / hexane 1: 1 solution. The precipitate obtained through the filter was dissolved in dimethylformamide again, and then precipitated again in water acidified to pH 3 and dried in a vacuum oven.^oDry to C.

[Nuclear Magnetic Resonance (NMR) Analysis]

The chemical shift value (δ) of the synthesized material measured by ¹ H NMR (400 MHz, DMSO- d ₆ , 25 ° C., ppm) was 12.87 (broad, COOH), 7.49 (t, J = 7.3 Hz, 4H), 7.42 (t, J = 7.3 Hz, 2H), 7.26 (d, J = 7.5 Hz, 4H), 3.61-3.54 (m, 4H), 3.28-3.20 (m, 2H).

¹³C NMR (100 MHz, DMSO-d ₆The chemical shift values (δ) of the synthesized materials, measured at 25 ° C., ppm), were 176.21, 173.99, 132.45, 129.37, 129.04, 127.44, 42.03, and 40.11.

Therefore, it can be confirmed that the compound represented by the formula (3A) of the synthesized material.

3. Comparative example  One_ Polymer  Synthesis and Film Manufacturing

(1) polymer synthesis

Into a three-neck round bottom flask were added the same number of moles of the first monomer of formula 2A (0.20149 g, 0.30 mmol) and 2,2'-bis (trifluoromethyl) benzidine (0.09653 g, 0.30 mmol). 0.15 g), triphenylphosphite (0.5 ml, 1.90 mmol), pyridine (0.5 ml), and 4 ml of anhydrous N-methyl-2-pyrrolidone were added to prepare a 7.5 wt% solution. At this time, the synthesized first monomer of Formula 2A and 2,2'-bis (trifluoromethyl) benzidine are added in the same mole number.

The flask is equipped with a nitrogen inlet and outlet, and a mechanical stirrer and the solution is stirred at 100 ° C. for 8 hours. After the reaction, the reaction solution is precipitated in water / methanol 1: 1 solution. The precipitated polymer is filtered, washed several times with methanol and dried at 80 ^o C in a vacuum oven. The dried polymer is dissolved in dimethylacetamide again, precipitated in methanol, filtered and dried in a vacuum oven at 180 ° C.

(2) polymer synthesis confirmation

Yield of polymer of Comparative Example 1: 99.50%

The chemical shift value (δ) of the polymer of Comparative Example 1 measured by ¹ H NMR (400 MHz, DMSO- d ₆ , 100 ° C, ppm) was 10.72 (s, 2H), 8.64 (s, 2H), 8.56 (d , J = 7.6 Hz, 2H), 8.36 (s, 2H), 8.24-8.13 (m, 4H), 8.12 (s, 2H), 7.95 (d, J = 8.7 Hz, 2H), 7.67 (d, J = 8.7 Hz, 2H), 7.42 (d, J = 8.6 Hz, 2H).

Fourier Transform Infrared Spectroscopy of the polymer of Comparative Example 1 is shown in FIG. 3.

Elemental Analysis of the Polymer of Comparative Example 1

      found: C 57.70%, H 2.58%, N 6.01%

      Calcd: C 57.99%, H 2.12%, N 5.88%

Therefore, it can be confirmed that the polymer of Comparative Example 1 includes the polymerized unit represented by the formula (A1).

(3) film manufacturing

The polymer of Comparative Example 1 is prepared. 0.15 g of polymer is dissolved in 4 ml of dimethylacetamide to prepare a 3.75 wt% polymer solution. The polymer solution is applied to a glass plate having a width of 5 cm and a length of 5 cm through a syringe filter (5.0 μm). The film is obtained by evaporating the solvent in a vacuum oven for 2 hours at room temperature, one hour at 40 ° C., and 18 hours at 180 ^° C. The thickness of the film produced was 20 μm.

4. Comparative example  2 __ Polymer  Synthesis and Film Manufacturing

(1) polymer synthesis

Into a three-necked round bottom flask, the second monomer of formula 3A (0.53719 g, 1.16 mmol) and 2,2'-bis (trifluoromethyl) benzidine (0.37202 g, 1.16 mmol) were added in the same molar number, and calcium chloride ( 0.3 g), triphenylphosphite (1.2 ml, 4.56 mmol), pyridine (1.2 ml), and 6 ml of anhydrous N-methyl-2-pyrrolidone were added to prepare a 15 wt% solution.

 The flask is equipped with a nitrogen inlet and outlet, and a mechanical stirrer and the solution is stirred at 100 ° C. for 8 hours. After the reaction, the reaction solution is precipitated in water / methanol 1: 1 solution. The precipitated polymer is filtered, washed several times with methanol and dried at 80 ° C. in a vacuum oven. The polymer is again dissolved in dimethylacetamide, precipitated in methanol, filtered and dried in a vacuum oven at 180 ° C.

(2) polymer synthesis confirmation

Yield of polymer of Comparative Example 2: 93.73%

The chemical shift value (δ) of the polymer of Comparative Example 3 measured by ¹ H NMR (400 MHz, DMSO-d 6, 100 ° C., ppm) was 10.21 (s, 2H), 8.15 (s, 2H), 7.85 (d, J = 7.9 Hz, 2H), 7.53 (t, J = 7.8 Hz, 4H), 7.44 (t, J = 6.9 Hz, 2H), 7.41 (d, J = 7.9 Hz, 4H), 7.34 (d, J = 8.4 Hz, 2H), 3.81-3.69 (m, 4H), 3.02-2.89 (m, 2H).

Infrared spectroscopic analysis of the polymer of Comparative Example 2 is the same as FIG.

Assay of polymer of Comparative Example 2:

found: C 59.80%, H 3.32%, N 6.82%

Calcd: C 61.13%, H 3.24%, N 7.50%

Therefore, it can be seen that the polymer of Comparative Example 2 includes a polymer unit represented by the formula (B1).

(3) film manufacturing

A film is prepared in the same manner as in Comparative Example 1. However, the polymer of the comparative example 2 is used. In the case of Comparative Example 2, due to fracture, a film could not be produced.

5. Experimental Example  One __ Polymer  Synthesis and Film Manufacturing

(1) polymer synthesis

A second monomer of Formula 3A and a first monomer of Formula 2A synthesized in a three-neck round bottom flask were added at a 3: 7 ratio (second monomer: 0.10072 g, 0.22 mmol; First monomer: 0.33860 g, 0.22 mmol). 2,2'-bis (trifluoromethyl) benzidine (0.23173 g, 0.73 mmol) is added. At this time, the number of moles of 2,2'-bis (trifluoromethyl) benzidine added is equal to the sum of the number of moles of the synthesized first monomer of Formula 2A and the number of moles of synthesized second monomer of Formula 3A. To this was prepared a 15 wt% solution by adding calcium chloride (0.25 g), triphenylphosphite (1.0 ml, 3.80 mmol), pyridine (1.0 ml) and 4.5 ml of anhydrous N-methyl-2-pyrrolidone.

The flask is equipped with a nitrogen inlet and outlet, and a mechanical stirrer and the solution is stirred at 100 ° C. for 8 hours. After the reaction, the reaction solution is precipitated in water / methanol 1: 1 solution. The precipitated polymer is filtered and washed several times with methanol and dried at 80 ° C in a vacuum oven. The dried polymer is dissolved in dimethylacetamide again, precipitated in methanol, filtered and dried in a vacuum oven at 180 ° C.

(2) polymer synthesis confirmation

Yield of polymer of Experimental Example 1: 99.26%

The chemical shift value (δ) of the polymer of Experimental Example 1 measured by ¹ H NMR (400 MHz, DMSO- d ₆ , 100 ° C, ppm) was 10.78 (s, 1.4H), 10.21 (s, 0.6H), 8.65 (s, 0.6H), 8.57 (d, J = 8.2 Hz, 0.6H), 8.38 (s, 0.6H), 8.36 (s, 1.4H), 8.19-8.16 (m, 1.2H), 8.13 (s, 0.6H), 7.96 (d, J = 8.4 Hz, 1.4H), 7.86 (d, J = 10.2 Hz, 1.4H), 7.68 (d, J = 8.44 Hz, 1.4H), 7.52 (t, J = 3.64 Hz, 2.8H), 7.44-7.39 (m, 4.8H), 7.34 (d, J = 9.2 Hz, 1.4H), 3.81-3.69 (m, 2.8H), 3.02-2.89 (m, 1.4H).

Elemental Analysis of the Polymer of Experimental Example 1

found: C 57.79%, H 2.40%, N 5.53%

Calcd: C 58.93%, H 2.46%, N 6.37%

Therefore, it can be confirmed that the polymer of Experimental Example 1 includes a polymerized unit represented by Formula A1 and a polymerized unit represented by Formula B1.

(3) film manufacturing

A film is prepared in the same manner as in Comparative Example 1. However, the polymer of Experimental Example 1 is used. The thickness of the film produced was 32 μm.

6. Experimental Example  2 __ Polymer  Synthesis and Film Manufacturing

(1) polymer synthesis

A second monomer of formula 3A and a first monomer of formula 2A synthesized in a three-neck round bottom flask were mixed at a 5: 5 ratio (second monomer: 0.21593 g, 0.47 mmol; first monomer, 0.31214 g, 0.47 mmol). Put it in. 2,2'-bis (trifluoromethyl) benzidine (0.29908 g, 0.94 mmol) is further added to the flask. At this time, the number of moles of 2,2'-bis (trifluoromethyl) benzidine added is equal to the sum of the number of moles of the first monomer and the number of moles of the second monomer. Calcium chloride (0.25 g), triphenylphosphite (1.0 ml, 3.80 mmol), and pyridine (1.0 ml) and 5.5 ml of anhydrous N-methyl-2-pyrrolidone were added thereto to prepare a 15 wt% solution. . The flask is equipped with a nitrogen inlet and outlet, and a mechanical stirrer and the solution is stirred at 100 ^° C. for 8 hours. After the reaction, the reaction solution is precipitated in water / methanol 1: 1 solution. The precipitated polymer is filtered and washed several times with methanol and dried at 80 ° C in a vacuum oven. The polymer was dissolved in dimethylacetamide again, precipitated in methanol, filtered and dried in a vacuum oven at 180 ° C.

(2) polymer synthesis confirmation

Yield of the polymer of Experimental Example 1: 97.50%

The chemical shift value (δ) of the polymer of Experiment 3 measured by ¹ H NMR (400 MHz, DMSO- d ₆ , 100 ° C, ppm) was 10.78 (s, 1.4H), 10.21 (s, 0.6H), 8.65 (s, 0.6H), 8.57 (d, J = 8.2 Hz, 0.6H), 8.38 (s, 0.6H), 8.36 (s, 1.4H), 8.19-8.16 (m, 1.2H), 8.13 (s, 0.6H), 7.96 (d, J = 8.4 Hz, 1.4H), 7.86 (d, J = 10.2 Hz, 1.4H), 7.68 (d, J = 8.44 Hz, 1.4H), 7.52 (t, J = 3.64 Hz, 2.8H), 7.44-7.39 (m, 4.8H), 7.34 (d, J = 9.2 Hz, 1.4H), 3.81-3.69 (m, 2.8H), 3.02-2.89 (m, 1.4H).

Elemental Analysis of the Polymer of Experimental Example 1

found: C58.13%, H 2.65%, N 5.81%

Calcd: C 59.56%, H 2.68%, N 6.69%

Therefore, it can be seen that the polymer of Comparative Example 2 includes the polymerized unit represented by the general formula (A1) and the polymerized unit represented by the general formula (B1).

 (3) film manufacturing

A film is prepared in the same manner as in Comparative Example 1. However, the polymer of Experimental Example 3 is used. The thickness of the film produced was 31 μm.

7. Experimental Example  3 __ Polymer  Synthesis and Film Manufacturing

(1) polymer synthesis

A second monomer of formula 3A and a first monomer of formula 2A synthesized in a three-neck round bottom flask were mixed in a 7: 3 ratio (second monomer: 0.23130 g, 0.50 mmol; first monomer, 0.14215 g, 0.21 mmol). Put it in. 2,2'-bis (trifluoromethyl) benzidine (0.22703 g, 0.71 mmol) is further added to the flask. At this time, the number of moles of 2,2'-bis (trifluoromethyl) benzidine added is equal to the sum of the number of moles of the first monomer and the number of moles of the second monomer. A 15 wt% solution is prepared by further adding calcium chloride (0.15 g), triphenylphosphite (1.0 ml, 3.80 mmol), pyridine (1.0 ml), and 4 ml of anhydrous N-methyl-2-pyrrolidone. . The flask was equipped with a nitrogen inlet and outlet, and a mechanical stirrer and the mixed solution was stirred at 100 ° C. for 8 hours. After the reaction, the reaction solution is precipitated in water / methanol 1: 1 solution. The precipitated polymer is filtered, washed several times with methanol and dried at 80 ° C. in a vacuum oven. The polymer is again dissolved in dimethylacetamide, precipitated in methanol, filtered and dried in a vacuum oven at 180 ° C.

(2) polymer synthesis confirmation

Yield of the polymer of Experimental Example 3: 96.56%

The chemical shift value (δ) of the polymer of Experiment 3 measured by ¹ H NMR (400 MHz, DMSO- d ₆ , 100 ° C, ppm) was 10.78 (s, 1H), 10.21 (s, 1H), 8.65 (s , 1H), 8.57 (d, J = 8.2 Hz, 1H), 8.38 (s, 1H), 8.36 (s, 1H), 8.19-8.16 (m, 2H), 8.13 (s, 1H), 7.96 (d, J = 8.4 Hz, 1H), 7.86 (d, J = 10.2 Hz, 1H), 7.68 (d, J = 8.44 Hz, 1H), 7.52 (t, J = 3.64 Hz, 2H), 7.44-7.39 (m, 4H), 7.34 (d, J = 9.2 Hz, 1H), 3.81-3.69 (m, 2H), 3.02-2.89 (m, 1H).

Infrared spectroscopic analysis of the polymer of Experimental Example 3 was the same as FIG.

Elemental Analysis of the Polymer of Experimental Example 3

found: C 59.05%, H 2.90%, N 6.24%

Calcd: C 60.19%, H 2.90%, N 7.01%

Therefore, it can be seen that the polymer of Experimental Example 3 includes a polymerized unit represented by Formula A1 and a polymerized unit represented by Formula B1.

(3) film manufacturing

A film is prepared in the same manner as in Comparative Example 1. However, the polymer of Experimental Example 3 is used. The thickness of the produced film was 39 μm.

8. Characterization

(1) cutoffwavelength

For each of the films of Comparative Example 1, Experimental Example 1, Experimental Example 2, and Experimental Example 3, the temperature at which the permeability began to appear was immediately determined.

(2) transmittance

For each of the films of Comparative Example 1, Experimental Example 1, Experimental Example 2, and Experimental Example 3, the transmittance of light with a wavelength of 400 nm was measured.

For each of the films of Comparative Example 1, Experimental Example 1, Experimental Example 2, and Experimental Example 3, the transmittance of light with a wavelength of 5550 nm was measured.

(3) thermogravimetric analysis

Thermogravimetric analysis was heated to 5 ℃ / min, and the weight of the polymer of Comparative Example 1, Comparative Example 2, Experimental Example 1, Experimental Example 2, and Experimental Example 3 according to the temperature was observed. Thermogravimetric analysis was performed using a thermogravimetric analyzer and analyzed for nitrogen and air conditions respectively. The temperature of the polymer was measured when the weight of the film was reduced by 5%.

(4) Differential Scanning Calorimetry

It heated up at 5 degree-C / min under nitrogen conditions, and the heat flow amount of the polymer of the comparative example 1, the comparative example 2, the experiment example 1, the experiment example 2, and the experiment example 3 with temperature was immediately made. The glass transition temperature was calculated from the second heat flow of the polymers.

(5) thermomechanical analysis

Thermogravimetric analysis was heated to 5 ℃ / min, and the change in the volume of the films of Comparative Example 1, Experimental Example 1, Experimental Example 2, and Experimental Example 3 with temperature.

In the case of Comparative Example 2, a film could not be produced. In comparison, the blocking wavelength, transmittance and coefficient of thermal expansion of the film of 2 could not be measured.

 Table 1 shows the results of evaluating the characteristics of Comparative Example 1, Comparative Example 2, Experimental Example 1, Experimental Example 2, and Experimental Example 3.

λ ⁰
(nm) T _{400 nm}
(%) T _550nm
(%) T _d5 (℃) T _g (℃) CTE (ppm / ℃) In N2 In air 2 ^nd run 3 ^rd run Comparative Example 1 371 11.2 87.1 456 459 > 350 8.7 9.0 Experimental Example 1 371 17.1 89.1 433 427 > 350 21.0 20.6 Experimental Example 2 371 23.3 89.3 412 409 > 350 26.0 26.0 Experimental Example 3 365 40.1 90.0 399 393 > 350 32.4 32.0 Comparative Example 2 - - - 399 394 > 350 - - λ ^{0 :} cutoffwavelength: the wavelength at which the film begins to show transmission
T _400nm : transmittance of film at 400nm,
T _550nm : the transmittance of the film at 550nm,
T _d5 : Thermogravimetric analysis showed that the temperature was reduced by 5%.
T _g : glass transition temperature
CTE: coefficient of thermal expansion

Referring to Table 1, Experimental Example 1, Experimental Example 2, and Experimental Example 3 may have excellent heat resistance and permeability. Experimental Example 3 exhibits a relatively low cutoff wavelength (eg, 370 nm or less).

Transmittance of light of 400 nm wavelength of Experimental Example 1, Experimental Example 2, and Experimental Example 3 may be greater than the transmittance of light of the 400nm wavelength of Comparative Example 1. For example, Experimental Example 1, Experimental Example 2, and Experimental Example 3 may have a transmittance of 15% or more for light having a wavelength of 400 nm. In Experimental Example 2 and Experimental Example 3, the polymer used to prepare the film may satisfy the range of 20:80 to 80:20 of the polymerized unit represented by Formula A1 to the polymerized unit represented by Formula B1. Accordingly, the film can exhibit higher transmittance. Experimental Example 2 and Experimental Example 3 may have a transmittance of 20% or more for light having a wavelength of 400nm. The transmittance of light of 550 nm wavelength of Experimental Example 1, Experimental Example 2, and Experimental Example 3 may be greater than that of light of 550 nm wavelength of Comparative Example 1. From this, it can be seen that Experimental Example 1, Experimental Example 2, and Experimental Example 3 have high transmittance.

As a result of thermogravimetric analysis, the temperature when the weight of the films of Experimental Example 1, Experimental Example 2, and Experimental Example 5 was reduced by 5% was 380 ° C or more. From this, it can be seen that the films of Experimental Example 1, Experimental Example 2, and Experimental Example 3 have relatively excellent heat resistance.

The glass transition temperature of the films of Experimental Example 1, Experimental Example 2, and Experimental Example 3 was 350 degreeC or more. From this, it can be seen that the films of Experimental Example 1, Experimental Example 2, and Experimental Example 3 are difficult to deform at high temperature.

The thermal expansion coefficients of the films of Experimental Example 1, Experimental Example 2, and Experimental Example 3 were low.

Table 2 shows the results of evaluating the solubility of the polymers of Comparative Example 1, Comparative Example 2, Experimental Example 1, Experimental Example 2, and Experimental Example 3 according to the type of solvent. Solubility was evaluated at room temperature (about 25 ℃).

Solvents PAI 1 PAI 2 PAI 3 PAI 4 PAI 5 NMP + + + + + DMAc + + + + + DMF + + + + + DMSO + + + + + m-cresol + + + + + THF + + + + - Chlororoform - - - - - Ethyl acetate s- s- s- s- - Acetone - + + + + Methanol - - - - -

(+: Dissolved,-: not dissolved, s-swelled) (NMP: N-methylpyrrolidone, DMAc: N, N-dimethylacetamide, DMF: N, N-dimethylformamide, DMSO : Dimethyl sulfoxide, THF: tetrahydrofuran, EA: ethyl acetate)

Referring to Table 2, the polymers of Experimental Example 1, Experimental Example 2, and Experimental Example 3 were N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylform Soluble in amide (DMF), dimethyl sulfoxide (DMSO), m-cresol, tetrahydrofuran (THF), and acetone. Since the polymers of the experimental examples are dissolved in various kinds of solvents, the polymers may be improved in applicability. For example, when polymers are used in the manufacture of electronic devices, the constraints on the choice of solvent in the manufacturing process of the electronic device can be reduced.

The foregoing detailed description is not intended to limit the invention to the disclosed embodiments, and may be used in various other combinations, modifications, and environments without departing from the spirit of the invention. The appended claims should be construed to include other embodiments.

Claims (13)

A polymerization unit represented by the following formula (A); And
Polyamide-imide containing the polymerization unit represented by following formula (B).
[Formula A]

In formula (A), L ₁ includes at least one substituted or unsubstituted aromatic compound having 6 to 30 carbon atoms, and X ₁ , X ₂ , and X ₃ are each independently hydrogen, deuterium, or an alkyl group having 1 to 5 carbon atoms. , A halogen substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen substituted alkoxy group having 1 to 5 carbon atoms, and a is an integer of 1 to 1000.
[Formula B]

In formula (B), Ar ₁ and Ar ₂ are each independently an unsubstituted aromatic ring having 6 to 18 carbon atoms, an alkyl, alkoxy, halogenated alkyl, or halogenated alkoxy substituted aromatic ring having 6 to 18 carbon atoms, b is 1 to 1000 Is an integer between.
The method of claim 1,
In Formula (A), L ₁ is any one selected from compounds represented by Formula (A0).
[Formula A0]

,

,

,

In formula (A0), X ₁₀ , X ₂₀ , and X ₃₀ are each independently hydrogen, deuterium, alkyl group of 1 to 5 carbon atoms, halogen substituted alkyl group of 1 to 5 carbon atoms, alkoxy group of 1 to 5 carbon atoms, and carbon number Any of 1 to 5 halogen substituted alkoxy groups. The method of claim 1,
In Formula A, any two of X ₁ , X ₂ , and X ₃ may each independently represent a halogen substituted alkyl group having 1 to 5 carbon atoms and a halogen substituted alkoxy group having 1 to 5 carbon atoms,
Polyamide-imide, wherein the other of X ₁ , X ₂ , and X ₃ is hydrogen. The method of claim 1,
The polyamide-imide of the ratio of the polymerized unit represented by the formula (A) to the polymerized unit represented by the formula (B) is 20:80 to 80:20. The method of claim 1,
The polymerization unit represented by the formula (A) is a polyamide-imide represented by the following formula (A1).
[Formula A1]

The method of claim 1,
The polymerization unit represented by the formula (B) is a polyamide-imide represented by the following formula (B1).
[Formula B1]

The method of claim 1,
Polyamide-imide having a number average molecular weight of 10,000 to 200,000. The method of claim 1,
The polymer unit represented by the formula (A) is a polyamide-imide bonded to the polymer unit represented by the formula (B). The method of claim 1,
A film comprising said polyamide-imide. The method of claim 1,
A substrate comprising said polyamide-imide;
A first electrode on the substrate;
An emission layer on the first electrode; And
An electronic device comprising a second electrode on the light emitting layer.
Polyamide-imide represented by following formula (1).
[Formula 1]

In Formula 1, L ₁ includes at least one or more substituted or unsubstituted aromatic compounds having 6 to 30 carbon atoms, and X ₁ , X ₂ , and X ₃ are each independently hydrogen, deuterium, or an alkyl group having 1 to 5 carbon atoms. , A halogen substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen substituted alkoxy group having 1 to 5 carbon atoms, and Ar ₁ and Ar ₂ are each independently 6 to 18 carbon atoms. Unsubstituted aromatic ring or alkyl, alkoxy, halogenated alkyl, or halogenated alkoxy substituted C6-C18 aromatic ring, n is an integer from 10 to 2,000, a is an integer from 1 to 1000, b is 1 Is an integer between 1000 and 1000.
The method of claim 11,
In Formula 1, L ₁ is any one selected from compounds represented by Formula A0 below.
[Formula A0]

,

,

,

In formula (A0), X ₁₀ , X ₂₀ , and X ₃₀ are each independently hydrogen, deuterium, alkyl group of 1 to 5 carbon atoms, halogen substituted alkyl group of 1 to 5 carbon atoms, alkoxy group of 1 to 5 carbon atoms, and carbon number Any of 1 to 5 halogen substituted alkoxy groups. The method of claim 11,
In Formula 1, the ratio of a to b is 20: 80 to 80: 20 polyamide-imide.

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