Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/14—Polyamide-imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a polyamideimide resin film.
• Aromatic polyamide-imide resins are mostly polymers having an amorphous structure and exhibit excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to their rigid chain structure. Such polyamide-imide resins are widely used as materials for electric / electronic, space, aviation, and automobiles.
• the wholly aromatic polyamide-imide resin is mostly insoluble and infusible in spite of its excellent heat resistance, thereby deteriorating moldability and processability, which makes it difficult to use conventional processing equipment for processing the resin.
• the polyamide-imide resin when used as a flexible display material, it is required to have excellent optical properties in addition to thermal and mechanical properties, and it is difficult to satisfy these properties at the required level at the same time.
• the present invention is to provide a polyamideimide resin film having a colorless transparent and excellent mechanical properties and high elasticity and heat resistance.
• the present invention is to provide a method for producing a polyamideimide resin film having colorless transparent and excellent mechanical properties and high elasticity and heat resistance.
• an imide block including the first repeating unit represented by Formula 1 below; And an amide block comprising any one selected from the group consisting of a second repeating unit represented by the following Formula 2 and a third repeating unit represented by the following Formula 3; and a polyamideimide block copolymer comprising the following:
• a polyamideimide resin film may be provided, wherein the molar ratio of 2 repeating units: third repeating unit is from 10:90 to 50:50 and has a yellow index of 3.80 or less.
• a group an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms;
• ⁇ are each independently a single bond or- ⁇ -;
• X 2 and ' are the same or different from each other in each repeating unit, and each independently a divalent aromatic organic group having 6 to 30 carbon atoms containing at least one trifluoromethyl group (-0 ⁇ 3 ); The aromatic organic groups are present alone;
• the term "comprising 1" embodies a particular characteristic, region, integer, step, operation, element, and / or component, and other specific characteristics, region, integer, step, operation, element, component, and / or group. It does not exclude the presence or absence of a.
• first and 1 second 1 are used to distinguish one element from the other, and is not limited by the ordinal.
• first component may also be referred to as the second component, and similarly, the second component may be referred to as the first component.
• a weight average molecular weight means the weight average molecular weight of polystyrene conversion measured by the GPC method.
• a detector and an analytical column such as a conventionally known analytical device and a differential refractive index detector (Refractive Index Detector) may be used, Temperature conditions, solvents and f low rates can be applied. Specific examples of the measurement conditions include a temperature of 30 ° ( :), a chloroform solvent and a f low rate of 1 mL / min.
• a first repeating unit represented by Chemical Formula 1 An imide block comprising: and an amide block including any one selected from the group consisting of a second repeating unit represented by Formula 2 and a third repeating unit represented by Formula 3; and a polyamideimide block aerial including Including a coalescing, wherein the molar ratio of the second repeating unit to the third repeating unit is from 10:90 to 50: 2019/231100 1 »(: 1 ⁇ 1 ⁇ 2019/004154
• a polyamideimide resin film having a yellowness index of 50 and below 3.80.
• the polyamideimide block copolymer including the second repeating unit: the third repeating unit in a specific content is used, the polyamide is colorless and transparent, and has excellent mechanical properties and high elasticity and heat resistance.
• the mid resin film can be provided and completed the invention.
• the molar ratio of the second repeating unit to the third repeating unit included in the polyamideimide block copolymer is 10:90 to 50:50, a polymer internal structure capable of improving elasticity while maintaining high mechanical properties ( Feature), thereby making it easy to form a film, while providing colorless, transparent and excellent mechanical properties.
• the degree of polymerization [[varies in ⁇ 66 !]) of the imide block is 50 or more, or 90 or more.
• the polyamideimide resin film of this embodiment can have a lower yellow index, for example a yellow index of less than 3.80.
• the polyamideimide block copolymer is as described above; As described above, according to the control of the reaction conditions such as the combination of monomers used in the synthesis process, it may have a relatively high weight average molecular weight and a low polydispersity index. Specifically, the polyamideimide block copolymer may have a weight average molecular weight of 100, 000 yaw / mi 0 1 to 800, 000 and / or polydispersity index 1) 1) of 1 to 5,
• the polyamideimide resin film may include a polyamideimide block copolymer having such a weight average molecular weight and a polydispersity index while having a high transmittance and a low yellow index.
• the polyamide-imide resin film of the embodiment may be colorless and transparent but have excellent mechanical properties and high elasticity and heat resistance, and more specifically, based on a thickness of 50 ⁇ 2 according to the measuring method of 0 882;
• One elastic modulus of the polyamideimide resin film is 5.50 GPa or more, or 5.50 7.00 2019/231100 1 »(: 1 ⁇ 1 ⁇ 2019/004154
• the thickness of the polyamide amide resin film is not particularly limited, considering the optical properties, mechanical properties and elastic modulus of the film, the polyamideimide resin film may have a thickness of 10 to 100 10 1.
• the polyamideimide block copolymer described above will be described in more detail.
• the thermal, mechanical and optical properties of the copolymer can be improved simultaneously.
• the mechanical properties and heat resistance of the polyamide-imide copolymer are limited by limiting the diacyl halide, dicarboxylic acid and dicarboxylate compound to a specific structure and limiting the molar ratio thereof in preparing the copolymer. While maintaining at an excellent level, it was confirmed that the optical properties of the resin can be improved together.
• the polyamideimide block copolymer may include an imide block including the first repeating unit represented by Formula 1 below.
• imide-derived repeating unit first repeating unit
• Seedlings 2 are the same or different from each other in each repeating unit, each independently in,, -01, -, -1, - ⁇ -001 3, ⁇ 3, -01 3 in 02, - - 2019/231100 1 »(: 1 ⁇ 1 ⁇ 2019/004154
• the single bond means a chemical bond when the simply connected group next grave 1, the amount in the formula (1).
• Seedling 2 is the same or different in each repeating unit, and each independently, ⁇ , -01,-,-, -1, ⁇ 3 , -001 3 , ⁇ 3 , -01 3 , 0 2 ,
• ⁇ 3 ⁇ 4,- ⁇ 2 (: 2 3 ⁇ 4, silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, aliphatic organic groups having 1 to 10 carbon atoms, or aromatic organic groups having 6 to 20 carbon atoms.
• 111 and 11) 1 may be each independently an integer of 0 to 3.
• each independently may be an aliphatic organic group having 3 to 10 carbon atoms.
• the first repeating unit may include a repeating unit represented by the following Chemical Formula 1-1:
• the polyamideimide block copolymer may include an amide block including any one selected from the group consisting of a second repeating unit represented by Formula 2 and a third repeating unit represented by Formula 3 below.
• the molar ratio of the following second repeating unit: low 3 repeating units in the polyamideimide block copolymer may be 10:90 to 50:50.
• X 2 and tax 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 group (-0 3 );
• E 2 , E 2 ' , ⁇ And Fig. 4 ' are each independently a single bond or- ⁇ -.
• the second repeating unit may include a repeating unit represented by the following Chemical Formula 2-1.
• the three repeating units may include repeating units represented by the following Formula 3-1.
• the above-mentioned pulliamideimide block copolymer has a molar ratio of 10:90 to 50:50 of the second repeating unit and the third repeating unit, and by satisfying the molar ratio, the copolymer and thermal properties, mechanical properties and optical properties Can be improved at the same time.
• the molar ratio of the second repeating unit and the third repeating unit If it is out of range, problems such as increase of hazes or yellowing may occur.
• the molar ratio of the imide block: amide block may be 3: 7 to 6: 4.
• the mechanical, thermal and optical properties of the polyamideimide resin film can all be improved to a high level.
• the molar ratio of the imide block: amide block is 3: 7 to 4: 6
• the molar ratio of the second repeating unit to the third repeating unit is 20:80 to 50: 50, or 30:70 to 45:55, more preferably about 40:60.
• the molar ratio of the imide block to the amide block when the molar ratio of the imide block to the amide block is 4.5: 5.5 to 4: 6, the molar ratio of the second repeating unit to the third repeating unit is from 20:80 to 40: 60 may be.
• the degree of polymerization of the imide block in the polyamideimide block copolymer may be 50 or more, or 90 or more.
• the degree of polymerization of the imide block can be confirmed through the molar ratio of the reactants forming the imide block.
• polyamideimide block copolymer may further include a fourth repeating unit represented by the following Formula 4 in addition to the imide block and the amide block:
• Fig. 1 ' is the same or different in each repeating unit, and each independently contains a divalent aromatic organic group having 6 to 30 carbon atoms;
• eu ⁇ 2 (: 2 3 ⁇ 4, may be a silyl group, an aromatic organic group having 1 to date 1 ⁇ an aliphatic organic group, or a group having 6 to 20 carbon atoms having 1 to 10 carbon atoms in the three aliphatic organic.
• 113 and 1113 may be independently an integer of 0 to 3, respectively.
• 'Are the same or different in each repeating unit, and each independently one or more tripulolumethyl groups
• ⁇ May each independently be a single bond or- ⁇ -.
• the polyamide-imide block copolymer including both the imide block and the amide block may satisfy the molar ratio between the above-described second repeating unit and the third repeating unit and the molar ratio between the imide block and the amide block in a specific range. , The mechanical, thermal and optical properties of the copolymer can be improved simultaneously.
• a manufacturing method of a polyamideimide resin film may be provided.
• the diamine compound and the aromatic tetracarboxylic acid or anhydride thereof are reacted in a molar ratio of 1: 0.98 to 1: 1.02 to form an imide block, which is 10: 90 to 50: 50 of isophthalic acid or a derivative thereof: terephthalic acid.
• the polyamideimide block copolymer obtained through reacting the mixture containing the molar ratio and the aromatic diamine may provide a polyamideimide resin film having colorless and transparent, excellent mechanical properties and high elasticity and heat resistance.
• the degree of polymerization of the imide block is 50 (units) or more, Or 90 (units) or more, and thus the polyamideimide resin film thus prepared may have a lower yellowness index, for example, a yellowness index of 3.80 or less, and also have a relatively high weight average molecular weight and a low level. It can have a polydispersity index (PDI) of, and can also have a colorless, transparent and higher elasticity.
• PDI polydispersity index
• the degree of polymer izat ion of the imide block can be determined through the molar ratio of the reactants forming the imide block.
• the degree of polymerization (DP) of the step-growth polymer can be represented by the following general formula (1).
• 3 ⁇ 4 is the degree of polymerization
• I) is the degree of reaction (near 0 group). 011).
• the closer the reaction is to 100% the higher the degree of polymerization and the higher the molecular weight.
• the degree of polymerization can be predicted through the following general formula (2).
• Xn is the degree of polymerization
• p means the extent of the reaction ion
• r means stoi chiometic rat io of reactant.
• the degree of polymerization of the polymer may be calculated as 99. In addition In the case of the polymer polymerized by 1/2, the degree of polymerization may be calculated as 3.
• the specific example of the said diamine compound, aromatic tetracarboxylic acid, or its anhydride is not limited,
• the diamine compound (for example, diamine containing the said Formula 1) which can form the repeating unit of Formula 1 mentioned above, Aromatic tetracarboxylic acid or anhydrides thereof (for example, tetracarboxylic acid or anhydrides thereof including a chemical structure except---in Chemical Formula 1) can be used.
• the polyamideimide block copolymer may be formed by reacting the formed imide block with a mixture containing isophthalic acid or a derivative thereof: terephthalic acid at a molar ratio of 10:90 to 50:50 and aromatic diamine. Can be.
• the molar ratio of the second repeating unit to the third repeating unit included in the polyamideimide block copolymer is 10:90 to 50:50, a polymer internal structure capable of improving elasticity while maintaining high mechanical properties ( Feature), thereby making it easy to form a film, while providing colorless, transparent and excellent mechanical properties.
• the polyamideimide block copolymer is a mixture of a diamine compound and an aromatic tetracarboxylic acid or an anhydride thereof in an appropriate solvent to initiate the reaction, the product of the initiating step and isophthalic acid or a derivative thereof: terephthalic acid
• the polyamideimide block copolymer may be synthesized by reacting a mixture containing a derivative in a molar ratio of 10:90 to 50:50 and aromatic diamine.
• Synthesizing the polyamideimide block copolymer may include chemically imidating or thermally imidating the product of the initiating step. More specifically, with respect to the result of the initiation step, a compound such as acetic anhydride (pyridine), pyridine (pyridine) is added to induce a chemical imidization reaction, or by Azeotropic Dist i 1 lation (azeotropic distillation) Inducing a thermal imidization reaction of amic acid may be performed. Wherein the thermal imidization may be performed at a temperature of at least 100 ° C, or 100 ° C to 350 ° C temperature, or 150 ° C to about 250 C in O.
• a compound such as acetic anhydride (pyridine), pyridine (pyridine) is added to induce a chemical imidization reaction, or by Azeotropic Dist i 1 lation (azeotropic distillation)
• a thermal imidization reaction of amic acid may be performed.
• the thermal imidization may be performed at
• low temperature solution polymerization, interfacial polymerization, melt polymerization, solid phase polymerization, and the like may be used to prepare the polyamideimide block copolymer.
• the resultant of the initiation step the molar ratio of the sum of the mixture and the aromatic diamine is 3: 7 to 6: 4 2019/231100 1 »(: 1 ⁇ 1 ⁇ 2019/004154
• the result of the initiation step may be the result of the reaction between the diamine compound and the aromatic tetracarboxylic acid or anhydride thereof, ie an amic acid compound or an imide compound.
• the ratio of the resultant moiety of the sum of the mixture and the aromatic diamine is 3: 7 to 6: 4, and the isophthalic acid or a derivative thereof: terephthalic acid
• the molar ratio of of the derivative may be from 30:70 to 45:55.
• the resultant of the initiation step the molar ratio of the sum total of the mixture and the aromatic diamine is 4.5: 5.5 to 6: 4, and 20 of the isophthalic acid or derivative thereof: terephthalic acid : 80 to 40: 60, more preferably about 40: 60.
• the mechanical properties, thermal properties and optical properties of the polyamideimide resin film can all 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.
• the polyamideimide resin film of the embodiment may be provided by forming a film from the formed liamideimide block copolymer. More specifically, the polyamideimide resin film may be prepared by conventional methods such as a dry method and a wet method using the polyamideimide block copolymer. For example, the polyimide film may be obtained by coating a solution including the copolymer on an arbitrary support to form a film, and drying the solvent by evaporating the solvent from the film. If necessary, stretching and heat treatment of the polyimide film may be performed.
• the polyamideimide resin film may be prepared by preparing the film and stretching the polyamideimide block copolymer described at a predetermined temperature, for example, a temperature of 100 or more.
• a predetermined temperature for example, a temperature of 100 or more.
• a predetermined stretching ratio for example, stretching of about 5% or less at a temperature of 150 to 280 ° (:) It is possible to provide a stretched polyamide-imide resin film by stretching at a rate of about 0.1% ⁇ ⁇ as a ratio.
• a polyamideimide resin film may be provided that is colorless and transparent but has excellent mechanical properties and high elasticity and corrosion resistance, and the polyamideimide resin film may have a display substrate and a display protective film due to the above-described characteristics.
• polyamide-imide block copolymer A-1 including the first to fourth repeating units having the following structure (weight Average molecular weight about 600, 000 g- / mol).
• the obtained polyamide-imide block copolymer has a molar ratio (imide block: amide block) relative to the sum of the first repeating unit and the second repeating unit: the third repeating unit and the fourth repeating unit.
• 60 the molar ratio of the first repeating unit: the second repeating unit is about 60: 40
• the molar ratio of the third repeating unit: the fourth repeating unit is about 30: 70.
• Example 1 to adjust the monomer input ratio to satisfy the molar ratio shown in Table 1 below to prepare a polyamide-imide copolymer.
• the polyamide-imide copolymer obtained in Examples and Comparative Examples was dissolved in dimethylacetamide to prepare a solution of about 10 wt%.
• the solution was cast on a glass plate through a Bar Coater equipment, and the drying temperature was sequentially controlled to 80 ° C and 140 ° C.
• polyamide-imide films of Examples and Baegyo having a thickness of 50 were prepared.
• Elastic modulus (EM, GPa) was measured for a film having a thickness of 30 ⁇ 2 _ according to the instant method of ASTM D 882 using a universal testing machine. 3. Yellow index measurement
• the yellowness index was measured according to the measuring method of ASTM D1925 using a UV-2600 UV-Vis Spectrometer (SHIMADZU). And the result is shown in Table 1.

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Citations (5)

• 2018
  • 2018-05-31 KR KR1020180062983A patent/KR20190136813A/ko not_active Application Discontinuation
• 2019
  • 2019-04-08 WO PCT/KR2019/004154 patent/WO2019231100A1/ko active Application Filing
  • 2019-04-22 TW TW108114034A patent/TWI706972B/zh active

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