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WO2019135500A1 - Film d'un copolymère poly(amide-imide) aromatique et procédé de production associé - Google Patents

Film d'un copolymère poly(amide-imide) aromatique et procédé de production associé Download PDF

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Publication number
WO2019135500A1
WO2019135500A1 PCT/KR2018/015472 KR2018015472W WO2019135500A1 WO 2019135500 A1 WO2019135500 A1 WO 2019135500A1 KR 2018015472 W KR2018015472 W KR 2018015472W WO 2019135500 A1 WO2019135500 A1 WO 2019135500A1
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Prior art keywords
amide
aromatic
imide
copolymer
poly
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PCT/KR2018/015472
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English (en)
Korean (ko)
Inventor
유비오
박순용
박영석
최일환
태영지
박관열
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180153913A external-priority patent/KR102350095B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP18898057.7A priority Critical patent/EP3640286A4/fr
Priority to CN201880047443.2A priority patent/CN110914345B/zh
Priority to JP2020501819A priority patent/JP7081770B2/ja
Priority to US16/636,233 priority patent/US11655323B2/en
Publication of WO2019135500A1 publication Critical patent/WO2019135500A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • 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 an aromatic poly (amide-imide) copolymer film and a process for producing the same.
  • the aromatic polyimide resin is a polymer having mostly an amorphous structure and exhibits excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to its rigid chain structure.
  • Such a polyimide resin is widely used as an electric / electronic material.
  • the polyimide resin has a limitation in use due to the limitation of the deep brown color due to the formation of the charge transfer complex (CTC) of the TI electrons present in the imide chain.
  • CTC charge transfer complex
  • a method of inhibiting the resonance structure formation of TI electrons by introducing an aliphatic cyclic compound is introducing aliphatic cyclic compound.
  • the polyimide resin according to the above proposals is difficult to exhibit sufficient heat resistance by a bending structure or an aliphatic cyclic compound, and a film produced using the polyimide resin still has a limit to exhibit poor mechanical properties.
  • the present invention also provides a process for producing the aromatic poly (amide-imide) copolymer film.
  • (Amide-imide) copolymer film is impregnated with ultrapure water for 24 hours, and after the 2 'S phase impregnation, the aromatic poly (amide-imide) This is the weight measured by drying for 30 minutes.
  • Also disclosed herein is a process for the production of aromatic poly (amide-imide) copolymers by reacting an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic dicarbonyl monomer to form an aromatic poly (amide-imide) copolymer; (Amide-imide) copolymer film obtained by dissolving the aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms, A manufacturing method is provided.
  • Aromatic polyester according to the specific implementation of the invention below (amide-imide) is decided More specifically, description will be given to the copolymer film and a production method thereof.
  • An aromatic poly (amide-imide) copolymer film having a retardation (Rth) of 3,000 nm or more and a water absorption rate according to the general formula (1) of 3.6% or less can be provided.
  • the present inventors have found that a polymer film produced by using an aromatic poly (amide-imide) copolymer formed from an aromatic monomer and applying the production method described later exhibits a retardation in the thickness direction with respect to a wavelength of 550 nm Rth) of 3,000 ran or more and a water absorption rate according to the following general formula (1) is 3.6% or less.
  • the aromatic poly (amide-imide) copolymer film of this embodiment may have a retardation (Rth) in the thickness direction of 3,000 ran or more, or 3,000 nm to 4,500 nm in a thickness direction at a wavelength of 550 nm in an unstretched state,
  • Rth retardation
  • the index and the haze value are lowered and the mechanical strength can be improved and the water absorption property can be lowered according to the orientation of the polymer inside the film.
  • the aromatic poly (amide-imide) copolymer film of the embodiment may have a water absorption rate of 3.6% or less, or 2.0 to 3.6% according to the general formula 1.
  • the retardation (Rth) value in the thickness direction The yellow index and the haze value are lowered and the mechanical strength can be improved according to the orientation of the polymer in the film and the water absorption can be lowered.
  • the retardation (Rth) in the thickness direction can be confirmed by a commonly known measuring method and measuring device.
  • a device for measuring the retardation (Rth) in the thickness direction Axoscan, a prism coupler (trade name) manufactured by AXOMETRICS, and the like can be given.
  • the refractive index (589 nm) of the polyamide-imide resin film was input to the measuring apparatus, and the temperature was 25 ° C and the humidity was 40% ,
  • the retardation in the thickness direction of the polyamide-imide resin film was measured using light having a wavelength of 590 nm, and the measured retardation value (measured value by automatic measurement (automatic calculation) of the measuring apparatus) Based on the thickness of the film.
  • (Diameter: about 1 ⁇ 1 ) of the stage it is not particularly limited, but it may be a size of 76 mm long, 52 mm wide, and 13 mm thick.
  • the value of the refractive index (589 " of the polyamide-imide resin film) used in the measurement of the retardation in the thickness direction (the value of the refractive index of the polyamide-imide resin film is preferably the same as that of the polyamide-imide resin film forming the film to be the object of measurement of retardation
  • An amidimide resin film is formed on the surface of the substrate, and then the unoriented film is used as a measurement sample (and when the film to be measured is an unstretched film, the film can be used as a measurement sample as it is) ),
  • a refractive index measuring apparatus product name: manufactured by Atago Co., Ltd., product name: ⁇ -11) was used, and a light source of 589 1 was used, and at a temperature of 23 ⁇ C (In the direction perpendicular to the thickness direction) of the light guide 589 11111 .
  • the refractive index in the in-plane direction of the film becomes constant in any direction in the plane, and by measuring the refractive index, the inherent refractive index of the polyamide-imide resin film can be measured
  • the inherent refractive index (589) of the polyamide-imide resin film is measured using an unoriented film, and the obtained measurement value is used for the measurement of the retardation in the thickness direction described above.
  • the size of the polyamide-imide resin film, a film of the test sample is, if the size that can be used in the refractive index jeukjeong device is not particularly limited, and a side 1 (Payne square (length and breadth 10 11), the size of a thickness of 13 .
  • a polymeric resin film having an internal structure which is generally rigid ( ⁇ (1)) may have a relatively high haze or yellowness or a low light transmittance.
  • the aromatic poly (amide-imide) copolymer film of the embodiment exhibits retardation (1 1 ) in the thickness direction as described above, and has a crystalline rigid (? % Or less, thereby preventing water penetration and the like, and accordingly, it can have a low haze value and a high transmittance.
  • Copolymer films can have higher mechanical strength while having lower yellow index and haze values.
  • the aromatic poly (amide-imide) copolymer film may have a thickness in the range of 1 / ⁇ 1 to 100 / film and may have a haze of 2% or less and a visible light transmittance of 98% or more in this thickness range have.
  • the aromatic poly (amide-imide) copolymer film of the embodiment after forming a copolymer using a predetermined aromatic monomer, the copolymer formed in accordance with a production method described later is mixed with an amide containing an aliphatic group having 3 or more carbon atoms Soluble in a solvent and coating the same, and may have the above-described characteristics depending on such monomer selection and a specific production method.
  • the aromatic poly (amide-imide) copolymer film may comprise an aromatic poly (amide-imide) copolymer between an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic dicarbonyl monomer,
  • the aromatic poly (amide-imide) copolymer may be an imide of an aromatic diamine monomer, an aromatic dianhydride monomer, and a polyamic acid copolymerized with an aromatic dicarbonyl monomer.
  • the repeating unit derived from the aromatic dicarbonyl monomer has a total moles of repeating units derived from the aromatic dianhydride monomer and the aromatic dicarbonyl monomer Based on the total weight of the composition.
  • the repeating unit derived from the aromatic dicarbonyl monomer may be a copolymer of 10 to 60 mol% of 4,4'-biphenyldicarbonyl repeating units; 10 to 50 mol% of isopthaloyl repeating units; And 20 to 70 mol% of terephthaloyl repeating units.
  • the aromatic poly (amide-imide) copolymer film of this embodiment has improved mechanical properties as well as improved mechanical properties And has a colorless transparent optical property 2019/135500 1 »(: 1 ⁇ 1 ⁇ 2018/015472
  • the aromatic poly (amide-imide) copolymer contained in the aromatic poly (amide-imide) copolymer film of the embodiment may be a block copolymer or a random copolymer.
  • the aromatic poly (amide-imide) copolymer comprises a first unit structure derived from copolymerization of the aromatic dianhydride monomer and the aromatic dianhydride monomer; And a second unit structure derived from copolymerization of the aromatic diamine monomer and the aromatic dicarbonyl monomer.
  • the aromatic poly (amide-imide) copolymer is obtained by copolymerizing the aromatic diamine monomer, the aromatic dianhydride monomer and the aromatic dicarbonyl monomer, And may include randomly copolymerized unit structures.
  • Such a polyamic acid forms an aromatic poly (amide-imide) copolymer having imide bond and amide bond simultaneously by imidization.
  • the repeating unit derived from the aromatic dicarbonyl monomer has a total of repeating units derived from the aromatic dianhydride monomer and the aromatic dicarbonyl monomer And may be contained in an amount of 51 mol% or more based on the molar amount.
  • the repeating unit derived from the aromatic dicarbonyl monomer is contained in an amount of less than 51 mol% based on the total moles of repeating units derived from the aromatic dianhydride monomer and the aromatic dicarbonyl monomer, the aromatic poly (amide- Imide) copolymer film, the optical properties such as surface hardness, elastic modulus, mechanical properties such as tensile strength, yellow index, and transmittance may be lowered.
  • the maximum value of the content of the repeating units derived from the aromatic dicarbonyl monomer relative to the total moles of the repeating units derived from the aromatic dianhydride monomer and the aromatic dicarbonyl monomer is not particularly limited, Or less, or 85 mol% or less, or 80 mol% or less have.
  • the aromatic dicarbonyl monomer may be selected from the group consisting of 4,4'-biphenyldi carbonyl chloride (BPC), isophthaloyl chloride (I PC) and terephthaloyl chloride (terephthaloyl chloride ide, TPC).
  • BPC 4,4'-biphenyldi carbonyl chloride
  • I PC isophthaloyl chloride
  • TPC terephthaloyl chloride ide
  • the isopthaloyl chloride (IPC) and the terephthaloyl chloride (TPC) are compounds in which two carbonyl groups are bonded at the position of meta or para to the central phenylene group.
  • BPC 4,4'-biphenyldicarbonyl chloride
  • IPC isopthaloyl chloride
  • TPC terephthaloyl chloride
  • the repeating unit derived from the aromatic dicarbonyl monomer may be a repeating unit derived from 10 to 60 mol% of 4,4'-biphenyldicarbonyl repeating unit; 10 to 50 mol% of isopthaloyl repeating units; And 20 to 7 mole% terephthaloyl repeating units.
  • BPC isophthaloyl chloride
  • IPC isophthaloyl chloride
  • TPC terephthaloyl chloride
  • the 4,4'-biphenyldicarbonyl chloride (BPC) is contained in an amount of less than 10 mol% based on the total molar amount of the aromatic dicarbonyl monomer, the scratch resistance and mechanical properties are not effectively improved. If it is contained in an amount exceeding 60 mol%, there may be a problem that the haze of the film after coating and curing is high. Accordingly, the 4,4'-biphenyldicarbonyl chloride (BPC) is present in an amount of 10 mol% or more, 12 mol% or more, or 14 mol% or more, based on the total moles of the aromatic dicarbonyl monomer. Or less, and 60 mol% or less, or 55 mol% or less.
  • the isophthaloyl chloride (IPC) is present in an amount of 10 mol% or more, or 14 mol% or more, based on the total moles of the aromatic dicarbonyl monomer. And may be contained in an amount of 50 mol% or less.
  • the terephthaloyl chloride (TPC) may be used in an amount of 20 mol% or more, 35 mol% or more, and preferably 20 mol% or more, based on the total moles of the aromatic dicarbonyl monomer. Or less, and 60 mol% or less, or 55 mol% or less.
  • the molar ratio of the aromatic dianhydride monomer to the aromatic dicarbonyl monomer in the aromatic poly (amide-imide) copolymer may be from 1: 0.95 to 1: 1.05. Specifically, in the aromatic poly (amide-imide) copolymer, the molar ratio of (aromatic dianhydride monomer) to (aromatic dianhydride monomer and aromatic dicarbonyl monomer) may be 1: 1.
  • the aromatic diamine monomer may be selected from the group consisting of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (tr ifuoromethyl) -4,4'- , TFDB), 1,3-cyclohexanediamine (13CHD), or meta-methylenediamine (mMDA).
  • 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (TFDB) as the aromatic diamine monomer improves hardness and maintains a low yellow index 2019/135500 1 »(: 1 ⁇ 1 ⁇ 2018/015472
  • the aromatic dianhydride monomer may be 3,3 ', 4,4'-diphenyltetracarboxylic acid dianhydride (3,3', 4,4'-biphenyl tetracarboxylic acid dianhydride, BPDA) , Cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA), or 2,2-bis (3,4-dicarboxyphenyl) nucleus fluoropropane dianhydride (2, 2 '-bis (3,4-di carboxypheny 1) hexa f 1 uor opr opane di anhydride, 6FDA).
  • 1,2,3,4-tetracarboxylic dianhydride Cyclobutane-1,2,3,4-tetracarboxylic dianhydride
  • the aromatic poly (amide-imide) copolymer film is dispersed in the polymer base material containing the aromatic poly (amide-imide) copolymer.
  • ultraviolet absorber examples include benzotriazole compounds, benzophenone compounds, benzoate compounds, cyanoacrylate compounds, salicylic ester compounds, oxybenzophenone compounds, triazine compounds, and inorganic compounds , But the present invention is not limited to these.
  • benzotriazole compound examples include 2- (-hydroxyphenyl) benzotriazole, 2- (-hydroxy-5'-methylphenyl) benzotriazole, 2- Phenyl) - 5-carboxylic acid butyl ester benzotriazole, 2- (2'-hydroxy-5-methylphenyl) - 5,6-dichloro-benzotriazole, 2- (2-hydroxy-5-methyl Phenyl-5-ethylsulfone benzotriazole, 2- (7-hydroxy-5'-t-butylphenyl) Benzotriazole, 2- (2-hydroxy-t-aminophenyl) benzotriazole, 2- (2-hydroxy-3 ', 5'- 3 ', 5-dimethylphenyl) -5 (2-methylphenyl) benzotriazole, 2- (2-stearyloxy- (2-hydroxy-3'5-di-1-butylphenyl) -5- (2-hydroxy-5-carboxylate) benzotriazole ethyl ester,
  • benzophenone-based compounds include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-41-octoxybenzophenone, 2-hydroxy- Carboxybenzophenone, 2,2-dihydroxy-4,4-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2, Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzophenone, 2,2,4,4-tetrahydroxybenzophenone, 2,5- dihydroxy- 4-hydroxy-5-benzoylphenyl) methane, and the like can be given as examples of the bis (2-methoxybenzophenone).
  • benzoate compound examples include phenylysarsylate, 4-biphenylsulfate, 2,5-1-butyl-4-hydroxybenzoic acid 11- nuclear decyl ester, 2,4-di- 3, 5-di-t-butyl-4-hydroxybenzoate, and the like.
  • cyanoacrylate compound ethyl-2-cyano-3,3-diphenylacrylate can be exemplified.
  • salicylic ester compounds include phenyl salicylate and 4-butylphenyl salicylate.
  • oxybenzophenone compounds include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-tetra-oxybenzophenone.
  • examples of the inorganic compound include titanium oxide, zinc oxide, cerium oxide, iron oxide, barium sulfate and the like.
  • benzotriazole-based, benzophenone is preferable to use one of the nongye and specifically, 2- (2'-hydroxy-5 'O _ 61 ⁇ octylphenyl) benzotriazole [2- (2'-( Urine [ « 7- 5'-1 61 ° -0 7 1 613 ⁇ 4 , 1: ratio 611201 : 1 320 1 6] and octadecyl-3- (3,5- ) -propionate [0 8 acid 60 1-3- (3, 5-obtain and ⁇ _1 61) 111 1- 4-one (1 10 1) 1 16] 3 ⁇ 4 ⁇ 1) _ 1) 1 1 Ke 011 6] may be further included.
  • Such an aromatic compound may be added during the production of the aromatic poly (amide-imide) copolymer film, whereby the yellow index and haze of the aromatic poly (amide-imide) copolymer film may be lowered and the mechanical properties The moisture absorption characteristics can be improved.
  • aromatic compound is selected from the group consisting of aromatic poly (amide-imide) copolymers having a weight average molecular weight of from 0.001 to 10 parts by weight .
  • the aromatic poly (amide-imide) copolymer is from 10,000 to 1,000, 000 for ⁇ 0 1, or 50,000 to 1,000,000 seedlings / 1110 1, or 50,000 to 500,000 / 1110 1, or 50,000 to 300,000 ⁇ ⁇ 0 1 parts by weight of May have an average molecular weight.
  • the aromatic poly (amide-imide) copolymer is a Pursuant to 03 363 25 to 55 _ a pencil hardness haese measured for the specimens having a thickness of ⁇ (1 11 633) may be equal to or greater than the rating 3 ⁇ 4.
  • the aromatic poly (amide-imide) The tensile strength measured for a specimen having a thickness of 25 to 55 according to the condition 38 is 180 Or more, 200 Or higher than 220 Wa. The higher the tensile strength is, the better the mechanical properties are, and the upper limit is not limited. However, for example, 300 Wa or less, 280 Or less, or less than or equal to 270 minutes. 2019/135500 1 »(: 1 ⁇ 1 ⁇ 2018/015472
  • the aromatic poly (amide-imide) copolymer may have a tensile elongation of 18% or more as measured on a specimen having a thickness of 25 to 55 ⁇ based on Showa 38.
  • the tensile elongation may be 20% or more, 22% or more, or 25% or more.
  • the aromatic poly (amide-imide) copolymer was measured for a specimen having a thickness of 25 to 55 in Table 424, and the transmittance
  • a process for producing an aromatic poly (amide-imide) copolymer comprising reacting an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic dicarbonyl monomer to form an aromatic poly (amide-imide) copolymer; And an aromatic poly (amide-imide) copolymer of the above-described embodiment, which comprises coating a coating liquid formed by dissolving the aromatic poly (amide imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms, A process for producing a coalesced film can be provided.
  • the polymerization conditions for forming the aromatic poly (amide-imide) copolymer are not particularly limited.
  • a polyamic acid is formed using the aromatic diamine monomer, the aromatic dianhydride monomer, and the aromatic dicarbonyl monomer And imidizing it to form the copolymer.
  • the polymerization for the formation of the polyamic acid can be carried out by solution polymerization under an inert atmosphere of from 0 to 100.
  • the solvent for forming the polyamic acid include - Dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, acetone, N-methyl-2-pyrrolidone, tetrahydrofuran, chloroform, gamma-butyrolactone and the like can be used.
  • Imidization after the formation of the polyamic acid can be performed thermally or chemically.
  • compounds such as acetyl anhydride, pyridines can be used for chemical imidization.
  • an aromatic poly (amide-imide) copolymer prepared by coating a substrate with a coating solution formed by dissolving the aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms
  • the film may have a retardation (Rth) in the thickness direction of 3,000 nm or more and a water absorption rate according to the general formula (1) of 3.6% or less with respect to a wavelength of 550 nm in an unstretched state.
  • the aromatic poly (amide-imide) copolymer film may have a haze of 2% or less and a visible light transmittance of 98% or more at a thickness of Urn to 100 // m.
  • the properties of such an aromatic poly (amide-imide) copolymer film appear to be attributed to the use of the above-mentioned amide solvent including an aliphatic group having 3 or more carbon atoms. More specifically, the amide solvent containing an aliphatic group having 3 or more carbon atoms increases the solubility of the poly (amide-imide) polymer, and may have a more advantageous effect on the orientation of the polymer when the coating is dried.
  • the films formed from the copolymers can have properties such as low yellow index, haze index, high mechanical strength, and low hygroscopicity.
  • the amide solvent including the aliphatic group having 3 or more carbon atoms include methyl 3-methoxypropionate, 3-methoxy-N, N-dimethylopropionamide N, N-dimethylpropionamide) and N, N-dimethylpropionamide (N, N-dimethylpropionamide).
  • the aromatic poly (amide-imide) copolymer film may have the above-described characteristics depending on the specific monomers used in the synthesis of the aromatic poly (amide-imide) copolymer and the content thereof have.
  • the aromatic dicarbonyl monomer may be contained in an amount of 51 mol% or more based on the total moles of the aromatic dianhydride monomer and the aromatic dicarbonyl monomer.
  • the aromatic dicarbonyl monomer may include 10 to 60 mol% of 4,4'-biphenyldicarbonyl chloride; 10 to 50 mol% of isophthaloyl chlorides; And 20 to 70 mol% of terephthaloyl chloride.
  • the coating solution formed by dissolving the above aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms is 2- (-hydroxy-5'-tert-octylphenyl) benzotriazole [2- Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) di-tert-butyl-4-hydroxyphenyl) -propionate] may further include at least one aromatic compound.
  • aromatic compounds can be dispersed in the polymeric substrate comprising the aromatic poly (amide-imide) copolymer in the finally produced aromatic poly (amide-imide) copolymer film, and thus the aromatic poly (amide- Imide) copolymers can have properties such as low yellow index, haze index, high mechanical strength, and low hygroscopicity.
  • the method of coating the coating liquid formed by dissolving the aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms is not particularly limited. For example, Coating methods and apparatuses commonly known in the art can be used.
  • the type of the substrate is not limited, and examples include various organic or inorganic substrates, glass substrates, paper substrates, polymer substrates, metal substrates, and the like.
  • ⁇ Effects of the Invention 2019/135500 1 »(: 1 ⁇ 1 ⁇ 2018/015472
  • the aromatic poly (amide-imide) copolymer according to the present invention exhibits excellent scratch resistance and mechanical properties It is possible to provide a polyamide-imide film having an improved shielding function.
  • Nitrogen was passed through a 1001 4- l1 ⁇ 2- liter round-bottomed flask (reactor) equipped with a stirrer, a nitrogen inlet, a dropping funnel, a temperature controller and a condenser Dimethylacetamide (0 ⁇ 42.5 ⁇ ) was filled, the temperature of the reactor was adjusted to 25 ° (:
  • the polyamic acid solution was poured into the polyamic acid solution to dilute to a solid content of 5% or less and precipitated with methanol (1).
  • the precipitated solids were filtered and dried at 100 ° C for 6 hours or longer to obtain a solid A poly (amide-imide) copolymer (acid # 1) was obtained.
  • the obtained poly (amide-imide) copolymer (0) at time # 1) was dissolved in dimethyl propionamide, 1 - [1] 11161; 1 17 1 1 ) 1 (1 01131 (1 6 ) to prepare a polymer solution of about 15%.
  • the polymer solution was applied onto a plastic substrate (11 eggs) (-75 3 , ⁇ BE 2019/135500 1 »(: 1 ⁇ 1 ⁇ 2018/015472
  • the polymer solution was uniformly adjusted in thickness using a film applicator, dried in a Matze oven for 10 minutes at room temperature, cured at 250 ° C for 30 minutes while flowing nitrogen, 50.0 < / RTI > Example 1
  • Polyester obtained in Comparative Example 1 (amide-imide) copolymer (on # 1) 100 parts by weight compared to the aromatic compound, 0 ⁇ 3 (1607 1-3- (3, 5 - ( ⁇ O 61. !; . Technique - Liver -
  • the polymer solution was poured into a plastic substrate (75 cm 3 ), and the thickness of the polymer solution was uniformly adjusted using a film applicator. After drying in a Matiz oven for 10 minutes, the coating was cured for 30 minutes at 250 ° C with nitrogen flow, A film was obtained.
  • Example 2
  • the polymer solution was applied onto a plastic substrate (egg ratio: 75
  • the polymer solution was uniformly adjusted in thickness using a film applicator and dried in a Matiz oven at 80 for 10 minutes. Then, 250 And cured for 30 minutes to obtain a time film having a thickness of 50.0 peeled from the substrate.
  • Example 3
  • the aromatic compound 100 parts by weight of the poly (amide-imide) copolymer (acid # 1) obtained in Comparative Example 1, 2019/135500 1 »(: 1 ⁇ 1 ⁇ 2018/015472
  • the polymer solution was poured into a plastic substrate (75 ⁇ in comparative form) and the polymer solution was uniformly adjusted in thickness using a film applicator.
  • the polymer solution was dried in a Matiz oven for 20 minutes at 60 ⁇ , (&Quot;:") for 30 minutes to peel off the substrate to a thickness of 50.0 A film was obtained.
  • Comparative Example 2 Comparative Example 2
  • the polyamic acid solution was poured into the polyamic acid solution to dilute to a solid content of 5% or less and precipitated with methanol (1).
  • the precipitated solids were filtered and dried at 100 ° C (for 6 hours or more under vacuum to obtain poly (Amide-imide) copolymer (Si # 2) was obtained.
  • the weight average molecular weight of the amide-imide copolymer was about 154,197.
  • Example 4 The polymer solution was uniformly adjusted in thickness using a film applicator, dried in a Matze oven at 120 ° C for 15 minutes, cured at 250 ° C for 30 minutes while flowing nitrogen, And obtained a film having a thickness of 49.8 ⁇ 1 . 2019/135500 Example 1 (1 ⁇ ⁇ 2018/015472 Example 4
  • the aromatic compound 0 8 (1 60 1-3- (3,5- (11-1 61 ' )) was added to 100 parts by weight of the poly (amide-imide) copolymer obtained in the above Comparative Example 2 One;
  • the polymer solution was uniformly adjusted to a thickness of 80 ⁇ m using a film applicator, dried in a Matiz oven for 10 minutes, and then cured for 30 minutes at 250 ° C. with flowing nitrogen, A film having a thickness of 50.0 _ peeled from the substrate was obtained.
  • Example 5
  • Aromatic compounds were prepared from 100 parts by weight of the poly (amide-imide) copolymer (( 0- ? 1) # 2) obtained in Comparative Example 2, 3,5- -1611; - 1-4-1 3 ⁇ 4 year 1 ( «:, 1) 11 611: 1) 1) 1 [011 6 (1 ( ⁇ 1010) 5 parts by weight of N, N - dimethyl-propionamide 0 11161: 1; a polymer solution of about 15% was prepared and dissolved in 1 17 1 1) 1 sheet 1 01 131 (16).
  • the polymer solution was poured into a plastic substrate and the thickness of the polymer solution was uniformly adjusted using a film applicator. 2019/135500 1 »(: 1 ⁇ 1 ⁇ 2018/015472
  • the water absorption rate was calculated according to the following general formula (1).
  • silver is a weight determined by impregnating the aromatic poly (amide-imide) copolymer film with ultrapure water for 24 hours,
  • the poly (amide-imide) copolymer films of the comparative examples have relatively low It has been confirmed that the shielding function is low due to inclination.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un film d'un copolymère poly(amide-imide) aromatique ayant un retardement élevé et présentant un faible taux d'absorption de l'humidité, ainsi qu'un procédé de production associé.
PCT/KR2018/015472 2018-01-03 2018-12-07 Film d'un copolymère poly(amide-imide) aromatique et procédé de production associé Ceased WO2019135500A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18898057.7A EP3640286A4 (fr) 2018-01-03 2018-12-07 Film d'un copolymère poly(amide-imide) aromatique et procédé de production associé
CN201880047443.2A CN110914345B (zh) 2018-01-03 2018-12-07 聚(酰胺-酰亚胺)共聚物膜及其制备方法
JP2020501819A JP7081770B2 (ja) 2018-01-03 2018-12-07 芳香族ポリ（アミド－イミド）共重合体フィルムとその製造方法
US16/636,233 US11655323B2 (en) 2018-01-03 2018-12-07 Poly(amide-imide) copolymer film and method for preparing same

Applications Claiming Priority (4)

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KR10-2018-0000881 2018-01-03
KR20180000881 2018-01-03
KR1020180153913A KR102350095B1 (ko) 2018-01-03 2018-12-03 방향족 폴리(아미드-이미드) 공중합체 필름과 이의 제조 방법
KR10-2018-0153913 2018-12-03

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JP2020050864A (ja) * 2018-09-20 2020-04-02 住友化学株式会社 組成物

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KR970006356A (ko) * 1995-07-13 1997-02-19 하기주 방향족 폴리 아미드, 광학적 이방성 도우프와 성형물, 및 이들의 제조방법
KR20090071036A (ko) * 2007-12-27 2009-07-01 주식회사 코오롱 폴리이미드 필름 및 그 제조방법
KR20130013202A (ko) * 2011-07-27 2013-02-06 주식회사 엘지화학 내 흡습성이 우수한 감광성 수지 조성물
KR20150076114A (ko) * 2013-12-26 2015-07-06 코오롱인더스트리 주식회사 투명 폴리아마이드―이미드 수지 및 이를 이용한 필름
WO2017010566A1 (fr) * 2015-07-16 2017-01-19 宇部興産株式会社 Composition de solution d'acide polyamique et film de polyimide

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KR970006356A (ko) * 1995-07-13 1997-02-19 하기주 방향족 폴리 아미드, 광학적 이방성 도우프와 성형물, 및 이들의 제조방법
KR20090071036A (ko) * 2007-12-27 2009-07-01 주식회사 코오롱 폴리이미드 필름 및 그 제조방법
KR20130013202A (ko) * 2011-07-27 2013-02-06 주식회사 엘지화학 내 흡습성이 우수한 감광성 수지 조성물
KR20150076114A (ko) * 2013-12-26 2015-07-06 코오롱인더스트리 주식회사 투명 폴리아마이드―이미드 수지 및 이를 이용한 필름
WO2017010566A1 (fr) * 2015-07-16 2017-01-19 宇部興産株式会社 Composition de solution d'acide polyamique et film de polyimide

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* Cited by examiner, † Cited by third party
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JP2020050864A (ja) * 2018-09-20 2020-04-02 住友化学株式会社 組成物

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