WO2020209625A1 - 폴리아미드-이미드 블록 공중합체, 이의 제조방법 및 이를 포함하는 폴리아미드-이미드 필름 - Google Patents
폴리아미드-이미드 블록 공중합체, 이의 제조방법 및 이를 포함하는 폴리아미드-이미드 필름 Download PDFInfo
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- 0 *C(*)(*)*N(C(c1ccc(CC(Cc(cc2)cc(C(N3C(*)(*)*)=O)c2C3=O)(C(F)(F)F)C(F)(F)F)cc11)=O)C1=O Chemical compound *C(*)(*)*N(C(c1ccc(CC(Cc(cc2)cc(C(N3C(*)(*)*)=O)c2C3=O)(C(F)(F)F)C(F)(F)F)cc11)=O)C1=O 0.000 description 1
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/711—Monoisocyanates or monoisothiocyanates containing oxygen in addition to isocyanate oxygen
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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
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- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- 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
- C08G73/12—Unsaturated polyimide precursors
- C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Definitions
- the present invention relates to a polyamide-imide block copolymer, a method for preparing the same, and a polyamide-imide film comprising the same.
- 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 a rigid chain structure. These polyimide resins are widely used as materials for electric/electronic, space, aviation, and automobiles.
- the wholly aromatic polyimide resin is mostly insoluble and insoluble, resulting in poor molding and processability, and thus it is difficult to use conventional processing equipment for processing the resin.
- polyimide resins are limited in use because they have a dark brown color limit due to the formation of CTC (charge transfer complex) of ⁇ electrons present in the imide chain.
- CTC charge transfer complex
- a method of restricting the movement of ⁇ electrons by introducing a strong electron attracting group such as trifluoromethyl (-CF 3 ) group A method of reducing the formation of the CTC by introducing a sulfone (-SO 2 -) group, an ether (-O-) group, etc. to the main chain to form a curved structure; Alternatively, a method of inhibiting the formation of a resonance structure of ⁇ electrons by introducing an alicyclic compound has been proposed.
- the polyimide resin according to the above proposals is difficult to exhibit sufficient heat resistance due to a bent structure or an alicyclic compound, and a film manufactured using the polyimide resin still has a limitation in showing poor mechanical properties.
- polyimide resins are formed by imidization of polyamic acid as a precursor.
- the final curing is performed in a curing process at a high temperature of 300°C or higher, the physical properties of electrical wiring or substrates are degraded.
- semiconductor it may cause a problem of deteriorating the electrical properties of or destroying semiconductor properties.
- the present invention is to provide a polyamide-imide block copolymer that is colorless and transparent and exhibits excellent heat resistance, chemical resistance and mechanical properties.
- the present invention is to provide a method for preparing the polyamide-imide block copolymer.
- the present invention is to provide a polyamide-imide film comprising the polyamide-imide block copolymer.
- a polyamide-imide block copolymer comprising a first repeating unit represented by the following formula (1), a second repeating unit represented by the following formula (2), and a third repeating unit represented by the following formula (3) to provide:
- A is the same or different from each other in each repeating unit, and is a substituted or unsubstituted tetravalent organic group
- E 1 , E 2 , E 3 , E 4 , E 5 , E 6 and E 7 are the same in each repeating unit or different from each other, and each independently a single bond or -NH-,
- Z 1 is the same or different from each other in each repeating unit, and is a trivalent organic group derived from at least one compound selected from the group consisting of triacyl halides, triamines and tricarboxylic acids,
- Z 2 is the same or different from each other in each repeating unit, and is a divalent organic group derived from at least one compound selected from the group consisting of diacyl halide, diamine and dicarboxylic acid,
- R 1 is the same in each repeating unit or different from each other, hydrogen or an alkyl group having 1 to 10 carbon atoms
- L is the same in each repeating unit or different from each other, direct bond or alkylene having 1 to 10 carbon atoms,
- the total sum of repeating units in which Y 1 , Y 2 and Y 3 is substituted with a photocurable functional group is 10 to 80 mole %.
- a method for preparing the polyamide-imide block copolymer is provided. Further, according to the present invention, a polyamide-imide film comprising the polyamide-imide block copolymer is provided.
- first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.
- the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by the GPC method.
- a commonly known analysis device a detector such as a Refractive Index Detector, and a column for analysis can be used. Conditions, solvents, and flow rates can be applied.
- a polyamide-imide comprising a first repeating unit represented by Formula 1, a second repeating unit represented by Formula 2, and a third repeating unit represented by Formula 3 Block copolymers are provided.
- the polyamide-imide copolymer is applied in various fields, and it is required to simultaneously satisfy several physical properties.
- a brancher structure having three reactive substituents in the amide block is included, and at least one of the amide and imide blocks is crosslinked. It was confirmed that the polyamide-imide-based block copolymer copolymerized by introducing possible photocurable functional groups in a specific molar ratio can exhibit excellent mechanical properties while being colorless and transparent.
- Branches in the polyamide block may impart a stable network structure in the copolymer, and improve physical properties by improving not only intramolecular crosslinking but also intermolecular interactions. Furthermore, it was confirmed that the photocurable functional group can induce crosslinking between molecules, thereby strengthening the network structure and improving the chemical resistance of the film. In addition, it was confirmed that the solubility was improved so that it was easy to apply to the solution process when making a film.
- A is the same or different from each other in each repeating unit, and is a substituted or unsubstituted tetravalent organic group
- E 1 is the same in each repeating unit or different from each other, and each independently a single bond or -NH-,
- R 1 is the same or different from each other in each repeating unit, hydrogen or an alkyl group having 1 to 10 carbon atoms
- L is the same or different from each other in each repeating unit, and is a direct bond or alkylene having 1 to 10 carbon atoms.
- A may be any one selected from compounds represented by:
- Y 1 may be a compound represented by the following formula Y-1 or Y-2:
- R 3 is each independently a (meth) acrylate group or a functional group represented by Formula 4,
- R 1 , L are as described above,
- n3, n4 and n5 are each independently 0 to 4, provided that at least one of n3, n4 and n5 is 1 or more,
- the first repeating unit may include a repeating unit represented by the following Formula 1-1:
- Y 1 is as previously defined.
- E 2 , E 3 and E 4 are the same or different from each other in each repeating unit, and each independently a single bond or -NH-,
- Z 1 is the same or different from each other in each repeating unit, and is a trivalent organic group derived from at least one compound selected from the group consisting of triacyl halides, triamines and tricarboxylic acids,
- Z 1 may be any one selected from compounds represented by:
- Y 2 may be a compound represented by the above-described Chemical Formula Y-1 or Y-2.
- the second repeating unit may include a repeating unit represented by the following Formula 2-1:
- Y 2 is as previously defined in Formula 1.
- E 5 , E 6 and E 7 are the same or different from each other in each repeating unit, and each independently a single bond or -NH-,
- Z 2 is the same or different from each other in each repeating unit, and is a divalent organic group derived from at least one compound selected from the group consisting of diacyl halide, diamine and dicarboxylic acid,
- Z 2 may be any one selected from compounds represented by:
- Y 3 may be a compound represented by the above-described formula Y-1 or Y-2.
- the third repeating unit may include a repeating unit represented by the following Formula 3-1:
- Y 3 is as defined above.
- Y 1 , Y 2 and Y 3 are represented by a (meth)acrylate group and the above formula 4 10 mol% to 80 mol%, preferably 30 mol% to 70% mol of the repeating unit substituted with one or more photocurable functional groups selected from the group consisting of the functional groups represented.
- the polyimide-based block copolymer is colorless and transparent, and can exhibit improved mechanical properties. In addition, it makes it possible to further improve the chemical resistance of the film.
- a photocurable functional group having a specific structure in at least one of the amide and imide blocks mechanical properties may be improved by forming a crosslinked structure between molecules.
- a photocurable functional group at the terminal in the above content range solubility is excellent, and various solvents can be used.
- the copolymerization is easy even in the low-temperature chemical imidization process, so that a colorless and transparent copolymer can be produced.
- the photocurable functional group When the photocurable functional group is included in a small amount outside the above lower limit, the effect of improving mechanical properties is deteriorated due to insufficient crosslinking between molecules, and when it is included in an excessive amount outside the upper limit, it is fragile when manufactured into a film, resulting in reduced durability. I can.
- 100 moles of the total repeating unit refers to the entire repeating unit contained in the polyamide-imide block copolymer, for example, a first repeating unit as an imide repeating unit, a second repeating unit as an amide repeating unit, and a second repeating unit. It means that the total sum of 3 repeating units is converted to 100 moles, and the repeating unit in which Y 1 , Y 2 and Y 3 is substituted with a photocurable functional group is selected from among the first repeating unit, the second repeating unit, and the third repeating unit.
- Y 1 , Y 2 and Y 3 in the repeating unit means the total sum of repeating units substituted with a photocurable functional group.
- the polyamide-imide block copolymer has a molar ratio of 10 : 90 to 90:10, preferably 30:70 to 70:30.
- the thermal properties, mechanical properties, and optical properties of the copolymer can be simultaneously improved.
- the first repeating unit which is the imide repeating unit
- the solubility decreases and the yellowness increases
- the transparency of the film significantly decreases
- the modulus is Decreases and mechanical properties may deteriorate.
- the polyamide-imide block copolymer according to an embodiment of the present invention may have a weight average molecular weight (GPC measurement) of 5,000 to 300,000 g/mol, preferably 15,000 to 150,000 g/mol. When the weight average molecular weight is satisfied, the mechanical properties, thermal properties, and optical properties of the present invention can be further improved.
- GPC measurement weight average molecular weight
- a step of substituting a hydroxyl group with (meth)acrylate in addition to the usual imidization step is included. It was prepared through a two or more synthetic process.
- the imidation step of such a conventional polymerization method proceeds with a thermal imidization reaction conducted at a high temperature, and there is a problem that it is difficult to apply to a product requiring transparency due to browning of the polyimide produced accordingly.
- the step of substituting with a photocurable functional group such as a (meth)acrylate group has low reactivity, and thus it is difficult to control the substitution amount as desired.
- a method of preparing a polyamide-imide block copolymer according to an embodiment of the present invention includes, first, reacting a diamine compound with a dianhydride compound to form a polyamic acid block.
- the monomer component used in the above step may be appropriately selected so that the final prepared copolymer satisfies the repeating unit represented by Formula 1 above.
- the diamine compound may include a diamine compound containing a hydroxyl group, and in the imidation reaction by the hydroxyl group, a photocurable substituent is introduced at the same time as the chemical formula imidation reaction, and thus a polyamide-imide copolymer having excellent physical properties Can be manufactured.
- the diamine compound containing a hydroxyl group may be preferably an aromatic diamine, for example, 3,3'-dihydroxy benzidine (3,3'-dihydroxy benzidine, DHBZ), 2,2 -Bis(3-hydroxy-4-aminophenyl)hexafluoropropane (2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane), 2,2-bis(3-amino-4-hydroxyphenyl) ) Hexafluoropropane (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane) or a combination thereof, but is not limited thereto.
- aromatic diamine for example, 3,3'-dihydroxy benzidine (3,3'-dihydroxy benzidine, DHBZ), 2,2 -Bis(3-hydroxy-4-aminophenyl)hexafluoropropane (2,2-bis(3-hydroxy-4-aminophenyl)hexa
- the dianhydride compound is 3,3',4,4'-biphenyl tetracarboxylic dianhydride (3,3',4,4'-biphenyl tetracarboxylic dianhydride, BPDA), bicyclo [2.2 .2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicycle[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, BTDA), 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, DSDA), 4,4'- (hexafluoroisopropylidene) Diphthalic anhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 6FDA), 4,4'
- the method for preparing a polyamide-imide block copolymer according to an embodiment of the present invention is selected from the group consisting of triacyl halide, triamine, and tricarboxylic acid in the result of the polyamic acid block formation step.
- the monomer component used in the above step may be appropriately selected so that the finally prepared copolymer satisfies the repeating unit structure represented by the above-described Chemical Formulas 2 and 3.
- a stable network is formed in the copolymer by introducing a branch structure in the polyamide block, thereby further enhancing mechanical properties. You can improve.
- benzene-1,3,5-tricarbonyl trichloride for example, benzene-1,3,5-Tricarboxylic acid (benzene-1,3,5-tricarboxylic acid), benzene-1,3,5-triamine (benzene-1,3,5-triamine), benzene-1,2,4-tri Amine (benzene-1,2,4-triamine), cyclohexane-1,3,5-triamine (cyclohexane-1,3,5-triamine), cyclohexane-1,2,4-triamine (cyclohexane- 1,2,4-triamine), and pyrimidine-2,4,6-triamine (pyrimidine-2,4,6-triamine), and the like, but are limited thereto. It is not.
- the diamine compound may include a diamine compound containing a hydroxyl group, and the photocurable functional group may be introduced even in the amide block by the addition reaction of the imidation reaction by the hydroxyl group.
- the diamine compound containing a hydroxyl group the components used in the step of forming the polyamic acid block may be the same.
- examples of the diacyl halide include isophthaloyl dichloride, terephthaloylchloride, and the like
- examples of the dicarboxylic acid include i. Sophthalic acid (isophthalic acid), terephthalic acid (terephthalic acid) may be mentioned, but is not limited thereto.
- the diamine compound substituted with a hydroxyl group may be included in an amount of 10 mol% to 80 mol%, preferably, 30 mol% to 70 mol%. It may be included in mole percent.
- the content ratio corresponds to the molar ratio of the repeating units in which Y 1 , Y 2 and Y 3 are substituted with a photocurable functional group in the polyamide-imide copolymer described above.
- the hydroxyl group may be substituted with a photocurable functional group in the imidization step described later.
- a method for preparing a polyamide-imide block copolymer according to an embodiment of the present invention is, in the mixture containing the polyamic acid block and the polyamide block, a compound containing a (meth)acrylate group and the above formula (4). And adding at least one compound from among the compounds containing the functional groups to be imidized.
- the type of the compound containing the (meth)acrylate group and the compound containing the functional group represented by Formula 4 is not particularly limited, but, for example, the compound containing a (meth)acrylate group (Meth) acrylic anhydride ((Meth) acrylic anhydride), the compound containing the functional group represented by the formula (4) is 2-isocyanatoethyl (meth) acrylate (2-Isocyanatoethyl (meth) acrylate) I can.
- a process of introducing a photocurable functional group to a hydroxyl group in the block may be performed simultaneously with the chemical imidization reaction of the polyamic acid block.
- the imidation step may be performed at a low temperature of 20 °C to 100 °C, compared to the conventional high-temperature thermal imidization step, it is possible to improve the thermal stability of the polymerized copolymer, yellowing, etc. It is not easy to apply to a transparent film.
- the chemical imidation reaction is excellent in reactivity, and photocurable functional groups can be substituted within a desired content range. Due to the photocurable functional group, the mechanical properties of the copolymer can be improved by crosslinking between molecules, and the excellent solubility of the photocurable functional group makes it easy to process a solution when forming a film.
- the hydroxyl group contained in the polyamic acid block and the polyamide block may be substituted with a (meth)acrylate group or a functional group represented by the following formula (4):
- R 1 is the same or different from each other in each repeating unit, hydrogen or an alkyl group having 1 to 10 carbon atoms
- L is the same or different from each other in each repeating unit, and is a direct bond or alkylene having 1 to 10 carbon atoms.
- additives such as crosslinking agents, curing accelerators, phosphorus-based flame retardants, antifoaming agents, leveling agents, gel inhibitors, or their It may further comprise a mixture.
- an organic solvent may be further included to improve coating properties.
- organic solvent examples include dimethyl sulfoxide; N-methyl-2-pyrrolidone; N,N-dimethylformamide (DMF); N,N-dimethylacetamide (DMAc); N-methylformamide (NMF); Alcohols selected from the group consisting of methanol, ethanol, 2-methyl-1-butanol and 2-methyl-2-butanol; ketones selected from the group consisting of ⁇ -butyrolactone, cyclohexanone, 3-hexanone, 3-heptanone, 3-octanone, acetone and methyl ethyl ketone; Tetrahydrofuran; Trichloroethane; And one or more selected from the group consisting of combinations thereof, but are not limited thereto.
- a polyamide-imide film including the above-described polyamide-imide block copolymer is provided.
- the film according to the present invention has excellent thermal stability, excellent mechanical properties, and excellent optical properties.
- the polyamide-imide film has a yellow index (YI) of 1.5 to 1.75, measured according to ASTM D1925, for a specimen having a thickness of 20 to 100 ⁇ m, It is preferably 1.5 to 1.7.
- YI yellow index
- the polyamide-imide film may have a modulus of 4.0 GPa to 5.0 GPa, preferably 4.2 GPa to 5.0 GPa, according to ASTM D648.
- a modulus value in the above range excellent mechanical properties can be obtained, and thus it is easy to be applied to various electric and electronic products.
- the modulus can be measured using DMA q800.
- the polyamide-imide film may be prepared by a conventional method such as a dry method or a wet method using the polyamide-imide block copolymer.
- the polyamide-imide film may be obtained by coating a solution containing the polyamide-imide block copolymer on an arbitrary support to form a film, and drying by evaporating a solvent from the film. have. If necessary, stretching and heat treatment may be performed on the polyamide-imide film.
- the solubility is remarkably improved by the photocurable substituent at the terminal, so that the solution process can be easily performed.
- the polyamide-imide film according to the present invention can be used as a material for various molded articles requiring high mechanical and optical properties along with colorless transparency.
- the polyimide-imide film containing the polyamide-imide block copolymer is a display substrate, a protective film for a display, a touch panel, a cover film for a flexible or foldable device, etc. Can be applied as
- the polyamide-imide block copolymer according to the present invention enables the provision of a polyimide-imide film, which is excellent in thermal stability and chemical resistance, and at the same time has excellent mechanical properties, and which can realize excellent optical properties.
- Preparation Example 1 15 g of a polyamide-imide copolymer (A-4) was prepared in the same manner, except that 225 mmol of 2-isocyanatoethyl (meth)acrylate was used instead of 225 mmol of methacrylic anhydride. Got it. Accordingly, it was confirmed that the molar ratio of the repeating units substituted with 2-isocyanatoethyl (meth)acrylate was 33 mol%.
- BHT butylated hydroxy toluene
- a polyimide-based block copolymer (B-4) including a repeating unit represented by Formula a-1 and a repeating unit represented by Formula a-2 was used.
- the molar ratio of the repeating units of the formula a-1 to the formula a-2 is 50:50.
- the polyamide-imide block copolymer samples obtained in Preparation Examples and Comparative Preparation Examples were dissolved in methyl ethyl ketone (MEK) to prepare a solution of about 15 wt%.
- MEK methyl ethyl ketone
- the solution was cast on a glass plate through a bar coater, and at this time, the drying temperature was dried at 90° C. for 15 minutes and then photocured using a UV curing machine. Thereafter, heat treatment was performed at 170° C. for 15 minutes, followed by peeling to prepare polyamide-imide films of Examples and Comparative Examples having a thickness of 50 ⁇ m.
- a-1 is a structure in which a methacrylate group is substituted with a photocurable functional group
- a-2 is Is a substituted structure
- a-3 is a structure in which a carboxy group is substituted.
- glass transition temperatures were measured using a TMA IC600 device, and the values are shown in Table 2 below.
- modulus (Modulus, GPa) was measured using DMA q800, and the results are shown in Table 2.
- the prepared film samples were immersed in acetone and N-methyl-1,2-pyrrolidone (NMP), respectively, and allowed to stand at room temperature (25° C.) for 5 minutes, and then taken out to change the film according to the following criteria. Evaluated.
- Comparative Example 1 it was confirmed that all properties were deteriorated compared to the examples of the present invention by using a copolymer that does not include a three-dimensional crosslinked structure.
- Comparative Example 3 it was confirmed that the repeating unit containing the photocurable functional group was 90 mol%, and the overcured film was too brittle and could be easily broken, and accordingly, the physical properties were lowered compared to the Example.
- Comparative Example 4 was a case where a carboxyl terminal group was included instead of the photocurable functional group of the present invention, and it was confirmed that the transparency of the thin film was significantly lowered and the physical properties were lowered compared to the Example.
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Abstract
Description
구분 | 공중합체 | 3차원 브랜쳐 구조 포함 여부 | 광경화성 작용기(몰%)* | 공중합체의중량평균분자량 |
실시예 1 | A-1 | O | a-1/33% | 35,700 |
실시예 2 | A-2 | O | a-1/20% | 42,800 |
실시예 3 | A-3 | O | a-1/50% | 39,900 |
실시예 4 | A-4 | O | a-2/33% | 36,800 |
비교예 1 | B-1 | X | a-1/33% | 38,200 |
비교예 2 | B-2 | O | a-1/5% | 47,000 |
비교예 3 | B-3 | O | a-1/90% | 39,800 |
비교예 4 | B-4 | O | a-3/50% | 490,000 |
구분 | 황색지수 | 유리전이온도(℃) | 모듈러스(GPa) | 내화학성 |
실시예 1 | 1.69 | 187 | 4.56 | ○ |
실시예 2 | 1.69 | 180 | 4.20 | ○ |
실시예 3 | 1.72 | 188 | 4.08 | ○ |
실시예 4 | 1.75 | 175 | 4.00 | ○ |
비교예 1 | 1.79 | 160 | 3.90 | ○ |
비교예 2 | 1.62 | 165 | 3.81 | X |
비교예 3 | 2.28 | 179 | 3.42 | ○ |
비교예 4 | 2.05 | 152 | 3.15 | X |
Claims (18)
- 하기 화학식 1로 표시되는 제1 반복 단위; 하기 화학식 2로 표시되는 제2 반복 단위; 및 하기 화학식 3으로 표시되는 제3 반복 단위를 포함하는, 폴리아미드-이미드 블록 공중합체:[화학식 1][화학식 2][화학식 3]상기 화학식 1 내지 3에서,A는 각각의 반복 단위에서 동일하거나 서로 상이하며, 치환 또는 비치환된 4가의 유기기이고,E 1, E 2, E 3, E 4, E 5, E 6 및 E 7은 각각의 반복 단위에서 동일하거나 서로 상이하며, 각각 독립적으로 단일 결합 또는 -NH-이고,Z 1는 각각의 반복 단위에서 동일하거나 서로 상이하며, 트리아실 할라이드, 트리아민 및 트리카르복실산으로 이루어진 군에서 선택된 1종 이상의 화합물로부터 유도된 3가의 유기기이고,Z 2는 각각의 반복 단위에서 동일하거나 서로 상이하며, 디아실 할라이드, 디아민 및 디카르복실산으로 이루어진 군에서 선택된 1종 이상의 화합물로부터 유도된 2가의 유기기이고,Y 1, Y 2, 및 Y 3는 각각의 반복단위에서 동일하거나 서로 상이하며, 각각 독립적으로 탄소수 6 내지 30인 2가의 방향족 유기기이며, 상기 방향족 유기기는 단독으로 존재하거나; 2개 이상의 방향족 유기기가 서로 접합되어 2가의 축합 고리를 형성하거나; 또는 2개 이상의 방향족 유기기가 단일 결합, 플루오레닐렌기, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) 2-, -Si(CH 3) 2-, -(CH 2) p-(여기서 1≤p≤10), -(CF 2) q-(여기서 1≤q≤10), -C(CH 3) 2-, -C(CF 3) 2-, 또는 -C(=O)NH-에 의해 연결되고, 단, Y 1, Y 2 및 Y 3 중 적어도 하나는 (메트)아크릴레이트기 및 하기 화학식 4로 표시되는 작용기로 이루어진 군에서 선택된 하나 이상의 광경화성 작용기로 치환되며,[화학식 4]R 1은 각각의 반복 단위에서 동일하거나 서로 상이하며, 수소 또는 탄소수 1 내지 10의 알킬기이고, L은 각각의 반복단위에서 동일하거나 서로 상이하며, 직접 결합 또는 탄소수 1 내지 10의 알킬렌이고,반복 단위 총 100몰에 대하여, Y 1, Y 2 및 Y 3가 광경화성 작용기로 치환된 반복 단위의 총 합은 10몰% 내지 80몰%임.
- 제 1항에 있어서,상기 폴리아미드-이미드 블록 공중합체에 포함되는 반복 단위 총 100몰에 대하여, Y 1, Y 2 및 Y 3가 광경화성 작용기로 치환된 반복 단위의 총 합은 30몰% 내지 70몰%인, 폴리아미드-이미드 블록 공중합체.
- 제 1항에 있어서,상기 Y 1, Y 2 및 Y 3는 각각 독립적으로 하기 화학식 Y-1 또는 Y-2로 표시되는 화합물인, 폴리아미드-이미드 블록 공중합체:[화학식 Y-1][화학식 Y-2]상기 화학식 Y-1 및 화학식 Y-2에서,R 3는 각각 독립적으로 (메트)아크릴레이트기 또는 화학식 4로 표시되는 작용기이고,[화학식 4]R 1은 각각의 반복단위에서 동일하거나 서로 상이하며, 수소 또는 탄소수 1 내지 10의 알킬기이고, L은 각각의 반복단위에서 동일하거나 서로 상이하며, 직접 결합 또는 탄소수 1 내지 10의 알킬렌이고,n3, n4 및 n5는 각각 독립적으로 0 내지 4이며, 단, n3, n4 및 n5 중 적어도 하나는 1 이상이고,R 4는 각각 독립적으로 단일 결합, -O-, -S-, -C(=O)-, -CH(OH)-, -S(=O) 2-, -Si(CH 3) 2-, -(CH 2) p- (여기서 1≤p≤10), -(CF 2) q- (여기서 1≤q≤10), -C(CH 3) 2-, -C(CF 3) 2-, 또는 -C(=O)NH- 임.
- 제 1항에 있어서,상기 제1 반복 단위에 대하여, 제2 반복 단위 및 제3 반복 단위의 총 합의 몰비가 10:90 내지 90:10인, 폴리아미드-이미드 블록 공중합체.
- 제 1항에 있어서,중량 평균 분자량이 5,000 내지 300,000g/mol인, 폴리아미드-이미드 블록 공중합체.
- 디아민 화합물을 디안하이드라이드 화합물과 반응시켜 폴리아믹산 블록을 형성하는 단계;상기 폴리아믹산 블록 형성 단계의 결과물에, 트리아실 할라이드, 트리아민 및 트리카르복실산으로 이루어진 군에서 선택된 1종 이상의 화합물 및 디아실 할라이드, 디아민 및 디카르복실산으로 이루어진 군에서 선택된 1종 이상의 화합물을 혼합하고, 이를 반응시켜 폴리아미드 블록을 형성하는 단계; 및상기 폴리아믹산 블록 및 폴리아미드 블록을 포함하는 혼합물에, (메트)아크릴레이트기를 포함하는 화합물 및 하기 화학식 4로 표시되는 작용기를 포함하는 화합물 중 적어도 하나의 화합물을 첨가하여 이미드화하는 단계;를 포함하고,상기 디아민 화합물 총 100몰에 대하여, 수산기가 치환된 디아민 화합물은 10몰% 내지 80몰%로 포함되는, 폴리아미드-이미드 블록 공중합체의 제조방법:[화학식 4]상기 식 중에서, R 1은 각각의 반복 단위에서 동일하거나 서로 상이하며, 수소 또는 탄소수 1 내지 10의 알킬기이고, L은 각각의 반복단위에서 동일하거나 서로 상이하며, 직접 결합 또는 탄소수 1 내지 10의 알킬렌임.
- 제 12항에 있어서,상기 (메트)아크릴레이트기를 포함하는 화합물은 (메트)아크릴산 무수물((Meth)acrylic anhydride)이고,상기 화학식 4로 표시되는 작용기를 포함하는 화합물은 2-아이소사이아나토에틸 (메트)아크릴레이트 (2-Isocyanatoethyl (meth)acrylate)인, 폴리아미드-이미드 블록 공중합체의 제조방법.
- 제 12항에 있어서,상기 이미드화 단계에서, 폴리아믹산 블록 및 폴리아미드 블록에 포함된 수산기가 (메트)아크릴레이트기 또는 화학식 4로 표시되는 작용기로 치환되는, 폴리아미드-이미드 블록 공중합체의 제조방법.
- 제 12항에 있어서,상기 이미드화 단계는 20 ℃ 내지 100 ℃에서 수행되는, 폴리아미드-이미드 블록 공중합체의 제조방법.
- 제1항에 따른 폴리아미드-이미드 블록 공중합체를 포함하는, 폴리아미드-이미드 필름.
- 제16항에 있어서,ASTM D1925 기준에 따른 황변 지수(Y.I.)가 1.5 내지 1.75인, 폴리아미드-이미드 필름.
- 제16항에 있어서,모듈러스가 4.0 GPa 내지 5.0GPa인, 폴리아미드-이미드 필름.
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CN202080011534.8A CN113396176B (zh) | 2019-04-09 | 2020-04-09 | 聚酰胺-酰亚胺嵌段共聚物、其制备方法和包含其的聚酰胺-酰亚胺膜 |
EP20787094.0A EP3910003A4 (en) | 2019-04-09 | 2020-04-09 | POLYAMIDE-IMIDE BLOCK COPOLYMER, METHOD FOR PREPARING IT, AND POLYAMIDE-IMIDE FILM COMPRISING IT |
US17/432,886 US20220220308A1 (en) | 2019-04-09 | 2020-04-09 | Polyamide-imide block copolymers, preparation method thereof and polyamide-imide film comprising the same |
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WO2023013224A1 (ja) * | 2021-08-03 | 2023-02-09 | 日本化薬株式会社 | ポリイミド樹脂、該ポリイミド樹脂を含有する樹脂組成物及びその硬化物 |
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CN113396176A (zh) | 2021-09-14 |
EP3910003A4 (en) | 2022-03-23 |
KR20200119124A (ko) | 2020-10-19 |
JP2022527878A (ja) | 2022-06-07 |
TW202043336A (zh) | 2020-12-01 |
US20220220308A1 (en) | 2022-07-14 |
TWI793414B (zh) | 2023-02-21 |
JP7196386B2 (ja) | 2022-12-27 |
EP3910003A1 (en) | 2021-11-17 |
CN113396176B (zh) | 2024-01-12 |
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