WO2018004195A1 - 폴리이미드계 블록 공중합체 및 이를 포함하는 폴리이미드계 필름 - Google Patents
폴리이미드계 블록 공중합체 및 이를 포함하는 폴리이미드계 필름 Download PDFInfo
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- WO2018004195A1 WO2018004195A1 PCT/KR2017/006601 KR2017006601W WO2018004195A1 WO 2018004195 A1 WO2018004195 A1 WO 2018004195A1 KR 2017006601 W KR2017006601 W KR 2017006601W WO 2018004195 A1 WO2018004195 A1 WO 2018004195A1
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- carbon atoms
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- 0 *C(*)(N(C(C1=C2C=IC=C1)=O)C2=O)I Chemical compound *C(*)(N(C(C1=C2C=IC=C1)=O)C2=O)I 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
Classifications
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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
- 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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
-
- 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
- C08G73/12—Unsaturated polyimide precursors
-
- 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 polyimide block copolymer and a polyimide film comprising the same.
- Aromatic polyimide 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 polyimide resins are widely used as electrical / electronic materials.
- polyimide resins have many limitations in use because they have a dark brown limitation due to CTC (charge transfer complex) formation of ⁇ electrons present in the imide chain.
- a method of introducing an aliphatic ring compound to inhibit resonance structure formation of ⁇ electrons has been proposed.
- the present invention is to provide a polyimide-based block copolymer that is colorless transparent and exhibits excellent mechanical properties.
- the present invention is to provide a polyimide film containing the polyimide block copolymer.
- a polyimide-based block copolymer comprising:
- R 12 is each independently -H, -F, -CI, -Br, -I, -CF 3 , -CC1 3 , -CBr 3 / -CI 3 , -NO2,-CN, -COCH 3 , -C0 2 C 2 H 5 / 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; nl and ml are each independently an integer from 0 to 3;
- ⁇ is the same or different at each repeating unit, and each independently contains a divalent aromatic organic group having 6 to 30 carbon atoms;
- E 11 , E 12 and E 13 are each independently a single bond or —NH—;
- Zio is the same or different at each repeat unit and is a trivalent linking group derived from at least one compound selected from the group consisting of triacyl halides, tricarboxylic acids and tricarboxylates, respectively;
- X 20 and X 3 o are the same or different from each other and each independently include a divalent aromatic organic group having 6 to 30 carbon atoms;
- E 21 , E 22 , E 23 , E 31 , E 32 , and E 33 are each independently a single bond or -NH-;
- A is a divalent aromatic organic group having 6 to 20 carbon atoms, a divalent heteroaromatic organic group having 4 to 20 carbon atoms, a divalent alicyclic organic group having 6 to 20 carbon atoms, or two
- a polyimide film comprising the polyimide block copolymer.
- a polyimide block copolymer and a polyimide film including the same according to embodiments of the present invention will be described in detail.
- 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 polyimide-based block copolymer comprising:
- R 12 are each independently -H, -F, -CI, -Br, -I, -CF 3 , -CC1 3 / -CBr 3 , -CI 3 , -N0 2 ,-CN, -COCH 3 / -CO2C2H5
- nl and ml are each independently an integer from 0 to 3;
- ⁇ is the same or different at each repeating unit, and each independently contains a divalent aromatic organic group having 6 to 30 carbon atoms;
- E «E 12 and E l3 are each independently a single bond or -NH-;
- Zio is the same or different at each repeat unit and is a trivalent linking group derived from at least one compound selected from the group consisting of triacyl halides, tricarboxylic acids and tricarboxylates, respectively;
- X 20 and X 3 o are the same or different from each other and each independently comprise a divalent aromatic organic group having 6 to 30 carbon atoms;
- E 2i , E 22 , E 23 , E 31 , E 32 , and E 33 are each independently a single bond or —NH—;
- Z 20 and Z 3 o are the same or different from each other and are selected from the group consisting of diacyl halides, dicarboxylic acids and dicarboxylates, respectively
- A is a divalent aromatic organic group having 6 to 20 carbon atoms, a divalent heteroaromatic organic group having 4 to 20 carbon atoms, a divalent alicyclic organic group having 6 to 20 carbon atoms, or 2
- the brancher may impart a network structure to the copolymer, and a network having a robust and stable structure may be formed by the block copolymerization of the repeating unit including the same.
- This robust and stable network structure allows the polyimide-based block copolymer to be colorless and transparent while exhibiting improved mechanical properties.
- polyimide block co-polymer is the second repeating unit
- the polyimide-based block copolymer, two carbonyl groups connected to both sides of A in Z 2 o are bonded to each other in a meta position with respect to A, and on both sides of A in Z 3Q
- the two carbonyl groups linked together have a structure bonded to the para position with respect to A.
- the polyimide-based block copolymer exhibits excellent processability resulting from the meta position bonding of the second repeating unit, and also has excellent mechanical properties resulting from the para position bonding of the third repeating unit (particularly hardness and Modulus).
- the polyimide block copolymer may include a group (Z 2 o) in which the first repeating unit into which a trivalent branch (Zio) is introduced, and two carbonyl groups bonded to a meta position
- the polyimide-based block copolymer is excellent in the processability of the resin itself to facilitate the formation of a film using the same, and to provide a film having colorless transparent and improved mechanical properties.
- each repeating unit contained in the poly-based block copolymer will be described.
- the polyimide block copolymer includes a first repeating unit represented by Chemical Formula 1.
- the polyimide-based block copolymer may include two or more first repeating units represented by Formula 1, and these repeating units may have the same or different structures.
- the single bond refers to a case where R 11 in Chemical Formula 1 is a chemical bond that simply connects groups adjacent to each other.
- R 12 is independently -H, -F, -CI, -Br, -I, -CF 3, - CC1 3 / -CBr 3 / -CI 3 / -NO2, -CN, - COCH3, -C0 2 C 2 H 5 , a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms.
- nl and ml are each independently an integer of 0 to 3.
- nl and ml may be each independently 0 or 1.
- ⁇ is the same or different from each repeating unit, and each independently includes a divalent aromatic organic group having 6 to 30 carbon atoms.
- ⁇ ⁇ ⁇ may be a divalent organic group represented by the following structural formula:
- R b are each independently -H, -F, -CI, -Br, -I, -CF 3 / -CC1 3 / -CBr 3 / -CI 3 , -NO2,-
- CN -COCH 3 / -C0 2 C 2 H 5 / 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;
- E12 and El 3 are each independently a single bond or -NH-.
- the single bond means a case where E 12 and E i3 are chemical bonds that simply connect the groups or repeating units next to each other.
- Z i o is a brancher having three semi-cyclic substituents, the same or different from each other in each repeating unit, and in the group consisting of triacyl halides, tricarboxylic acids and tricarboxylates, respectively.
- Tri-valent linking groups derived from one or more compounds selected.
- Z i o is an aromatic triacyl halide having 6 to 20 carbon atoms, an aromatic tricarboxylic acid having 6 to 20 carbon atoms, an aromatic tricarboxylate having 6 to 20 carbon atoms, and an N-containing heteroaromatic triacyl halide having 4 to 20 carbon atoms.
- It may be a trivalent linking group derived from one or more compounds selected from the group consisting of 20 alicyclic tricarboxylates.
- Zio may be a group selected from the group represented by the following structural formula:
- the first repeating unit may include a repeating unit represented by the following Formula and 1-c:
- Ri2 and R14 are each independently -H, -F, -CI, -Br, -I, -C3 ⁇ 4, -CC1 3 , -CBr 3 , -CI 3 , -N0 2 , -CN, -COCH3, ⁇ C0 2 C 2 H 5, 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;
- nl and ml are each independently an integer from 0 to 3;
- n2 and m2 are each independently an integer of 1-4.
- Y 20 may be the same or different from each other, and each independently include a divalent aromatic organic value having 6 to 30 carbon atoms.
- Y 20 may be a divalent organic group represented by the following structural formula:
- R b ' is each independently -H, -F, -CI, -Br, -I, -CF 3 / -CC1 3 , -CBr 3 , -CI 3 , -N0 2 / -CN, -COCH 3 ,- C0 2 C 2 H 5 , 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;
- E 21 , E 22 and E 23 are each independently a single bond or -NH-.
- the single bond means a case where E 2i , E22 and E 23 are chemical bonds that simply connect the groups or repeating units next to each other.
- Z 2 o is selected from the group represented by the following structural formula Group work
- R 21 is —H, —F, —CI, —Br, —I, a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms ego,
- al is an integer from 0 to 3
- a2 is an integer of 0-2.
- Z 2 o may be a group selected from the group represented by the following structural formula:
- the Z 2 o isophthaloyl dichloride IPC
- isophthalic acid isophthalic acid
- cyclonucleic acid -1,3-dicarbonyl chloride cyclohexane-l, 3-dicarbonyl chloride
- ⁇ 1 "cyclohexane-l, 3-dicarboxylic acid pyridine-3,5-dicarbonyl chloride, pyridine-3,5- Dicarboxylic acid (pyridine- 3,5-dicarboxylic acid), pyrimidine-2,6-dicarbonyl chloride, and pyrimidine-2,6-dicarboxylic acid
- It may be a divalent linking group derived from one or more compounds selected from the group consisting of.
- the second repeating unit may include a repeating unit represented by the following Chemical Formula 2-a:
- R 23 is each independently -H, -F, -CI, -Br, -I, -CF 3 / -CC1 3 , -CBr 3 / -CI 3 / -N0 2 ,-
- CN -COCH 3 / -C0 2 C 2 H 5 , a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms; ⁇
- n3 and m3 are each independently an integer of 1 to 4;
- E 2i , E 22 and E 23 are each independently a single bond or —NH—;
- Z 2 o is a group selected from the group represented by the following structural formula:
- the second repeating unit may include a repeating unit represented by the following Chemical Formula 2-b:
- R23 is each independently -H, -F, -CI, -Br, -I, -CF 3 , -CC1 3 / -CBr 3 / -CI 3 , -N0 2 / -CN, -COCH 3 / -C0 2 C 2 H 5 / 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;
- n3 and m3 are each independently an integer of 1-4.
- the polyimide-based block copolymer includes a third repeating unit represented by Formula 3 together with a second repeating unit represented by Formula 2 above.
- VII 3 o are the same or different from each other, and each independently include a divalent aromatic organic group having 6 to 30 carbon atoms.
- ⁇ 3 ⁇ can be a divalent organic group represented by the following structural formula
- R b ' is each independently -H, -F, -CI, -Br, -I, -CF 3 , -CC1 3 / -CBr 3 / -CI 3 , -N0 2 / -CN, -COCH 3 / - C0 2 C 2 H 5 , 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;
- E 31 , E 32 and E 33 are each independently a single bond or -NH-.
- the single bond is E 32 and E 33 are chemical bonds that simply connect the groups or repeating units next to each other, wherein in Formula 3, Zso is the same or different from each other and is a diacyl halide or dicarboxylic acid, respectively.
- two carbonyl groups connected to both sides of A in Z 3 o are bonded to each other in a para position with respect to A.
- Z 3 ° is a group selected from the group represented by the following structural formula
- R3! And R 32 are each independently —H, —F, —CI, —Br, —I, a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or 6 to 20 carbon atoms. Is an aromatic organic group,
- bl and b2 are each independently an integer of 0 to 3;
- b3 is an integer of 0-2.
- the z 3 being a group o is selected from the group represented by the following structural formula: "
- Zso is terephthaloyl chloride (TPC), terephthalic acid, terephthalic acid, cyclonucleic acid-1,4-dicarbonyl chloride, cyclonucleic acid-1, 4-dicarboxylic acid (cyclohexane-l, 4-dicarboxylic acid), pyridine-2,5-dicarbonyl Pyridine-2,5-dicarbonyl chloride, pyridine-2,5-dicarboxylic acid, pyrimidine-2,5-dicarbonyl chloride chloride), pyrimidine-2,5-dicarboxylic acids retaliation (pyrimidine-2,5-dicarboxylic acid) , 4, 4 '- biphenyl dicarboxylic chloride (4, 4' -biphenyldicarbonyl chloride, BPC) and 4,4 ' It may be a divalent linking group derived from one or more compounds selected from the group consisting of -biphenyl
- R 34 are each independently -H, -F, -CI, -Br, -I, -CF 3 / -CC1 3 / -CBr 3 / -CI 3 , -N0 2 ,-CN, -COCH 3 / -CO2C2H5
- n4 and m4 are each independently an integer of 1 to 4;
- E3i, E32 and E 33 are each independently a single bond or -NH-;
- Z 3 o is a group selected from the group represented by the following structural formula:
- the third repeating unit may include a repeating unit represented by the following Chemical Formula 3-b or 3-c:
- R32 is each independently -F, -CI, -Br, -I, -CF 3 , -CC1 3 , -CBr 3 , -CI 3 , -N0 2 ,-CN, -COCH 3 / -C0 2 C 2 H 5 / a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms;
- n4 and m4 are each independently an integer of 1-4. According to the exemplary embodiment of the present invention, the presence of the second repeating unit represented by Formula 2 and the third repeating unit represented by Formula 3 in the polyimide block copolymer may be confirmed through NMR spectra.
- the polyimide block copolymer is 10.80 ppm or more and 11.00 i H NMR (300 MHz, DMSO-d6, Standards TMS) spectrum having at least one peak in the ⁇ range below ppm and at least one peak in the ⁇ range above 10.60 ppm and below 10.80 ppm.
- the peak according to Z 2Q (including two carbonyl groups bonded to a meta position) of the second repeating unit is ⁇ of 10.80 ppm or more and 11.00 ppm or less Observed within range;
- the peak according to the third repeating unit (including two carbonyl groups bonded at the para position) can be observed within the ⁇ range of ia 60 ppm or more and less than 10.80 ppm.
- the molar ratio of the first repeating unit: the second repeating unit is 1: 0.1 to 1: 10
- the molar ratio of the second repeating unit: the third repeating unit is 1: 0.5 to 1: 4 may be.
- the molar ratio of the first repeating unit: the second repeating unit: the third repeating unit may be 1: 0.8: 0.2 to 1: 0.2: 0.8.
- Z i introduced into the first repeating unit is a brancher which gives a network structure to the copolymer, and a network having a stable and stable structure to the copolymer by block copolymerization of the repeating unit including the same. Can be formed. Therefore, when the molar ratio of the first repeating unit is too low, the network structure may not be formed in the copolymer sufficiently, and the effect of improving physical properties may be insignificant. However, when the molar ratio of the first repeating unit is too high, gelation may occur in the polymerization process.
- the polyimide-based block copolymer comprising simultaneously the first repeating unit, the second repeating unit and the third repeating unit in the above-described molar ratio is mainly derived from the first repeating unit in which the brancher (Z i ) is introduced.
- the polyimide-based block copolymer may have a high molecular weight as compared with a general polyimide resin having a solid and stable network structure. Specifically, the polyimide block copolymer
- the polyimide block copolymer may have a weight average molecular weight of 100,000 to 5,000,000 g / mol, preferably 200,000 to 1,000,000 g / mol, more preferably 300,000 to 750,000 g / mol, even more preferably 500,000 to 650,000 g / mol.
- the polyimide block copolymer is 3.0 or less, 2.90 or less, black is 180 or less, or 2.70 or less, or 2.60 or less, or 2.55 or less, measured according to ASTM D1925 for a specimen having a thickness of 30 ⁇ 2. It can represent the yellow index (Yi) of (Yi).
- the polyimide block copolymer is 3.0 or less, 2.90 or less, black is 180 or less, or 2.70 or less, or 2.60 or less, or 2.55 or less, measured according to ASTM D1925 for a specimen having a thickness of 30 ⁇ 2. It can represent the yellow index (Yi) of (Yi).
- the polyimide block copolymer is 3.
- It can be prepared by a method comprising a (sequential polymerization method).
- the polymerization conditions for producing the polyimide block copolymer are not particularly limited.
- the polymerization for the formation of the polyamic acid may be carried out by solution polymerization under 0 to 100 ° C in an inert atmosphere.
- ⁇ , ⁇ -dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone, ⁇ -methyl-2-pyridone, tetrahydrofuran, chloroform, gamma-butyrolactone, etc. This can be used.
- the imidization after formation of the polyamic acid can be carried out thermally or chemically.
- compounds such as acetic anhydride and pyridine can be used for chemical imidization. have.
- a polyimide film including the polyimide block copolymer described above is provided.
- the polyimide-based film including the polyimide-based block copolymer may be used as a material for various molded articles requiring high mechanical properties with colorless transparency.
- the polyimide film including the polyimide block copolymer may be applied as a display substrate, a display protective film, a touch panel, a cover film of a flexible or foldable device, and the like.
- the polyimide film may be prepared by a conventional method such as a dry method or a wet method using the polyimide block copolymer.
- 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 may be performed on the polyimide film.
- the polyimide-based film may be colorless, transparent and have excellent mechanical properties as manufactured using the polyimide-based block copolymer.
- the polyimide film may exhibit a pencil hardness of HB grade or higher measured according to ASTM D3363.
- the polyimide film has a yellow index of 3.0 or less, 2.90 or less, or 2.80 or less, black or less, 2.70 or less, or 2.60 or less, or 2.55 or less, measured according to ASTM D1925 at a thickness of 30 ⁇ 2. , YI).
- the polyimide-based block copolymer according to the present invention makes it possible to provide a polyimide-based film which is colorless and transparent and exhibits excellent mechanical properties.
- Example 1 is an NMR spectrum of a polyimide copolymer obtained in Example 1
- FIG. 2 is an NMR spectrum of the polyimide copolymer obtained in Comparative Example 1.
- FIG. 3 is an NMR spectrum of a polyimide copolymer obtained in Comparative Example 2.
- the copolymer obtained in Example 1 was dissolved in ⁇ , ⁇ -dimethylacetamide (dimethylacetamide) to prepare a polymer solution of about 25% (w / V).
- the polymer solution was poured onto a glass plate and cast a thickness of the polymer solution to 335 an using a film applicator, and dried (repeated twice) with hot air at 80 ° C. for 10 minutes.
- Slowly heating (maintained for 30 minutes at 250 ° C.) for 2 hours from 100 ° C to 250 ° C while letting nitrogen to it, and then slowly angled to obtain a film with a thickness of 30 ⁇ 2 peeled off the glass plate.
- Example 2 Except for using the copolymer obtained in Example 2 instead of the copolymer obtained in Example 1, a film having a thickness of 30 cm 2 Pa and a film having a thickness of 50 ⁇ 2 was obtained in the same manner as in Example 3. Comparative Example 4
- Example 1 the copolymer, rather than the Comparative Example 2, the air, except for using the copolymer of Example 3 and the film and the film having a thickness of 50 ⁇ 2 ⁇ the same method thickness 30 ⁇ 2 / zm as obtained in the obtained in each Got it.
- Comparative Example 6 Comparative Example 6
- Pencil Hardness Tester was used to measure the pencil hardness for a film with a thickness of 30 ⁇ 2 according to the ASTM D3363 (750 gf) measuring method.
- Elastic modulus EM, GPa
- ultimate tensile strength TS, MPa
- tensile elongation for films with a thickness of 30 ⁇ 2 according to the measurement method of ASTM D 882 using a universal testing machine elongation, TE,%) was measured.
- Haze value of a film having a thickness of 30 ⁇ 2 was measured using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES) according to the measuring method of ASTM D1003. (5) Folding strength
- the fracture strength of the film was evaluated using an MIT type folding endurance tester! Specifically, the specimen (lcm * 7cm) of the film was loaded into the seismic strength tester and bent to fracture at an angle of 135 ° , a radius of curvature of 0.8 mm and a load of 250 g at a speed of 175 rpm on the left and right sides of the specimen. Reciprocating bending cycles were measured. (6) processability
- the film according to Examples 2 and 3 has a low yellow index and low haze, which is colorless and transparent but has excellent mechanical properties and high pencil hardness. And the copolymer of the said Example 1 and 2 showed transparency equivalent to the film of thickness 30 +/- 2 / m, even when shape
- the film of Comparative Example 4 exhibited a similar level of colorless transparency to the film according to the examples, but was found to have a low pencil hardness and poor mechanical properties.
- the film of Comparative Example 5 exhibited pencil hardness and mechanical properties similar to those of the films according to the examples, but exhibited poor fracture strength. And, when the copolymer of Comparative Example 2 is molded into a film having a thickness of 50 ⁇ 2, the thickness of 30 ⁇ 2 It hazed rapidly compared with the film of, and it was confirmed that workability was bad.
- the film of Comparative Example 6 showed a similar level of yellow index as compared to the film according to the examples, but was found to have poor pencil hardness and fracture strength.
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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CN201780007017.1A CN108473678B (zh) | 2016-06-30 | 2017-06-22 | 基于聚酰亚胺的嵌段共聚物及包含其的基于聚酰亚胺的膜 |
JP2018533163A JP6728542B2 (ja) | 2016-06-30 | 2017-06-22 | ポリイミド系ブロック共重合体およびこれを含むポリイミド系フィルム |
EP17820471.5A EP3375806B1 (en) | 2016-06-30 | 2017-06-22 | Polyimide-based block copolymer and polyimide-based film comprising same |
US16/064,405 US10689489B2 (en) | 2016-06-30 | 2017-06-22 | Polyimide-based block copolymer and polyimide-based film comprising the same |
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KR1020170077971A KR101854771B1 (ko) | 2016-06-30 | 2017-06-20 | 폴리이미드계 블록 공중합체 및 이를 포함하는 폴리이미드계 필름 |
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