WO2020096283A1 - Polyamide resin, method for producing same, and polyamide film and resin laminate comprising same - Google Patents

Polyamide resin, method for producing same, and polyamide film and resin laminate comprising same Download PDF

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Publication number
WO2020096283A1
WO2020096283A1 PCT/KR2019/014714 KR2019014714W WO2020096283A1 WO 2020096283 A1 WO2020096283 A1 WO 2020096283A1 KR 2019014714 W KR2019014714 W KR 2019014714W WO 2020096283 A1 WO2020096283 A1 WO 2020096283A1
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formula
polyamide
repeating unit
polyamide resin
mol
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PCT/KR2019/014714
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French (fr)
Korean (ko)
Inventor
최일환
태영지
박순용
박영석
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주식회사 엘지화학
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Priority claimed from KR1020190125890A external-priority patent/KR102261850B1/en
Priority claimed from KR1020190137545A external-priority patent/KR102412532B1/en
Priority claimed from KR1020190137544A external-priority patent/KR102423808B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP19881153.1A priority Critical patent/EP3786212A4/en
Priority to US17/059,975 priority patent/US20210214497A1/en
Priority to JP2020566280A priority patent/JP7074280B2/en
Priority to CN201980036380.5A priority patent/CN112204074B/en
Publication of WO2020096283A1 publication Critical patent/WO2020096283A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • 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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids

Definitions

  • the present invention is capable of realizing excellent mechanical properties, and relates to a polyamide resin having improved transparency, a manufacturing method thereof, and a polyamide film and a resin laminate 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 a rigid chain structure. These polyimide resins are widely used as electrical / electronic materials.
  • the polyimide resin has a dark brown color due to the formation of the charge transfer complex (CTC) of Pi-electrons present in the imide chain, and thus it is difficult to secure transparency.
  • CTC charge transfer complex
  • the surface is easily scratched It has a very weak scratch resistance.
  • the amide repeat unit and isop derived from terephthaloyl chloride during polyamide polymerization due to the difference in solubility and reactivity (stereo hindrance) and reaction rate of terephthaloyl chloride or isophthaloyl chloride used in the synthesis of polyamide resins
  • the amide repeat unit derived from thaloyl chloride is difficult to polymerize ideally and alternatively without forming a block.
  • the polymerization reaction proceeds in a state in which the monomer used for synthesizing the polyamide resin is dissolved in a solvent, the molecular weight of the final synthesized polyamide resin is secured to a sufficient level due to deterioration by moisture or hybridization with the solvent. it's difficult.
  • the present invention can realize excellent mechanical properties, and relates to a polyamide resin having transparency.
  • the present invention is to provide a method for producing a polyamide resin for synthesizing the polyamide resin.
  • the present invention is to provide a polyamide film and a resin laminate comprising the polyamide resin.
  • a repeating unit represented by the following Chemical Formula 1 or a first polyamide segment including a block composed of the same; And a repeating unit represented by the following Chemical Formula 2, or a second polyamide segment comprising a block consisting of the first polyamide segment and the second polyamide segment comprising a cross-repeating unit represented by the following Chemical Formula 3
  • Polyamide resins that form the main chain.
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and in Formula 3, A is the first polyamide segment, and B is the second polyamide segment.
  • the compound represented by the following formula (7) and the compound represented by the formula (8) are melt-kneaded, and solidifying the melt-kneaded material to form a complex; And reacting the complex with an aromatic diamine monomer.
  • a method for producing a polyamide resin is provided.
  • X is a halogen or a hydroxyl group.
  • the first polyamide segment including a repeating unit represented by Formula 1 or a block composed of the same; And a second polyamide segment including a repeating unit represented by Formula 2 or a block composed of the first polyamide segment and a second polyamide segment comprising cross-repeating units represented by Formula 3 above.
  • a polyamide film is provided, comprising a polyamide resin forming a backbone.
  • the first polyamide segment including a repeating unit represented by Formula 1 or a block composed of the same; And a second polyamide segment including a repeating unit represented by Formula 2 or a block composed of the first polyamide segment and a second polyamide segment comprising cross-repeating units represented by Formula 3 above.
  • a base material comprising a polyamide resin forming a main chain; And a hard coating layer formed on at least one surface of the substrate.
  • the repeating unit represented by the formula (1), or a first polyamide segment comprising a block consisting of; And a repeating unit represented by Chemical Formula 2, or a second polyamide segment including a block consisting of the first polyamide segment and the second polyamide segment including a cross-repeating unit represented by Chemical Formula 3 Polyamide resins that form the backbone can be provided.
  • the present inventors such as the polyamide resin of one embodiment, the first polyamide segment comprising a repeating unit represented by the formula (1), or a block consisting of it; And a second polyamide segment including a repeating unit represented by Formula 2 or a block composed of the first polyamide segment and a second polyamide segment comprising cross-repeating units represented by Formula 3 above.
  • the length growth of the first polyamide segment which is a polymer block composed of repeating units derived from terephthaloyl chloride inside the polyamide resin, is minimized, thereby lowering the crystallinity of the polyamide resin to reduce the transparent polyamide resin. It was confirmed through experiments that it can be implemented and the invention was completed.
  • the main chain of the polyamide resin is a first polyamide segment including an amide repeating unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound, as shown in Chemical Formula 3, and 1,3-
  • a second polyamide segment comprising alternating amide repeating units derived from a combination of an aromatic diacyl compound and an aromatic diamine compound, or repeating units derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound, alternately (alternatively) can form a polymerization chain. That is, the second polyamide segment is located between the first polyamide segments, and may serve to inhibit length growth of the first polyamide segments.
  • the haze value of the polyamide resin can be remarkably lowered while the crystal properties of the first polyamide segment are reduced, thereby realizing excellent transparency.
  • the main chain of the polyamide resin is a first polyamide segment including an amide repeating unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound, as shown in Chemical Formula 3, and 1,3-aromatic
  • the second polyamide segment comprising alternating amide repeating units derived from a combination of a diacyl compound and an aromatic diamine compound, or repeating units derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound ( alternatively) forming the polymerization chain appears to be due to the formation of a melt-kneaded composite in the method of preparing a polyamide resin of another embodiment of the present invention described below.
  • substitution means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.
  • substituted or unsubstituted refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; Primary amino group; Carboxy group; Sulfonic acid group; Sulfonamide groups; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Haloalkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Alkoxysilylalkyl groups; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms,
  • a substituent having two or more substituents may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
  • a haloalkyl group can be used as the substituent, and examples of the haloalkyl group include a trifluoromethyl group.
  • the alkyl group is a monovalent functional group derived from alkane, and may be a straight chain or a branched chain, and the carbon number of the straight chain alkyl group is not particularly limited, but is preferably 1 to 20.
  • the branched chain alkyl group has 3 to 20 carbon atoms.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-non
  • the aryl group is a monovalent functional group derived from arenes, and is not particularly limited, but is preferably 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group.
  • the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.
  • the aryl group may be substituted or unsubstituted.
  • the arylene groups are divalent functional groups derived from arenes, and the descriptions of the aryl groups described above may be applied except that they are divalent functional groups.
  • it may be a phenylene group, biphenylene group, terphenylene group, naphthalene group, fluorenyl group, pyrenyl group, phenanthrenyl group, perylene group, tetrasenyl group, anthracenyl group, and the like.
  • the arylene group may be substituted or unsubstituted.
  • the heteroaryl group includes one or more non-carbon atoms, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S.
  • the number of carbon atoms is not particularly limited, and preferably 4 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic.
  • heterocyclic group examples include thiophene group, furanyl group, pyrrol group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Jolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, di
  • the heteroarylene group has 2 to 20 carbon atoms, or 2 to 10 carbon atoms, or 6 to 20 carbon atoms.
  • the heteroaryl group containing O, N or S is an arylene group, and the description of the above-described heteroaryl group can be applied, except that it is a divalent functional group.
  • the heteroarylene group may be substituted or unsubstituted.
  • halogen examples include fluorine, chlorine, bromine or iodine.
  • the polyamide resin may include a repeating unit represented by Chemical Formula 1, or a first polyamide segment including a block composed of the same; And it may include a second polyamide segment comprising a repeating unit represented by the formula (2), or a block consisting of it.
  • Ar 1 and Ar 2 are the same or different from each other, and each independently is an arylene group having 6 to 20 carbon atoms substituted with one or more substituents selected from the group consisting of an alkyl group, a haloalkyl group, and an amino group. , More preferably, it may be a 2,2'-bis (trifluoromethyl) -4,4'-biphenylene group.
  • Ar 1 and Ar 2 may be divalent organic functional groups derived from aromatic diamine monomers, and specific examples of the aromatic diamine monomers are 2,2'-bis (trifluoro Methyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine), 2,2'-dimethyl-4,4'-diaminobenzidine (2,2 '-dimethyl-4,4'-diaminobenzidine),4,4'-diaminodiphenyl sulfone, 4,4 '-(9-fluorenylidene) dianiline (4,4 '-(9-fluorenylidene) dianiline), bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2', 5,5'-tetra Chlorobenzidine (2,2 ', 5,5'-tetrachlorobenz
  • the aromatic diamine monomer is 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB ) Or 2,2'-dimethyl-4,4'-diaminobenzidine.
  • the first polyamide segment may include a repeating unit represented by Chemical Formula 1 or a block composed of a repeating unit represented by Chemical Formula 1.
  • a specific example of the repeating unit represented by Chemical Formula 1 may include a repeating unit represented by Chemical Formula 1-1.
  • the repeating unit represented by Formula 1 is an amide repeating unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound, specifically an amide formed by amidation reaction of terephthaloyl chloride or terephthalic acid with an aromatic diamine monomer It is a repeating unit, and due to the linear molecular structure, chain packing and alignment in the polymer can be kept constant, and the surface hardness and mechanical properties of the polyamide film can be improved.
  • 1,4-aromatic diacyl compound examples include terephthaloyl chloride or terephthalic acid.
  • aromatic diamine monomer 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine), 2,2'-dimethyl-4,4'-diaminobenzidine, 4,4'-diaminodiphenyl sulfone , 4,4 '-(9-fluorenylidene) dianiline (4,4'-(9-fluorenylidene) dianiline), bis (4- (4-aminophenoxy) phenyl) sulfone (bis (4- ( 4-aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine (2,2', 5,5'-tetrachlorobenzidine (2,2',
  • the 1,4-aromatic diacyl compound includes terephthaloyl chloride, or terephthalic acid
  • the aromatic diamine compound is 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine It may include.
  • the number average molecular weight of the first polyamide segment is 100 g / mol or more and 5000 g / mol or less, or 100 g / mol or more and 3000 g / mol or less, or 100 g / mol or more and 2500 g / mol or less, or 100 g / mol or more and 2450 g / mol or less.
  • the number average molecular weight of the first polyamide segment is increased to more than 5000 g / mol, the crystallinity of the polyamide resin may increase as the chain of the first polyamide segment becomes too long, thereby increasing It can be difficult to ensure transparency by having a haze value.
  • the number average molecular weight of the first polyamide segment is not limited to an example of a measurement method, but can be confirmed, for example, through SAXS (Small-angle X-ray scattering) analysis.
  • the first polyamide segment may be represented by Formula 5 below.
  • Ar 1 is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and a is an integer of 1 to 5.
  • Chemical Formula 5 when a is 1, Chemical Formula 5 may be a repeating unit represented by Chemical Formula 1.
  • Chemical Formula 5 when a is 2 to 5, Chemical Formula 5 may be a block composed of repeating units represented by Chemical Formula 1.
  • the description of Ar 1 includes the contents described in Formula 1 above.
  • the proportion of repeating units represented by Formula 1 is 40 mol% to 95 mol%, 50 mol% to 95 mol%, or 60 mol% to 95 mol%, Or 70 mol% to 95 mol%, or 50 mol% to 90 mol%, or 50 mol% to 85 mol%, or 60 mol% to 85 mol%, or 70 mol% to 85 mol%, or 80 mol% to 85 mol%, or 82 mol% to 85 mol%.
  • the polyamide resin in which the repeating unit represented by Chemical Formula 1 is contained in the above-described content can secure a sufficient level of molecular weight to secure excellent mechanical properties.
  • the second polyamide segment may include a repeating unit represented by Chemical Formula 2 or a block composed of a repeating unit represented by Chemical Formula 2.
  • the repeating unit represented by Chemical Formula 2 is an amide repeating unit derived from a combination of a 1,3-aromatic diacyl compound and an aromatic diamine compound, or derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound. Repeating units, or mixtures thereof.
  • the repeating unit represented by Chemical Formula 2 includes: a repeating unit represented by Chemical Formula 2-1; Or a repeating unit represented by the following formula 2-2; It may include one of the repeating unit.
  • Ar 2 is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.
  • the detailed description of Ar 2 includes the above-described contents in Chemical Formula 2.
  • the repeating unit represented by Formula 2-1 is an amide repeating unit derived from a combination of a 1,3-aromatic diacyl compound and an aromatic diamine compound, specifically a repeat formed by amidation reaction of isophthaloyl chloride and an aromatic diamine monomer
  • the unit is a repeating unit represented by Chemical Formula 2-2, an amide repeating unit derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound, specifically, an amidation reaction of a phthaloyl chloride and an aromatic diamine monomer It is a repeating unit formed by.
  • 1,2-aromatic diacyl compound examples include phthaloyl chloride or phthalic acid.
  • specific examples of the 1,3-aromatic diacyl compound include isophthaloyl chloride or isophthalic acid.
  • aromatic diamine monomer 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine), 2, 2'-dimethyl-4,4'-diaminobenzidine, 4,4'-diaminodiphenyl sulfone, 4 , 4 '-(9-fluorenylidene) dianiline (4,4'-(9-fluorenylidene) dianiline), bis (4- (4-aminophenoxy) phenyl) sulfone (bis (4- (4- aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'--
  • the 1,2-aromatic diacyl compound comprises phthaloyl chloride, or phthalic acid
  • the 1,3-aromatic diacyl compound comprises isophthaloyl chloride or isophthalic acid
  • the aromatic diamine compound 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine.
  • repeating unit represented by Chemical Formula 2-1 include a repeating unit represented by Chemical Formula 2-4.
  • repeating unit represented by Chemical Formula 2-2 include a repeating unit represented by Chemical Formula 2-5.
  • the second polyamide segment may be represented by Formula 6 below.
  • Ar 2 is an independently substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and b is 1 to 3, or 1 to 2 Is an integer.
  • Chemical Formula 6 when b is 1, Chemical Formula 6 may be a repeating unit represented by Chemical Formula 2.
  • Formula 6 when b is 2 to 3, Formula 6 may be a block composed of repeating units represented by Formula 2.
  • the repeating unit represented by Chemical Formula 2 is a repeating unit formed by the amidation reaction of isophthaloyl chloride, isophthalic acid or phthaloyl chloride, phthalic acid with an aromatic diamine monomer, and due to the curved molecular structure, chain packing and It has the property of interfering with the alignment, and increases the amorphous region in the polyamide resin, thereby improving the optical properties and the fracture strength of the polyamide film.
  • the molecular weight of the polyamide resin can be increased.
  • the proportion of repeating units represented by Formula 2 is 5 mol% to 60 mol%, 5 mol% to 50 mol%, or 5 mol% to 40 mol%, Or 5 mol% to 30 mol%, or 10 mol% to 50 mol%, or 15 mol% to 50 mol%, or 15 mol% to 40 mol%, or 15 mol% to 30 mol%, or 15 mol% to 20 mol%, or 15 mol% to 18 mol%.
  • the polyamide resin in which the repeating unit represented by Chemical Formula 2 is contained in the above-mentioned content can inhibit the length growth of the chain consisting of only the specific repeating unit represented by Chemical Formula 1, thereby lowering the crystallinity of the resin. Accordingly, it is possible to secure excellent transparency by having a low haze value.
  • the content of the repeating units represented by Formula 1 is 60 mol% to 90 mol%, or 70 mol% to 95 mol%, or 50 mol% To 90 mol%, or 50 mol% to 85 mol%, or 60 mol% to 85 mol%, or 70 mol% to 85 mol%, or 80 mol% to 85 mol%, or 82 mol% to 85 mol%
  • the content of the repeating unit represented by Formula 2 is 5 mol% to 40 mol%, or 5 mol% to 30 mol%, or 10 mol% to 50 mol%, or 15 mol% to 50 mol%, or 15 mol% To 40 mol%, or 15 mol% to 30 mol%, or 15 mol% to 20 mol%, or 15 mol% to 18 mol%.
  • the polyamide resin increases the molar content of the repeating unit represented by Formula 1, and the polyamide film according to chain packing and alignment in the polymer by the linear molecular structure of the repeating unit represented by Formula 1 Crystallization of the resin by inhibiting the length growth of the chain consisting of only the specific repeating unit represented by the formula (1) despite the relatively small molar content of the repeating unit represented by the formula (2) while maximizing the effect of improving the surface hardness and mechanical properties
  • the properties can be lowered, and accordingly, a low haze value can be obtained to ensure excellent transparency.
  • the first polyamide segment and the second polyamide segment may form a main chain including a cross-repeating unit represented by Chemical Formula 3. That is, the crosslinking unit represented by Chemical Formula 3 may be included in the main chain of the polyamide resin of the embodiment.
  • the main chain of the polyamide resin is a first polyamide segment and a 1,3-aromatic segment containing an amide repeat unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound, as shown in Chemical Formula 3 above.
  • a second polyamide segment comprising alternating amide repeating units derived from a combination of a diacyl compound and an aromatic diamine compound, or amide repeating units derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound ( alternatively) a polymerization chain can be achieved. That is, the second polyamide segment is located between the first polyamide segments, and may serve to inhibit length growth of the first polyamide segments.
  • the haze value of the polyamide resin can be remarkably lowered while the crystal properties of the first polyamide segment are reduced, thereby realizing excellent transparency.
  • cross-repeating unit represented by Chemical Formula 3 may be a repeating unit represented by Chemical Formula 4 below.
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and a1 and a2 are the same as each other, or Different, each independently an integer of 1 to 10, or 1 to 5, b1 and b2 are the same or different from each other, and each independently an integer of 1 to 5, or 1 to 3.
  • the main chain of the polyamide resin of the embodiment includes a cross-repeating unit represented by Chemical Formula 3, can be confirmed through the haze value of the polyamide resin, and more specifically SAXS (Small-angle X-ray scattering). ) Can be confirmed through analysis.
  • SAXS Mall-angle X-ray scattering
  • the weight average molecular weight of the polyamide resin is 330000 g / mol or more, 420000 g / mol or more, or 500000 g / mol or more, or 330000 g / mol to 1000000 g / mol, or 420000 g / mol to 1000000 g / mol, Or 500000 g / mol to 1000000 g / mol, or 420000 g / mol to 800000 g / mol, or 420000 g / mol to 600000 g / mol, or 450000 g / mol to 550,000 g / mol.
  • the weight average molecular weight of the polyamide resin is measured to be high, which appears to be due to the formation of a melt-kneaded composite in the polyamide resin manufacturing method of another embodiment of the present invention described below.
  • weight average molecular weight of the polyamide resin is reduced to less than 330000 g / mol, mechanical properties such as flexibility and pencil hardness are reduced.
  • the polyamide resin may have a molecular weight distribution of 3.0 or less, or 2.9 or less, or 2.8 or less, or 1.5 to 3.0, or 1.5 to 2.9, or 1.6 to 2.8, or 1.8 to 2.8. Through this narrow range of molecular weight distribution, the polyamide resin may have improved mechanical properties such as bending properties and hardness properties. When the molecular weight distribution of the polyamide resin is excessively wider than 3.0, it is difficult to improve the mechanical properties described above to a sufficient level.
  • the haze measured by ASTM D1003 of the polyamide resin is 3.0% or less, or 1.5% or less, 1.00% or less, or 0.85% or less, or 0.10% to 3.0%, or 0.10% to 1.5%, or 0.10% to 1.00 %, Or 0.50% to 1.00%, or 0.80% to 1.00%, or 0.81% to 0.97%.
  • the haze measured by ASTM D1003 of the polyamide resin increases to more than 3.0%, the opacity increases, making it difficult to secure a sufficient level of transparency.
  • the polyamide resin has a weight average molecular weight of 330000 g / mol or more, 420000 g / mol or more, or 500000 g / mol or more, or 330000 g / mol to 1000000 g / mol, or 420000 g / mol to 1000000 g / mol, or 500000 g / mol to 1000000 g / mol, or 420000 g / mol to 800000 g / mol, or 420000 g / mol to 600000 g / mol, or 450000 g / mol to 550,000 g / mol
  • haze measured by ASTM D1003 is 3.0% or less, or 1.5% or less, 1.00% or less, or 0.85% or less, or 0.10% to 3.0%, or 0.10% to 1.5%, or 0.10% to 1.00%, or 0.50% to 1.00%, or 0.80% to 1.00%, or 0.81% to 0.97%.
  • the relative viscosity of the polyamide resin is 45000 cps or more, 60000 cps or more, or 45000 cps to 500000 cps, or 60000 cps to 500000 cps, or 70000 cps to 400000 cps, or 80000 cps to It may be 300000 cps, or 100000 cps to 200000 cps, or 110000 cps to 174000 cps.
  • a method for producing a polyamide resin may be provided.
  • the present inventors as in the method for producing a polyamide resin according to another embodiment, when the compound represented by the formula (7) and the compound represented by the formula (8) are mixed at a temperature above the melting point, represented by the formula (7) Through the melting of the compound and the compound represented by Chemical Formula 8, a complex of uniformly mixed monomers can be prepared, and upon reacting with the aromatic diamine monomer, an amide repeating unit derived from the compound represented by Chemical Formula 7, Or it was confirmed through experiments that the block consisting of this, the amide repeating unit derived from the compound represented by the formula (8), or the block consisting of it can alternately (alternatively) polymerize.
  • the polyamide resin manufacturing method of the other embodiment the polyamide resin of the one embodiment can be obtained.
  • each of the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 exhibits different aspects in solubility and reactivity due to chemical structural differences.
  • the compound represented by the formula (7) and the compound represented by the formula (8) do not simply physically mix, and form a complex by melting and kneading at a temperature higher than each melting point. Through, each monomer was induced to react relatively uniformly with the aromatic diamine monomer.
  • the compound represented by the formula (7) and the compound represented by the formula (8) are dissolved in a solvent and reacted with an aromatic diamine monomer in a solution state, resulting in deterioration due to moisture or a solvent. Due to the hybridization with the molecular weight of the polyamide resin finally synthesized there was a limit to decrease, due to the difference in solubility of the compound represented by the formula (7) and the compound represented by the formula (8) derived from the compound represented by the formula (7) As the amide repeating unit was formed predominantly dominant, a long block was formed to increase the crystallinity of the polyamide resin, and it was difficult to secure transparency.
  • the composite obtained by melt-kneading the compound represented by the formula (7) and the compound represented by the formula (8) has a temperature lower than each melting point (10 ° C to 30 ° C below zero, or Upon reaction with the aromatic diamine monomer dissolved in the organic solvent in the form of a solid powder through cooling at 0 ° C to 30 ° C, or 10 ° C to 30 ° C, it was confirmed that the molecular weight of the final synthesized polyamide resin was improved. Through the experiment, it was confirmed that excellent mechanical properties were secured.
  • the method for producing a polyamide resin according to another embodiment includes the steps of melt-kneading the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8, and solidifying the melt-kneaded material to form a complex. can do.
  • X is halogen or a hydroxyl group.
  • X is chlorine.
  • Specific examples of the compound represented by Chemical Formula 7 include terephthaloyl chloride or terephthalic acid.
  • the compound represented by Chemical Formula 7 may form a repeating unit represented by Chemical Formula 1 by amidation reaction of an aromatic diamine monomer, and due to the linear molecular structure, chain packing and alignment in the polymer are kept constant. Can improve the surface hardness and mechanical properties of the polyamide film.
  • X is halogen or a hydroxyl group.
  • X is chlorine.
  • Specific examples of the compound represented by Chemical Formula 8 include phthaloyl chloride, phthalic acid, isophthaloyl chloride, or isophthalic acid.
  • the compound represented by Chemical Formula 8 may form a repeating unit represented by Chemical Formula 2 through amidation reaction of an aromatic diamine monomer, and due to a curved molecular structure, it prevents chain packing and alignment in the polymer. It has a personality and can increase the amorphous region in the polyamide resin, thereby improving the optical properties and the fracture strength of the polyamide film.
  • the repeating unit represented by Formula 2 derived from the compound represented by Formula 8 is included in the polyamide resin together with the repeating unit represented by Formula 1, the molecular weight of the polyamide resin can be increased.
  • the melt-kneading is the compound represented by the formula (7) and the formula It means that the compound represented by 8 is mixed at a temperature above the melting point.
  • each monomer is an aromatic diamine monomer And to react relatively uniformly.
  • the amide repeat unit derived from the compound represented by the formula (7) is formed predominantly leading to the formation of a long block.
  • Crystallinity of the polyamide resin increases, overcomes the limitation that it is difficult to ensure transparency, and, as in the above embodiment, the first polyamide segment and the second polyamide segment alternately (alternatively) to the formula (3) It becomes possible to form a main chain including the displayed cross-repeating unit.
  • the compound represented by Formula 8 is 5 parts by weight to 60 parts by weight, or 5 parts by weight to 50 parts by weight, or 5 parts by weight to 25 parts by weight, or 10 parts by weight to 30 parts by weight, or 15 parts by weight to 25 parts by weight.
  • a technical effect of increasing transmittance and clarity can be realized.
  • 100 parts by weight of the compound represented by the formula (7) when the compound represented by the formula (8) is mixed in an amount of less than 5 parts by weight, it becomes opaque and a technical problem of increasing hazeness occurs.
  • the compound represented by Chemical Formula 8 is excessively mixed in excess of 60 parts by weight with respect to 100 parts by weight of the displayed compound, a technical problem that physical properties (hardness, tensile strength, etc.) decrease may occur.
  • the coagulation refers to a physical change of solidifying by cooling the melt-kneaded material in a molten state to a temperature below a melting point, and the complex formed thereby is in a solid state.
  • the composite may be a solid powder obtained through an additional grinding process.
  • the step of melt-kneading the compound represented by the formula (7) and the compound represented by the formula (8), and solidifying the melt-kneaded material to form a complex the compound represented by the formula (7) and the formula (8) Mixing the compound at a temperature of 50 ° C. or higher; And cooling the resultant product of the mixing step.
  • the terephthaloyl chloride has a melting point of 81.3 °C to 83 °C
  • the isophthaloyl chloride (Isophthaloyl chloride) has a melting point of 43 °C to 44 °C
  • the phthaloyl chloride (Phthaloyl chloride) ) May have a melting point of 6 °C to 12 °C.
  • the formula (7) Melting and kneading may proceed because the temperature is higher than the melting point of both the compound represented by and the compound represented by Chemical Formula 8.
  • the resultant of the melt-kneading step is 5 ° C. or less, or 10 ° C. to 5 ° C., or 5 ° C. to 5 ° C., and the compound represented by Chemical Formula 7 and the Since the temperature is lower than the melting point of all of the compounds represented by Chemical Formula 8, more uniform solid powder can be obtained through cooling.
  • the step of crushing the product of the cooling step may be further included.
  • a complex of solid content may be prepared in powder form, and the powder obtained after the pulverizing step may have an average particle diameter of 1 mm to 10 mm.
  • the pulverizer used for pulverizing to such a particle size is, specifically, a pin mill, a hammer mill, a screw mill, a roll mill, a disc mill, or a jog.
  • a mill, a sieve, a jaw crusher, or the like can be used, but is not limited to the above-described example.
  • the formula Excellent mechanical properties of the polyamide resin are secured by improving the molecular weight of the final synthesized polyamide resin by minimizing the deterioration by moisture of the compound represented by 7 and the compound represented by the formula (8) or mixing with a solvent. Can be.
  • the method for producing a polyamide resin according to another embodiment is after the step of melt-kneading the compound represented by the formula (7) and the compound represented by the formula (8), and solidifying the melt-kneaded product to form a complex, the And reacting the complex with an aromatic diamine monomer.
  • the reaction in the step of reacting the complex with an aromatic diamine monomer may be performed under an inert gas atmosphere at a temperature condition of minus 25 ° C to 25 ° C, or a temperature of minus 25 ° C to 0 ° C.
  • the aromatic diamine monomer is specifically, for example, 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine) , 2,2'-dimethyl-4,4'-diaminobenzidine, 4,4'-diaminodiphenyl sulfone ), 4,4 '-(9-fluorenylidene) dianiline (4,4'-(9-fluorenylidene) dianiline), bis (4- (4-aminophenoxy) phenyl) sulfone (bis (4- (4-aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine (2,2', 5,5'-tetrachlorobenzidine), 2,7-diaminofluorene (2,7- diaminofluorene), 4,
  • the aromatic diamine monomer is 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB), 2,2'-dimethyl-4,4'-diaminobenzidine, m-xylylenediamine, or p-xyleneylene Diamine (p-xylylenediamine) can be used.
  • the step of reacting the complex with an aromatic diamine monomer includes: dissolving the aromatic diamine monomer in an organic solvent to prepare a diamine solution; And adding the composite powder to the diamine solution.
  • the aromatic diamine monomer included in the diamine solution may exist dissolved in an organic solvent.
  • the solvent are not particularly limited, for example, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-di Ethyl acetamide, N, N-dimethylpropionamide, 3-methoxy-N, N-dimethylpropionamide, dimethylsulfoxide, acetone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone , Tetrahydrofuran, chloroform, gamma-butyrolactone, ethyl lactate, methyl 3-methoxypropionate, methyl isobutyl ketone, toluene, xylene, methanol, ethanol and other general-purpose organic solvents can be used
  • the complex powder reacts with the aromatic diamine monomer dissolved in the diamine solution. Accordingly, by improving the molecular weight of the polyamide resin to be finally synthesized by minimizing the deterioration by moisture of the compound represented by the formula (7) and the compound represented by the formula (8) or hybridization with a solvent, the polyamide resin Excellent mechanical properties can be secured.
  • the complex powder may be prepared in the form of a powder in a solid form through the step of crushing the resultant product in the cooling step, and the powder obtained after the crushing step has an average particle diameter of 1 mm. To 10 mm.
  • the repeating unit represented by the following formula (1), or a first polyamide segment comprising a block consisting of; And a repeating unit represented by the following Chemical Formula 2, or a second polyamide segment comprising a block consisting of the first polyamide segment and the second polyamide segment comprising a cross-repeating unit represented by the following Chemical Formula 3 A polyamide film comprising a polyamide resin forming a main chain can be provided.
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and in Formula 3, A is the first polyamide segment, and B is the second polyamide segment.
  • the contents of the polyamide resin may include all of the contents described above in one embodiment.
  • the polyamide film may include the polyamide resin of one embodiment or a cured product thereof, and the cured product means a material obtained through a curing process of the polyamide resin of the embodiment.
  • the polyamide film When a film is produced using the polyamide resin of the above-described embodiment, excellent optical and mechanical properties can be realized, and flexibility is also provided, which can be used as a material for various molded articles.
  • the polyamide film may be applied to a display substrate, a display protective film, a touch panel, a window cover of a foldable device, and the like.
  • the thickness of the polyamide film is not particularly limited, but can be freely adjusted, for example, within a range of 0.01 ⁇ m to 1000 ⁇ m.
  • the thickness of the polyamide film increases or decreases by a specific value, physical properties measured in the polyamide film may also change by a certain value.
  • the polyamide film may be prepared by a conventional method such as a dry method or a wet method using the polyamide resin of the above embodiment.
  • the polyamide film may be obtained by coating a solution containing the polyamide resin of the above embodiment on an arbitrary support to form a film, and evaporating a solvent from the film to dry it, if necessary. , The stretching and heat treatment for the polyamide film may be further performed.
  • the polyamide film may exhibit colorless and transparent and excellent mechanical properties as it is manufactured using the polyamide resin of the embodiment.
  • the haze value measured according to ASTM D1003 for a specimen having a thickness of 50 ⁇ 2 ⁇ m is 3.0% or less, or 1.5% or less, 1.00% or less, or 0.85% or less. , Or 0.10% to 3.0%, or 0.10% to 1.5%, or 0.10% to 1.00%, or 0.50% to 1.00%, or 0.80% to 1.00%, or 0.81% to 0.97%.
  • the haze measured by ASTM D1003 of the polyamide film increases to more than 3.0%, the opacity increases, making it difficult to ensure a sufficient level of transparency.
  • the polyamide film the yellow index value (yellow index, YI) measured in accordance with ASTM E313 for a specimen having a thickness of 50 ⁇ 2 ⁇ m, 4.0 or less, or 3.0 or less, or 0.5 to 4.0, or 0.5 to 3.0.
  • YI yellow index
  • the polyamide film may have a transmittance (T, @ 550nm) of visible light having a wavelength of 550 nm for a specimen having a thickness of 50 ⁇ 2 ⁇ m, or greater than 86%, or 86% to 90%, 388
  • the transmittance (T, @ 388 nm) to ultraviolet rays of nm wavelength may be 50.00% or more, or 60.00% or more.
  • the polyamide film the cutting strength measured for a specimen having a thickness of 50 ⁇ 2 ⁇ m (angle of 135 ° at a speed of 175 rpm, a radius of curvature of 0.8 mm and a number of reciprocating fracture breaks at a load of 250 g )
  • the value may be 4000 Cycle or more, or 7000 Cycle or more, or 9000 Cycle or more, or 4000 Cycle to 20000 Cycle, or 7000 Cycle to 20000 Cycle, or 9000 Cycle to 20000 Cycle.
  • the polyamide film has a pencil hardness (Pencil Hardness) value of 1H or more, or 3H or more, or 1H to 4H, or 3H measured according to ASTM D3363 for a specimen having a thickness of 50 ⁇ 2 ⁇ m. To 4H.
  • Pencil Hardness Pencil Hardness
  • the repeating unit represented by the following formula (1) or a first polyamide segment comprising a block consisting of; And a repeating unit represented by the following Chemical Formula 2, or a second polyamide segment comprising a block consisting of the first polyamide segment and the second polyamide segment comprising a cross-repeating unit represented by the following Chemical Formula 3
  • a base material comprising a polyamide resin forming a main chain; And a hard coating layer formed on at least one surface of the substrate.
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and in Formula 3, A is the first polyamide segment, and B is the second polyamide segment.
  • the contents of the polyamide resin may include all of the contents described above in one embodiment.
  • the substrate may include the polyamide resin of one embodiment, or may include a polymer film of the other embodiment.
  • the contents of the polyamide resin may include all of the contents described above in one embodiment, and the contents of the polymer film may include all of the contents described above in another embodiment.
  • a hard coating layer may be formed on at least one surface of the substrate.
  • a hard coating layer may be formed on one surface or both surfaces of the substrate.
  • the opposite side of the substrate is made of polyimide-based, polycarbonate-based, polyester-based, polyalkyl (meth) acrylate-based, polyolefin-based, and polycyclic olefin-based polymers.
  • a polymer film including at least one polymer selected from the group may be formed.
  • the hard coating layer may have a thickness of 0.1 ⁇ m to 100 ⁇ m.
  • the hard coating layer can be used without any limitation as long as it is a material known in the hard coating field, for example, the hard coating layer is a binder resin of a photocurable resin; And inorganic particles or organic particles dispersed in the binder resin.
  • the photo-curable resin contained in the hard coating layer is a polymer of a photo-curable compound that can cause a polymerization reaction when light such as ultraviolet rays is irradiated, and may be common in the art.
  • the photocurable compound may be a polyfunctional (meth) acrylate-based monomer or oligomer, wherein the number of (meth) acrylate-based functional groups is 2 to 10, or 2 to 8, or 2 to 7 It is advantageous in terms of securing physical properties of the hard coating layer.
  • the photocurable compound may include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hepta ( Meth) acrylate, tripentaerythritol hepta (meth) acrylate, trilene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane polyethoxy tri (meth) ) May be one or more selected from the group consisting of acrylates.
  • the inorganic particles may be, for example, metal atoms such as silica, aluminum, titanium, and zinc, or oxides and nitrides thereof, respectively, and silica particles, aluminum oxide particles, titanium oxide particles, or zinc oxide particles may be used independently. have.
  • the inorganic particles may have an average radius of 100 nm or less, or 5 to 100 nm.
  • the type of the organic particles is also not limited, and for example, polymer particles having an average particle diameter of 10 nm to 100 ⁇ m may be used.
  • the resin laminate may be used as a substrate or cover window of a display device, and may be used as a substrate or cover window of a flexible display device with high light transmittance and low haze characteristics and high flexibility and bending durability. That is, the display device including the resin laminate or the flexible display device including the resin laminate may be implemented.
  • a polyamide resin having improved transparency a method for manufacturing the same, and a polyamide film and a resin laminate comprising the same may be provided.
  • Example 1 shows a 13 C-NMR spectrum of the polyamide resin obtained in Example 1 (1).
  • Fig. 2 shows the 13 C-NMR spectrum of the polyamide resin obtained in Example 2 (1).
  • terephthaloyl chloride TPC; melting point: 83 ° C
  • IPC isophthaloyl chloride
  • acyl chloride complex was pulverized with a jaw crusher to prepare a powder having an average particle diameter of 5 mm.
  • TPC Terephthaloyl chloride
  • IPC isophthaloyl chloride
  • the acyl chloride complex powder obtained in Preparation Example 1 was stirred while adding 8.972 g (0.0442 mol), and the amide formation reaction was performed at 0 ° C. for 12 hours.
  • N, N-dimethylacetamide (DMAc) was added to dilute the solid content to 5% or less, precipitated with 1 L of methanol, and filtered the precipitated solid content. Thereafter, the mixture was dried in a vacuum at 100 ° C. for 6 hours or more to prepare a polyamide resin in a solid form.
  • DMAc N, N-dimethylacetamide
  • the polyamide resin obtained in (1) of Example 1 was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 10% (w / V).
  • the polymer solution was applied on a polyimide base film (UPILEX-75s, UBE), and the thickness of the polymer solution was uniformly adjusted using a film applicator.
  • a polyamide resin was prepared in the same manner as in Example 1 (1), except that the acyl chloride composite powder obtained in Preparation Example 2 was used instead of the acyl chloride composite powder obtained in Preparation Example 1.
  • the polyamide resin obtained in (1) of Example 2 is terephthaloyl chloride (terephthaloyl chloride, TPC) and 2,2'-bis (trifluoromethyl)- 85 mol% of the first repeating unit obtained by the amide reaction of 4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB), and isophthaloyl chloride, IPC) and 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB) It was confirmed that 15 mol% of 2 repeat units were contained.
  • TPC terephthaloyl chloride
  • the polyamide film was obtained in the same manner as in Example 1 (2), except that the polyamide resin obtained in Example 1 (1) was used instead of the polyamide resin obtained in Example 1 (1). Was prepared.
  • TPC terephthaloyl chloride
  • IPphthal isophthaloyl chloride
  • TPC terephthaloyl chloride
  • IPC isophthaloyl chloride
  • IPC isophthaloyl chloride
  • TPC A polyamide resin was prepared in the same manner as in Example 1 (1), except that 7.358 g (0.0362 mol) was added to proceed with the amide formation reaction.
  • 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine in powder form (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB) 14.153 g ( 0.0442 mol) was added, and the mixture was stirred at 0 ° C. for 12 hours.
  • N, N-dimethylacetamide (DMAc) was added to dilute the solid content to 5% or less, precipitated with 1 L of methanol, and filtered the precipitated solid content. Thereafter, the mixture was dried in a vacuum at 100 ° C. for 6 hours or more to prepare a polyamide resin in a solid form.
  • DMAc N, N-dimethylacetamide
  • Thickness The thickness of the polyamide film was measured using a thickness measuring device.
  • Yellow index (Y.I.): Using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES), the yellow index of the polyamide film was measured according to the measurement method of ASTM E313.
  • PDI polydispersity index
  • the evaluation temperature was 50-75 ° C (about 65 ° C)
  • DMF 100wt% solvent Using, a flow rate of 1 mL / min, the sample is prepared at a concentration of 1 mg / mL, and then supplied for 25 minutes in an amount of 100 ⁇ L, the molecular weight can be obtained using an assay curve formed using a polystyrene standard.
  • the polystyrene standard 7 kinds of 3940/9600/31420/113300/327300/1270000/4230000 were used.
  • Relative viscosity a solution containing a polyamide resin (solvent: dimethylacetamide (DMAc), solid content: 10 wt%) using a 25 ⁇ 0.2 ° C. reflux system to rotate a non-Newtonian material of ASTM D 2196 Brookfield viscometer DV-2T is used as a viscometer test method, and brookfield's silicone oil is used as a standard material using a number of standard solutions having a viscosity range of 5000 cps to 200000 cps, spindle LV-4 (64) , 0.3 ⁇ 100RPM was measured, the unit was used as cps (mPa.s).
  • Pencil Hardness The pencil hardness of the polyamide film was measured according to the method of ASTM D3363 using a Pencil Hardness Tester. Specifically, after fixing the pencils of various hardness to the tester and scratching the polyamide film, when the degree of scratching on the polyamide film was observed with the naked eye or a microscope, when more than 70% of the total number of scratches was not scratched, the The value corresponding to the hardness of the pencil was evaluated by the pencil hardness of the polyamide film.
  • the hardness of the pencil increases in the order of B grade, F grade, and H grade, and within the same grade, the hardness increases as the number increases. Within the grade, the hardness increases as the number increases.
  • the polyamide resin of the embodiment prepared using the acyl chloride composite powder according to Preparation Examples 1 to 2 has a high weight average molecular weight of 463000 g / mol to 512000 g / mol, and a relative viscosity It was measured as high as 110000 cps to 174000 cps.
  • the polyamide film obtained from the polyamide resin of Examples it was confirmed that excellent transparency can be secured through a low yellowness index of 2.68 to 2.89 and a haze value of 0.81% to 0.97% at a thickness of approximately 50 ⁇ m.
  • the polyamide resin of the comparative example in which the acyl chloride composite powders according to Preparation Examples 1 to 2 were not used at all was 321,000 g / mol to 412,000 g / mol, and the molecular weight was reduced compared to the example, and the viscosity was 18,000. It decreased from cps to 54,000 cps compared to the example.
  • the polyamide resin of Reference Example 1 in which acyl chloride was dissolved in an amide solvent and treated as a solution, exhibited a very low molecular weight of 321,000 g / mol, the viscosity was greatly reduced to 18000 cps, and the number of reciprocating bending cycles. It was confirmed that the fracture strength was decreased at 6351, and the internal strength was decreased compared to the example. This seems to be because, in Reference Example 1, when the acyl chloride was dissolved, water deterioration and hybridization with the amide solvent occurred.

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Abstract

The present invention relates to a polyamide resin having a main chain having a structure in which two polyamide segments cross each other, a method for producing same, and a polyamide film and a resin laminate comprising same.

Description

폴리아미드 수지, 이의 제조방법, 및 이를 포함하는 폴리아미드 필름 및 수지 적층체Polyamide resin, manufacturing method thereof, and polyamide film and resin laminate comprising same
관련 출원(들)과의 상호 인용Cross-citation with relevant application (s)
본 출원은 2018년 11월 5일자 한국 특허 출원 제10-2018-0134755호; 2018년 12월 3일자 한국 특허 출원 제10-2018-0153911호; 2019년 2월 1일자 한국 특허 출원 제10-2019-0014022호; 2019년 3월 26일자 한국 특허 출원 제10-2019-0034611호; 2019년 10월 11일자 한국 특허 출원 제10-2019-0125890호; 2019년 10월 31일자 한국 특허 출원 제10-2019-0137544호; 및 2019년 10월 31일자 한국 특허 출원 제10-2019-0137545호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application is filed on November 5, 2018, Korean Patent Application No. 10-2018-0134755; Korean Patent Application No. 10-2018-0153911 dated December 3, 2018; Korean Patent Application No. 10-2019-0014022 dated February 1, 2019; Korean Patent Application No. 10-2019-0034611 dated March 26, 2019; Korean Patent Application No. 10-2019-0125890 filed on October 11, 2019; Korean Patent Application No. 10-2019-0137544 dated October 31, 2019; And priority interest based on Korean Patent Application No. 10-2019-0137545 filed on October 31, 2019, and all contents disclosed in the documents of the Korean patent applications are included as part of this specification.
본 발명은 우수한 기계적물성을 구현할 수 있으며, 투명성이 향상된 폴리아미드 수지, 이의 제조방법, 및 이를 포함하는 폴리아미드 필름 및 수지 적층체에 관한 것이다.The present invention is capable of realizing excellent mechanical properties, and relates to a polyamide resin having improved transparency, a manufacturing method thereof, and a polyamide film and a resin laminate comprising the same.
방향족 폴리이미드 수지는 대부분 비결정성 구조를 갖는 고분자로서, 강직한 사슬 구조로 인해 뛰어난 내열성, 내화학성, 전기적 특성, 및 치수 안정성을 나타낸다. 이러한 폴리이미드 수지는 전기/전자 재료로 널리 사용되고 있다.Aromatic polyimide 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 electrical / electronic materials.
그러나, 폴리이미드 수지는 이미드 사슬 내에 존재하는 Pi-전자들의 CTC (charge transfer complex) 형성으로 인해 짙은 갈색을 띠어 투명성을 확보하기 어려운 한계가 있고, 이를 포함하는 폴리이미드 필름의 경우 표면이 쉽게 긁혀 내스크래치성이 매우 약한 단점을 갖고 있다. However, the polyimide resin has a dark brown color due to the formation of the charge transfer complex (CTC) of Pi-electrons present in the imide chain, and thus it is difficult to secure transparency. In the case of a polyimide film containing the same, the surface is easily scratched It has a very weak scratch resistance.
이러한 폴리이미드 수지의 한계점을 개선하고자 아미드 그룹이 도입된 폴리 아미드 수지에 대한 연구가 활발히 진행되고 있다. 아미드 구조는 분자간 또는 분자내 수소결합을 유발하여 수소결합 등의 상호작용으로 내스크래치성이 개선되어졌다.In order to improve the limitations of the polyimide resin, research into a polyamide resin in which an amide group is introduced has been actively conducted. The amide structure induces hydrogen bonding between molecules or molecules, thereby improving scratch resistance through interactions such as hydrogen bonding.
하지만, 폴리아미드 수지 합성에 사용되는 테레프탈로일 클로라이드, 또는 이소프탈로일 클로라이드의 용해도 차이 및 반응성(입체장애), 반응속도 차이로 인해 폴리아미드 중합시 테레프탈로일 클로라이드로부터 유래한 아미드 반복단위와 이소프탈로일 클로라이드로부터 유래한 아미드 반복단위가 블록을 형성하지 않으면서, 이상적으로(ideal), 교차적으로(alternatively) 중합되기 어렵다.However, the amide repeat unit and isop derived from terephthaloyl chloride during polyamide polymerization due to the difference in solubility and reactivity (stereo hindrance) and reaction rate of terephthaloyl chloride or isophthaloyl chloride used in the synthesis of polyamide resins The amide repeat unit derived from thaloyl chloride is difficult to polymerize ideally and alternatively without forming a block.
이에, para 아실 클로라이드 단량체로부터 유래한 아미드 반복단위에 의한 블록이 형성되어, 폴리아미드 수지의 결정성이 증가함에 따라 헤이즈에 의해 투명성이 불량해지는 한계가 있다.As a result, a block formed by an amide repeating unit derived from a para acyl chloride monomer is formed, and as the crystallinity of the polyamide resin increases, there is a limit in that transparency becomes poor by haze.
뿐만 아니라, 폴리아미드 수지 합성에 사용되는 단량체가 용매에 용해된 상태로 중합반응이 진행됨에 따라, 수분에 의한 변질 또는 용매와의 혼성으로 인해 최종 합성되는 폴리아미드 수지의 분자량이 충분한 수준으로 확보되기 어렵다.In addition, as the polymerization reaction proceeds in a state in which the monomer used for synthesizing the polyamide resin is dissolved in a solvent, the molecular weight of the final synthesized polyamide resin is secured to a sufficient level due to deterioration by moisture or hybridization with the solvent. it's difficult.
이에, 투명성과 기계적 물성을 동시에 구현할 수 있는 폴리아미드 수지의 개발이 요구되고 있다.Accordingly, there is a need to develop a polyamide resin capable of simultaneously implementing transparency and mechanical properties.
본 발명은 우수한 기계적물성을 구현할 수 있으며, 투명성을 갖는 폴리아미드 수지에 관한 것이다. The present invention can realize excellent mechanical properties, and relates to a polyamide resin having transparency.
또한, 본 발명은 상기의 폴리아미드 수지를 합성하기 위한 폴리아미드 수지의 제조방법을 제공하기 위한 것이다.In addition, the present invention is to provide a method for producing a polyamide resin for synthesizing the polyamide resin.
또한, 본 발명은 상기의 폴리아미드 수지를 포함한 폴리아미드 필름 및 수지 적층체를 제공하기 위한 것이다.In addition, the present invention is to provide a polyamide film and a resin laminate comprising the polyamide resin.
상기 과제를 해결하기 위하여, 본 명세서에서는, 하기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 하기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트;를 포함하고, 상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 하기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성하는, 폴리아미드 수지를 제공한다.In order to solve the above problems, in the present specification, a repeating unit represented by the following Chemical Formula 1, or a first polyamide segment including a block composed of the same; And a repeating unit represented by the following Chemical Formula 2, or a second polyamide segment comprising a block consisting of the first polyamide segment and the second polyamide segment comprising a cross-repeating unit represented by the following Chemical Formula 3 Provided are polyamide resins that form the main chain.
[화학식1][Formula 1]
Figure PCTKR2019014714-appb-I000001
Figure PCTKR2019014714-appb-I000001
[화학식2][Formula 2]
Figure PCTKR2019014714-appb-I000002
Figure PCTKR2019014714-appb-I000002
[화학식3][Formula 3]
Figure PCTKR2019014714-appb-I000003
Figure PCTKR2019014714-appb-I000003
상기 화학식1 내지 2 에서, Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이고, 상기 화학식3에서, A는 상기 제1폴리아미드 세그먼트이고, 상기 B는 제2폴리아미드 세그먼트이다.In Formulas 1 to 2, Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and in Formula 3, A is the first polyamide segment, and B is the second polyamide segment.
본 명세서에서는 또한, 하기 화학식7로 표시되는 화합물 및 하기 화학식8로 표시되는 화합물을 용융혼련시키고, 상기 용융혼련물을 응고시켜 복합체를 형성하는 단계; 및 상기 복합체를 방향족 디아민 단량체와 반응시키는 단계;를 포함하는, 폴리아미드 수지의 제조방법이 제공된다.In the present specification, the compound represented by the following formula (7) and the compound represented by the formula (8) are melt-kneaded, and solidifying the melt-kneaded material to form a complex; And reacting the complex with an aromatic diamine monomer. A method for producing a polyamide resin is provided.
[화학식7][Formula 7]
Figure PCTKR2019014714-appb-I000004
Figure PCTKR2019014714-appb-I000004
[화학식8][Formula 8]
Figure PCTKR2019014714-appb-I000005
Figure PCTKR2019014714-appb-I000005
상기 화학식7 내지 8 에서, X는 할로겐, 또는 수산화기이다.In the above formulas 7 to 8, X is a halogen or a hydroxyl group.
본 명세서에서는 또한, 상기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 상기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트;를 포함하고, 상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 상기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성하는 폴리아미드 수지를 포함하는, 폴리아미드 필름이 제공된다.In the present specification, the first polyamide segment including a repeating unit represented by Formula 1 or a block composed of the same; And a second polyamide segment including a repeating unit represented by Formula 2 or a block composed of the first polyamide segment and a second polyamide segment comprising cross-repeating units represented by Formula 3 above. A polyamide film is provided, comprising a polyamide resin forming a backbone.
본 명세서에서는 또한, 상기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 상기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트;를 포함하고, 상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 상기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성하는 폴리아미드 수지를 포함한 기재; 및 상기 기재의 적어도 일면에 형성되는 하드 코팅층;을 포함하는 수지 적층체가 제공된다.In the present specification, the first polyamide segment including a repeating unit represented by Formula 1 or a block composed of the same; And a second polyamide segment including a repeating unit represented by Formula 2 or a block composed of the first polyamide segment and a second polyamide segment comprising cross-repeating units represented by Formula 3 above. A base material comprising a polyamide resin forming a main chain; And a hard coating layer formed on at least one surface of the substrate.
이하 발명의 구체적인 구현예에 따른 폴리아미드 수지, 이의 제조방법, 및 이를 포함하는 폴리아미드 필름 및 수지 적층체에 대하여 보다 상세하게 설명하기로 한다. Hereinafter, a polyamide resin according to a specific embodiment of the present invention, a method for manufacturing the same, and a polyamide film and a resin laminate comprising the same will be described in more detail.
Ⅰ. 폴리아미드 수지Ⅰ. Polyamide resin
발명의 일 구현예에 따르면, 상기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 상기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트;를 포함하고, 상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 상기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성하는 폴리아미드 수지가 제공될 수 있다.According to one embodiment of the invention, the repeating unit represented by the formula (1), or a first polyamide segment comprising a block consisting of; And a repeating unit represented by Chemical Formula 2, or a second polyamide segment including a block consisting of the first polyamide segment and the second polyamide segment including a cross-repeating unit represented by Chemical Formula 3 Polyamide resins that form the backbone can be provided.
본 발명자들은 상기 일 구현예의 폴리아미드 수지와 같이, 상기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 상기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트;를 포함하고, 상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 상기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성함에 따라, 폴리아미드 수지 내부에 테레프탈로일 클로라이드로부터 유도된 반복단위로 이루어진 고분자 블록인 상기 제1 폴리아미드 세그먼트의 길이 성장을 최소화하여, 폴리아미드 수지의 결정성을 낮춰 투명한 폴리아미드 수지를 구현할 수 있음을 실험을 통해 확인하고 발명을 완성하였다.The present inventors, such as the polyamide resin of one embodiment, the first polyamide segment comprising a repeating unit represented by the formula (1), or a block consisting of it; And a second polyamide segment including a repeating unit represented by Formula 2 or a block composed of the first polyamide segment and a second polyamide segment comprising cross-repeating units represented by Formula 3 above. As the main chain is formed, the length growth of the first polyamide segment, which is a polymer block composed of repeating units derived from terephthaloyl chloride inside the polyamide resin, is minimized, thereby lowering the crystallinity of the polyamide resin to reduce the transparent polyamide resin. It was confirmed through experiments that it can be implemented and the invention was completed.
구체적으로, 상기 폴리아미드 수지의 주쇄는 상기 화학식3과 같이, 1,4-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복단위를 포함한 제1 폴리아미드 세그먼트, 그리고 1,3-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복단위, 또는 1,2-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 반복단위를 포함한 제2 폴리아미드 세그먼트가 서로 번갈아가며(alternatively) 중합사슬을 이룰 수 있다. 즉, 상기 제2 폴리아미드 세그먼트가 제1폴리아미드 세그먼트 사이에 위치하며, 제1폴리아미드 세그먼트의 길이 성장을 억제하는 역할을 할 수 있다.Specifically, the main chain of the polyamide resin is a first polyamide segment including an amide repeating unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound, as shown in Chemical Formula 3, and 1,3- A second polyamide segment comprising alternating amide repeating units derived from a combination of an aromatic diacyl compound and an aromatic diamine compound, or repeating units derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound, alternately (alternatively) can form a polymerization chain. That is, the second polyamide segment is located between the first polyamide segments, and may serve to inhibit length growth of the first polyamide segments.
이처럼, 상기 제1폴리아미드 세그먼트의 길이 성장이 억제되면, 제1폴리아미드 세그먼트의 결정특성이 감소하면서, 폴리아미드 수지의 헤이즈값을 현저히 낮출 수 있기 때문에, 우수한 투명성 구현이 가능하다. As described above, when the length growth of the first polyamide segment is suppressed, the haze value of the polyamide resin can be remarkably lowered while the crystal properties of the first polyamide segment are reduced, thereby realizing excellent transparency.
한편, 상기 폴리아미드 수지의 주쇄가 상기 화학식3과 같이, 1,4-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복단위를 포함한 제1 폴리아미드 세그먼트, 그리고 1,3-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복단위, 또는 1,2-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 반복단위를 포함한 제2 폴리아미드 세그먼트가 서로 번갈아가며(alternatively) 중합사슬을 이루는 것은, 후술하는 본 발명의 다른 구현예의 폴리아미드 수지 제조방법상 용융혼련복합체 형성에 따른 것으로 보인다.On the other hand, the main chain of the polyamide resin is a first polyamide segment including an amide repeating unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound, as shown in Chemical Formula 3, and 1,3-aromatic The second polyamide segment comprising alternating amide repeating units derived from a combination of a diacyl compound and an aromatic diamine compound, or repeating units derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound ( alternatively) forming the polymerization chain appears to be due to the formation of a melt-kneaded composite in the method of preparing a polyamide resin of another embodiment of the present invention described below.
이하, 본 발명을 보다 상세히 설명한다. Hereinafter, the present invention will be described in more detail.
본 명세서에서 특별한 제한이 없는 한 다음 용어는 하기와 같이 정의될 수 있다.In the present specification, unless otherwise specified, the following terms may be defined as follows.
본 명세서에서, 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless specifically stated otherwise.
본 명세서에서, 치환기의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다. In the present specification, examples of the substituent are described below, but are not limited thereto.
본 명세서에서, "치환"이라는 용어는 화합물 내의 수소 원자 대신 다른 작용기가 결합하는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정되지 않으며, 2 이상 치환되는 경우, 2 이상의 치환기는 서로 동일하거나 상이할 수 있다.In the present specification, the term "substitution" means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 시아노기; 니트로기; 히드록시기; 카르보닐기; 에스테르기; 이미드기; 아미드기; 1차 아미노기; 카르복시기; 술폰산기; 술폰아미드기; 포스핀옥사이드기; 알콕시기; 아릴옥시기; 알킬티옥시기; 아릴티옥시기; 알킬술폭시기; 아릴술폭시기; 실릴기; 붕소기; 알킬기; 할로알킬기; 시클로알킬기; 알케닐기; 아릴기; 아르알킬기; 아르알케닐기; 알킬아릴기; 알콕시실릴알킬기; 아릴포스핀기; 또는 N, O 및 S 원자 중 1개 이상을 포함하는 헤테로고리기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환되거나, 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환 또는 비치환된 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 바이페닐기일 수 있다. 즉, 바이페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수도 있다. 바람직하게는 상기 치환기로는 할로알킬기를 사용할 수 있으며, 상기 할로알킬기의 예로는 트리플루오로메틸기를 들 수 있다.The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; Primary amino group; Carboxy group; Sulfonic acid group; Sulfonamide groups; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Haloalkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Alkoxysilylalkyl groups; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected. Preferably, a haloalkyl group can be used as the substituent, and examples of the haloalkyl group include a trifluoromethyl group.
본 명세서에서,
Figure PCTKR2019014714-appb-I000006
, 또는
Figure PCTKR2019014714-appb-I000007
는 다른 치환기에 연결되는 결합을 의미하고, 직접결합은 L 로 표시되는 부분에 별도의 원자가 존재하지 않은 경우를 의미한다. In this specification,
Figure PCTKR2019014714-appb-I000006
, or
Figure PCTKR2019014714-appb-I000007
Means a bond connected to another substituent, and a direct bond means a case where a separate atom does not exist in a portion represented by L.
본 명세서에 있어서, 알킬기는 알케인(alkane)으로부터 유래한 1가의 작용기로, 직쇄 또는 분지쇄일 수 있고, 상기 직쇄 알킬기의 탄소수는 특별히 한정되지 않으나 1 내지 20인 것이 바람직하다. 또한, 상기 분지쇄 알킬기의 탄소수는 3 내지 20이다. 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실, 2,6-디메틸헵탄-4-일 등이 있으나, 이들에 한정되지 않는다. 상기 알킬기는 치환 또는 비치환될 수 있다.In the present specification, the alkyl group is a monovalent functional group derived from alkane, and may be a straight chain or a branched chain, and the carbon number of the straight chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the branched chain alkyl group has 3 to 20 carbon atoms. Specific examples of the alkyl group are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- Propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like, but is not limited to these. The alkyl group may be substituted or unsubstituted.
본 명세서에 있어서, 아릴기는 아렌(arene)으로부터 유래한 1가의 작용기로, 특별히 한정되지 않으나 탄소수 6 내지 20인 것이 바람직하며, 단환식 아릴기 또는 다환식 아릴기일 수 있다. 상기 아릴기가 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 아릴기는 치환 또는 비치환될 수 있다.In the present specification, the aryl group is a monovalent functional group derived from arenes, and is not particularly limited, but is preferably 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted.
본 명세서에 있어서, 아릴렌기는 아렌(arene)으로부터 유래한 2가의 작용기로, 이들은 2가의 작용기인 것을 제외하고는 전술한 아릴기의 설명이 적용될 수 있다. 예를 들어, 페닐렌기, 바이페닐렌기, 터페닐렌기, 나프탈렌기, 플루오레닐기, 파이레닐기, 페난트레닐기, 페릴렌기, 테트라세닐기, 안트라센닐기 등이 될 수 있다. 상기 아릴렌기는 치환 또는 비치환될 수 있다.In the present specification, the arylene groups are divalent functional groups derived from arenes, and the descriptions of the aryl groups described above may be applied except that they are divalent functional groups. For example, it may be a phenylene group, biphenylene group, terphenylene group, naphthalene group, fluorenyl group, pyrenyl group, phenanthrenyl group, perylene group, tetrasenyl group, anthracenyl group, and the like. The arylene group may be substituted or unsubstituted.
본 명세서에 있어서, 헤테로아릴기는 탄소가 아닌 원자, 이종원자를 1 이상 포함하는 것으로서, 구체적으로 상기 이종 원자는 O, N, Se 및 S 등으로 이루어진 군에서 선택되는 원자를 1 이상 포함할 수 있다. 탄소수는 특별히 한정되지 않으나, 탄소수 4 내지 20인 것이 바람직하며, 상기 헤테로아릴기는 단환식 또는 다환식일 수 있다. 헤테로고리기의 예로는 티오펜기, 퓨라닐기, 피롤기, 이미다졸릴기, 티아졸릴기, 옥사졸릴기, 옥사디아졸릴기, 피리딜기, 바이피리딜기, 피리미딜기, 트리아지닐기, 트리아졸릴기, 아크리딜기, 피리다지닐기, 피라지닐기, 퀴놀리닐기, 퀴나졸리닐기, 퀴녹살리닐기, 프탈라지닐기, 피리도 피리미딜기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀리닐기, 인돌릴기, 카바졸릴기, 벤즈옥사졸릴기, 벤즈이미다졸릴기, 벤조티아졸릴기, 벤조카바졸릴기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤리닐기(phenanthroline), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 페노티아지닐기, 아지리딜기, 아자인돌릴기, 이소인돌릴기, 인다졸릴기, 퓨린기(purine), 프테리딜기(pteridine), 베타-카볼릴기, 나프티리딜기(naphthyridine), 터-피리딜기, 페나지닐기, 이미다조피리딜기, 파이로피리딜기, 아제핀기, 피라졸릴기 및 디벤조퓨라닐기 등이 있으나, 이에 한정되는 것은 아니다. 상기 헤테로아릴기는 치환 또는 비치환될 수 있다.In the present specification, the heteroaryl group includes one or more non-carbon atoms, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, and preferably 4 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrol group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Jolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nanthrolyl group (phenanthroline), thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, aziridyl group, azaindoleyl group, isoindoleyl group, inda Sleepy group, purine group, pteridyl group, beta-carbonyl group, naphthyridyl group (na phthyridine), ter-pyridyl group, phenazinyl group, imidazopyridyl group, pyropyridyl group, azepine group, pyrazolyl group and dibenzofuranyl group, but are not limited thereto. The heteroaryl group may be substituted or unsubstituted.
본 명세서에서, 헤테로 아릴렌기는, 탄소수는 2 내지 20, 또는 2 내지 10, 또는 6 내지 20 이다. 이종원자로 O, N 또는 S를 함유한 아릴렌기로, 2가의 작용기인 것을 제외하고는 전술한 헤테로아릴기의 설명이 적용될 수 있다. 상기 헤테로 아릴렌기는 치환 또는 비치환될 수 있다.In the present specification, the heteroarylene group has 2 to 20 carbon atoms, or 2 to 10 carbon atoms, or 6 to 20 carbon atoms. The heteroaryl group containing O, N or S is an arylene group, and the description of the above-described heteroaryl group can be applied, except that it is a divalent functional group. The heteroarylene group may be substituted or unsubstituted.
본 명세서에 있어서, 할로겐의 예로는 불소, 염소, 브롬 또는 요오드가 있다. In the present specification, examples of halogen include fluorine, chlorine, bromine or iodine.
상기 폴리아미드 수지는 상기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 상기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트를 포함할 수 있다. The polyamide resin may include a repeating unit represented by Chemical Formula 1, or a first polyamide segment including a block composed of the same; And it may include a second polyamide segment comprising a repeating unit represented by the formula (2), or a block consisting of it.
상기 화학식1 및 화학식2에서, Ar1 및 Ar2는 서로 동일하거나 상이하며, 각각 독립적으로 알킬기, 할로알킬기, 및 아미노기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환된 탄소수 6 내지 20의 아릴렌기이며, 보다 바람직하게는 2,2'-비스(트리플루오로메틸)-4,4'-비페닐렌기 일 수 있다.In Formulas 1 and 2, Ar 1 and Ar 2 are the same or different from each other, and each independently is an arylene group having 6 to 20 carbon atoms substituted with one or more substituents selected from the group consisting of an alkyl group, a haloalkyl group, and an amino group. , More preferably, it may be a 2,2'-bis (trifluoromethyl) -4,4'-biphenylene group.
보다 구체적으로, 상기 화학식1 및 화학식2에서, Ar1 및 Ar2는 방향족 디아민 단량체로부터 유도된 2가의 유기 작용기일 수 있으며, 상기 방향족 디아민 단량체의 구체적인 예로는 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine), 2,2'-디메틸-4,4'-디아미노벤지딘(2,2'-dimethyl-4,4'- diaminobenzidine), 4,4'-디아미노디페닐 술폰(4,4'-diaminodiphenyl sulfone), 4,4'-(9-플루오레닐리덴)디아닐린(4,4'-(9-fluorenylidene)dianiline), 비스(4-(4-아미노페녹시)페닐) 술폰(bis(4-(4-aminophenoxy)phenyl)sulfone), 2,2',5,5'-테트라클로로벤지딘(2,2',5,5'-tetrachlorobenzidine), 2,7-디아미노플루오렌(2,7-diaminofluorene), 4,4-디아미노옥타플루오로비페닐(4,4-diaminooctafluorobiphenyl), m-페닐렌디아민(m-phenylenediamine), p-페닐렌디아민(p-phenylenediamine), 4,4'-옥시다이아닐린(4,4'-oxydianiline), 2,2'-디메틸-4,4'-디아미노비페닐(2,2'-dimethyl-4,4'-diaminobiphenyl), 2,2-비스[4-(4-아미노페녹시)페닐]프로판(2,2-bis[4-(4-aminophenoxy)phenyl]propane), 1,3-비스(4-아미노페녹시)벤젠(1,3-bis(4-aminophenoxy)benzene), 및 4,4'-디아미노벤즈아닐라이드(4,4'-diaminobenzanilide)로 이루어진 군에서 선택된 1종 이상을 들 수 있다. 보다 바람직하게는, 상기 방향족 디아민 단량체는 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine, TFDB) 또는 2,2'-디메틸-4,4'-디아미노벤지딘(2,2'-dimethyl-4,4'- diaminobenzidine)일 수 있다.More specifically, in Formulas 1 and 2, Ar 1 and Ar 2 may be divalent organic functional groups derived from aromatic diamine monomers, and specific examples of the aromatic diamine monomers are 2,2'-bis (trifluoro Methyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine), 2,2'-dimethyl-4,4'-diaminobenzidine (2,2 '-dimethyl-4,4'-diaminobenzidine),4,4'-diaminodiphenyl sulfone, 4,4 '-(9-fluorenylidene) dianiline (4,4 '-(9-fluorenylidene) dianiline), bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2', 5,5'-tetra Chlorobenzidine (2,2 ', 5,5'-tetrachlorobenzidine), 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, m-phenylenediamine, p-phenylenediamine, 4,4'-oxydianiline, 2,2'-dimethyl -4,4'-diaminobiphenyl (2,2'-dimethyl-4,4'-diaminobiphenyl), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (2,2-bis [4- (4-aminophenoxy) phenyl] propane), 1,3-bis (4-aminophenoxy) benzene, and 4,4'-diaminobenzanyl And one or more selected from the group consisting of rides (4,4'-diaminobenzanilide). More preferably, the aromatic diamine monomer is 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB ) Or 2,2'-dimethyl-4,4'-diaminobenzidine.
상기 제1폴리아미드 세그먼트는 상기 화학식1로 표시되는 반복단위, 또는 상기 화학식1로 표시되는 반복단위로 이루어진 블록을 포함할 수 있다. The first polyamide segment may include a repeating unit represented by Chemical Formula 1 or a block composed of a repeating unit represented by Chemical Formula 1.
상기 화학식1로 표시되는 반복단위의 구체적인 예로는 하기 화학식1-1로 표시되는 반복단위를 들 수 있다.A specific example of the repeating unit represented by Chemical Formula 1 may include a repeating unit represented by Chemical Formula 1-1.
[화학식1-1][Formula 1-1]
Figure PCTKR2019014714-appb-I000008
Figure PCTKR2019014714-appb-I000008
상기 화학식1로 표시되는 반복단위는 1,4-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복 단위, 구체적으로 테레프탈로일 클로라이드 또는 테레프탈산과 방향족 디아민 단량체의 아미드화 반응으로 형성된 아미드 반복단위이며, 선형 분자 구조로 인하여, 고분자 내에서 체인 패킹과 배열(Align)이 일정하게 유지될 수 있고, 폴리아미드 필름의 표면 경도 및 기계적 물성을 향상시킬 수 있다.The repeating unit represented by Formula 1 is an amide repeating unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound, specifically an amide formed by amidation reaction of terephthaloyl chloride or terephthalic acid with an aromatic diamine monomer It is a repeating unit, and due to the linear molecular structure, chain packing and alignment in the polymer can be kept constant, and the surface hardness and mechanical properties of the polyamide film can be improved.
상기 1,4-방향족 디아실 화합물의 구체적인 예로는 테레프탈로일 클로라이드, 또는 테레프탈산를 들 수 있다. 또한, 상기 방향족 디아민 단량체의 예로는, 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine), 2,2'-디메틸-4,4'-디아미노벤지딘(2,2'-dimethyl-4,4'- diaminobenzidine), 4,4'-디아미노디페닐 술폰(4,4'-diaminodiphenyl sulfone), 4,4'-(9-플루오레닐리덴)디아닐린(4,4'-(9-fluorenylidene)dianiline), 비스(4-(4-아미노페녹시)페닐) 술폰(bis(4-(4-aminophenoxy)phenyl)sulfone), 2,2',5,5'-테트라클로로벤지딘(2,2',5,5'-tetrachlorobenzidine), 2,7-디아미노플루오렌(2,7-diaminofluorene), 4,4-디아미노옥타플루오로비페닐(4,4-diaminooctafluorobiphenyl), m-페닐렌디아민(m-phenylenediamine), p-페닐렌디아민(p-phenylenediamine), 4,4'-옥시다이아닐린(4,4'-oxydianiline), 2,2'-디메틸-4,4'-디아미노비페닐(2,2'-dimethyl-4,4'-diaminobiphenyl), 2,2-비스[4-(4-아미노페녹시)페닐]프로판(2,2-bis[4-(4-aminophenoxy)phenyl]propane), 1,3-비스(4-아미노페녹시)벤젠(1,3-bis(4-aminophenoxy)benzene), m-자일리렌디아민(m-xylylenediamine), p-자일리렌디아민(p-xylylenediamine) 및 4,4'-디아미노벤즈아닐라이드(4,4'-diaminobenzanilide)로 이루어진 군에서 선택된 1종 이상을 들 수 있다.Specific examples of the 1,4-aromatic diacyl compound include terephthaloyl chloride or terephthalic acid. In addition, examples of the aromatic diamine monomer, 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine), 2,2'-dimethyl-4,4'-diaminobenzidine, 4,4'-diaminodiphenyl sulfone , 4,4 '-(9-fluorenylidene) dianiline (4,4'-(9-fluorenylidene) dianiline), bis (4- (4-aminophenoxy) phenyl) sulfone (bis (4- ( 4-aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine (2,2', 5,5'-tetrachlorobenzidine), 2,7-diaminofluorene ), 4,4-diaminooctafluorobiphenyl, m-phenylenediamine, p-phenylenediamine, 4,4'-oxydianiline (4,4'-oxydianiline), 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis [4- ( 4-aminophenoxy) phenyl] propane (2,2-bis [4- (4-aminophenoxy) phenyl] propane), 1,3-bis (4-ah Nophenoxy) benzene (1,3-bis (4-aminophenoxy) benzene), m-xylylenediamine, p-xylylenediamine and 4,4'-diaminobenzanyl And one or more selected from the group consisting of rides (4,4'-diaminobenzanilide).
바람직하게는 상기 1,4-방향족 디아실 화합물은 테레프탈로일 클로라이드, 또는 테레프탈산을 포함하며, 상기 방향족 디아민 화합물은 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민을 포함할 수 있다.Preferably, the 1,4-aromatic diacyl compound includes terephthaloyl chloride, or terephthalic acid, and the aromatic diamine compound is 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine It may include.
상기 제1 폴리아미드 세그먼트의 수평균 분자량이 100 g/mol 이상 5000 g/mol 이하, 또는 100 g/mol 이상 3000 g/mol 이하, 또는 100 g/mol 이상 2500 g/mol 이하, 또는 100 g/mol 이상 2450 g/mol 이하일 수 있다. 상기 제1 폴리아미드 세그먼트의 수평균 분자량이 5000 g/mol 초과로 증가하게 되면, 상기 제1 폴리아미드 세그먼트의 사슬이 지나치게 길어짐에 따라, 폴리아미드 수지의 결정성이 증가할 수 있고, 이에 따라 높은 헤이즈값을 가져 투명성을 확보하기 어려울 수 있다. 상기 제1 폴리아미드 세그먼트의 수평균 분자량은 측정하는 방법의 예가 한정되는 것은 아니나, 예를 들어, SAXS(Small-angle X-ray scattering) 분석을 통해 확인할 수 있다.The number average molecular weight of the first polyamide segment is 100 g / mol or more and 5000 g / mol or less, or 100 g / mol or more and 3000 g / mol or less, or 100 g / mol or more and 2500 g / mol or less, or 100 g / mol or more and 2450 g / mol or less. When the number average molecular weight of the first polyamide segment is increased to more than 5000 g / mol, the crystallinity of the polyamide resin may increase as the chain of the first polyamide segment becomes too long, thereby increasing It can be difficult to ensure transparency by having a haze value. The number average molecular weight of the first polyamide segment is not limited to an example of a measurement method, but can be confirmed, for example, through SAXS (Small-angle X-ray scattering) analysis.
상기 제1폴리아미드 세그먼트는 하기 화학식5로 표시될 수 있다. The first polyamide segment may be represented by Formula 5 below.
[화학식5][Formula 5]
Figure PCTKR2019014714-appb-I000009
Figure PCTKR2019014714-appb-I000009
상기 화학식5 에서, Ar1은 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이고, a는 1 내지 5의 정수이다. 상기 화학식 5에서, a가 1인 경우, 상기 화학식5는 상기 화학식1로 표시되는 반복단위일 수 있다. 상기 화학식 5에서, a가 2 내지 5인 경우, 상기 화학식5는 상기 화학식1로 표시되는 반복단위로 이루어진 블록일 수 있다. 상기 화학식5 에서, Ar1에 대한 설명은 상기 화학식1에서 상술한 내용을 포함한다.In Formula 5, Ar 1 is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and a is an integer of 1 to 5. In Chemical Formula 5, when a is 1, Chemical Formula 5 may be a repeating unit represented by Chemical Formula 1. In Chemical Formula 5, when a is 2 to 5, Chemical Formula 5 may be a block composed of repeating units represented by Chemical Formula 1. In Formula 5, the description of Ar 1 includes the contents described in Formula 1 above.
상기 폴리아미드 수지에 함유된 모든 반복단위를 기준으로, 상기 화학식1로 표시되는 반복단위의 비율이 40 몰% 내지 95 몰%, 50 몰% 내지 95 몰%, 또는 60 몰% 내지 95 몰%, 또는 70 몰% 내지 95 몰%, 또는 50 몰% 내지 90 몰%, 또는 50 몰% 내지 85 몰%, 또는 60 몰% 내지 85 몰%, 또는 70 몰% 내지 85 몰%, 또는 80 몰% 내지 85 몰%, 또는 82 몰% 내지 85 몰%일 수 있다. Based on all the repeating units contained in the polyamide resin, the proportion of repeating units represented by Formula 1 is 40 mol% to 95 mol%, 50 mol% to 95 mol%, or 60 mol% to 95 mol%, Or 70 mol% to 95 mol%, or 50 mol% to 90 mol%, or 50 mol% to 85 mol%, or 60 mol% to 85 mol%, or 70 mol% to 85 mol%, or 80 mol% to 85 mol%, or 82 mol% to 85 mol%.
이처럼, 상기 화학식1로 표시되는 반복단위가 상술한 함량으로 함유된 폴리아미드 수지는 충분한 수준의 분자량을 확보하여 우수한 기계적 물성을 확보할 수 있다.As described above, the polyamide resin in which the repeating unit represented by Chemical Formula 1 is contained in the above-described content can secure a sufficient level of molecular weight to secure excellent mechanical properties.
상기 제2폴리아미드 세그먼트는 상기 화학식2로 표시되는 반복단위, 또는 상기 화학식2로 표시되는 반복단위로 이루어진 블록을 포함할 수 있다. 상기 화학식2로 표시되는 반복단위는 1,3-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복단위, 또는 1,2-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 반복단위, 또는 이들의 혼합물을 포함할 수 있다.The second polyamide segment may include a repeating unit represented by Chemical Formula 2 or a block composed of a repeating unit represented by Chemical Formula 2. The repeating unit represented by Chemical Formula 2 is an amide repeating unit derived from a combination of a 1,3-aromatic diacyl compound and an aromatic diamine compound, or derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound. Repeating units, or mixtures thereof.
보다 구체적으로, 상기 화학식2로 표시되는 반복단위는, 하기 화학식2-1로 표시되는 반복단위; 또는 하기 화학식2-2로 표시되는 반복단위; 중 1종의 반복단위를 포함할 수 있다.More specifically, the repeating unit represented by Chemical Formula 2 includes: a repeating unit represented by Chemical Formula 2-1; Or a repeating unit represented by the following formula 2-2; It may include one of the repeating unit.
[화학식2-1][Formula 2-1]
Figure PCTKR2019014714-appb-I000010
Figure PCTKR2019014714-appb-I000010
[화학식2-2][Formula 2-2]
Figure PCTKR2019014714-appb-I000011
Figure PCTKR2019014714-appb-I000011
상기 화학식2-1 내지 2-2에서, Ar2는 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이다. Ar2에 관한 자세한 설명은 상기 화학식2에서 상술한 내용을 포함한다.In Formulas 2-1 to 2-2, Ar 2 is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms. The detailed description of Ar 2 includes the above-described contents in Chemical Formula 2.
상기 화학식2-1로 표시되는 반복단위는 1,3-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복 단위, 구체적으로 이소프탈로일 클로라이드와 방향족 디아민 단량체의 아미드화 반응으로 형성된 반복단위이며, 상기 화학식2-2로 표시되는 반복단위는 1,2-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복 단위, 구체적으로 프탈로일 클로라이드와 방향족 디아민 단량체의 아미드화 반응으로 형성된 반복단위이다.The repeating unit represented by Formula 2-1 is an amide repeating unit derived from a combination of a 1,3-aromatic diacyl compound and an aromatic diamine compound, specifically a repeat formed by amidation reaction of isophthaloyl chloride and an aromatic diamine monomer The unit is a repeating unit represented by Chemical Formula 2-2, an amide repeating unit derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound, specifically, an amidation reaction of a phthaloyl chloride and an aromatic diamine monomer It is a repeating unit formed by.
상기 1,2-방향족 디아실 화합물의 구체적인 예로는 프탈로일 클로라이드, 또는 프탈산을 들 수 있다. 또한, 상기 1,3-방향족 디아실 화합물의 구체적인 예로는 이소프탈로일 클로라이드 또는 이소프탈산을 들 수 있다. 상기 방향족 디아민 단량체의 예로는, 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine), 2,2'-디메틸-4,4'-디아미노벤지딘(2,2'-dimethyl-4,4'- diaminobenzidine), 4,4'-디아미노디페닐 술폰(4,4'-diaminodiphenyl sulfone), 4,4'-(9-플루오레닐리덴)디아닐린(4,4'-(9-fluorenylidene)dianiline), 비스(4-(4-아미노페녹시)페닐) 술폰(bis(4-(4-aminophenoxy)phenyl)sulfone), 2,2',5,5'-테트라클로로벤지딘(2,2',5,5'-tetrachlorobenzidine), 2,7-디아미노플루오렌(2,7-diaminofluorene), 4,4-디아미노옥타플루오로비페닐(4,4-diaminooctafluorobiphenyl), m-페닐렌디아민(m-phenylenediamine), p-페닐렌디아민(p-phenylenediamine), 4,4'-옥시다이아닐린(4,4'-oxydianiline), 2,2'-디메틸-4,4'-디아미노비페닐(2,2'-dimethyl-4,4'-diaminobiphenyl), 2,2-비스[4-(4-아미노페녹시)페닐]프로판(2,2-bis[4-(4-aminophenoxy)phenyl]propane), 1,3-비스(4-아미노페녹시)벤젠(1,3-bis(4-aminophenoxy)benzene), m-자일리렌디아민(m-xylylenediamine), p-자일리렌디아민(p-xylylenediamine) 및 4,4'-디아미노벤즈아닐라이드(4,4'-diaminobenzanilide)로 이루어진 군에서 선택된 1종 이상을 들 수 있다.Specific examples of the 1,2-aromatic diacyl compound include phthaloyl chloride or phthalic acid. Further, specific examples of the 1,3-aromatic diacyl compound include isophthaloyl chloride or isophthalic acid. Examples of the aromatic diamine monomer, 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine), 2, 2'-dimethyl-4,4'-diaminobenzidine, 4,4'-diaminodiphenyl sulfone, 4 , 4 '-(9-fluorenylidene) dianiline (4,4'-(9-fluorenylidene) dianiline), bis (4- (4-aminophenoxy) phenyl) sulfone (bis (4- (4- aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine (2,2', 5,5'-tetrachlorobenzidine), 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, m-phenylenediamine, p-phenylenediamine, 4,4'-oxydianiline (4 , 4'-oxydianiline), 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'-dimethyl-4,4'-diaminobiphenyl), 2,2-bis [4- (4- Aminophenoxy) phenyl] propane (2,2-bis [4- (4-aminophenoxy) phenyl] propane), 1,3-bis (4-aminophen Si) benzene (1,3-bis (4-aminophenoxy) benzene), m-xylylenediamine, p-xylylenediamine and 4,4'-diaminobenzanilide ( 4,4'-diaminobenzanilide).
바람직하게는 상기 1,2-방향족 디아실 화합물은 프탈로일 클로라이드, 또는 프탈산을 포함하며, 상기 1,3-방향족 디아실 화합물은 이소프탈로일 클로라이드 또는 이소프탈산을 포함하고, 상기 방향족 디아민 화합물은 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민을 포함할 수 있다.Preferably, the 1,2-aromatic diacyl compound comprises phthaloyl chloride, or phthalic acid, and the 1,3-aromatic diacyl compound comprises isophthaloyl chloride or isophthalic acid, and the aromatic diamine compound 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine.
상기 화학식2-1로 표시되는 반복단위의 구체적인 예로는 하기 화학식2-4로 표시되는 반복단위를 들 수 있다.Specific examples of the repeating unit represented by Chemical Formula 2-1 include a repeating unit represented by Chemical Formula 2-4.
[화학식2-4][Formula 2-4]
Figure PCTKR2019014714-appb-I000012
Figure PCTKR2019014714-appb-I000012
상기 화학식2-2로 표시되는 반복단위의 구체적인 예로는 하기 화학식2-5로 표시되는 반복단위를 들 수 있다.Specific examples of the repeating unit represented by Chemical Formula 2-2 include a repeating unit represented by Chemical Formula 2-5.
[화학식2-5][Formula 2-5]
Figure PCTKR2019014714-appb-I000013
Figure PCTKR2019014714-appb-I000013
한편, 상기 제2폴리아미드 세그먼트는 하기 화학식6으로 표시될 수 있다.Meanwhile, the second polyamide segment may be represented by Formula 6 below.
[화학식6][Formula 6]
Figure PCTKR2019014714-appb-I000014
Figure PCTKR2019014714-appb-I000014
상기 화학식6 에서, Ar2는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이고, b는 1 내지 3, 또는 1 내지 2의 정수이다. 상기 화학식 6에서, b가 1인 경우, 상기 화학식6는 상기 화학식2로 표시되는 반복단위일 수 있다. 상기 화학식6에서, b가 2 내지 3인 경우, 상기 화학식6는 상기 화학식2로 표시되는 반복단위로 이루어진 블록일 수 있다. In the above formula (6), Ar 2 is an independently substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and b is 1 to 3, or 1 to 2 Is an integer. In Chemical Formula 6, when b is 1, Chemical Formula 6 may be a repeating unit represented by Chemical Formula 2. In Formula 6, when b is 2 to 3, Formula 6 may be a block composed of repeating units represented by Formula 2.
상기 화학식2로 표시되는 반복단위는 이소프탈로일 클로라이드, 이소프탈산 또는 프탈로일 클로라이드, 프탈산과 방향족 디아민 단량체의 아미드화 반응으로 형성된 반복단위이며, 굽은형 분자 구조로 인하여, 고분자 내에서 체인 패킹과 배열(Align)을 방해하는 성격을 가지고 있으며, 폴리아미드 수지에 무정형 영역을 증가시켜, 폴리아미드 필름의 광학적 물성 및 내절 강도를 향상시킬 수 있다. 또한, 상기 화학식1로 표시되는 반복단위와 함께 폴리아미드 수지에 포함됨에 따라, 폴리아미드 수지의 분자량을 증가시킬 수 있다.The repeating unit represented by Chemical Formula 2 is a repeating unit formed by the amidation reaction of isophthaloyl chloride, isophthalic acid or phthaloyl chloride, phthalic acid with an aromatic diamine monomer, and due to the curved molecular structure, chain packing and It has the property of interfering with the alignment, and increases the amorphous region in the polyamide resin, thereby improving the optical properties and the fracture strength of the polyamide film. In addition, as it is included in the polyamide resin together with the repeating unit represented by Formula 1, the molecular weight of the polyamide resin can be increased.
상기 폴리아미드 수지에 함유된 모든 반복단위를 기준으로, 상기 화학식2로 표시되는 반복단위의 비율이 5 몰% 내지 60 몰%, 5 몰% 내지 50 몰%, 또는 5 몰% 내지 40 몰%, 또는 5 몰% 내지 30 몰%, 또는 10 몰% 내지 50 몰%, 또는 15 몰% 내지 50 몰%, 또는 15 몰% 내지 40 몰%, 또는 15 몰% 내지 30 몰%, 또는 15 몰% 내지 20 몰%, 또는 15 몰% 내지 18 몰%일 수 있다. Based on all the repeating units contained in the polyamide resin, the proportion of repeating units represented by Formula 2 is 5 mol% to 60 mol%, 5 mol% to 50 mol%, or 5 mol% to 40 mol%, Or 5 mol% to 30 mol%, or 10 mol% to 50 mol%, or 15 mol% to 50 mol%, or 15 mol% to 40 mol%, or 15 mol% to 30 mol%, or 15 mol% to 20 mol%, or 15 mol% to 18 mol%.
이처럼, 상기 화학식2로 표시되는 반복단위가 상술한 함량으로 함유된 폴리아미드 수지는 상기 화학식1로 표시되는 특정 반복단위만로 이루어진 사슬의 길이성장을 저해하여, 수지의 결정성을 낮출 수 있고, 이에 따라 낮은 헤이즈값을 가져 우수한 투명성을 확보할 수 있다.As described above, the polyamide resin in which the repeating unit represented by Chemical Formula 2 is contained in the above-mentioned content can inhibit the length growth of the chain consisting of only the specific repeating unit represented by Chemical Formula 1, thereby lowering the crystallinity of the resin. Accordingly, it is possible to secure excellent transparency by having a low haze value.
보다 구체적으로, 상기 폴리아미드 수지에 함유된 모든 반복단위를 기준으로, 상기 화학식1로 표시되는 반복단위의 함량이 60 몰% 내지 90 몰%, 또는 70 몰% 내지 95 몰%, 또는 50 몰% 내지 90 몰%, 또는 50 몰% 내지 85 몰%, 또는 60 몰% 내지 85 몰%, 또는 70 몰% 내지 85 몰%, 또는 80 몰% 내지 85 몰%, 또는 82 몰% 내지 85 몰%이고, 상기 화학식2로 표시되는 반복단위의 함량이 5 몰% 내지 40 몰%, 또는 5 몰% 내지 30 몰%, 또는 10 몰% 내지 50 몰%, 또는 15 몰% 내지 50 몰%, 또는 15 몰% 내지 40 몰%, 또는 15 몰% 내지 30 몰%, 또는 15 몰% 내지 20 몰%, 또는 15 몰% 내지 18 몰%일 수 있다.More specifically, based on all the repeating units contained in the polyamide resin, the content of the repeating units represented by Formula 1 is 60 mol% to 90 mol%, or 70 mol% to 95 mol%, or 50 mol% To 90 mol%, or 50 mol% to 85 mol%, or 60 mol% to 85 mol%, or 70 mol% to 85 mol%, or 80 mol% to 85 mol%, or 82 mol% to 85 mol% , The content of the repeating unit represented by Formula 2 is 5 mol% to 40 mol%, or 5 mol% to 30 mol%, or 10 mol% to 50 mol%, or 15 mol% to 50 mol%, or 15 mol % To 40 mol%, or 15 mol% to 30 mol%, or 15 mol% to 20 mol%, or 15 mol% to 18 mol%.
즉, 상기 폴리아미드 수지는 상기 화학식1로 표시되는 반복단위의 몰 함량을 높여, 화학식1로 표시되는 반복단위의 선형 분자 구조에 의한 고분자 내에서 체인 패킹과 배열(Align)에 따른 폴리아미드 필름의 표면 경도 및 기계적 물성 향상효과를 극대화 시키면서도, 화학식2로 표시되는 반복단위가 상대적으로 적은 몰 함량임에도 불구하고 상기 화학식1로 표시되는 특정 반복단위만로 이루어진 사슬의 길이성장을 저해하여, 수지의 결정성을 낮출 수 있고, 이에 따라 낮은 헤이즈값을 가져 우수한 투명성을 확보할 수 있다.That is, the polyamide resin increases the molar content of the repeating unit represented by Formula 1, and the polyamide film according to chain packing and alignment in the polymer by the linear molecular structure of the repeating unit represented by Formula 1 Crystallization of the resin by inhibiting the length growth of the chain consisting of only the specific repeating unit represented by the formula (1) despite the relatively small molar content of the repeating unit represented by the formula (2) while maximizing the effect of improving the surface hardness and mechanical properties The properties can be lowered, and accordingly, a low haze value can be obtained to ensure excellent transparency.
상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 상기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성할 수 있다. 즉, 상기 일 구현예의 폴리아미드 수지의 주쇄에는 상기 화학식 3으로 표시되는 교차반복단위가 포함될 수 있다. The first polyamide segment and the second polyamide segment may form a main chain including a cross-repeating unit represented by Chemical Formula 3. That is, the crosslinking unit represented by Chemical Formula 3 may be included in the main chain of the polyamide resin of the embodiment.
구체적으로, 상기 폴리아미드 수지의 주쇄는 상기 화학식3과 같이, 1,4-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복단위를 포함한 제1 폴리아미드 세그먼트와 1,3-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래 아미드 반복단위, 또는 1,2-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복단위를 포함한 제2 폴리아미드 세그먼트가 서로 번갈아가며(alternatively) 중합사슬을 이룰 수 있다. 즉, 상기 제2 폴리아미드 세그먼트가 제1폴리아미드 세그먼트 사이에 위치하며, 제1폴리아미드 세그먼트의 길이 성장을 억제하는 역할을 할 수 있다.Specifically, the main chain of the polyamide resin is a first polyamide segment and a 1,3-aromatic segment containing an amide repeat unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound, as shown in Chemical Formula 3 above. A second polyamide segment comprising alternating amide repeating units derived from a combination of a diacyl compound and an aromatic diamine compound, or amide repeating units derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound ( alternatively) a polymerization chain can be achieved. That is, the second polyamide segment is located between the first polyamide segments, and may serve to inhibit length growth of the first polyamide segments.
이처럼, 상기 제1폴리아미드 세그먼트의 길이 성장이 억제되면, 제1폴리아미드 세그먼트의 결정특성이 감소하면서, 폴리아미드 수지의 헤이즈값을 현저히 낮출 수 있기 때문에, 우수한 투명성 구현이 가능하다. As described above, when the length growth of the first polyamide segment is suppressed, the haze value of the polyamide resin can be remarkably lowered while the crystal properties of the first polyamide segment are reduced, thereby realizing excellent transparency.
한편, 상기 폴리아미드 수지의 주쇄가 상기 화학식3과 같이, 테레프탈로일 클로라이드, 또는 테레프탈산으로부터 유도된 아미드 반복단위를 함유한 제1 폴리아미드 세그먼트와 이소프탈로일 클로라이드, 이소프탈산 또는 프탈로일 클로라이드, 프탈산으로부터 유도된 아미드 반복단위를 포함한 제2 폴리아미드 세그먼트가 서로 번갈아가며(alternatively) 중합사슬을 이루는 것은, 후술하는 본 발명의 다른 구현예의 폴리아미드 수지 제조방법상 용융혼련복합체 형성에 따른 것으로 보인다.On the other hand, the first polyamide segment and isophthaloyl chloride, isophthalic acid or phthaloyl chloride, wherein the main chain of the polyamide resin contains an amide repeating unit derived from terephthaloyl chloride, or terephthalic acid, as in Chemical Formula 3, The second polyamide segment containing the amide repeating unit derived from phthalic acid alternately (alternatively) to form a polymerization chain, seems to be due to the formation of a melt-kneaded composite in the polyamide resin manufacturing method of another embodiment of the present invention described later.
보다 구체적으로, 상기 화학식 3으로 표시되는 교차반복단위는 하기 화학식4로 표시되는 반복단위일 수 있다.More specifically, the cross-repeating unit represented by Chemical Formula 3 may be a repeating unit represented by Chemical Formula 4 below.
[화학식4][Formula 4]
Figure PCTKR2019014714-appb-I000015
Figure PCTKR2019014714-appb-I000015
상기 화학식4 에서, Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이고, a1 및 a2는 서로 동일하거나 상이하며, 각각 독립적으로 1 내지 10, 또는 1 내지 5의 정수이고, b1 및 b2는 서로 동일하거나 상이하며, 각각 독립적으로 1 내지 5, 또는 1 내지 3의 정수이다.In Formula 4, Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and a1 and a2 are the same as each other, or Different, each independently an integer of 1 to 10, or 1 to 5, b1 and b2 are the same or different from each other, and each independently an integer of 1 to 5, or 1 to 3.
상기 일 구현예의 폴리아미드 수지의 주쇄에는 상기 화학식 3으로 표시되는 교차반복단위가 포함되는 것은, 상기 폴리아미드 수지의 헤이즈값을 통해서 확인할 수 있으며, 보다 구체적으로는 SAXS(Small-angle X-ray scattering) 분석을 통해 확인할 수 있다.The main chain of the polyamide resin of the embodiment includes a cross-repeating unit represented by Chemical Formula 3, can be confirmed through the haze value of the polyamide resin, and more specifically SAXS (Small-angle X-ray scattering). ) Can be confirmed through analysis.
상기 폴리아미드 수지의 중량평균 분자량이 330000 g/mol 이상, 420000 g/mol 이상, 또는 500000 g/mol 이상, 또는 330000 g/mol 내지 1000000 g/mol, 또는 420000 g/mol 내지 1000000 g/mol, 또는 500000 g/mol 내지 1000000 g/mol, 또는 420000 g/mol 내지 800000 g/mol, 또는 420000 g/mol 내지 600000 g/mol, 또는 450000 g/mol 내지 550000 g/mol 일 수 있다.The weight average molecular weight of the polyamide resin is 330000 g / mol or more, 420000 g / mol or more, or 500000 g / mol or more, or 330000 g / mol to 1000000 g / mol, or 420000 g / mol to 1000000 g / mol, Or 500000 g / mol to 1000000 g / mol, or 420000 g / mol to 800000 g / mol, or 420000 g / mol to 600000 g / mol, or 450000 g / mol to 550,000 g / mol.
상기 폴리아미드 수지의 중량평균 분자량이 높게 측정되는 것은, 후술하는 본 발명의 다른 구현예의 폴리아미드 수지 제조방법상 용융혼련복합체 형성에 따른 것으로 보인다. 상기 폴리아미드 수지는 중량평균 분자량이 330000 g/mol 미만으로 감소하게 되면, 굴곡성, 연필경도 등의 기계적 물성이 감소하는 문제가 있다. The weight average molecular weight of the polyamide resin is measured to be high, which appears to be due to the formation of a melt-kneaded composite in the polyamide resin manufacturing method of another embodiment of the present invention described below. When the weight average molecular weight of the polyamide resin is reduced to less than 330000 g / mol, mechanical properties such as flexibility and pencil hardness are reduced.
상기 폴리아미드 수지의 분자량 분포가 3.0 이하, 또는 2.9 이하, 또는 2.8 이하, 또는 1.5 내지 3.0, 또는 1.5 내지 2.9, 또는 1.6 내지 2.8, 또는 1.8 내지 2.8일 수 있다. 이러한 좁은 범위의 분자량분포를 통해 상기 폴리아미드 수지는 굴곡특성 내지 경도특성과 같은 기계적 물성이 향상될 수 있다. 상기 폴리아미드 수지의 분자량 분포가 3.0 초과로 지나치게 넓어지게 되면, 상술한 기계적물성을 충분한 수준까지 향상시키기 어려운 한계가 있다.The polyamide resin may have a molecular weight distribution of 3.0 or less, or 2.9 or less, or 2.8 or less, or 1.5 to 3.0, or 1.5 to 2.9, or 1.6 to 2.8, or 1.8 to 2.8. Through this narrow range of molecular weight distribution, the polyamide resin may have improved mechanical properties such as bending properties and hardness properties. When the molecular weight distribution of the polyamide resin is excessively wider than 3.0, it is difficult to improve the mechanical properties described above to a sufficient level.
상기 폴리아미드 수지의 ASTM D1003에 의해 측정한 헤이즈가 3.0% 이하, 또는 1.5% 이하, 1.00% 이하, 또는 0.85%이하, 또는 0.10% 내지 3.0%, 또는 0.10% 내지 1.5%, 또는 0.10% 내지 1.00%, 또는 0.50% 내지 1.00%, 또는 0.80% 내지 1.00%, 또는 0.81% 내지 0.97%일 수 있다. 상기 폴리아미드 수지의 ASTM D1003에 의해 측정한 헤이즈가 3.0% 초과로 증가하게 되면, 불투명성이 증대되어 충분한 수준의 투명성을 확보하기 어렵다.The haze measured by ASTM D1003 of the polyamide resin is 3.0% or less, or 1.5% or less, 1.00% or less, or 0.85% or less, or 0.10% to 3.0%, or 0.10% to 1.5%, or 0.10% to 1.00 %, Or 0.50% to 1.00%, or 0.80% to 1.00%, or 0.81% to 0.97%. When the haze measured by ASTM D1003 of the polyamide resin increases to more than 3.0%, the opacity increases, making it difficult to secure a sufficient level of transparency.
바람직하게는, 상기 폴리아미드 수지는 중량평균 분자량이 330000 g/mol 이상, 420000 g/mol 이상, 또는 500000 g/mol 이상, 또는 330000 g/mol 내지 1000000 g/mol, 또는 420000 g/mol 내지 1000000 g/mol, 또는 500000 g/mol 내지 1000000 g/mol, 또는 420000 g/mol 내지 800000 g/mol, 또는 420000 g/mol 내지 600000 g/mol, 또는 450000 g/mol 내지 550000 g/mol을 만족하면서, 동시에 ASTM D1003에 의해 측정한 헤이즈가 3.0% 이하, 또는 1.5% 이하, 1.00% 이하, 또는 0.85%이하, 또는 0.10% 내지 3.0%, 또는 0.10% 내지 1.5%, 또는 0.10% 내지 1.00%, 또는 0.50% 내지 1.00%, 또는 0.80% 내지 1.00%, 또는 0.81% 내지 0.97%일 수 있다.Preferably, the polyamide resin has a weight average molecular weight of 330000 g / mol or more, 420000 g / mol or more, or 500000 g / mol or more, or 330000 g / mol to 1000000 g / mol, or 420000 g / mol to 1000000 g / mol, or 500000 g / mol to 1000000 g / mol, or 420000 g / mol to 800000 g / mol, or 420000 g / mol to 600000 g / mol, or 450000 g / mol to 550,000 g / mol At the same time, haze measured by ASTM D1003 is 3.0% or less, or 1.5% or less, 1.00% or less, or 0.85% or less, or 0.10% to 3.0%, or 0.10% to 1.5%, or 0.10% to 1.00%, or 0.50% to 1.00%, or 0.80% to 1.00%, or 0.81% to 0.97%.
상기 폴리아미드 수지의 상대점도(ASTM D 2196 기준에 따라 측정)가 45000 cps 이상, 60000 cps 이상, 또는 45000 cps 내지 500000 cps, 또는 60000 cps 내지 500000 cps, 또는 70000 cps 내지 400000 cps, 또는 80000 cps 내지 300000 cps, 또는 100000 cps 내지 200000 cps, 또는 110000 cps 내지 174000 cps일 수 있다. 상기 폴리아미드 수지의 상대점도(ASTM D 2196 기준에 따라 측정)가 45000 cps 미만으로 감소하게 되면, 상기 폴리아미드 수지를 이용한 필름 성형공정에서, 성형가공성이 감소하여 성형 공정의 효율성이 감소하는 한계가 있다.The relative viscosity of the polyamide resin (measured according to ASTM D 2196 standard) is 45000 cps or more, 60000 cps or more, or 45000 cps to 500000 cps, or 60000 cps to 500000 cps, or 70000 cps to 400000 cps, or 80000 cps to It may be 300000 cps, or 100000 cps to 200000 cps, or 110000 cps to 174000 cps. When the relative viscosity of the polyamide resin (measured in accordance with ASTM D 2196 standard) decreases to less than 45000 cps, in the film forming process using the polyamide resin, the molding processability decreases, thereby limiting the efficiency of the molding process to decrease. have.
Ⅱ. 폴리아미드 수지의 제조 방법Ⅱ. Manufacturing method of polyamide resin
발명의 다른 구현예에 따르면, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 용융혼련시키고, 상기 용융혼련물을 응고시켜 복합체를 형성하는 단계; 및 상기 복합체를 방향족 디아민 단량체와 반응시키는 단계;를 포함하는, 폴리아미드 수지의 제조방법이 제공될 수 있다.According to another embodiment of the invention, the step of melt-kneading the compound represented by the formula (7) and the compound represented by the formula (8), and solidifying the melt-kneaded material to form a complex; And reacting the complex with an aromatic diamine monomer. A method for producing a polyamide resin may be provided.
본 발명자들은 상기 다른 구현예에 따른 폴리아미드 수지의 제조방법에서와 같이, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 녹는점 이상의 온도에서 혼합하게 되면, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물의 용융을 통해 균일하게 혼합된 단량체의 복합체를 제조할 수 있고, 이를 방향족 디아민 단량체와 반응시킴에 따라, 상기 화학식7로 표시되는 화합물로부터 유래한 아미드 반복단위, 또는 이로 이루어진 블록과, 상기 화학식8로 표시되는 화합물로부터 유래한 아미드 반복단위, 또는 이로 이루어진 블록이 번갈아가며(alternatively) 중합할 수 있음을 실험을 통해 확인하고 발명을 완성하였다.The present inventors, as in the method for producing a polyamide resin according to another embodiment, when the compound represented by the formula (7) and the compound represented by the formula (8) are mixed at a temperature above the melting point, represented by the formula (7) Through the melting of the compound and the compound represented by Chemical Formula 8, a complex of uniformly mixed monomers can be prepared, and upon reacting with the aromatic diamine monomer, an amide repeating unit derived from the compound represented by Chemical Formula 7, Or it was confirmed through experiments that the block consisting of this, the amide repeating unit derived from the compound represented by the formula (8), or the block consisting of it can alternately (alternatively) polymerize.
즉, 상기 다른 구현예의 폴리아미드 수지 제조방법에 의해, 상기 일 구현예의 폴리아미드 수지가 얻어질 수 있다.That is, by the polyamide resin manufacturing method of the other embodiment, the polyamide resin of the one embodiment can be obtained.
구체적으로, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물 각각은 화학구조적인 차이로 인해, 용해도 및 반응성에 있어 상이한 양상을 나타내기 때문에, 이들을 동시에 투입하더라도 상기 화학식7로 표시되는 화합물로부터 유래한 아미드 반복단위가 앞도적으로 우세하게 형성되면서 길이가 긴 블록을 형성하여 폴리아미드 수지의 결정성이 증가하고, 투명성을 확보하기 어려워지는 한계가 있었다.Specifically, each of the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 exhibits different aspects in solubility and reactivity due to chemical structural differences. As the amide repeating unit derived from was formed predominantly dominant, a long block was formed to increase the crystallinity of the polyamide resin, and it was difficult to secure transparency.
이에, 상기 다른 구현예의 폴리아미드 수지 제조방법에서는 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 단순히 물리적으로 혼합하지 않고, 각각의 녹는점 보다 높은 온도에서의 용융혼련에 의한 복합체 형성을 통해, 각각의 단량체가 방향족 디아민 단량체와 상대적으로 균등하게 반응하도록 유도하였다.Thus, in the polyamide resin manufacturing method of the other embodiment, the compound represented by the formula (7) and the compound represented by the formula (8) do not simply physically mix, and form a complex by melting and kneading at a temperature higher than each melting point. Through, each monomer was induced to react relatively uniformly with the aromatic diamine monomer.
한편, 기존 폴리아미드 수지 합성시에는, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 용매에 용해시킨 후 용액상태로 방향족 디아민 단량체와 반응시킴에 따라, 수분에 의한 변질이나, 용매와의 혼성으로 인해 최종 합성되는 폴리아미드 수지의 분자량이 감소하는 한계가 있었고, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물의 용해도 차이로 인해 상기 화학식7로 표시되는 화합물로부터 유래한 아미드 반복단위가 앞도적으로 우세하게 형성되면서 길이가 긴 블록을 형성하여 폴리아미드 수지의 결정성이 증가하고, 투명성을 확보하기 어려워지는 한계가 있었다.On the other hand, when the existing polyamide resin is synthesized, the compound represented by the formula (7) and the compound represented by the formula (8) are dissolved in a solvent and reacted with an aromatic diamine monomer in a solution state, resulting in deterioration due to moisture or a solvent. Due to the hybridization with the molecular weight of the polyamide resin finally synthesized there was a limit to decrease, due to the difference in solubility of the compound represented by the formula (7) and the compound represented by the formula (8) derived from the compound represented by the formula (7) As the amide repeating unit was formed predominantly dominant, a long block was formed to increase the crystallinity of the polyamide resin, and it was difficult to secure transparency.
이에, 상기 다른 구현예의 폴리아미드 수지 제조방법에서는 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물의 용융혼련으로 얻어지는 복합체를 각각의 녹는점보다 낮은 온도(영하 10 ℃내지 30 ℃, 또는 0 ℃ 내지 30 ℃, 또는 10 ℃ 내지 30 ℃에서의 냉각을 통한 고형 분말 형태로 유기용매에 용해된 방향족 디아민 단량체와 반응시킴에 따라, 최종 합성되는 폴리아미드 수지의 분자량이 향상됨을 확인하였고, 이를 통해 우수한 기계적물성이 확보됨을 실험을 통해 확인하였다. Thus, in the method for producing a polyamide resin of the other embodiment, the composite obtained by melt-kneading the compound represented by the formula (7) and the compound represented by the formula (8) has a temperature lower than each melting point (10 ° C to 30 ° C below zero, or Upon reaction with the aromatic diamine monomer dissolved in the organic solvent in the form of a solid powder through cooling at 0 ° C to 30 ° C, or 10 ° C to 30 ° C, it was confirmed that the molecular weight of the final synthesized polyamide resin was improved. Through the experiment, it was confirmed that excellent mechanical properties were secured.
구체적으로, 상기 다른 구현예에 따른 폴리아미드 수지의 제조방법은 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 용융혼련시키고, 상기 용융혼련물을 응고시켜 복합체를 형성하는 단계를 포함할 수 있다.Specifically, the method for producing a polyamide resin according to another embodiment includes the steps of melt-kneading the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8, and solidifying the melt-kneaded material to form a complex. can do.
상기 화학식7로 표시되는 화합물에서, X는 할로겐, 또는 수산화기이다. 바람직하게는 상기 화학식7에서, X는 염소이다. 상기 화학식7로 표시되는 화합물의 구체적인 예로는 테레프탈로일 클로라이드 또는 테레프탈산을 들 수 있다. In the compound represented by Chemical Formula 7, X is halogen or a hydroxyl group. Preferably, in Chemical Formula 7, X is chlorine. Specific examples of the compound represented by Chemical Formula 7 include terephthaloyl chloride or terephthalic acid.
상기 화학식7로 표시되는 화합물은 방향족 디아민 단량체의 아미드화 반응으로 상기 화학식1로 표시되는 반복단위를 형성할 수 있으며, 선형 분자 구조로 인하여, 고분자 내에서 체인 패킹과 배열(Align)이 일정하게 유지될 수 있고, 폴리아미드 필름의 표면 경도 및 기계적 물성을 향상시킬 수 있다.The compound represented by Chemical Formula 7 may form a repeating unit represented by Chemical Formula 1 by amidation reaction of an aromatic diamine monomer, and due to the linear molecular structure, chain packing and alignment in the polymer are kept constant. Can improve the surface hardness and mechanical properties of the polyamide film.
상기 화학식8로 표시되는 화합물에서, X는 할로겐, 또는 수산화기이다. 바람직하게는 상기 화학식8에서, X는 염소이다. 상기 화학식8로 표시되는 화합물의 구체적인 예로는 프탈로일 클로라이드, 프탈산, 이소프탈로일 클로라이드, 또는 이소프탈산을 들 수 있다. In the compound represented by Chemical Formula 8, X is halogen or a hydroxyl group. Preferably, in Chemical Formula 8, X is chlorine. Specific examples of the compound represented by Chemical Formula 8 include phthaloyl chloride, phthalic acid, isophthaloyl chloride, or isophthalic acid.
상기 화학식8로 표시되는 화합물은 방향족 디아민 단량체의 아미드화 반응으로 상기 화학식2로 표시되는 반복단위를 형성할 수 있으며, 굽은형 분자 구조로 인하여, 고분자 내에서 체인 패킹과 배열(Align)을 방해하는 성격을 가지고 있으며, 폴리아미드 수지에 무정형 영역을 증가시켜, 폴리아미드 필름의 광학적 물성 및 내절 강도를 향상시킬 수 있다. 또한, 상기 화학식8로 표시되는 화합물로부터 유래된 상기 화학식2로 표시되는 반복단위가 화학식1로 표시되는 반복단위와 함께 폴리아미드 수지에 포함됨에 따라, 폴리아미드 수지의 분자량을 증가시킬 수 있다.The compound represented by Chemical Formula 8 may form a repeating unit represented by Chemical Formula 2 through amidation reaction of an aromatic diamine monomer, and due to a curved molecular structure, it prevents chain packing and alignment in the polymer. It has a personality and can increase the amorphous region in the polyamide resin, thereby improving the optical properties and the fracture strength of the polyamide film. In addition, as the repeating unit represented by Formula 2 derived from the compound represented by Formula 8 is included in the polyamide resin together with the repeating unit represented by Formula 1, the molecular weight of the polyamide resin can be increased.
한편, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 용융혼련시키고, 상기 용융혼련물을 응고시켜 복합체를 형성하는 단계에서, 상기 용융혼련은 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 녹는점 이상의 온도에서 혼합하는 것을 의미한다.On the other hand, in the step of melt-kneading the compound represented by the formula (7) and the compound represented by the formula (8), and solidifying the melt-kneaded product to form a complex, the melt-kneading is the compound represented by the formula (7) and the formula It means that the compound represented by 8 is mixed at a temperature above the melting point.
이처럼, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 단순히 물리적으로 혼합하지 않고, 각각의 녹는점 보다 높은 온도에서의 용융혼련에 의한 복합체 형성을 통해, 각각의 단량체가 방향족 디아민 단량체와 상대적으로 균등하게 반응하도록 유도할 수 있다.In this way, the compound represented by the formula (7) and the compound represented by the formula (8) do not simply physically mix, but through the formation of a complex by melt kneading at a temperature higher than each melting point, each monomer is an aromatic diamine monomer And to react relatively uniformly.
이에 따라, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물의 용해도 차이로 인해 상기 화학식7로 표시되는 화합물로부터 유래한 아미드 반복단위가 앞도적으로 우세하게 형성되면서 길이가 긴 블록을 형성하여 폴리아미드 수지의 결정성이 증가하고, 투명성을 확보하기 어려워지는 한계를 극복하고, 상기 일 구현예와 같이, 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트가 서로 번갈아가며(alternatively) 상기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성할 수 있게 된다.Accordingly, due to the difference in solubility between the compound represented by the formula (7) and the compound represented by the formula (8), the amide repeat unit derived from the compound represented by the formula (7) is formed predominantly leading to the formation of a long block. Crystallinity of the polyamide resin increases, overcomes the limitation that it is difficult to ensure transparency, and, as in the above embodiment, the first polyamide segment and the second polyamide segment alternately (alternatively) to the formula (3) It becomes possible to form a main chain including the displayed cross-repeating unit.
이때, 상기 화학식7로 표시되는 화합물 100 중량부에 대하여, 상기 화학식8로 표시되는 화합물이 5 중량부 내지 60 중량부, 또는 5 중량부 내지 50 중량부, 또는 5 중량부 내지 25 중량부, 또는 10 중량부 내지 30 중량부, 또는 15 중량부 내지 25 중량부로 혼합될 수 있다. 이를 통해, 투과도 및 clarity가 증가하는 기술적 효과가 구현될 수 있다. 상기 화학식7로 표시되는 화합물 100 중량부에 대하여, 상기 화학식8로 표시되는 화합물이 5 중량부 미만으로 지나치게 적게 혼합될 경우, 불투명해지며, Hazeness가 증가하는 기술적 문제가 발생하며, 상기 화학식7로 표시되는 화합물 100 중량부에 대하여, 상기 화학식8로 표시되는 화합물이 60 중량부 초과로 지나치게 과량 혼합될 경우 물리적인 특성(경도, 인장강도 등)이 감소하는 기술적 문제가 발생할 수 있다.At this time, with respect to 100 parts by weight of the compound represented by Formula 7, the compound represented by Formula 8 is 5 parts by weight to 60 parts by weight, or 5 parts by weight to 50 parts by weight, or 5 parts by weight to 25 parts by weight, or 10 parts by weight to 30 parts by weight, or 15 parts by weight to 25 parts by weight. Through this, a technical effect of increasing transmittance and clarity can be realized. With respect to 100 parts by weight of the compound represented by the formula (7), when the compound represented by the formula (8) is mixed in an amount of less than 5 parts by weight, it becomes opaque and a technical problem of increasing hazeness occurs. When the compound represented by Chemical Formula 8 is excessively mixed in excess of 60 parts by weight with respect to 100 parts by weight of the displayed compound, a technical problem that physical properties (hardness, tensile strength, etc.) decrease may occur.
또한, 상기 용융혼련물을 응고시켜 복합체를 형성함에 있어, 상기 응고란 용융상태의 용융혼련물을 녹는점 이하의 온도로 냉각시켜 고체화 시키는 물리적 변화를 의미하며, 이로인해 형성되는 복합체는 고체상태일 수 있다. 보다 바람직하게는 상기 복합체는 추가적인 분쇄공정등을 통해 얻어지는 고체분말일 수 있다.In addition, in forming a complex by solidifying the melt-kneaded material, the coagulation refers to a physical change of solidifying by cooling the melt-kneaded material in a molten state to a temperature below a melting point, and the complex formed thereby is in a solid state. Can be. More preferably, the composite may be a solid powder obtained through an additional grinding process.
한편, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 용융혼련시키고, 상기 용융혼련물을 응고시켜 복합체를 형성하는 단계는, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 50 ℃ 이상의 온도에서 혼합시키는 단계; 및 상기 혼합단계의 결과물을 냉각시키는 단계;를 포함할 수 있다.On the other hand, the step of melt-kneading the compound represented by the formula (7) and the compound represented by the formula (8), and solidifying the melt-kneaded material to form a complex, the compound represented by the formula (7) and the formula (8) Mixing the compound at a temperature of 50 ° C. or higher; And cooling the resultant product of the mixing step.
상기 테레프탈로일 클로라이드(Terephthaloyl chloride)는 81.3 ℃내지 83 ℃의 녹는점을 가지며, 상기 이소프탈로일 클로라이드(Isophthaloyl chloride)는 43 ℃내지 44 ℃의 녹는점을 가지며, 상기 프탈로일 클로라이드(Phthaloyl chloride)는 6 ℃내지 12 ℃의 녹는점을 가질 수 있다. 이에 따라, 이들을 50 ℃ 이상, 또는 90 ℃이상, 또는 50 ℃내지 120 ℃, 또는 90 ℃ 내지 120 ℃, 또는 95 ℃ 내지 110 ℃, 또는 100 ℃ 내지 110 ℃의 온도에서 혼합할 경우, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물 모두의 녹는점 보다 높은 온도조건이므로 용융혼련이 진행될 수 있다.The terephthaloyl chloride has a melting point of 81.3 ℃ to 83 ℃, the isophthaloyl chloride (Isophthaloyl chloride) has a melting point of 43 ℃ to 44 ℃, the phthaloyl chloride (Phthaloyl chloride) ) May have a melting point of 6 ℃ to 12 ℃. Accordingly, when they are mixed at a temperature of 50 ° C or higher, or 90 ° C or higher, or 50 ° C to 120 ° C, or 90 ° C to 120 ° C, or 95 ° C to 110 ° C, or 100 ° C to 110 ° C, the formula (7) Melting and kneading may proceed because the temperature is higher than the melting point of both the compound represented by and the compound represented by Chemical Formula 8.
상기 혼합 단계의 결과물을 냉각시키는 단계에서는, 상기 용융혼련 단계의 결과물을 5 ℃ 이하, 또는 영하10 ℃ 내지 5 ℃, 또는 영하 5 ℃ 내지 5 ℃에 방치함으로써, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물 모두의 녹는점 보다 낮은 온도조건이므로 냉각을 통해 보다 균일한 고형분말을 수득할 수 있다.In the step of cooling the resultant of the mixing step, the resultant of the melt-kneading step is 5 ° C. or less, or 10 ° C. to 5 ° C., or 5 ° C. to 5 ° C., and the compound represented by Chemical Formula 7 and the Since the temperature is lower than the melting point of all of the compounds represented by Chemical Formula 8, more uniform solid powder can be obtained through cooling.
한편, 상기 혼합 단계의 결과물을 냉각시키는 단계 이후에, 상기 냉각단계의 결과물을 분쇄시키는 단계를 더 포함할 수 있다. 상기 분쇄단계를 통해, 고형분의 복합체를 분말 형태로 제조할 수 있으며, 분쇄 단계 후 얻어지는 분말은 평균입경이 1 mm 내지 10 mm일 수 있다. Meanwhile, after the step of cooling the product of the mixing step, the step of crushing the product of the cooling step may be further included. Through the pulverizing step, a complex of solid content may be prepared in powder form, and the powder obtained after the pulverizing step may have an average particle diameter of 1 mm to 10 mm.
이와 같은 입경으로 분쇄하기 위해 사용되는 분쇄기는 구체적으로, 핀 밀(pin mill), 해머 밀(hammer mill), 스크류 밀(screw mill), 롤 밀(roll mill), 디스크 밀(disc mill), 조그 밀(jog mill) 또는 시브(sieve), jaw crusher 등을 사용할 수 있으나, 상술한 예에 한정되는 것은 아니다.The pulverizer used for pulverizing to such a particle size is, specifically, a pin mill, a hammer mill, a screw mill, a roll mill, a disc mill, or a jog. A mill, a sieve, a jaw crusher, or the like can be used, but is not limited to the above-described example.
이처럼, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물의 용융혼합물을 녹는점보다 낮은 온도에서의 냉각을 통한 고형분, 구체적으로 고형분말 형태로 방향족 디아민 단량체와 반응시킴에 따라, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물의 수분에 의한 변질이나, 용매와의 혼성을 최소화하여 최종 합성되는 폴리아미드 수지의 분자량을 향상시킴에 따라, 폴리아미드 수지의 우수한 기계적물성이 확보될 수 있다.As described above, as the molten mixture of the compound represented by the formula (7) and the compound represented by the formula (8) is cooled at a temperature lower than the melting point, it reacts with the solid diamine monomer in the form of solid powder, specifically, solid powder, the formula Excellent mechanical properties of the polyamide resin are secured by improving the molecular weight of the final synthesized polyamide resin by minimizing the deterioration by moisture of the compound represented by 7 and the compound represented by the formula (8) or mixing with a solvent. Can be.
또한, 상기 다른 구현예에 따른 폴리아미드 수지의 제조방법은 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 용융혼련시키고, 상기 용융혼련물을 응고시켜 복합체를 형성하는 단계 이후, 상기 복합체를 방향족 디아민 단량체와 반응시키는 단계를 포함할 수 있다.In addition, the method for producing a polyamide resin according to another embodiment is after the step of melt-kneading the compound represented by the formula (7) and the compound represented by the formula (8), and solidifying the melt-kneaded product to form a complex, the And reacting the complex with an aromatic diamine monomer.
상기 복합체를 방향족 디아민 단량체와 반응시키는 단계에서의 반응은, 영하 25 ℃ 내지 영상 25 ℃의 온도 조건, 또는 영하 25 ℃ 내지 0 ℃의 온도 조건에서, 불활성 기체 분위기 하에 수행될 수 있다. The reaction in the step of reacting the complex with an aromatic diamine monomer may be performed under an inert gas atmosphere at a temperature condition of minus 25 ° C to 25 ° C, or a temperature of minus 25 ° C to 0 ° C.
상기 방향족 디아민 단량체는, 구체적으로 예를 들어2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine), 2,2'-디메틸-4,4'-디아미노벤지딘(2,2'-dimethyl-4,4'- diaminobenzidine), 4,4'-디아미노디페닐 술폰(4,4'-diaminodiphenyl sulfone), 4,4'-(9-플루오레닐리덴)디아닐린(4,4'-(9-fluorenylidene)dianiline), 비스(4-(4-아미노페녹시)페닐) 술폰(bis(4-(4-aminophenoxy)phenyl)sulfone), 2,2',5,5'-테트라클로로벤지딘(2,2',5,5'-tetrachlorobenzidine), 2,7-디아미노플루오렌(2,7-diaminofluorene), 4,4-디아미노옥타플루오로비페닐(4,4-diaminooctafluorobiphenyl), m-페닐렌디아민(m-phenylenediamine), p-페닐렌디아민(p-phenylenediamine), 4,4'-옥시다이아닐린(4,4'-oxydianiline), 2,2'-디메틸-4,4'-디아미노비페닐(2,2'-dimethyl-4,4'-diaminobiphenyl), 2,2-비스[4-(4-아미노페녹시)페닐]프로판(2,2-bis[4-(4-aminophenoxy)phenyl]propane), 1,3-비스(4-아미노페녹시)벤젠(1,3-bis(4-aminophenoxy)benzene), m-자일리렌디아민(m-xylylenediamine), p-자일리렌디아민(p-xylylenediamine) 및 4,4'-디아미노벤즈아닐라이드(4,4'-diaminobenzanilide)로 이루어진 군에서 선택된 1종 이상을 포함할 수 있다. The aromatic diamine monomer is specifically, for example, 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine) , 2,2'-dimethyl-4,4'-diaminobenzidine, 4,4'-diaminodiphenyl sulfone ), 4,4 '-(9-fluorenylidene) dianiline (4,4'-(9-fluorenylidene) dianiline), bis (4- (4-aminophenoxy) phenyl) sulfone (bis (4- (4-aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine (2,2', 5,5'-tetrachlorobenzidine), 2,7-diaminofluorene (2,7- diaminofluorene), 4,4-diaminooctafluorobiphenyl, m-phenylenediamine, p-phenylenediamine, 4,4'-oxydi Aniline (4,4'-oxydianiline), 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (2,2-bis [4- (4-aminophenoxy) phenyl] propane), 1,3-ratio S (4-aminophenoxy) benzene (1,3-bis (4-aminophenoxy) benzene), m-xylylenediamine, p-xylylenediamine and 4,4'- It may include one or more selected from the group consisting of diaminobenzanilide (4,4'-diaminobenzanilide).
보다 바람직하게는, 상기 방향족 디아민 단량체로는 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine, TFDB), 2,2'-디메틸-4,4'-디아미노벤지딘(2,2'-dimethyl-4,4'- diaminobenzidine), m-자일리렌디아민(m-xylylenediamine), 또는 p-자일리렌디아민(p-xylylenediamine)을 사용할 수 있다.More preferably, the aromatic diamine monomer is 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB), 2,2'-dimethyl-4,4'-diaminobenzidine, m-xylylenediamine, or p-xyleneylene Diamine (p-xylylenediamine) can be used.
보다 구체적으로, 상기 복합체를 방향족 디아민 단량체와 반응시키는 단계는, 상기 방향족 디아민 단량체를 유기 용매에 용해시켜 디아민 용액을 제조하는 단계; 및 상기 디아민 용액에 복합체 분말을 첨가하는 단계;를 포함할 수 있다.More specifically, the step of reacting the complex with an aromatic diamine monomer includes: dissolving the aromatic diamine monomer in an organic solvent to prepare a diamine solution; And adding the composite powder to the diamine solution.
상기 방향족 디아민 단량체를 유기 용매에 용해시켜 디아민 용액을 제조하는 단계에서, 상기 디아민 용액에 포함된 방향족 디아민 단량체는 유기 용매에 용해된 상태로 존재할 수 있다. 상기 용매의 예가 크게 한정되는 것은 아니나, 예를 들어, N-메틸포름아미드, N,N-디메틸포름아미드, N,N-디에틸포름아미드, N,N-디메틸아세트아미드, N,N-디에틸아세트아미드, N,N-디메틸프로피온아미드, 3-메톡시-N,N-디메틸프로피온아미드, 디메틸설폭사이드, 아세톤, N-메틸-2-피롤리돈, N-에틸-2-피롤리돈, 테트라하이드로퓨란, 클로로포름, 감마-부티로락톤, 에틸락테이트, 메틸3-메톡시프로피오네이트, 메틸 이소부틸 케톤, 톨루엔, 자일렌, 메탄올, 에탄올 등 일반적인 범용 유기용매가 제한없이 사용될 수 있다.In the step of preparing a diamine solution by dissolving the aromatic diamine monomer in an organic solvent, the aromatic diamine monomer included in the diamine solution may exist dissolved in an organic solvent. Examples of the solvent are not particularly limited, for example, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-di Ethyl acetamide, N, N-dimethylpropionamide, 3-methoxy-N, N-dimethylpropionamide, dimethylsulfoxide, acetone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone , Tetrahydrofuran, chloroform, gamma-butyrolactone, ethyl lactate, methyl 3-methoxypropionate, methyl isobutyl ketone, toluene, xylene, methanol, ethanol and other general-purpose organic solvents can be used without limitation .
상기 디아민 용액에 복합체 분말을 첨가하는 단계에서, 상기 복합체 분말은 디아민 용액내에 용해된 방향족 디아민 단량체와 반응하게 된다. 이에 따라, 상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물의 수분에 의한 변질이나, 용매와의 혼성을 최소화하여 최종 합성되는 폴리아미드 수지의 분자량을 향상시킴에 따라, 폴리아미드 수지의 우수한 기계적물성이 확보될 수 있다.In the step of adding the complex powder to the diamine solution, the complex powder reacts with the aromatic diamine monomer dissolved in the diamine solution. Accordingly, by improving the molecular weight of the polyamide resin to be finally synthesized by minimizing the deterioration by moisture of the compound represented by the formula (7) and the compound represented by the formula (8) or hybridization with a solvent, the polyamide resin Excellent mechanical properties can be secured.
상기 복합체 분말은 상기 혼합 단계의 결과물을 냉각시키는 단계 이후, 상기 냉각단계의 결과물을 분쇄시키는 단계를 통해, 고형분의 복합체를 분말 형태로 제조할 수 있으며, 분쇄 단계 후 얻어지는 분말은 평균입경이 1 mm 내지 10 mm일 수 있다.After the step of cooling the resultant product of the mixing step, the complex powder may be prepared in the form of a powder in a solid form through the step of crushing the resultant product in the cooling step, and the powder obtained after the crushing step has an average particle diameter of 1 mm. To 10 mm.
Ⅲ. 폴리아미드 필름Ⅲ. Polyamide film
발명의 또 다른 구현예에 따르면, 하기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 하기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트;를 포함하고, 상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 하기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성하는 폴리아미드 수지를 포함하는 폴리아미드 필름이 제공될 수 있다.According to another embodiment of the invention, the repeating unit represented by the following formula (1), or a first polyamide segment comprising a block consisting of; And a repeating unit represented by the following Chemical Formula 2, or a second polyamide segment comprising a block consisting of the first polyamide segment and the second polyamide segment comprising a cross-repeating unit represented by the following Chemical Formula 3 A polyamide film comprising a polyamide resin forming a main chain can be provided.
[화학식1][Formula 1]
Figure PCTKR2019014714-appb-I000016
Figure PCTKR2019014714-appb-I000016
[화학식2][Formula 2]
Figure PCTKR2019014714-appb-I000017
Figure PCTKR2019014714-appb-I000017
[화학식3][Formula 3]
Figure PCTKR2019014714-appb-I000018
Figure PCTKR2019014714-appb-I000018
상기 화학식1 내지 2 에서, Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이고, 상기 화학식3에서, A는 상기 제1폴리아미드 세그먼트이고, B는 상기 제2폴리아미드 세그먼트이다. 상기 폴리아미드 수지에 관한 내용은 상기 일 구현예에서 상술한 내용을 모두 포함할 수 있다.In Formulas 1 to 2, Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and in Formula 3, A is the first polyamide segment, and B is the second polyamide segment. The contents of the polyamide resin may include all of the contents described above in one embodiment.
보다 구체적으로 상기 폴리아미드 필름은 상기 일 구현예의 폴리아미드 수지 또는 이의 경화물을 포함할 수 있으며, 상기 경화물이란, 상기 일 구현예의 폴리아미드 수지의 경화공정을 거쳐 얻어지는 물질을 의미한다.More specifically, the polyamide film may include the polyamide resin of one embodiment or a cured product thereof, and the cured product means a material obtained through a curing process of the polyamide resin of the embodiment.
상기 일 구현예의 폴리아미드 수지를 이용하여 필름을 제조하는 경우, 우수한 광학적 물성 및 기계적 물성을 구현할 수 있는 동시에, 유연성까지 구비하게 되어, 다양한 성형품의 재료로 사용될 수 있다. 예를 들어, 상기 폴리아미드 필름은 디스플레이용 기판, 디스플레이용 보호 필름, 터치 패널, 폴더블 기기의 윈도우 커버 등에 적용될 수 있다.When a film is produced using the polyamide resin of the above-described embodiment, excellent optical and mechanical properties can be realized, and flexibility is also provided, which can be used as a material for various molded articles. For example, the polyamide film may be applied to a display substrate, a display protective film, a touch panel, a window cover of a foldable device, and the like.
상기 폴리아미드 필름의 두께가 크게 한정되는 것은 아니나, 예를 들어, 0.01 ㎛ 내지 1000 ㎛ 범위내에서 자유롭게 조절 가능하다. 상기 폴리아미드 필름의 두께가 특정 수치만큼 증가하거나 감소하는 경우 폴리아미드 필름에서 측정되는 물성 또한 일정 수치만큼 변화할 수 있다.The thickness of the polyamide film is not particularly limited, but can be freely adjusted, for example, within a range of 0.01 μm to 1000 μm. When the thickness of the polyamide film increases or decreases by a specific value, physical properties measured in the polyamide film may also change by a certain value.
상기 폴리아미드 필름은 상기 일 구현예의 폴리아미드 수지를 사용하여 건식법, 습식법과 같은 통상적인 방법에 의해 제조될 수 있다. 예컨대, 상기 폴리아미드 필름은, 상기 일 구현예의 폴리아미드 수지를 포함하는 용액을 임의의 지지체 상에 코팅하여 막을 형성하고, 상기 막으로부터 용매를 증발시켜 건조하는 방법으로 얻어질 수 있으며, 필요에 따라, 상기 폴리아미드 필름에 대한 연신 및 열 처리가 더 수행될 수도 있다.The polyamide film may be prepared by a conventional method such as a dry method or a wet method using the polyamide resin of the above embodiment. For example, the polyamide film may be obtained by coating a solution containing the polyamide resin of the above embodiment on an arbitrary support to form a film, and evaporating a solvent from the film to dry it, if necessary. , The stretching and heat treatment for the polyamide film may be further performed.
상기 폴리아미드 필름은 상기 일 구현예의 폴리아미드 수지를 사용하여 제조됨에 따라 무색 투명하면서도 우수한 기계적 물성을 나타낼 수 있다. The polyamide film may exhibit colorless and transparent and excellent mechanical properties as it is manufactured using the polyamide resin of the embodiment.
구체적으로, 상기 폴리아미드 필름은, 50 ± 2 ㎛의 두께를 갖는 시편에 대해 ASTM D1003에 의거하여 측정된 헤이즈(haze) 값이 3.0% 이하, 또는 1.5% 이하, 1.00% 이하, 또는 0.85%이하, 또는 0.10% 내지 3.0%, 또는 0.10% 내지 1.5%, 또는 0.10% 내지 1.00%, 또는 0.50% 내지 1.00%, 또는 0.80% 내지 1.00%, 또는 0.81% 내지 0.97%일 수 있다. 상기 폴리아미드 필름의 ASTM D1003에 의해 측정한 헤이즈가 3.0% 초과로 증가하게 되면, 불투명성이 증대되어 충분한 수준의 투명성을 확보하기 어렵다.Specifically, the haze value measured according to ASTM D1003 for a specimen having a thickness of 50 ± 2 μm is 3.0% or less, or 1.5% or less, 1.00% or less, or 0.85% or less. , Or 0.10% to 3.0%, or 0.10% to 1.5%, or 0.10% to 1.00%, or 0.50% to 1.00%, or 0.80% to 1.00%, or 0.81% to 0.97%. When the haze measured by ASTM D1003 of the polyamide film increases to more than 3.0%, the opacity increases, making it difficult to ensure a sufficient level of transparency.
그리고, 상기 폴리아미드 필름은, 50 ± 2 ㎛의 두께를 갖는 시편에 대해 ASTM E313에 의거하여 측정된 황색 지수 값(yellow index, YI)이, 4.0 이하, 또는 3.0 이하, 또는 0.5 내지 4.0, 또는 0.5 내지 3.0일 수 있다. 상기 폴리아미드 필름의 ASTM E313에 의거하여 측정된 황색 지수 값(yellow index, YI)이 4.0 초과로 증가하게 되면, 불투명성이 증대되어 충분한 수준의 투명성을 확보하기 어렵다.And, the polyamide film, the yellow index value (yellow index, YI) measured in accordance with ASTM E313 for a specimen having a thickness of 50 ± 2 ㎛, 4.0 or less, or 3.0 or less, or 0.5 to 4.0, or 0.5 to 3.0. When the yellow index value (YI) measured in accordance with ASTM E313 of the polyamide film increases to more than 4.0, it is difficult to secure a sufficient level of transparency by increasing opacity.
그리고, 상기 폴리아미드 필름은 50 ± 2 ㎛의 두께를 갖는 시편에 대해, 550 nm 파장의 가시광선에 대한 투과율(T, @550nm)이 86% 이상, 또는 86% 내지 90%일 수 있고, 388 nm 파장의 자외선에 대한 투과율(T, @388nm)이 50.00% 이상, 또는 60.00% 이상일 수 있다. In addition, the polyamide film may have a transmittance (T, @ 550nm) of visible light having a wavelength of 550 nm for a specimen having a thickness of 50 ± 2 μm, or greater than 86%, or 86% to 90%, 388 The transmittance (T, @ 388 nm) to ultraviolet rays of nm wavelength may be 50.00% or more, or 60.00% or more.
그리고, 상기 폴리아미드 필름은, 50 ± 2 ㎛의 두께를 갖는 시편에 대해 측정된 내절 강도(175 rpm의 속도로 135° 의 각도, 0.8 mm의 곡률 반경 및 250 g의 하중에서의 파단 왕복굽힙횟수) 값이 4000 Cycle 이상, 또는 7000 Cycle 이상, 또는 9000 Cycle 이상, 또는 4000 Cycle 내지 20000 Cycle, 또는 7000 Cycle 내지 20000 Cycle, 또는 9000 Cycle 내지 20000 Cycle일 수 있다. And, the polyamide film, the cutting strength measured for a specimen having a thickness of 50 ± 2 μm (angle of 135 ° at a speed of 175 rpm, a radius of curvature of 0.8 mm and a number of reciprocating fracture breaks at a load of 250 g ) The value may be 4000 Cycle or more, or 7000 Cycle or more, or 9000 Cycle or more, or 4000 Cycle to 20000 Cycle, or 7000 Cycle to 20000 Cycle, or 9000 Cycle to 20000 Cycle.
그리고, 상기 폴리아미드 필름은, 50 ± 2 ㎛의 두께를 갖는 시편에 대해 ASTM D3363에 의거하여 측정된 연필 경도 (Pencil Hardness) 값이 1H 이상, 또는 3H 이상, 또는 1 H 내지 4H, 또는 3 H 내지 4H일 수 있다.And, the polyamide film has a pencil hardness (Pencil Hardness) value of 1H or more, or 3H or more, or 1H to 4H, or 3H measured according to ASTM D3363 for a specimen having a thickness of 50 ± 2 μm. To 4H.
Ⅳ. 수지 적층체Ⅳ. Resin laminate
발명의 또 다른 구현예에 따르면, 하기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 하기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트;를 포함하고, 상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 하기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성하는 폴리아미드 수지를 포함한 기재; 및 상기 기재의 적어도 일면에 형성되는 하드 코팅층;을 포함하는 수지 적층체가 제공될 수 있다.According to another embodiment of the invention, the repeating unit represented by the following formula (1), or a first polyamide segment comprising a block consisting of; And a repeating unit represented by the following Chemical Formula 2, or a second polyamide segment comprising a block consisting of the first polyamide segment and the second polyamide segment comprising a cross-repeating unit represented by the following Chemical Formula 3 A base material comprising a polyamide resin forming a main chain; And a hard coating layer formed on at least one surface of the substrate.
[화학식1][Formula 1]
Figure PCTKR2019014714-appb-I000019
Figure PCTKR2019014714-appb-I000019
[화학식2][Formula 2]
Figure PCTKR2019014714-appb-I000020
Figure PCTKR2019014714-appb-I000020
[화학식3][Formula 3]
Figure PCTKR2019014714-appb-I000021
Figure PCTKR2019014714-appb-I000021
상기 화학식1 내지 2 에서, Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이고, 상기 화학식3에서, A는 상기 제1폴리아미드 세그먼트이고, B는 상기 제2폴리아미드 세그먼트이다. 상기 폴리아미드 수지에 관한 내용은 상기 일 구현예에서 상술한 내용을 모두 포함할 수 있다.In Formulas 1 to 2, Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, and in Formula 3, A is the first polyamide segment, and B is the second polyamide segment. The contents of the polyamide resin may include all of the contents described above in one embodiment.
상기 기재는 상기 일 구현예의 폴리아미드 수지를 포함할 수 있고, 상기 다른 구현예의 고분자 필름을 포함할 수도 있다. 상기 폴리아미드 수지에 관한 내용은 상기 일 구현예에서 상술한 내용을 모두 포함할 수 있고, 상기 고분자 필름에 관한 내용은 상기 다른 구현예에서 상술한 내용을 모두 포함할 수 있다.The substrate may include the polyamide resin of one embodiment, or may include a polymer film of the other embodiment. The contents of the polyamide resin may include all of the contents described above in one embodiment, and the contents of the polymer film may include all of the contents described above in another embodiment.
상기 기재의 적어도 일면에는 하드 코팅층이 형성될 수 있다. 상기 기재의 일면, 또는 양면 모두에 하드 코팅층이 형성될 수 있다. 상기 기재의 일면에만 하드 코팅층이 형성될 경우, 상기 기재의 반대면에는 폴리이미드계, 폴리카보네이트계, 폴리에스터계, 폴리알킬(메트)아크릴레이트계, 폴리올레핀계 및 폴리사이클릭올레핀계 고분자로 이루어진 군에서 선택된 1종 이상의 고분자를 포함한 고분자 필름이 형성될 수 있다.A hard coating layer may be formed on at least one surface of the substrate. A hard coating layer may be formed on one surface or both surfaces of the substrate. When a hard coating layer is formed on only one side of the substrate, the opposite side of the substrate is made of polyimide-based, polycarbonate-based, polyester-based, polyalkyl (meth) acrylate-based, polyolefin-based, and polycyclic olefin-based polymers. A polymer film including at least one polymer selected from the group may be formed.
상기 하드 코팅층은 0.1㎛ 내지 100㎛의 두께를 가질 수 있다. The hard coating layer may have a thickness of 0.1㎛ to 100㎛.
상기 하드 코팅층은 하드코팅분야에서 알려진 재질이면 큰 제한 없이 사용할 수 있으며, 예를 들어 상기 하드 코팅층은 광경화성 수지의 바인더 수지; 및 상기 바인더 수지에 분산된 무기 입자 또는 유기 입자를 포함할 수 있다. The hard coating layer can be used without any limitation as long as it is a material known in the hard coating field, for example, the hard coating layer is a binder resin of a photocurable resin; And inorganic particles or organic particles dispersed in the binder resin.
상기 하드코팅층에 포함되는 광경화형 수지는 자외선 등의 광이 조사되면 중합 반응을 일으킬 수 있는 광경화형 화합물의 중합체로서, 당업계에서 통상적인 것일 수 있다. 다만, 바람직하게는, 상기 광경화형 화합물은 다관능성 (메트)아크릴레이트계 단량체 또는 올리고머일 수 있고, 이때 (메트)아크릴레이트계 관능기의 수는 2 내지 10, 또는 2 내지 8, 또는 2 내지 7인 것이, 하드코팅층의 물성 확보 측면에서 유리하다. 또는, 상기 광경화형 화합물은 펜타에리스리톨 트리(메트)아크릴레이트, 펜타에리스리톨 테트라(메트)아크릴레이트, 디펜타에리스리톨 펜타(메트)아크릴레이트, 디펜타에리스리톨 헥사(메트)아크릴레이트, 디펜타에리스리톨 헵타(메트)아크릴레이트, 트리펜타에리스리톨 헵타(메트)아크릴레이트, 트릴렌 디이소시아네이트, 자일렌 디이소시아네이트, 헥사메틸렌 디이소시아네이트, 트리메틸올프로판 트리(메트)아크릴레이트, 및 트리메틸올프로판 폴리에톡시 트리(메트)아크릴레이트로 이루어진 군에서 선택되는 1종 이상일 수 있다.The photo-curable resin contained in the hard coating layer is a polymer of a photo-curable compound that can cause a polymerization reaction when light such as ultraviolet rays is irradiated, and may be common in the art. However, preferably, the photocurable compound may be a polyfunctional (meth) acrylate-based monomer or oligomer, wherein the number of (meth) acrylate-based functional groups is 2 to 10, or 2 to 8, or 2 to 7 It is advantageous in terms of securing physical properties of the hard coating layer. Alternatively, the photocurable compound may include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hepta ( Meth) acrylate, tripentaerythritol hepta (meth) acrylate, trilene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane polyethoxy tri (meth) ) May be one or more selected from the group consisting of acrylates.
상기 무기 입자는 예를 들어 실리카, 알루미늄, 티타늄, 징크 등의 금속 원자, 또는 이의 산화물, 질화물 등일 수 있으며, 각각 독립적으로 실리카 미립자, 알루미늄 옥사이드 입자, 티타늄 옥사이드 입자, 또는 징크 옥사이드 입자 등을 사용할 수 있다.The inorganic particles may be, for example, metal atoms such as silica, aluminum, titanium, and zinc, or oxides and nitrides thereof, respectively, and silica particles, aluminum oxide particles, titanium oxide particles, or zinc oxide particles may be used independently. have.
상기 무기 입자는 100 nm 이하, 또는 5 내지 100 nm 의 평균반경을 가질 수 있다. 상기 유기 입자의 종류 또한 한정되는 것은 아니며, 예를 들어 10 nm 내지 100 ㎛의 평균 입경을 갖는 고분자 입자를 사용할 수 있다. The inorganic particles may have an average radius of 100 nm or less, or 5 to 100 nm. The type of the organic particles is also not limited, and for example, polymer particles having an average particle diameter of 10 nm to 100 μm may be used.
상기 수지 적층체는 디스플레이 장치의 기판 또는 커버 윈도우 등으로 사용 가능하고, 높은 광투과성 및 낮은 헤이즈 특성과 함께 높은 유연성 및 굽힘 내구성을 가져서 플렉서블 디스플레이 장치의 기판 또는 커버 윈도우로 사용 가능하다. 즉, 상기 수지 적층체가 포함된 디스플레이 장치, 또는 상기 수지 적층체가 포함된 플렉서블 디스플레이 장치가 구현될 수 있다.The resin laminate may be used as a substrate or cover window of a display device, and may be used as a substrate or cover window of a flexible display device with high light transmittance and low haze characteristics and high flexibility and bending durability. That is, the display device including the resin laminate or the flexible display device including the resin laminate may be implemented.
본 발명에 따르면, 우수한 기계적물성을 구현할 수 있으며, 투명성이 향상된 폴리아미드 수지, 이의 제조방법, 및 이를 포함하는 폴리아미드 필름 및 수지 적층체가 제공될 수 있다.According to the present invention, excellent mechanical properties may be realized, and a polyamide resin having improved transparency, a method for manufacturing the same, and a polyamide film and a resin laminate comprising the same may be provided.
도 1은 실시예1의 (1)에서 얻은 폴리아미드 수지의 13C-NMR 스펙트럼을 나타낸 것이다.1 shows a 13 C-NMR spectrum of the polyamide resin obtained in Example 1 (1).
도 2는 실시예2의 (1)에서 얻은 폴리아미드 수지의 13C-NMR 스펙트럼을 나타낸 것이다.Fig. 2 shows the 13 C-NMR spectrum of the polyamide resin obtained in Example 2 (1).
발명을 하기의 실시예에서 보다 상세하게 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다.The invention is described in more detail in the following examples. However, the following examples are only illustrative of the present invention, and the contents of the present invention are not limited by the following examples.
<제조예 : 아실클로라이드 복합체의 제조><Production Example: Preparation of acyl chloride complex>
제조예1Preparation Example 1
교반기, 질소 주입기, 적하 깔대기, 및 온도 조절기가 구비된 1000 mL의 4-neck 둥근 플라스크(반응기)에, 테레프탈로일 클로라이드(terephthaloyl chloride, TPC; 녹는점 : 83 ℃) 549.4 g(2.704 몰)과 이소프탈로일 클로라이드(isophthaloyl chloride, IPC; 녹는점 44 ℃) 120.6 g(0.594 몰)를 첨가하여, 100 ℃에서 3 시간 동안 용융혼련시킨다음, 0 ℃에서 12 시간 동안 냉각시켜 아실클로라이드(구체적으로, 테레프탈로일 클로라이드 및 이소프탈로일 클로라이드)의 복합체를 제조하였다. In a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller, terephthaloyl chloride (TPC; melting point: 83 ° C) 549.4 g (2.704 mol) and 120.4 g (0.594 mol) of isophthaloyl chloride (IPC; melting point 44 ° C) was added, melt-kneaded at 100 ° C for 3 hours, and then cooled at 0 ° C for 12 hours to obtain acyl chloride (specifically, A complex of terephthaloyl chloride and isophthaloyl chloride) was prepared.
이후, 상기 아실클로라이드 복합체를 jaw crusher로 분쇄하여 평균입경이 5mm인 분말로 제조하였다.Thereafter, the acyl chloride complex was pulverized with a jaw crusher to prepare a powder having an average particle diameter of 5 mm.
제조예2Preparation Example 2
테레프탈로일 클로라이드(terephthaloyl chloride, TPC; 녹는점 : 83 ℃) 569.5 g(2.803 몰)과 이소프탈로일 클로라이드(isophthaloyl chloride, IPC; 녹는점 44 ℃) 100.5 g(0.495 몰)를 첨가한 것을 제외하고는, 상기 제조예1과 동일한 방법으로 아실클로라이드 복합체 분말을 제조하였다. Terephthaloyl chloride (TPC; melting point: 83 ° C) 569.5 g (2.803 mol) and isophthaloyl chloride (IPC; melting point 44 ° C) 100.5 g (0.495 mol) were added except In the same manner as in Preparation Example 1, an acyl chloride complex powder was prepared.
<실시예: 폴리아미드 수지 및 필름의 제조><Example: Preparation of polyamide resin and film>
실시예 1Example 1
(1) 폴리아미드 수지(1) Polyamide resin
교반기, 질소 주입기, 적하 깔대기, 및 온도 조절기가 구비된 500 mL의 4-neck 둥근 플라스크(반응기)에 질소를 천천히 불어주면서, N,N-디메틸아세트아미드(N,N-dimethylacetamide, DMAc) 262 g을 채우고, 반응기의 온도를 0 ℃로 맞춘 후 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine, TFDB) 14.153 g(0.0442 몰)을 용해시켰다. 262 g of N, N-dimethylacetamide (DMAc) while slowly blowing nitrogen into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller And set the temperature of the reactor to 0 ° C., then 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine , TFDB) 14.153 g (0.0442 mol) was dissolved.
여기에, 상기 제조예1에서 얻어진 아실클로라이드 복합체 분말 8.972 g(0.0442 몰)을 첨가하면서 교반하고, 0 ℃조건에서 12 시간 동안 아미드 형성 반응을 진행하였다. Here, the acyl chloride complex powder obtained in Preparation Example 1 was stirred while adding 8.972 g (0.0442 mol), and the amide formation reaction was performed at 0 ° C. for 12 hours.
반응을 완료한 후, N,N-디메틸아세트아미드(N,N-dimethylacetamide, DMAc)를 투입하여 고형분 함량을 5% 이하가 되도록 희석하고, 이를 1L의 메탄올로 침전시키고, 침전된 고형분을 여과한 후, 100 ℃의 진공 상태에서 6시간 이상 건조하여 고형분 형태의 폴리아미드 수지를 제조하였다. After the completion of the reaction, N, N-dimethylacetamide (DMAc) was added to dilute the solid content to 5% or less, precipitated with 1 L of methanol, and filtered the precipitated solid content. Thereafter, the mixture was dried in a vacuum at 100 ° C. for 6 hours or more to prepare a polyamide resin in a solid form.
하기 도1에 기재된 13C-NMR을 통해, 상기 실시예1의 (1)에서 얻은 폴리아미드 수지에는 테레프탈로일 클로라이드(terephthaloyl chloride, TPC)와 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine, TFDB)의 아미드반응으로 얻어지는 제1반복단위 82몰%, 그리고 이소프탈로일 클로라이드(isophthaloyl chloride, IPC)와 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine, TFDB)의 아미드반응으로 얻어지는 제2반복단위 18몰%이 함유되어 있음을 확인하였다.Through the 13 C-NMR described in Figure 1, the polyamide resin obtained in (1) of Example 1, terephthaloyl chloride (terephthaloyl chloride, TPC) and 2,2'-bis (trifluoromethyl)- 82 mol% of the first repeating unit obtained by the amide reaction of 4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB), and isophthaloyl chloride, IPC) and 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB) It was confirmed that 18 mol% of 2 repeat units were contained.
(2) 폴리아미드 필름(2) Polyamide film
상기 실시예1의 (1)에서 얻은 폴리아미드 수지를 N,N-디메틸아세트아미드(N,N-dimethylacetamide)에 녹여 약 10%(w/V)의 고분자 용액을 제조하였다.The polyamide resin obtained in (1) of Example 1 was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 10% (w / V).
상기 고분자 용액을 폴리이미드 기재필름(UPILEX-75s, UBE 사) 상에 도포하고, 필름 어플리케이터를 이용하여 고분자 용액의 두께를 균일하게 조절하였다. The polymer solution was applied on a polyimide base film (UPILEX-75s, UBE), and the thickness of the polymer solution was uniformly adjusted using a film applicator.
이후, 80 ℃ 마티즈 오븐에서 15분 동안 건조한 후, 질소를 흘려주면서 250 ℃에서 30분 동안 경화시킨 후, 상기 기재필름으로부터 박리하여, 폴리아미드 필름을 얻었다.Thereafter, after drying for 15 minutes in an 80 ° C Matiz oven, curing was performed at 250 ° C for 30 minutes while flowing nitrogen, and then peeled from the base film to obtain a polyamide film.
실시예2Example 2
(1) 폴리아미드 수지(1) Polyamide resin
상기 제조예1에서 얻어진 아실클로라이드 복합체 분말 대신 상기 제조예2에서 얻어진 아실클로라이드 복합체 분말을 사용한 것을 제외하고는, 상기 실시예1의 (1)과 동일한 방법으로 폴리아미드 수지를 제조하였다.A polyamide resin was prepared in the same manner as in Example 1 (1), except that the acyl chloride composite powder obtained in Preparation Example 2 was used instead of the acyl chloride composite powder obtained in Preparation Example 1.
하기 도2에 기재된 13C-NMR을 통해, 상기 실시예2의 (1)에서 얻은 폴리아미드 수지에는 테레프탈로일 클로라이드(terephthaloyl chloride, TPC)와 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine, TFDB)의 아미드반응으로 얻어지는 제1반복단위 85몰%, 그리고 이소프탈로일 클로라이드(isophthaloyl chloride, IPC)와 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine, TFDB)의 아미드반응으로 얻어지는 제2반복단위 15몰%이 함유되어 있음을 확인하였다.Through the 13 C-NMR shown in Figure 2, the polyamide resin obtained in (1) of Example 2 is terephthaloyl chloride (terephthaloyl chloride, TPC) and 2,2'-bis (trifluoromethyl)- 85 mol% of the first repeating unit obtained by the amide reaction of 4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB), and isophthaloyl chloride, IPC) and 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB) It was confirmed that 15 mol% of 2 repeat units were contained.
(2) 폴리아미드 필름(2) Polyamide film
상기 실시예1의 (1)에서 얻은 폴리아미드 수지 대신, 상기 실시예2의 (1)에서 얻은 폴리아미드 수지를 사용한 것을 제외하고는, 상기 실시예1의 (2)와 동일한 방법으로 폴리아미드 필름을 제조하였다.The polyamide film was obtained in the same manner as in Example 1 (2), except that the polyamide resin obtained in Example 1 (1) was used instead of the polyamide resin obtained in Example 1 (1). Was prepared.
<비교예: 폴리아미드 수지 및 필름의 제조><Comparative Example: Preparation of polyamide resin and film>
비교예1Comparative Example 1
(1) 폴리아미드 수지(1) Polyamide resin
상기 제조예1에서 얻어진 아실클로라이드 복합체 분말 대신, 테레프탈로일 클로라이드(terephthaloyl chloride, TPC) 7.358 g(0.0362 몰) 및 이소프탈로일 클로라이드(isophthaloyl chloride, IPC) 1.615 g(0.0080 몰)을 동시에 첨가하여 아미드 형성 반응을 진행한 것을 제외하고는, 상기 실시예1의 (1)과 동일한 방법으로 폴리아미드 수지를 제조하였다.Instead of the acyl chloride complex powder obtained in Preparation Example 1, terephthaloyl chloride (TPC) 7.358 g (0.0362 mol) and isophthaloyl chloride (IPphthal) 1.615 g (0.0080 mol) were added simultaneously to amide. A polyamide resin was prepared in the same manner as in Example 1 (1), except that the formation reaction proceeded.
(2) 폴리아미드 필름(2) Polyamide film
상기 실시예1의 (1)에서 얻은 폴리아미드 수지 대신, 상기 비교예1의 (1)에서 얻은 폴리아미드 수지를 사용한 것을 제외하고는, 상기 실시예1의 (2)와 동일한 방법으로 폴리아미드 필름을 제조하였다.A polyamide film in the same manner as in (2) of Example 1, except that the polyamide resin obtained in (1) of Comparative Example 1 was used instead of the polyamide resin obtained in (1) of Example 1 above. Was prepared.
비교예2Comparative Example 2
(1) 폴리아미드 수지(1) Polyamide resin
상기 제조예1에서 얻어진 아실클로라이드 복합체 분말 대신, 테레프탈로일 클로라이드(terephthaloyl chloride, TPC) 7.358 g(0.0362 몰)을 먼저 첨가한 후, 약 5분 간격을 두고, 순차적으로 이소프탈로일 클로라이드(isophthaloyl chloride, IPC) 1.615 g(0.0080 몰)을 첨가하여 아미드 형성 반응을 진행한 것을 제외하고는, 상기 실시예1의 (1)과 동일한 방법으로 폴리아미드 수지를 제조하였다.Instead of the acyl chloride complex powder obtained in Preparation Example 1, terephthaloyl chloride (TPC) 7.358 g (0.0362 mol) was added first, followed by an interval of about 5 minutes, sequentially isophthaloyl chloride (isophthaloyl chloride) , IPC) A polyamide resin was prepared in the same manner as in Example 1 (1), except that 1.615 g (0.0080 mol) was added to proceed with the amide formation reaction.
(2) 폴리아미드 필름(2) Polyamide film
상기 실시예1의 (1)에서 얻은 폴리아미드 수지 대신, 상기 비교예2의 (1)에서 얻은 폴리아미드 수지를 사용한 것을 제외하고는, 상기 실시예1의 (2)와 동일한 방법으로 폴리아미드 필름을 제조하였다.A polyamide film in the same manner as in (2) of Example 1, except that instead of the polyamide resin obtained in (1) of Example 1, the polyamide resin obtained in (1) of Comparative Example 2 was used. Was prepared.
비교예3Comparative Example 3
(1) 폴리아미드 수지(1) Polyamide resin
상기 제조예1에서 얻어진 아실클로라이드 복합체 분말 대신, 이소프탈로일 클로라이드(isophthaloyl chloride, IPC) 1.615 g(0.0080 몰)을 먼저 첨가한 후, 약 5분 간격을 두고, 순차적으로 테레프탈로일 클로라이드(terephthaloyl chloride, TPC) 7.358 g(0.0362 몰)을 첨가하여 아미드 형성 반응을 진행한 것을 제외하고는, 상기 실시예1의 (1)과 동일한 방법으로 폴리아미드 수지를 제조하였다.Instead of the acyl chloride complex powder obtained in Preparation Example 1, isophthaloyl chloride (IPC) 1.615 g (0.0080 mol) was added first, followed by an interval of about 5 minutes, followed by sequentially terephthaloyl chloride. , TPC) A polyamide resin was prepared in the same manner as in Example 1 (1), except that 7.358 g (0.0362 mol) was added to proceed with the amide formation reaction.
(2) 폴리아미드 필름(2) Polyamide film
상기 실시예1의 (1)에서 얻은 폴리아미드 수지 대신, 상기 비교예3의 (1)에서 얻은 폴리아미드 수지를 사용한 것을 제외하고는, 상기 실시예1의 (2)와 동일한 방법으로 폴리아미드 필름을 제조하였다.A polyamide film in the same manner as in (2) of Example 1, except that the polyamide resin obtained in (1) of Comparative Example 3 was used instead of the polyamide resin obtained in (1) of Example 1 above. Was prepared.
<참고예: 폴리아미드 수지 및 필름의 제조><Reference example: Preparation of polyamide resin and film>
참고예1Reference Example 1
(1) 폴리아미드 수지(1) Polyamide resin
교반기, 질소 주입기, 적하 깔대기, 및 온도 조절기가 구비된 500 mL의 4-neck 둥근 플라스크(반응기)에 질소를 천천히 불어주면서, N,N-디메틸아세트아미드(N,N-dimethylacetamide, DMAc) 262 g을 채우고, 반응기의 온도를 0 ℃로 맞춘 후 테레프탈로일 클로라이드(terephthaloyl chloride, TPC) 7.358 g(0.0362 몰) 및 이소프탈로일 클로라이드(isophthaloyl chloride, IPC) 1.615 g(0.0080 몰)을 용해시켰다. 262 g of N, N-dimethylacetamide (DMAc) while slowly blowing nitrogen into a 500 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller After filling the reactor, the temperature of the reactor was adjusted to 0 ° C., and 7.358 g (0.0362 mol) of terephthaloyl chloride (TPC) and 1.615 g (0.0080 mol) of isophthaloyl chloride (IPC) were dissolved.
여기에, 분말 형태의 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민(2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine, TFDB) 14.153 g(0.0442 몰)을 첨가하면서 교반하고, 0 ℃조건에서 12 시간 동안 아미드 형성 반응을 진행하였다. Here, 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine in powder form (2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, TFDB) 14.153 g ( 0.0442 mol) was added, and the mixture was stirred at 0 ° C. for 12 hours.
반응을 완료한 후, N,N-디메틸아세트아미드(N,N-dimethylacetamide, DMAc)를 투입하여 고형분 함량을 5% 이하가 되도록 희석하고, 이를 1L의 메탄올로 침전시키고, 침전된 고형분을 여과한 후, 100 ℃의 진공 상태에서 6시간 이상 건조하여 고형분 형태의 폴리아미드 수지를 제조하였다.After the completion of the reaction, N, N-dimethylacetamide (DMAc) was added to dilute the solid content to 5% or less, precipitated with 1 L of methanol, and filtered the precipitated solid content. Thereafter, the mixture was dried in a vacuum at 100 ° C. for 6 hours or more to prepare a polyamide resin in a solid form.
(2) 폴리아미드 필름(2) Polyamide film
상기 실시예1의 (1)에서 얻은 폴리아미드 수지 대신, 상기 참고예1의 (1)에서 얻은 폴리아미드 수지를 사용한 것을 제외하고는, 상기 실시예1의 (2)와 동일한 방법으로 폴리아미드 필름을 제조하였다.A polyamide film in the same manner as in (2) of Example 1, except that the polyamide resin obtained in (1) of Reference Example 1 was used instead of the polyamide resin obtained in (1) of Example 1 above. Was prepared.
<실험예><Experimental Example>
상기 실시예, 비교예 및 참고예에서 얻어진 폴리아미드 수지 또는 폴리아미드 필름에 대하여 아래의 특성을 측정 또는 평가하였고, 그 결과를 아래 표 1에 나타내었다.The following properties were measured or evaluated for the polyamide resin or polyamide film obtained in the above Examples, Comparative Examples and Reference Examples, and the results are shown in Table 1 below.
(1) 두께: 두께측정장비를 이용하여 폴리아미드 필름의 두께를 측정하였다.(1) Thickness: The thickness of the polyamide film was measured using a thickness measuring device.
(2) 황색 지수(Y.I.): COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES)를 이용하여 ASTM E313의 측정법에 따라 폴리아미드 필름의 황색 지수를 측정하였다.(2) Yellow index (Y.I.): Using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES), the yellow index of the polyamide film was measured according to the measurement method of ASTM E313.
(3) 광 투과율(transmittance): Shimadzu UV-2600 UV-vis spectrometer를 이용하여 폴리아미드 필름에 대한 전 광선 투과율을 측정하였다. 측정 결과 중 388 nm 파장의 자외선에 대한 투과율(T, @388nm)과 550 nm 파장의 가시광선에 대한 투과율(T, @550nm)을 나타내었다.(3) Light transmittance: The total light transmittance of the polyamide film was measured using a Shimadzu UV-2600 UV-vis spectrometer. Among the measurement results, transmittance (T, @ 388nm) for ultraviolet light at a wavelength of 388 nm and transmittance (T, @ 550nm) for visible light at a wavelength of 550 nm were shown.
(4) Haze: COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES)를 이용하여 ASTM D1003의 측정법에 따라 폴리아미드 필름의 헤이즈 값을 측정하였다.(4) Haze: The haze value of the polyamide film was measured according to the measurement method of ASTM D1003 using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES).
(5) 분자량 및 분자량 분포(PDI, polydispersity index): 겔 투과 크로마토그래피(GPC: gel permeation chromatography, Waters사 제조)를 이용하여 폴리아미드 수지의 중량평균 분자량(Mw)과 수평균 분자량(Mn)을 측정하였고, 중량평균 분자량을 수평균 분자량으로 나누어 분자량 분포(PDI)를 계산하였다. 구체적으로, Polymer Laboratories PLgel MIX-B 300mm 길이 칼럼 2개가 이어진 600mm 길이 칼럼을 이용하여 Waters 2605 기기(검출기 : RI)를 통해, 평가 온도는 50~75 ℃(약 65 ℃)에서, DMF 100wt% 용매를 사용하여, 1mL/min의 유속, 샘플은 1mg/mL의 농도로 조제한 다음, 100 μL의 양으로 25분간 공급하며, 폴리스티렌 표준을 이용하여 형성된 검정 곡선을 이용하여 분자량을 구할 수 있다. 폴리스티렌 표준품의 분자량은 3940 / 9600 / 31420 / 113300 / 327300 / 1270000 / 4230000 의 7종을 사용하였다.(5) Molecular weight and molecular weight distribution (PDI, polydispersity index): The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyamide resin are determined by gel permeation chromatography (GPC). The molecular weight distribution (PDI) was calculated by dividing the weight average molecular weight by the number average molecular weight. Specifically, using a Polymer Laboratories PLgel MIX-B 300mm length column followed by a 600mm length column followed by a Waters 2605 instrument (detector: RI), the evaluation temperature was 50-75 ° C (about 65 ° C), DMF 100wt% solvent Using, a flow rate of 1 mL / min, the sample is prepared at a concentration of 1 mg / mL, and then supplied for 25 minutes in an amount of 100 μL, the molecular weight can be obtained using an assay curve formed using a polystyrene standard. As for the polystyrene standard, 7 kinds of 3940/9600/31420/113300/327300/1270000/4230000 were used.
(6) 굴곡성 : MIT 타입의 내절 강도 시험기 (folding endurance tester)를 이용하여 폴리아미드 필름의 내절 강도를 평가하였다. 구체적으로, 폴리아미드 필름의 시편(1cm*7cm)을 내절 강도 시험기에 로딩하고 시편의 왼쪽과 오른쪽에서 175 rpm의 속도로 135° 의 각도, 0.8 mm의 곡률 반경 및 250 g의 하중으로 굽혀서 파단할 때까지 왕복 굽힘 횟수(cycle)를 측정하였다.(6) Flexibility: The fracture strength of the polyamide film was evaluated using a MIT type folding endurance tester. Specifically, a specimen (1 cm * 7 cm) of a polyamide film was loaded into a fracture resistance tester and fractured at a speed of 175 rpm from the left and right sides of the specimen at an angle of 135 °, a radius of curvature of 0.8 mm, and a load of 250 g to break. Until the reciprocating bending cycle (cycle) was measured.
(7) 상대점도(Viscosity): 25±0.2℃ 항온환류 시스템을 이용하여 폴리아미드 수지가 함유된 용액(용매: 디메틸아세트아미드(DMAc), 고형분 10wt%)을 ASTM D 2196의 비뉴톤 물질의 회전점도계 시험방법으로 Brookfield viscometer DV-2T를 사용하고, brookfield사의 실리콘 오일(silicon oil)을 표준물질로 5000 cps 내지 200000 cps의 점도범위를 갖는 다수의 표준용액을 이용하여, spindle LV-4 (64), 0.3~100RPM으로 측정하였으며, 단위는 cps(mPa.s)단위를 사용하였다.(7) Relative viscosity (Viscosity): a solution containing a polyamide resin (solvent: dimethylacetamide (DMAc), solid content: 10 wt%) using a 25 ± 0.2 ° C. reflux system to rotate a non-Newtonian material of ASTM D 2196 Brookfield viscometer DV-2T is used as a viscometer test method, and brookfield's silicone oil is used as a standard material using a number of standard solutions having a viscosity range of 5000 cps to 200000 cps, spindle LV-4 (64) , 0.3 ~ 100RPM was measured, the unit was used as cps (mPa.s).
(8) 연필 경도: Pencil Hardness Tester를 이용하여 ASTM D3363의 측정법에 따라 폴리아미드 필름의 연필 경도를 측정하였다. 구체적으로, 상기 테스터에 다양한 경도의 연필을 고정하여 상기 폴리아미드 필름에 긁은 후, 상기 폴리아미드 필름에 흠집이 발생한 정도를 육안이나 현미경으로 관찰하여, 총 긁은 횟수의 70 % 이상 긁히지 않았을 때, 그 연필의 경도에 해당하는 값을 상기 폴리아미드 필름의 연필 경도로 평가하였다.(8) Pencil Hardness: The pencil hardness of the polyamide film was measured according to the method of ASTM D3363 using a Pencil Hardness Tester. Specifically, after fixing the pencils of various hardness to the tester and scratching the polyamide film, when the degree of scratching on the polyamide film was observed with the naked eye or a microscope, when more than 70% of the total number of scratches was not scratched, the The value corresponding to the hardness of the pencil was evaluated by the pencil hardness of the polyamide film.
상기 연필경도는 B등급, F등급, H등급 순으로 경도가 증가하게되며, 같은 등급내에서는 숫자가 커질수록 경도가 증가하게 된다. 등급내에서는 숫자가 커질수록 경도가 증가하게 된다.The hardness of the pencil increases in the order of B grade, F grade, and H grade, and within the same grade, the hardness increases as the number increases. Within the grade, the hardness increases as the number increases.
Figure PCTKR2019014714-appb-T000001
Figure PCTKR2019014714-appb-T000001
상기 표 1을 살펴보면, 상기 제조예 1 내지 2에 따른 아실클로라이드 복합체 분말을 이용하여 제조된 실시예의 폴리아미드 수지는, 463000 g/mol 내지 512000 g/mol의 높은 중량평균 분자량을 가지며, 상대점도가 110000 cps 내지 174000 cps로 높게 측정되었다. 또한, 실시예의 폴리아미드 수지로부터 얻어진 폴리아미드 필름의 경우, 대략 50 ㎛의 두께에서 2.68 내지 2.89의 낮은 황색 지수, 0.81% 내지 0.97%의 낮은 헤이즈값을 통해 우수한 투명성을 확보할 수 있음을 확인하였고, 3H 내지 4H 등급의 높은 연필 경도 및 9785 내지 12022의 왕복 굽힘 횟수(cycle)에서 파단되는 내절강도를 통해 우수한 기계적 물성(내스크래치성 및 내절강도)이 확보됨을 확인하였다.반면, 폴리아미드 수지 합성과정에서 상기 제조예 1 내지 2에 따른 아실클로라이드 복합체 분말이 전혀 사용되지 않은 비교예의 폴리아미드 수지는, 321,000 g/mol 내지 412,000 g/mol으로 실시예에 비해 분자량이 감소하였고, 점도가 18,000 cps 내지 54,000 cps로 실시예 대비 감소하였다.Looking at Table 1, the polyamide resin of the embodiment prepared using the acyl chloride composite powder according to Preparation Examples 1 to 2 has a high weight average molecular weight of 463000 g / mol to 512000 g / mol, and a relative viscosity It was measured as high as 110000 cps to 174000 cps. In addition, in the case of the polyamide film obtained from the polyamide resin of Examples, it was confirmed that excellent transparency can be secured through a low yellowness index of 2.68 to 2.89 and a haze value of 0.81% to 0.97% at a thickness of approximately 50 μm. , It was confirmed that excellent mechanical properties (scratch resistance and fracture strength) were secured through high pencil hardness of 3H to 4H grade and fracture strength broken at a reciprocating bending cycle of 9785 to 12022. In the process of resin synthesis, the polyamide resin of the comparative example in which the acyl chloride composite powders according to Preparation Examples 1 to 2 were not used at all was 321,000 g / mol to 412,000 g / mol, and the molecular weight was reduced compared to the example, and the viscosity was 18,000. It decreased from cps to 54,000 cps compared to the example.
반면, TPC 분말 및 IPC 분말을 각각 동시 또는 순차적으로 투입한 비교예1, 2, 3의 폴리아미드 수지로부터 얻어진 폴리아미드 필름의 경우, 대략 50 ㎛의 두께에서 황색 지수가 2.28 내지 25.10, 헤이즈값이 1.61% 내지 24.21%로 실시예보다 증가하여 투명성이 불량함을 확인하였다. 이는 비교예 1, 2, 3의 경우, TPC 분말과 IPC 분말간의 용해도 및 반응성 차이로 인해, TPC에 의한 블록이 과도하게 형성되어 폴리아미드 수지의 결정성이 증가됨에 따른 것으로 보인다.On the other hand, in the case of the polyamide films obtained from the polyamide resins of Comparative Examples 1, 2 and 3 in which TPC powder and IPC powder were respectively added simultaneously or sequentially, the yellow index at a thickness of approximately 50 μm is 2.28 to 25.10, and a haze value is obtained. It was confirmed that the transparency was poor by increasing from 1.61% to 24.21% than the examples. In the case of Comparative Examples 1, 2, and 3, it seems that the crystallinity of the polyamide resin increases due to the excessive formation of the block by TPC due to the difference in solubility and reactivity between the TPC powder and the IPC powder.
한편, acyl chloride를 amide계 용매 내에서 용해하여 solution으로 취급한 참고예1의 폴리아미드 수지는 321,000 g/mol의 매우 낮은 분자량을 나타내며, 점도가 18000 cps로 크게 감소하였고, 왕복 굽힘 횟수(cycle) 6351에서 파단되어 내절강도가 실시예보다 감소함을 확인하였다. 이는 참고예1에서 acyl chloride의 용해시, 수분에 의한 변질 및 amide계 용매와의 혼성이 발생했기 때문으로 보인다.On the other hand, the polyamide resin of Reference Example 1, in which acyl chloride was dissolved in an amide solvent and treated as a solution, exhibited a very low molecular weight of 321,000 g / mol, the viscosity was greatly reduced to 18000 cps, and the number of reciprocating bending cycles. It was confirmed that the fracture strength was decreased at 6351, and the internal strength was decreased compared to the example. This seems to be because, in Reference Example 1, when the acyl chloride was dissolved, water deterioration and hybridization with the amide solvent occurred.

Claims (20)

  1. 하기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 A first polyamide segment comprising a repeating unit represented by the following Chemical Formula 1, or a block consisting of it; And
    하기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트;를 포함하고,It includes a repeating unit represented by the following formula (2), or a second polyamide segment comprising a block consisting of;
    상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 하기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성하는, 폴리아미드 수지:The first polyamide segment and the second polyamide segment form a main chain including a cross-repeating unit represented by Chemical Formula 3 below:
    [화학식1][Formula 1]
    Figure PCTKR2019014714-appb-I000022
    Figure PCTKR2019014714-appb-I000022
    [화학식2][Formula 2]
    Figure PCTKR2019014714-appb-I000023
    Figure PCTKR2019014714-appb-I000023
    [화학식3][Formula 3]
    Figure PCTKR2019014714-appb-I000024
    Figure PCTKR2019014714-appb-I000024
    상기 화학식1 내지 2 에서, In Chemical Formulas 1 to 2,
    Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이고,Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms,
    상기 화학식3에서,In Chemical Formula 3,
    A는 상기 제1폴리아미드 세그먼트이고, A is the first polyamide segment,
    B는 상기 제2폴리아미드 세그먼트이다.B is the second polyamide segment.
  2. 제1항에 있어서,According to claim 1,
    ASTM D1003에 의해 측정한 헤이즈가 3.0 % 이하인, 폴리아미드 수지.A polyamide resin having a haze of 3.0% or less as measured by ASTM D1003.
  3. 제1항에 있어서,According to claim 1,
    상기 폴리아미드 수지의 중량평균 분자량이 330000 g/mol 이상인, 폴리아미드 수지.The polyamide resin having a weight average molecular weight of 330000 g / mol or more of the polyamide resin.
  4. 제1항에 있어서,According to claim 1,
    상기 폴리아미드 수지의 상대점도가 45000 cps 이상인, 폴리아미드 수지.The polyamide resin having a relative viscosity of 45000 cps or higher.
  5. 제1항에 있어서,According to claim 1,
    상기 폴리아미드 수지에 함유된 모든 반복단위를 기준으로, 상기 화학식2로 표시되는 반복단위의 함량이 5 몰% 내지 60 몰%인, 폴리아미드 수지.Based on all the repeating units contained in the polyamide resin, the content of the repeating unit represented by Formula 2 is 5 mol% to 60 mol%, polyamide resin.
  6. 제1항에 있어서,According to claim 1,
    상기 폴리아미드 수지에 함유된 모든 반복단위를 기준으로, 상기 화학식1로 표시되는 반복단위의 함량이 60 몰% 내지 90 몰%이고, 상기 화학식2로 표시되는 반복단위의 함량이 5 몰% 내지 40 몰%인, 폴리아미드 수지.Based on all the repeating units contained in the polyamide resin, the content of repeating units represented by Formula 1 is 60 mol% to 90 mol%, and the content of repeating units represented by Formula 2 is 5 mol% to 40 Molar%, polyamide resin.
  7. 제1항에 있어서,According to claim 1,
    상기 제1 폴리아미드 세그먼트의 수평균 분자량이 100 g/mol 이상 5000 g/mol 이하인, 폴리아미드 수지.The polyamide resin having a number average molecular weight of 100 g / mol or more and 5000 g / mol or less of the first polyamide segment.
  8. 제1항에 있어서,According to claim 1,
    상기 화학식2로 표시되는 반복단위는, The repeating unit represented by Formula 2,
    하기 화학식2-1로 표시되는 반복단위; 또는 하기 화학식2-2로 표시되는 반복단위 중 1종의 반복단위를 포함하는, 폴리아미드 수지:A repeating unit represented by the following Chemical Formula 2-1; Or a polyamide resin comprising one repeating unit among repeating units represented by the following Chemical Formula 2-2:
    [화학식2-1][Formula 2-1]
    Figure PCTKR2019014714-appb-I000025
    Figure PCTKR2019014714-appb-I000025
    [화학식2-2][Formula 2-2]
    Figure PCTKR2019014714-appb-I000026
    Figure PCTKR2019014714-appb-I000026
    상기 화학식2-1 내지 2-2에서,In Chemical Formulas 2-1 to 2-2,
    Ar2는 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이다.Ar 2 is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.
  9. 제1항에 있어서,According to claim 1,
    상기 화학식 3으로 표시되는 교차반복단위는 하기 화학식4로 표시되는 반복단위인, 폴리아미드 수지:The cross-repeating unit represented by Chemical Formula 3 is a repeating unit represented by Chemical Formula 4, a polyamide resin:
    [화학식4][Formula 4]
    Figure PCTKR2019014714-appb-I000027
    Figure PCTKR2019014714-appb-I000027
    화학식4 에서, In Formula 4,
    Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이고,Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms,
    a1 및 a2는 각각 독립적으로 1 내지 10의 정수이고, a1 and a2 are each independently an integer of 1 to 10,
    b1 및 b2는 각각 독립적으로 1 내지 5의 정수이다.b1 and b2 are each independently an integer of 1 to 5.
  10. 제1항에 있어서,According to claim 1,
    상기 화학식1로 표시되는 반복단위는 1,4-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복단위인, 폴리아미드 수지.The repeating unit represented by Chemical Formula 1 is an amide repeating unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound, a polyamide resin.
  11. 제10항에 있어서, The method of claim 10,
    상기 1,4-방향족 디아실 화합물은 테레프탈로일 클로라이드, 또는 테레프탈산을 포함하며,The 1,4-aromatic diacyl compound includes terephthaloyl chloride, or terephthalic acid,
    상기 방향족 디아민 화합물은 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민을 포함하는, 폴리아미드 수지.The aromatic diamine compound comprises 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, polyamide resin.
  12. 제1항에 있어서,According to claim 1,
    상기 화학식2로 표시되는 반복단위는 1,2-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복 단위; 또는 1,3-방향족 디아실 화합물과 방향족 디아민 화합물의 결합물로부터 유래된 아미드 반복 단위를 포함하는, 폴리아미드 수지.The repeating unit represented by Formula 2 includes an amide repeating unit derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound; Or an amide repeating unit derived from a combination of a 1,3-aromatic diacyl compound and an aromatic diamine compound.
  13. 제12항에 있어서, The method of claim 12,
    상기 1,2-방향족 디아실 화합물은 프탈로일 클로라이드, 또는 프탈산을 포함하며,The 1,2-aromatic diacyl compound includes phthaloyl chloride, or phthalic acid,
    상기 1,3-방향족 디아실 화합물은 이소프탈로일 클로라이드 또는 이소프탈산을 포함하고,The 1,3-aromatic diacyl compound comprises isophthaloyl chloride or isophthalic acid,
    상기 방향족 디아민 화합물은 2,2'-비스(트리플루오로메틸)-4,4'-비페닐디아민을 포함하는, 폴리아미드 수지.The aromatic diamine compound comprises 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, polyamide resin.
  14. 하기 화학식7로 표시되는 화합물 및 하기 화학식8로 표시되는 화합물을 용융혼련시키고, 상기 용융혼련물을 응고시켜 복합체를 형성하는 단계; 및Melting and kneading the compound represented by the following formula (7) and the compound represented by the following formula (8), and solidifying the melt-kneaded product to form a complex; And
    상기 복합체를 방향족 디아민 단량체와 반응시키는 단계;를 포함하는, 폴리아미드 수지의 제조방법:Reacting the complex with an aromatic diamine monomer; including, polyamide resin production method:
    [화학식7][Formula 7]
    Figure PCTKR2019014714-appb-I000028
    Figure PCTKR2019014714-appb-I000028
    [화학식8][Formula 8]
    Figure PCTKR2019014714-appb-I000029
    Figure PCTKR2019014714-appb-I000029
    상기 화학식7 내지 8 에서, In the above formulas 7 to 8,
    X는 할로겐, 또는 수산화기이다.X is halogen or a hydroxyl group.
  15. 제14항에 있어서,The method of claim 14,
    상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 용융혼련시키고, 상기 용융혼련물을 응고시켜 복합체를 형성하는 단계는,The step of melt-kneading the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8, and solidifying the melt-kneaded product to form a complex,
    상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 50 ℃이상의 온도에서 혼합시키는 단계; 및Mixing the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8 at a temperature of 50 ° C. or higher; And
    상기 혼합단계의 결과물을 냉각시키는 단계;를 포함하는, 폴리아미드 수지의 제조방법.Cooling the result of the mixing step; comprising, a method for producing a polyamide resin.
  16. 제14항에 있어서,The method of claim 14,
    상기 화학식7로 표시되는 화합물 및 상기 화학식8로 표시되는 화합물을 용융혼련시키고, 상기 용융혼련물을 응고시켜 복합체를 형성하는 단계에서,In the step of melt-kneading the compound represented by the formula (7) and the compound represented by the formula (8), and solidifying the melt-kneaded material to form a complex,
    상기 화학식7로 표시되는 화합물 100 중량부에 대하여, 상기 화학식8로 표시되는 화합물이 5 중량부 내지 60 중량부로 혼합되는, 폴리아미드 수지의 제조방법.Method for producing a polyamide resin, the compound represented by the formula (8) is mixed with 5 parts by weight to 60 parts by weight with respect to 100 parts by weight of the compound represented by the formula (7).
  17. 제14항에 있어서, The method of claim 14,
    상기 복합체를 방향족 디아민 단량체와 반응시키는 단계는, Reacting the complex with an aromatic diamine monomer,
    상기 방향족 디아민 단량체를 유기 용매에 용해시켜 디아민 용액을 제조하는 단계; 및 상기 디아민 용액에 복합체 분말을 첨가하는 단계;를 포함하는, 폴리아미드 수지의 제조방법.Preparing a diamine solution by dissolving the aromatic diamine monomer in an organic solvent; And adding a composite powder to the diamine solution.
  18. 하기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 하기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트;를 포함하고, 상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 하기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성하는 폴리아미드 수지를 포함하는, 폴리아미드 필름:A first polyamide segment comprising a repeating unit represented by the following Chemical Formula 1, or a block consisting of it; And a repeating unit represented by the following Chemical Formula 2, or a second polyamide segment comprising a block consisting of the first polyamide segment and the second polyamide segment comprising a cross-repeating unit represented by the following Chemical Formula 3 A polyamide film comprising a polyamide resin forming a backbone:
    [화학식1][Formula 1]
    Figure PCTKR2019014714-appb-I000030
    Figure PCTKR2019014714-appb-I000030
    [화학식2][Formula 2]
    Figure PCTKR2019014714-appb-I000031
    Figure PCTKR2019014714-appb-I000031
    [화학식3][Formula 3]
    Figure PCTKR2019014714-appb-I000032
    Figure PCTKR2019014714-appb-I000032
    상기 화학식1 내지 2 에서, In Chemical Formulas 1 to 2,
    Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이고,Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms,
    상기 화학식3에서,In Chemical Formula 3,
    A는 상기 제1폴리아미드 세그먼트이고, A is the first polyamide segment,
    B는 상기 제2폴리아미드 세그먼트이다.B is the second polyamide segment.
  19. 제18항에 있어서, The method of claim 18,
    45 ㎛ 이상 55 ㎛ 이하의 두께를 갖는 시편에 대해, ASTM D1003에 의해 측정한 헤이즈가 3.0 % 이하인, 폴리아미드 필름.For a specimen having a thickness of 45 µm or more and 55 µm or less, a polyamide film having a haze measured by ASTM D1003 of 3.0% or less.
  20. 하기 화학식1로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제1폴리아미드 세그먼트; 및 하기 화학식2로 표시되는 반복단위, 또는 이로 이루어진 블록을 포함한 제2폴리아미드 세그먼트;를 포함하고, 상기 제1폴리아미드 세그먼트 및 제2폴리아미드 세그먼트는 하기 화학식 3으로 표시되는 교차반복단위를 포함한 주쇄를 형성하는 폴리아미드 수지를 포함한 기재; 및 상기 기재의 적어도 일면에 형성되는 하드 코팅층;을 포함하는, 수지 적층체:A first polyamide segment comprising a repeating unit represented by the following Chemical Formula 1, or a block consisting of it; And a repeating unit represented by the following Chemical Formula 2, or a second polyamide segment comprising a block consisting of the first polyamide segment and the second polyamide segment comprising a cross-repeating unit represented by the following Chemical Formula 3 A base material comprising a polyamide resin forming a main chain; And a hard coating layer formed on at least one surface of the substrate; including, a resin laminate:
    [화학식1][Formula 1]
    Figure PCTKR2019014714-appb-I000033
    Figure PCTKR2019014714-appb-I000033
    [화학식2][Formula 2]
    Figure PCTKR2019014714-appb-I000034
    Figure PCTKR2019014714-appb-I000034
    [화학식3][Formula 3]
    Figure PCTKR2019014714-appb-I000035
    Figure PCTKR2019014714-appb-I000035
    상기 화학식1 내지 2 에서, In Chemical Formulas 1 to 2,
    Ar1 및 Ar2는 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 20의 아릴렌기, 또는 치환 또는 비치환된 탄소수 2 내지 20의 헤테로아릴렌기이고,Ar 1 and Ar 2 are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms,
    상기 화학식3에서,In Chemical Formula 3,
    A는 상기 제1폴리아미드 세그먼트이고, A is the first polyamide segment,
    B는 상기 제2폴리아미드 세그먼트이다.B is the second polyamide segment.
PCT/KR2019/014714 2018-11-05 2019-11-01 Polyamide resin, method for producing same, and polyamide film and resin laminate comprising same WO2020096283A1 (en)

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JP2020566280A JP7074280B2 (en) 2018-11-05 2019-11-01 Polyamide resin, its manufacturing method, and polyamide film and resin laminate containing it.
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