CN112126090B - Polyamide-imide film and method for producing the same - Google Patents
Polyamide-imide film and method for producing the same Download PDFInfo
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- CN112126090B CN112126090B CN201910556002.1A CN201910556002A CN112126090B CN 112126090 B CN112126090 B CN 112126090B CN 201910556002 A CN201910556002 A CN 201910556002A CN 112126090 B CN112126090 B CN 112126090B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The present invention provides a polyamide-imide film and a method for producing the same, the polyamide-imide film comprising: polyamide-imide polymers formed by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound; and silica particles having an average diameter of less than 0.5 aggregates/μm as observed in a cross section of the polyamide-imide film cut in the thickness direction of 150nm to 200nm 2 。
Description
Technical Field
Examples relate to polyamide-imide films having excellent optical properties and improved modulus, tensile strength and elongation, and methods of preparing the same.
Background
Polyamide-imide (PAI) is excellent in resistance to friction, heat and chemicals, and thus is applied to a first electric insulator, a coating agent, a binder, a resin for extrusion, a heat-resistant paint, a heat-resistant plate, a heat-resistant binder, heat-resistant fibers and a heat-resistant film.
Polyamide-imides are used in a variety of fields. For example, polyamide-imide is used as a powder for a coating agent such as a metal or a magnetic wire, and is mixed with other additives according to the application. Also, polyamide-imide is used as a coating for decoration and corrosion protection together with the fluoropolymer, and functions to adhere the fluoropolymer to a metal substrate. Also, polyamide-imide is also used in the coating of kitchen tools, and is also used as a membrane for gas separation due to its heat and chemical resistance characteristics, and also as a device for filtering contaminants such as carbon dioxide, hydrogen sulfide, and impurities in natural gas wells.
Recently, polyamide-imide films which are cheaper and excellent in optical, mechanical and thermal properties have been developed by film-forming polyamide-imides.
Disclosure of Invention
The object of the present invention is to provide a polyamide-imide film having excellent optical properties and improved modulus, tensile strength and elongation, and a method for producing the same. Examples provide a polyamide-imide film comprising: polyamide-imide polymers formed by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound; and silica particles having an average diameter of less than 0.5 aggregates/μm as observed in a cross section of the polyamide-imide film cut in the thickness direction of 150nm to 200nm 2 . Also, examples provide a polyamide-imide film production method comprising: a step of preparing a silica dispersion liquid in which silica particles are dispersed; a step of adding the silica dispersion liquid to an organic solvent; a step of preparing a polyamide-imide polymer solution by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent charged into the silica dispersion; a step of charging the polymer solution into a tank; a step of preparing a gel sheet by drying after extruding and casting the polymer solution in the tank; and a step of heat-treating the gel sheet.
The polyamide-imide film of the example has mechanical properties with improved modulus, tensile strength and elongation, while also being excellent in optical properties. In the example method for producing a polyamide-imide film, a film having improved mechanical properties, being colorless and transparent, and having excellent optical properties can be provided.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph (5000 x) of a cross section of the film obtained in example 1 cut in the thickness direction.
Fig. 2 is a scanning electron micrograph (10000 times) of a cross section of the film obtained in example 1 cut in the thickness direction.
Fig. 3 is a scanning electron micrograph (50000 times) of a cross section of the film obtained in example 1 cut in the thickness direction.
Fig. 4 is a scanning electron micrograph (5000 times) of a cross section of the film obtained in comparative example 2 cut in the thickness direction.
Fig. 5 is a scanning electron micrograph (10000 times) of a cross section of the film obtained in comparative example 2 cut in the thickness direction.
Fig. 6 is a scanning electron micrograph (50000 times) of a cross section of the film obtained in comparative example 2 cut in the thickness direction.
Detailed Description
The present invention will be described in more detail below. The examples may be modified into various forms without changing the gist of the present invention.
In this specification, unless otherwise indicated, "comprising" may mean that other structural elements are also included.
Also, it is to be understood that all numbers and expressions indicating amounts of structural elements, reaction conditions, etc. set forth in the specification are modified in all cases by "about" unless otherwise indicated.
And, unless otherwise indicated, "substituted" in the present specification means substituted with one or more substituents selected from the group consisting of deuterium, -F, -Cl, -Br, -I, hydroxy, cyano, nitro, amino, amidino, hydrazino, hydrazone, ester, keto, carboxyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, and the above-listed substituents may form a ring by being linked to each other.
In the present specification, the terms first, second, etc. are used to describe various structural elements, and the above structural elements are not limited to the above terms. The above terms are used only for the purpose of distinguishing one structural element from another.
Polyamide-imide film
The example provides a polyamide-imide film which has excellent optical properties and improved mechanical properties such as modulus, tensile strength and elongation.
An example polyamide-imide film comprises: polyamide-imide polymers formed by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound; and silica particles.
The polyamide-imide polymer includes imide repeating units derived from polymerization of the diamine compound and the dianhydride compound, and amide repeating units derived from polymerization of the diamine compound and the dicarbonyl compound.
The above polyamide-imide polymer may contain a repeating unit represented by the following chemical formula a and a repeating unit represented by the following chemical formula B:
chemical formula a:
chemical formula B:
in the above chemical formula a and chemical formula B,
e and J are independently selected from substituted or unsubstituted divalent C 6 -C 30 Aliphatic cyclic group, substituted or unsubstituted divalent C 4 -C 30 Aliphatic heterocyclic group, substituted or unsubstituted divalent C 6 -C 30 Aromatic ring group, substituted or unsubstituted divalent C 4 -C 30 Aromatic heterocyclic group, substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 2 -C 30 Alkenylene, substituted or unsubstituted C 2 -C 30 Alkynylene, -O-, -S-, -C (=o) -, -CH (OH) -, -S (=o) 2 -、-Si(CH 3 ) 2 -、-C(CH 3 ) 2 -and-C (CF) 3 ) 2 In the process, the step of obtaining the product,
e and j are independently selected from integers from 1 to 5,
when E is 2 or more, E of 2 or more is the same or different,
when J is 2 or more, J of 2 or more is the same or different,
g is a substituted or unsubstituted tetravalent C 6 -C 30 Aliphatic cyclic group, substituted or unsubstituted tetravalent C 4 -C 30 Aliphatic heterocyclic group, substituted or unsubstituted tetravalent C 6 -C 30 Aromatic ring group, substituted or unsubstituted tetravalent C 4 -C 30 An aromatic heterocyclic group, wherein the aliphatic heterocyclic group, the aromatic heterocyclic group or the aromatic heterocyclic group are present alone or bonded to each other to form a condensed ring, or are bonded to each other through a member selected from the group consisting of substituted and unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 2 -C 30 Alkenylene, substituted or unsubstituted C 2 -C 30 Alkynylene, -O-, -S-, -C (=o) -, -CH (OH) -, -S (=o) 2 -、-Si(CH 3 ) 2 -、-C(CH 3 ) 2 -and-C (CF) 3 ) 2 -a linker in (a) to be linked.
In the above polyamide-imide polymer, the molar ratio of imide repeating units to amide repeating units may be 10:90 to 25:75, but is not limited thereto. Specifically, the molar ratio of the imide repeating unit to the amide repeating unit may be 15:85 to 25:75 or 20:80 to 25:75, but is not limited thereto.
When the molar ratio of the imide repeating unit to the amide repeating unit is in the above range, the polyamide-imide film is excellent in optical properties such as permeability and haze and mechanical properties.
In the polyamide-imide polymer, the molar ratio of the repeating unit represented by the above chemical formula a to the repeating unit represented by the above chemical formula B may be 10:90 to 25:75, but is not limited thereto. Specifically, the molar ratio of the repeating unit represented by the above chemical formula a to the repeating unit represented by the above chemical formula B may be 15:85 to 25:75 or 20:80 to 25:75, but is not limited thereto.
The diamine compound is a compound which is imide-bonded to the dianhydride compound and amide-bonded to the dicarbonyl compound to form a copolymer.
The diamine compound is a compound represented by the following chemical formula 1.
Chemical formula 1: h 2 N-(E) e -NH 2
In the above-mentioned chemical formula 1,
e may be selected from substituted or unsubstituted divalent C 6 -C 30 Aliphatic cyclic group, substituted or unsubstituted divalent C 4 -C 30 Aliphatic heterocyclic group, substituted or unsubstituted divalent C 6 -C 30 Aromatic ring group, substituted or unsubstituted divalent C 4 -C 30 Aromatic heterocyclic group, substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 2 -C 30 Alkenylene, substituted or unsubstituted C 2 -C 30 Alkynylene, -O-, -S-, -C (=o) -, -CH (OH) -, -S (=o) 2 -、-Si(CH 3 ) 2 -、-C(CH 3 ) 2 -and-C (CF) 3 ) 2 -a medium.
E is an integer selected from 1 to 5, and in the case where E is 2 or more, E may be the same or different.
In the above chemical formula 1, (E) e May be selected from the group represented by the following chemical formulas 1-1a to 1-14 a:
more specifically, in the above chemical formula 1, (E) e May be a group represented by the above chemical formulas 1 to 6 b.
The diamine compound may be an aromatic diamine compound.
The diamine compound may contain a compound having a fluorine-containing substituent. Or the diamine compound may be composed of a compound having a fluorine-containing substituent. In this case, the fluorine-containing substituent may be a fluorinated hydrocarbon group, specifically, a trifluoromethyl group, but is not limited thereto.
For example, the diamine compound may include 2,2'-bis (trifluoromethyl) -4,4' -diaminobiphenyl (2, 2'-Bis (trifluoromethyl) -4,4' -diaminophenyl, TFDB) having the following structure, but is not limited thereto.
Since the dianhydride compound has a low birefringence value, it contributes to the optical properties such as the permeability of the polyamide-imide film.
The dianhydride compound is a compound represented by the following chemical formula 2.
Chemical formula 2:
in the above-mentioned chemical formula 2,
g is a substituted or unsubstituted tetravalent C 6 -C 30 Aliphatic cyclic group, substituted or unsubstituted tetravalent C 4 -C 30 Aliphatic heterocyclic group, substituted or unsubstituted tetravalent C 6 -C 30 Aromatic ring group, substituted or unsubstituted tetravalent C 4 -C 30 An aromatic heterocyclic group, wherein the aliphatic heterocyclic group, the aromatic heterocyclic group or the aromatic heterocyclic group are present alone or bonded to each other to form a condensed ring, or are selected from substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 2 -C 30 Alkenylene, substituted or unsubstituted C 2 -C 30 Alkynylene, -O-, -S-, -C (=o) -, -CH (OH) -, -S (=o) 2 -、-Si(CH 3 ) 2 -、-C(CH 3 ) 2 -and-C (CF) 3 ) 2 -a linker in (a) to be linked.
In the above chemical formula 2, G may be selected from the group represented by the following chemical formulas 2-1a to 2-9a, but is not limited thereto:
for example, in the above chemical formula 2, G may be a group represented by the above chemical formulas 2 to 8 a.
The dianhydride compound may be an aromatic dianhydride compound.
The dianhydride compound may contain a compound having a fluorine-containing substituent. Alternatively, the dianhydride compound may be composed of a compound having a fluorine-containing substituent. In this case, the fluorine-containing substituent may be a fluorinated hydrocarbon group, specifically a trifluoromethyl group, but is not limited thereto.
For example, the dianhydride compound may include 2,2'-Bis (3, 4-Dicarboxyphenyl) hexafluoropropane dianhydride (2, 2' -Bis- (3, 4-Dicarboxyphenyl) hexafluoropropane dianhydride, 6-FDA) having the following structure, but is not limited thereto.
The polyamic acid can be produced by polymerizing the diamine compound and the dianhydride compound.
The polyamic acid can then be converted to a polyimide by a dehydration reaction, the polyimide comprising imide repeating units.
The polyimide may form a repeating unit represented by the following chemical formula a.
Chemical formula a:
in the above chemical formula a, descriptions of E, G and e are as described above.
For example, the polyimide may include a repeating unit represented by the following chemical formula a-1, but is not limited thereto.
Chemical formula A-1:
n of the above chemical formula A-1 is an integer of 1 to 400.
The dicarbonyl compound is a compound represented by the following chemical formula 3.
Chemical formula 3:
in the above-mentioned chemical formula 3, a compound represented by formula 1,
j may be selected from substituted or unsubstituted divalent C 6 -C 30 Aliphatic cyclic group, substituted or unsubstituted divalent C 4 -C 30 Aliphatic heterocyclic group, substituted or unsubstituted divalent C 6 -C 30 Aromatic ring group, substituted or unsubstituted divalent C 4 -C 30 Aromatic heterocyclic group, substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 2 -C 30 Alkenylene, substituted or unsubstituted C 2 -C 30 Alkynylene, -O-, -S-, -C (=o) -, -CH (OH) -, -S (=o) 2 -、-Si(CH 3 ) 2 -、-C(CH 3 ) 2 -and-C (CF) 3 ) 2 -a medium.
J is an integer selected from 1 to 5, and J may be the same or different when J is 2 or more.
X is a halogen atom. Specifically, X may be F, cl, br, I or the like. More specifically, X may be Cl, but is not limited thereto.
In the above chemical formula 3, (J) j May be selected from the group represented by the following chemical formulas 3-1a to 3-14a, but is not limited thereto:
specifically, in the above chemical formula 3, (J) j May be selected from the group represented by the following chemical formulas 3-1b to 3-8b, but is not limited thereto:
more specifically, in the above chemical formula 3, (J) j It may be a group represented by the above chemical formula 3-2b or a group represented by 3-3 b.
The dicarbonyl compound may include at least two dicarbonyl compounds different from each other. The dicarbonyl compound may be composed of two dicarbonyl compounds different from each other.
The dicarbonyl compound may be an aromatic dicarbonyl compound.
For example, the dicarbonyl compound may comprise a 1 st dicarbonyl compound and/or a 2 nd dicarbonyl compound.
The 1 st dicarbonyl compound and the 2 nd dicarbonyl compound may be an aromatic dicarbonyl compound (aromatic dicarbonyl compound).
The 1 st dicarbonyl compound and the 2 nd dicarbonyl compound may be different compounds from each other.
For example, the 1 st dicarbonyl compound and the 2 nd dicarbonyl compound may be different aromatic dicarbonyl compounds, but are not limited thereto.
In the case where the 1 st dicarbonyl compound and the 2 nd dicarbonyl compound are aromatic dicarbonyl compounds, respectively, a benzene ring is contained, and thus it is possible to contribute to improvement of mechanical properties such as surface hardness and tensile strength of the produced polyamide-imide film.
The dicarbonyl compound may include terephthaloyl chloride (terephthaloyl chloride, TPC), 1'-biphenyl-4,4' -diacetyl chloride (1, 1'-biphenyl-4,4' -dicarbonyl dichloride, BPDC), or a combination thereof, but is not limited thereto.
For example, the 1 st dicarbonyl compound may include 1,1'-biphenyl-4,4' -diacetyl chloride, and the 2 nd dicarbonyl compound may include terephthaloyl chloride, but is not limited thereto.
Specifically, in the case of using 1,1'-biphenyl-4,4' -diacetyl chloride as the above-mentioned 1 st dicarbonyl compound and terephthaloyl chloride as the above-mentioned 2 nd dicarbonyl compound in proper combination, the polyamide-imide film produced may have oxidation resistance.
The repeating unit represented by the following chemical formula B can be formed by polymerizing the diamine compound and the dicarbonyl compound.
Chemical formula B:
in the above chemical formula B, descriptions of E, J, e and j are as described above.
For example, the amide repeating units represented by the chemical formulas B-1 and B-2 can be formed by polymerizing the diamine compound and the dicarbonyl compound.
Chemical formula B-1:
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x of the above formula B-1 is an integer of 1 to 400.
Chemical formula B-2:
y of the above chemical formula B-2 is an integer of 1 to 400.
The polyamide-imide film according to another example includes a polyamide-imide polymer formed by polymerizing an aromatic diamine compound including one diamine compound, an aromatic dianhydride compound including one aromatic dianhydride compound, and a dicarbonyl compound, which may include two dicarbonyl compounds.
Alternatively, the aromatic diamine compound may be composed of one diamine compound, the aromatic dianhydride compound may be composed of one aromatic dianhydride compound, and the dicarbonyl compound may be composed of two dicarbonyl compounds.
For example, the diamine compound may include 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, the dianhydride compound may include 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, and the dicarbonyl compound may include terephthaloyl chloride, 1' -biphenyl-4, 4' -diacetyl chloride, or a combination thereof, but is not limited thereto.
Alternatively, the diamine compound may be composed of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, the dianhydride compound may be composed of 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, and the dicarbonyl compound may be composed of terephthaloyl chloride and 1,1' -biphenyl-4, 4' -diacetyl chloride, but is not limited thereto.
An example is characterized in that a polyamide-imide film having uniformly improved optical characteristics, mechanical properties and flexibility can be obtained by appropriately adjusting the contents of the imide repeating units and the amide repeating units, without requiring a complicated process.
In addition, as in the prior art, a polyamide-imide film having improved optical properties, mechanical properties and flexibility can be obtained without the steps of precipitation, filtration, drying, redissolution, and the like.
The content of each of the imide repeating unit and the amide repeating unit can be adjusted by the amounts of the aromatic dianhydride compound and the dicarbonyl compound added.
The polyamide-imide film contains a polyamide-imide polymer and silica particles.
The first particles of the silica particles have an average particle diameter of 10nm to 40nm. Specifically, the first particle average particle diameter of the above-mentioned silica particles may be 15nm to 40nm, 15nm to 35nm, 20 to 40nm, 20 to 35nm or 25 to 35nm, but is not limited thereto.
The second particles of the above silica particles have an average particle diameter of 30nm to 80nm. Specifically, the second particle average particle diameter of the above silica particles may be 30nm to 75nm, 30 to 70nm, 35 to 75nm, 40 to 70nm, 40 to 65nm, 45 to 65nm, or 40 to 60nm, but is not limited thereto.
The first particles are particles of the smallest unit of aggregated silica particles, and the second particles are particles of a plurality of first particles aggregated and shown as one particle.
The ratio of the average particle diameter of the second particles to the average particle diameter of the first particles of the silica particles is 1.2 to 3.0. Specifically, the ratio of the average particle diameter of the second particles to the average particle diameter of the first particles of the above silica particles may be 1.2 to 2.5, 1.2 to 2.2, 1.2 to 2.0, 1.4 to 2.0, but is not limited thereto.
When the ratio of the average particle diameter of the second particles to the average particle diameter of the first particles of the silica particles is in the above range, dispersibility is further ensured, and the silica particles can be uniformly located in the base material.
The content of the silica particles is 50ppm to 600ppm based on the total weight of the polyamide-imide polymer. Specifically, the content of the silica particles may be 50ppm to 500ppm, 50ppm to 450ppm, 100ppm to 450ppm, 150ppm to 450ppm, 200ppm to 400ppm, or 230ppm to 350ppm based on the total weight of the polyamide-imide polymer, but is not limited thereto.
The average diameter of 150nm to 200nm observed in a cross section of a polyamide-imide film of one example cut in the thickness direction is less than 0.5 per mu m 2 . Specifically, 0 aggregates/μm having an average diameter of 150nm to 200nm as observed in a section of the above polyamide-imide film cut in the thickness direction 2 Up to 0.4/μm 2 0/μm 2 Up to 0.3/μm 2 0/μm 2 Up to 0.2/μm 2 0/μm 2 Up to 0.15 pieces/μm 2 0/μm 2 To 0.1/μm 2 Or 0/μm 2 To 0.05 pieces/μm 2 However, the present invention is not limited thereto.
The cross section of the film cut in the thickness direction may be a cross section of the film cut perpendicular to the thickness direction.
The agglomerates are blocks containing silica particles, and occur when the silica particles are unevenly dispersed.
Aggregates having an average diameter of 150nm to 200nm observed in a section of the polyamide-imide film cut in the thickness direction have 0.5 units/μm 2 In the above case, the aggregate containing the silica particles mayActs as a foreign matter to deteriorate mechanical properties and optical characteristics.
The average diameter refers to a diameter that is equivalent to an average circle when the aggregate is not a true circle. The diameter corresponding to a circle means a diameter of a circle when the shape of the observed aggregate is assumed to be a circle having the same projected area as that of the aggregate.
The polyamide-imide film satisfies the following condition of formula 1:
general formula 1: X/Y is more than or equal to 4 and less than or equal to 12
X: when the film was perforated at a speed of 10mm/min using a spherical tip of 2.5mm in UTM compression mode, the maximum perforation diameter (mm) including cracks was obtained
Y: modulus of the film (GPa)
The maximum diameter (X) of the perforations of the polyamide-imide film is 60mm or less on the basis of 50 μm. Specifically, the maximum diameter of the perforation may be 5mm to 60mm, 10mm to 60mm, 15mm to 60mm, 20mm to 60mm, 25mm to 60mm, or 25mm to 58mm, but is not limited thereto.
The compressive strength of the polyamide-imide film was 0.4 kgf/. Mu.m based on a thickness of 50. Mu.m. Specifically, the compressive strength may be 0.45kgf/μm or more or 0.46kgf/μm or more, but is not limited thereto.
The polyamide-imide film has a surface hardness of HB or more. Specifically, the surface hardness may be H or more or 2H or more, but is not limited thereto.
The polyamide-imide film has a light transmittance of 85% or more, measured at 550nm, based on a thickness of 50 μm. Specifically, the light transmittance may be 86% or more, 87% or more, 88.5% or more, or 88.8% or more, but is not limited thereto.
The polyamide-imide film has a light transmittance of 60% or more, measured at 388nm, based on a thickness of 50 μm. Specifically, the light transmittance measured at 388nm may be 62% or more, 63% or more, 63.3% or more, or 63.4% or more based on a thickness of 50 μm, but is not limited thereto.
The polyamide-imide film has a haze of 2% or less based on a thickness of 50 μm. Specifically, the haze may be 1.8% or less, 1.5% or less, 1.2% or less, 1.0% or less, 0.9% or less, 0.8% or less, or 0.7% or less, but is not limited thereto.
The polyamide-imide film has a yellowness of 5 or less based on a thickness of 50 μm. Specifically, the yellowness may be 3 or less, 2.8 or less, 2.7 or less, 2.5 or less, or 2.3 or less, but is not limited thereto.
The polyamide-imide film has a modulus of 5.0GPa or more based on a thickness of 50 μm. Specifically, the modulus may be 5.5GPa or more, 5.8GPa or more, 6.0GPa or more, 6.2GPa or more, or 6.4GPa or more, but is not limited thereto.
The polyamide-imide film had a tensile strength of 15kgf/mm based on a thickness of 50. Mu.m 2 The above. Specifically, the tensile strength may be 18kgf/mm 2 Above, 20kgf/mm 2 Above, 21kgf/mm 2 Above, 22kgf/mm 2 Above, 23kgf/mm 2 Above or 24kgf/mm 2 The above is not limited thereto.
The polyamide-imide film has a degree of elongation of 15% or more based on a thickness of 50. Mu.m. Specifically, the elongation may be 16% or more, 18% or more, 20% or more, or 21% or more, but is not limited thereto.
The various characteristics of the polyamide-imide film may be combined.
For example, the polyamide-imide film may have a modulus of 5.0GPa or more, an elongation of 15% or more, and a tensile strength of 15kgf/mm based on 50. Mu.m 2 As described above, the haze may be 2% or less, but is not limited thereto.
Preparation method of polyamide-imide film
Examples provide a method for producing a polyamide-imide film having excellent optical properties, in particular, improved modulus, tensile strength and elongation.
An example method for preparing a polyamide-imide film includes: a step of preparing a silica dispersion liquid in which silica particles are dispersed; a step of adding the silica dispersion liquid to an organic solvent; a step of preparing a polyamide-imide polymer solution by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent into which the silica dispersion is put; a step of charging the above polymer solution into a tank; a step of preparing a gel sheet by drying after extruding and casting the polymer solution in the tank; and a step of heat-treating the gel sheet. At this time, the viscosity of the above polymer solution may be 10 to 30 tens of thousands of cps.
In this case, the diamine compound, dianhydride compound, dicarbonyl compound, polyamide-imide polymer and silica particles are described above.
In an example method for producing a polyamide-imide film, first, a silica dispersion in which silica particles are dispersed is prepared.
In the step of preparing the silica dispersion liquid in which the silica particles are dispersed, the silica dispersion liquid is prepared by adding the silica particles to an organic solvent and then ultrasonic waves. In this case, the ultrasonic treatment is performed by performing ultrasonic treatment in a water tank for 5 to 30 minutes.
The content of silica particles in the above silica dispersion is 0.2 to 5 weight percent. Specifically, the content of the silica particles in the silica dispersion liquid may be 0.2 to 3 weight percent, 0.5 to 2 weight percent, 0.5 to 1.5 weight percent, or 1 weight percent, but is not limited thereto.
Next, the silica dispersion prepared as described above is poured into an organic solvent. At this time, the silica dispersion is charged under the condition that the content of silica particles is 50ppm to 600ppm based on the total weight of the polyamide-imide polymer. Specifically, the content of the silica particles may be 50ppm to 500ppm, 50ppm to 450ppm, 100ppm to 450ppm, 150ppm to 450ppm, 200ppm to 400ppm, or 230ppm to 350ppm based on the total weight of the polyamide-imide polymer, but is not limited thereto.
After the silica dispersion prepared as described above is put into an organic solvent, the silica particles can be uniformly dispersed in the organic solvent by stirring for about 30 minutes to 2 hours.
As shown in the above method, when the silica dispersion is charged before the polymerization reaction, the silica particles can participate in the polymerization process such as the step of obtaining the polyamic acid solution to form hydrogen bonds, and are therefore uniformly located in the substrate, thereby exhibiting an effect of improving the dispersibility.
Next, a polyamide-imide polymer solution is prepared by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent charged into the silica dispersion.
The dicarbonyl compound may include a 1 st dicarbonyl compound and a 2 nd dicarbonyl compound. At this time, the step of preparing the above polymer solution may include: a step of obtaining a first polymer solution by polymerizing a diamine compound, a dianhydride compound, a 1 st dicarbonyl compound, and a 2 nd dicarbonyl compound in an organic solvent; and a step of adding the second dicarbonyl compound to the first polymer solution to obtain a second polymer solution, but the method is not limited thereto.
The polymer solution contains a polyamide-imide polymer and an organic solvent.
The organic solvent may be one or more organic solvents selected from the group consisting of Dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), m-cresol (m-cresol), tetrahydrofuran (THF), and chloroform, but is not limited thereto. Specifically, the organic solvent may be dimethylacetamide (DMAc), but is not limited thereto.
The organic solvent used in preparing the polyamide-imide polymer solution and the organic solvent used in preparing the silica dispersion may be the same or different.
The step of obtaining the first polymer solution may be to polymerize the diamine compound, the dianhydride compound, the 1 st dicarbonyl compound, and the 2 nd dicarbonyl compound simultaneously or sequentially.
Specifically, in one example, the step of obtaining the first polymer solution may be to polymerize the diamine compound, the dianhydride compound, the 1 st dicarbonyl compound, and the 2 nd dicarbonyl compound at the same time.
In yet another example, the step of obtaining the first polymer solution described above may comprise: a step of obtaining a polyamic acid solution by polymerizing the diamine compound and the dianhydride compound; and a step of adding the 1 st dicarbonyl compound and the 2 nd dicarbonyl compound to the polyamic acid solution to polymerize the same. The polyamic acid solution is a solution containing polyamic acid.
In another example, the step of obtaining the first polymer solution described above may comprise: a step of obtaining a polyamic acid solution by polymerizing the diamine compound and the dianhydride compound; a step of obtaining a polyimide solution by subjecting the polyamic acid solution to a dehydration reaction; and a step of adding the 1 st dicarbonyl compound and the 2 nd dicarbonyl compound to the polyimide solution to polymerize the polyimide solution. The polyimide solution is a solution containing a polymer having an imide repeating unit.
In yet another example, the step of obtaining the first polymer solution described above may comprise: a step of obtaining an amide polymer solution by polymerizing the diamine compound, the 1 st dicarbonyl compound, and the 2 nd dicarbonyl compound; and adding the dianhydride compound to the amide polymer solution to polymerize the dianhydride compound. The above amide polymer solution is a solution containing a polymer having an amide repeating unit.
The copolymer contained in the first polymer solution contains an imide repeating unit derived from polymerization of the diamine compound and the dianhydride compound, and an amide repeating unit derived from polymerization of the diamine compound and the dicarbonyl compound.
For the step of obtaining the above-mentioned first polymer solution, a catalyst may be further added after the step of obtaining the above-mentioned second polymer solution or the step of preparing the polyamide-imide polymer solution.
Examples of the catalyst include, but are not limited to, beta-picoline, acetic anhydride, and the like.
The reaction rate can be increased by adding the catalyst, and the catalyst is effective for increasing the bonding force between or in the repeating unit structure.
In the step of adding the catalyst, drying and redissolving the polymer solution, or adding a solvent, the viscosity of the polymer solution may be appropriately adjusted so as to be suitable for the extrusion step.
In still another example, the step of obtaining the first polymer solution includes a step of adding the dianhydride compound, the 1 st dicarbonyl compound, and the 2 nd dicarbonyl compound to an excess amount of the diamine compound.
Specifically, the dianhydride compound may be contained in an amount of 10 to 25 mole% based on the total mole of the dianhydride compound, the 1 st dicarbonyl compound and the 2 nd dicarbonyl compound, but is not limited thereto.
When the content of the dianhydride compound is within the above range, the polyamide-imide film is excellent in mechanical properties such as modulus, tensile strength, elongation and surface hardness.
The dianhydride compound, the 1 st dicarbonyl compound, and the 2 nd dicarbonyl compound may be contained in an amount of 75 to 90 mol% based on the total mole of the 1 st dicarbonyl compound, and the 2 nd dicarbonyl compound, but the present invention is not limited thereto.
When the content of the dicarbonyl compound is within the above range, the polyamide-imide film is excellent in optical properties such as light permeability and haze.
In still another example, in the step of obtaining the first polymer solution, the 1 st dicarbonyl compound may be included in an amount of 50 to 70 mole percent based on the total mole of the 1 st dicarbonyl compound and the 2 nd dicarbonyl compound, but is not limited thereto.
The 1 st dicarbonyl compound is 1,1 '-biphenyl-4, 4' -diacetyl chloride, and the 2 nd dicarbonyl compound may be terephthaloyl chloride.
When the content of the 1 st dicarbonyl compound is less than 50 mol%, the tensile strength (modulus) of the polyamide-imide film may be lowered, and when it is more than 70 mol%, the optical properties such as haze may be lowered.
Preferably, in the step of obtaining the first polymer solution, an excess of diamine compound of i) equal to or more than the remaining reaction mass molar (mole) may be used; ii) 10 to 25 mole percent of a dianhydride compound based on the total mole of the dianhydride compound, the 1 st dicarbonyl compound and the 2 nd dicarbonyl compound; and iii) 75 to 90 mole percent of the 1 st dicarbonyl compound and the 2 nd dicarbonyl compound, based on the total mole of the dianhydride compound, the 1 st dicarbonyl compound and the 2 nd dicarbonyl compound.
Specifically, 50 to 70 mole percent of the 1 st dicarbonyl compound (1, 1 '-biphenyl-4, 4' -diacetyl chloride) and 30 to 50 mole percent of the 2 nd dicarbonyl compound (terephthaloyl chloride) may be used based on the total mole of the 1 st dicarbonyl compound and the 2 nd dicarbonyl compound.
In the step of obtaining the first polymer solution, by appropriately adjusting the respective contents of the imide repeating unit and the amide repeating unit, a polyamide-imide film having uniformly improved optical characteristics, mechanical properties and flexibility can be obtained without the conventional processes of precipitation, filtration, drying, redissolution, and the like.
After the step of obtaining the above-mentioned first polymer solution, a second polymer solution having a viscosity of 10 to 30 ten thousand cps can be obtained even if the above-mentioned 2 nd dicarbonyl compound is further added to the above-mentioned first polymer solution. Specifically, a second polymer solution having a viscosity of 10 to 25, 15 to 30 ten thousand cps may be obtained.
In the case where the viscosity of the second polymer solution is in the above range, the polyamide-imide film can be efficiently produced in the extrusion and casting process. The polyamide-imide film thus produced may have mechanical properties such as improved modulus.
The weight ratio of the 2 nd dicarbonyl compound added in the step of obtaining the above-mentioned first polymer solution to the 2 nd dicarbonyl compound added in the step of obtaining the above-mentioned second polymer solution may be 90:10 to 99:1, but is not limited thereto.
And, the 2 nd dicarbonyl compound added in the step of obtaining the above-mentioned second polymer solution is mixed with an organic solvent to be used as the 2 nd dicarbonyl compound solution prepared at a concentration of 5 to 20 weight percent, but is not limited thereto.
This facilitates accurate achievement of the desired viscosity.
In one example, the solid component included in the second polymer solution may be present in an amount of 10 to 20 weight percent. Specifically, the content of the solid component contained in the second polymer solution may be 12 to 18 weight percent, but is not limited thereto.
In the case where the content of the solid component contained in the second polymer solution is within the above-described range, the polyamide-imide film can be efficiently produced in the extrusion and casting process. The polyamide-imide film thus produced may have improved mechanical properties such as modulus and optical properties such as low yellowness.
After the second polymer solution is obtained, the pH of the second polymer solution may be adjusted by adding a neutralizing agent.
Examples of the neutralizing agent include, but are not limited to, amine neutralizing agents such as alkoxyamine, alkylamine, and alkanolamine.
The above neutralizing agent may be added in an amount of about 0.1 mole percent to about 10 mole percent based on the total number of moles of monomers in the above polyamide-imide polymer solution.
The pH of the second polymer solution adjusted by the above-described neutralizing agent may be about 4 to about 7. Specifically, the pH of the adjusted second polymer solution may be about 4.5 to about 7.
In the case where the pH of the second polymer solution is in the above range, damage to equipment occurring in the extrusion and casting processes described later can be prevented. Further, the mechanical properties of the polyamide-imide film may be reduced in yellowness, or the optical properties such as prevention of an increase in yellowness and improvement in modulus may be achieved.
After the step of preparing the above polymer solution, the above polymer solution is put into a tank.
At this time, the internal temperature of the above tank is preferably-20 ℃ to 20 ℃. This serves to prevent deterioration of the polymer solution charged and to reduce the moisture content.
After the step of charging the above-prepared polymer solution into the tank, vacuum defoaming may be further included for 30 minutes to 3 hours until the pressure in the above-mentioned tank is 0.1bar to 0.7 bar.
Alternatively, after the step of charging the polymer solution prepared as described above into the tank, a step of purging (purging) the tank with nitrogen gas at 1 to 2 gas pressures may be further included.
The vacuum defoaming step and the purging of the tank with nitrogen gas may be performed by a separate process.
For example, after the step of charging the above polymer solution into the tank, it may further include: a step of vacuum defoaming for 30 minutes to 3 hours until the pressure in the tank is 0.1bar to 0.7 bar; and a step of purging the tank with nitrogen gas at a pressure of 1 to 2.
For example, after the step of performing the vacuum defoaming, the step of purging the tank with nitrogen gas may be performed, but is not limited thereto.
By performing the above-described vacuum defoaming step and/or the step of purging the above-described tank with nitrogen gas, the physical properties of the surface of the produced polyamide-imide film can be improved.
Then, a gel sheet was prepared by drying after extruding and casting the polymer solution in the above tank.
When the above-mentioned extrusion and casting processes are performed, the organic solvent may be used.
The polymer solution is extruded and cast by a casting body such as a casting roll or a casting belt. At this time, the cast body was cast at a speed of about 0.5 m/min to about 15 m/min and a thickness of 200 μm to 700 μm. With extrusion and casting speeds within the above ranges, the polyamide-imide film produced by the example production method may have improved optical and mechanical properties.
That is, in the case where the above polymer solution has the viscosity as described above, extrusion and casting at the extrusion speed as described above may contribute to having improved optical and mechanical properties.
After the polymer solution is cast on a casting body, a solvent contained in the polymer solution is removed by a drying process, thereby forming a gel sheet on the casting body.
The drying process may be performed at a temperature of about 60 ℃ to about 150 ℃ for about 5 minutes to about 60 minutes.
Next, the polyamide-imide film of the example may be prepared through a step of heat-treating the above gel sheet.
The above heat treatment step may be performed at a temperature ranging from 80 ℃ to 500 ℃ at a rate of 2 ℃/min to 80 ℃/min for 5 minutes to 40 minutes or 5 minutes to 30 minutes.
The maximum temperature in the above heat treatment step may be 300 to 500 ℃ or 320 to 500 ℃. In more detail, the highest temperature in the above heat treatment step may be 350 to 500 ℃, 380 to 500 ℃, 400 to 500 ℃, 410 to 480 ℃, 410 to 470 ℃, or 410 to 450 ℃, but is not limited thereto.
The heat treatment step may further include a step of cooling the heat-treated sheet. The cooling step may include a first cooling step of cooling at a rate of 100 to 1000 ℃ per minute and a second cooling step of cooling at a rate of 40 to 400 ℃ per minute.
Specifically, after the above-described first temperature lowering step, a second temperature lowering step is performed.
And, the cooling speed of the first cooling step may be faster than that of the second cooling step.
For example, the maximum speed in the first cooling step is faster than the maximum speed in the second cooling step. Or the lowest speed in the first cooling step is faster than the lowest speed in the second cooling step.
The polyamide-imide polymer has oxidation resistance, and thus is hardly affected by oxygen contained in the atmosphere during the heat treatment step. Thus, the example polyamide-imide film may have improved mechanical and optical properties.
In addition, conventionally, in the production of polyimide films, yellowing of the films is prevented and transparency is ensured by nitrogen purging at the time of heat treatment in the molding process, but according to the above examples, polyamide-imide films excellent in optical characteristics can be obtained even without such nitrogen purging.
The description of the polyamide-imide film produced by the above-described process for producing a polyamide-imide film is referred to the description of the polyamide-imide film described above.
The present invention will be further specifically described below by way of examples. The following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
PREPARATION EXAMPLE 1 preparation of silica Dispersion
Silica particles (about 30nm of the first particle average particle diameter and about 50nm of the second particle average particle diameter) were put into dimethylacetamide (DMAc) as an organic solvent, and subjected to ultrasonic treatment in an ultrasonic water tank for 10 minutes, to prepare a 1 weight percent concentration silica dispersion.
Example 1
In a temperature-adjustable, double-jacketed, 1L glass reactor, 710.8g of dimethylacetamide as an organic solvent was charged under a nitrogen atmosphere at 10 ℃. Next, 2.75g of the silica dispersion (300 ppm based on the total weight of the polyamide-imide polymer) obtained in preparation example 1 was charged into the glass reactor and stirred for 1 hour.
64g (0.2 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl (TFDB) as an aromatic diamine was gradually charged into a glass reactor into which the silica dispersion was charged and dissolved.
Next, 17.76g (0.04 mol) of 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride as an aromatic dianhydride was gradually charged and stirred for 1 hour.
Then, 27.9g (0.1 mol) of 1,1 '-biphenyl-4, 4' -diacetyl chloride (BPDC) as the 1 st dicarbonyl compound was charged and stirred for 1 hour, and then 9.74g (0.048 mol) of terephthaloyl chloride as the 2 nd dicarbonyl compound was charged to a molar ratio of 96% and stirred for 1 hour, to prepare a first polymer solution.
After measuring the viscosity of the prepared first polymer solution, in the case where the measured viscosity cannot reach the desired viscosity, up to a viscosity of 20 tens of thousands of cps, a 10 weight percent terephthaloyl chloride solution was prepared in dimethylacetamide organic solvent and 1mL was added, and then the process of stirring was repeated for 30 minutes to prepare a second polymer solution.
Next, the second polymer solution was applied to a glass plate, and then dried with hot air at 80 ℃ for 30 minutes. After peeling the dried polyamide-imide polymer from the glass plate, it was fixed to a needle frame and heated at a rate of 2 to 80 c/min at a temperature range of 80 to 500 c and heat-treated for 30 minutes to obtain a polyamide-imide film having a thickness of 50 μm.
According to the above examples, until the yield reaches about 100% before the molding step (before coating), in this specification, "yield" means the moles (moles) of the material remaining in the solution to be coated relative to the moles (moles) of the material charged.
According to the conventional production method, the yield before the molding step is about 60%, because there is necessarily a loss of material in the steps of the polyimide-forming reaction, precipitation, filtration, drying, and the like.
Comparative example 1
A polyamide-imide film was produced in the same manner as in example 1, except that the silica dispersion liquid produced in production example 1 was not put into a glass reactor.
Comparative example 2
A polyamide-imide film was produced in the same manner as in example 1, except that the silica dispersion liquid produced in production example 1 was charged into a glass reactor after the production of the second polymer solution.
Comparative example 3
A polyamide-imide film was produced in the same manner as in example 1 except that 0.052mol of 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 0.082mol of 1,1' -biphenyl-4, 4' -diacetyl chloride and 0.066mol of terephthaloyl chloride in total were charged, and the silica dispersion produced in production example 1 was charged into a glass reactor after the production of the second polymer solution.
Comparative example 4
A polyamide-imide film was produced in the same manner as in example 1 except that 0.2mol of 2,2' -bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride was charged, terephthaloyl chloride and 1,1' -biphenyl-4, 4' -diacetyl chloride were not charged, the second particle average particle diameter of the silica particles was about 80nm, and the silica dispersion produced in production example 1 was charged into a glass reactor after producing the second polymer solution.
The types and contents of the components used in example 1 and comparative examples 1 to 4 are shown in table 1 below.
TABLE 1
Evaluation example
The films of example 1 and comparative examples 1 to 4 were subjected to the following physical properties measurement and evaluation. The results are shown in Table 2 below.
Evaluation example 1: determination of film thickness
The thickness was measured by measuring 5 points (points) in the width direction as an average value using a digital micrometer 547-401 of Sanfeng (Mitutoyo) corporation of Japan.
Evaluation example 2: determination of surface hardness
Surface hardness in pencil hardness tester (CT-PC) 1 CORE TECH, korea) was inserted into a pencil for pencil hardness measurement at an angle of 45 °, and a predetermined load (750 g) was applied and measured at a pencil speed of 300 mm/min. As the pencil, mitsubishi (Mitsubishi) pencil was used, and H-9H, F, HB, B-6B pencil having equal strength was used.
Evaluation example 3: determination of light permeability, ultraviolet (UV) permeability and haze
The light transmittance and haze were measured at 550nm using a haze meter NDH-5000W, manufactured by the electric decorative industry Co., ltd. The light permeability was measured at 388nm using a UV-VIS SPECTROPHOTOMETER (SPECTROPHOTOMER) (UV-2450) from Shimadzu corporation (Shimadzu).
Evaluation example 4: determination of yellowness
Yellowness (YI) is measured by a spectrophotometer (UltraScan PRO, hunter Associates Laboratory) using a CIE colorimeter.
Evaluation example 5: determination of modulus
The stress-strain curve was obtained by cutting 5cm or more in a direction perpendicular to the main shrinkage of the sample and 10mm in the main shrinkage direction using an Instron universal tester UTM 5566A, and stretching at a speed of 5mm/min until breakage at normal temperature after mounting clips at intervals of 5 cm. In the stress-strain curve described above, the load slope of the initial deformation is taken as modulus (GPa).
Evaluation example 6: determination of tensile Strength
Cutting with Instron universal tester UTM 5566A at a distance of 5cm or more in a direction perpendicular to the main shrinkage direction of the sample and 10mm in the main shrinkage direction, and stretching at a speed of 5mm/min at room temperature until breakage occurs after mounting clips at 5cm intervals, comprising This results in a stress-strain curve. In the stress-strain curve, the maximum force at which fracture occurs is taken as the tensile strength (kgf/mm) 2 )。
Evaluation example 7: determination of elongation
The stress-strain curve was obtained by cutting 5cm or more in a direction perpendicular to the main shrinkage of the sample and 10mm in the main shrinkage direction using an Instron universal tester UTM 5566A, and stretching at a speed of 5mm/min until breakage at normal temperature after mounting clips at intervals of 5 cm. In the stress-strain curve described above, the maximum ratio elongated until fracture occurs is elongation (%).
Evaluation example 8: scanning electron microscope photograph
The results of scanning electron microscopy at 5000 times, 10000 times and 50000 times for the films of example 1 and comparative example 2 are shown in fig. 1 to 6.
Specifically, in the case of example 1 (see FIG. 3), aggregates having an average diameter of 150nm to 200nm were not observed, whereas in the case of comparative example 2 (see FIG. 6), aggregates having an average diameter of about 4 μm were observed 2 2 aggregates with an average diameter of 150nm to 200nm (i.e., 0.5 aggregates/. Mu.m) 2 ). From this, it was confirmed that the aggregation phenomenon of silica particles was relatively more in the case of comparative example 2 than in example 1.
TABLE 2
From the above table 2, it was confirmed that in the case of example 1, it was confirmed that the surface hardness was excellent, the light permeability was high, the ultraviolet light permeability was high, the haze was low, the yellowness was low, the modulus was high, the tensile strength was high, and the elongation was high, as compared with comparative examples 1 to 5.
Specifically, in comparative example 1, no silica particles were addedThe decrease in modulus, elongation, tensile strength and rollability was confirmed in the case of comparative example 2, in which silica particles were added later, as compared with comparative example 1, and further decreased, as shown in the scanning electron micrographs of FIGS. 4 to 6, every about 4. Mu.m 2 2 aggregates with an average diameter of 150nm to 200nm (i.e., 0.5 aggregates/. Mu.m) 2 ) It was confirmed that dispersibility was lowered. In the case of comparative example 2, the agglomerate may cause a decrease in mechanical properties and an increase in haze as a foreign matter. In comparative examples 3 and 4, it was also confirmed that the surface hardness, haze, modulus, tensile strength, and elongation were reduced.
That is, the polyamide-imide film is produced by charging silica particles for a specific period of time, and the silica particles can be uniformly dispersed, whereby a polyamide-imide film having excellent optical properties and improved modulus, tensile strength and elongation can be obtained.
Claims (18)
1. A polyamide-imide film characterized in that,
the polyamide-imide film comprises:
polyamide-imide polymers formed by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound; and
the silica particles are used as a base material for the silica particles,
the average diameter of the aggregates of 150nm to 200nm observed in the section of the polyamide-imide film cut in the thickness direction is less than 0.5 per mu m 2 And (b)
Wherein the ratio of the average particle diameter of the second particles to the average particle diameter of the first particles of the silica particles is 1.2 to 3.0,
the first particles are particles of the smallest unit of aggregated silica particles, and the second particles are particles of a plurality of first particles aggregated and shown as one particle.
2. The polyamide-imide film according to claim 1, wherein the first particle average particle diameter of the silica particles is 10nm to 40nm, and the second particle average particle diameter of the silica particles is 30nm to 80nm.
3. The polyamide-imide film of claim 1, wherein the silica particles are present in an amount of 50ppm to 600ppm based on the total weight of the polyamide-imide polymer.
4. The polyamide-imide film as claimed in claim 1, wherein aggregates having an average diameter of 150nm to 200nm as viewed in a section of the polyamide-imide film cut in a thickness direction are 0 pieces/μm 2 Up to 0.3/μm 2 。
5. The polyamide-imide film of claim 1 wherein,
the diamine compound is represented by the following chemical formula 1,
the dianhydride compound is represented by the following chemical formula 2,
the dicarbonyl compound is represented by the following chemical formula 3:
chemical formula 1: h 2 N-(E) e -NH 2 ；
Chemical formula 2:
chemical formula 3:
in the above chemical formulas 1 to 3,
e and J are independently selected from substituted or unsubstituted divalent C 6 -C 30 Aliphatic cyclic group, substituted or unsubstituted divalent C 4 -C 30 Aliphatic heterocyclic group, substituted or unsubstituted divalent C 6 -C 30 Aromatic ring group, substituted or unsubstituted divalent C 4 -C 30 Aromatic heterocyclic group, substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 2 -C 30 Alkenylene, substituted or unsubstituted C 2 -C 30 Alkynylene, -O-, -S-, -C (=o) -, -CH (OH) -, -S (=o) 2 -、-Si(CH 3 ) 2 -、-C(CH 3 ) 2 -and-C (CF) 3 ) 2 -，
e and j are independently selected from integers from 1 to 5,
when E is 2 or more, E of 2 or more is the same or different,
when J is 2 or more, J of 2 or more is the same or different,
g is a substituted or unsubstituted tetravalent C 6 -C 30 Aliphatic cyclic group, substituted or unsubstituted tetravalent C 4 -C 30 Aliphatic heterocyclic group, substituted or unsubstituted tetravalent C 6 -C 30 Aromatic ring group, substituted or unsubstituted tetravalent C 4 -C 30 An aromatic heterocyclic group, wherein the aliphatic heterocyclic group, the aromatic heterocyclic group or the aromatic heterocyclic group are present alone or bonded to each other to form a condensed ring, or are bonded to each other through a member selected from the group consisting of substituted and unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 2 -C 30 Alkenylene, substituted or unsubstituted C 2 -C 30 Alkynylene, -O-, -S-, -C (=o) -, -CH (OH) -, -S (=o) 2 -、-Si(CH 3 ) 2 -、-C(CH 3 ) 2 -and-C (CF) 3 ) 2 The linking group in (c) is linked,
x is a halogen atom.
6. The polyamide-imide film according to claim 1, wherein the dianhydride compound is composed of a compound having a fluorine-containing substituent.
7. The polyamide-imide film according to claim 1, wherein the dicarbonyl compound comprises at least two dicarbonyl compounds different from each other.
8. The polyamide-imide film of claim 1, wherein the polyamide-imide polymer comprises a repeating unit represented by the following chemical formula a and a repeating unit represented by the following chemical formula B:
chemical formula a:
chemical formula B:
in the above chemical formula a and chemical formula B, E, G, J, e and j are described in claim 1.
9. The polyamide-imide film of claim 8, wherein the molar ratio of the repeating units represented by the above formula a to the repeating units represented by the above formula B in the above polyamide-imide polymer is 10:90 to 25:75.
10. The polyamide-imide film of claim 1, wherein said polyamide-imide film has a modulus of 5.0GPa or more, an elongation of 15% or more, and a tensile strength of 15kgf/mm based on a thickness of 50. Mu.m 2 The haze was 2% or less.
11. A method for producing a polyamide-imide film, comprising:
a step of preparing a silica dispersion liquid in which silica particles are dispersed;
a step of adding the silica dispersion liquid to an organic solvent;
a step of preparing a polyamide-imide polymer solution by polymerizing a diamine compound, a dianhydride compound, and a dicarbonyl compound in an organic solvent charged into the silica dispersion;
a step of charging the polymer solution into a tank;
a step of preparing a gel sheet by drying after extruding and casting the polymer solution in the tank; and
a step of heat-treating the gel sheet,
wherein the ratio of the average particle diameter of the second particles to the average particle diameter of the first particles of the silica particles is 1.2 to 3.0,
the first particles are particles of the smallest unit of aggregated silica particles, and the second particles are particles of a plurality of first particles aggregated and shown as one particle.
12. The method for producing a polyamide-imide film according to claim 11, wherein the first particle average particle diameter of the silica particles is 10nm to 40nm, and the second particle average particle diameter of the silica particles is 30nm to 80nm.
13. The method for producing a polyamide-imide film as claimed in claim 11, wherein the silica dispersion is produced by subjecting silica particles to ultrasonic treatment after the silica particles are put into an organic solvent.
14. The method for producing a polyamide-imide film according to claim 11, wherein the content of silica particles in the silica dispersion is 0.2 to 5% by weight.
15. The method for producing a polyamide-imide film as claimed in claim 11, wherein 0 agglomerates/μm are observed in a cross section of the polyamide-imide film cut in the thickness direction, the average diameter of which is 150nm to 200nm 2 Up to 0.3/μm 2 。
16. The method for producing a polyamide-imide film according to claim 11, wherein the heat treatment step is performed at a temperature ranging from 80 ℃ to 500 ℃ at a rate of 2 ℃/min to 80 ℃/min while being performed for 5 minutes to 40 minutes, and the highest temperature in the heat treatment step is 300 ℃ to 500 ℃.
17. The method for producing a polyamide-imide film according to claim 11, further comprising, after the step of charging the tank with the polymer solution:
a step of vacuum defoaming for 30 minutes to 3 hours until the pressure in the tank is 0.1bar to 0.7 bar; and
a step of purging the above tank with nitrogen gas at a pressure of 1 to 2.
18. The method for producing a polyamide-imide film as claimed in claim 11, wherein,
after the heat treatment step, the method further comprises the step of cooling the heat-treated sheet,
the cooling step comprises a first cooling step of cooling at a speed of 100 ℃ to 1000 ℃ per minute and a second cooling step of cooling at a speed of 40 ℃ to 400 ℃ per minute,
the first cooling step is followed by a second cooling step,
the cooling speed of the first cooling step is faster than that of the second cooling step.
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