KR20210127024A - Polyamide resin composition, and polymer film, resin laminate using the same - Google Patents

Abstract

The present invention relates to a polyamide resin composition that suppress excessive growth of a crystalline polymer chain length and thus enables transparency, surface hardness, and optical properties such as a yellowness, permeability, and refractive index to be improved. More specifically, the present invention relates to a polyamide resin wherein the average particle diameter of individual crystals measured by a small-angle X-ray scattering device is 8.0 nm or less, and an amorphous polymer chain exists between individual crystals having an average particle diameter of 8.0 nm or less, a polyamide resin composition containing a silica-based filler, and a polymer film and a resin laminate using the same.

Description

Polyamide resin composition, and polymer film and resin laminate using the same

The present invention provides a polyamide resin composition with improved transparency, improved surface hardness, and improved optical properties such as yellowness, transmittance, and refractive index by inhibiting excessive growth of a crystalline polymer chain length, and a polymer film and resin using the same It relates to a laminate.

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. Such polyimide resins are widely used as electrical/electronic materials.

However, the polyimide resin has a dark brown color due to the formation of a charge transfer complex (CTC) of Pi-electrons in the imide chain, and thus has a limitation in that it is difficult to secure transparency. It has a very weak scratch resistance.

In order to improve the limitations of such polyimide resins, studies on polyamide resins having amide groups introduced therein are being actively conducted. The amide structure induces intermolecular or intramolecular hydrogen bonds, and the scratch resistance is improved through interactions such as hydrogen bonds.

However, due to the difference in solubility, reactivity (steric hindrance), and reaction rate of terephthaloyl chloride or isophthaloyl chloride used for polyamide resin synthesis, amide repeating units derived from terephthaloyl chloride and isopropyl during polyamide polymerization An amide repeating unit derived from taloyl chloride is difficult to ideally and alternatively polymerize without forming a block.

Accordingly, a block is formed by the amide repeating unit derived from the para acyl chloride monomer, and as the crystallinity of the polyamide resin increases, the transparency becomes poor due to haze.

In addition, as the polymerization reaction proceeds while the monomer used for synthesizing the polyamide resin is dissolved in the solvent, the molecular weight of the final synthesized polyamide resin may be secured at a sufficient level due to deterioration due to moisture or mixing with the solvent. difficult.

Accordingly, there is a demand for the development of a polyamide resin capable of simultaneously implementing transparency and mechanical properties.

The present invention relates to a polyamide resin composition in which transparency is improved by suppressing excessive growth of a crystalline polymer chain length, surface hardness is improved, and optical properties such as yellowness, transmittance, and refractive index are improved.

Another object of the present invention is to provide a polymer film and a resin laminate using the polyamide resin composition.

In order to solve the above problems, in the present specification, the average particle diameter of individual crystals measured by a small-angle X-ray scattering device is 8.0 nm or less, and an amorphous polymer chain is formed between individual crystals having an average particle diameter of 8.0 nm or less. polyamide resins present; and a silica-based filler; provides a polyamide resin composition comprising.

In the present specification, there is also provided a polymer film comprising a cured product of the polyamide resin composition.

In the present specification, the substrate including the polymer film; and a hard coating layer formed on at least one surface of the substrate.

Hereinafter, a polyamide resin composition according to a specific embodiment of the present invention, and a polymer film and a resin laminate using the same will be described in more detail.

Unless otherwise limited herein, the following terms may be defined as follows.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, examples of the substituent are described below, but is not limited thereto.

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 as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent is substituted, is not limited, and when two or more substituted , two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amide group; primary amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; haloalkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; alkoxysilylalkyl group; an arylphosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected. Preferably, a haloalkyl group may be used as the substituent, and examples of the haloalkyl group include a trifluoromethyl group.

, 또는

는 다른 치환기에 연결되는 결합을 의미하고, 직접결합은 L 로 표시되는 부분에 별도의 원자가 존재하지 않은 경우를 의미한다. In this specification,

, or

denotes a bond connected to another substituent, and a direct bond denotes a case in which a separate atom does not exist in the portion represented by L .

In the present specification, the alkyl group is a monovalent functional group derived from an alkane, and may be straight-chain or branched, and the number of carbon atoms in the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms of the branched chain alkyl group is 3 to 20. Specific examples of the alkyl group 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-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. The alkyl group may be substituted or unsubstituted.

In the present specification, the aryl group is a monovalent functional group derived from arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted.

In the present specification, the arylene group is a divalent functional group derived from arene, and the description of the aryl group described above may be applied, except that these are divalent functional groups. For example, it may be a phenylene group, a biphenylene group, a terphenylene group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, and the like. The arylene group may be substituted or unsubstituted.

In the present specification, the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but preferably has 4 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, a triazinyl group Jolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl 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 Nonthrolinyl group (phenanthroline), thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, aziridyl group, azaindolyl group, isoindolyl group, inda Zolyl group, purine group, pteridine group, beta-carbolyl group, naphthyridine group, ter-pyridyl group, phenazinyl group, imidazopyridyl group, pyropyridyl group, azepine group , a pyrazolyl group and a dibenzofuranyl group, but is not limited thereto. The heteroaryl group may be substituted or unsubstituted.

In the present specification, the hetero arylene group has 2 to 20, or 2 to 10, or 6 to 20 carbon atoms. As an arylene group containing O, N or S as a heteroatom, the description of the heteroaryl group described above may be applied, except that it is a divalent functional group. The hetero arylene group may be substituted or unsubstituted.

In the present specification, examples of halogen include fluorine, chlorine, bromine or iodine.

In the present specification, (meth) acryl is meant to include both acryl and methacryl.

Hereinafter, the present invention will be described in more detail.

1. Polyamide resin composition

According to one embodiment of the invention, the average particle diameter of individual crystals measured by a small-angle X-ray scattering device is 8.0 nm or less, and an amorphous polymer chain exists between individual crystals having an average particle diameter of 8.0 nm or less. amide resins; and a silica-based filler. A polyamide resin composition comprising may be provided.

As described above, the present inventors have found that the average particle diameter of individual crystals measured by a small-angle X-ray scattering device is 8.0 nm or less, and an amorphous polymer chain exists between individual crystals having an average particle diameter of 8.0 nm or less. While the amide resin has excellent mechanical properties of the crystalline polymer, as the growth of individual crystals constituting the crystal structure is slowed and has a relatively small size, the amide resin has a remarkably low level of haze and yellowness, along with It was confirmed through an experiment that it can have high flexibility and bending durability, and the invention was completed.

On the other hand, when an amorphous polymer chain does not exist between individual crystals in the polyamide resin, as the average particle diameter of individual crystals measured by a small-angle X-ray scattering device increases to more than 8.0 nm, the polyamide The proportion or size of the portion having crystallinity in the resin is excessively grown, so that the crystal properties are strongly realized, the flexibility or bending durability of the polymer itself is lowered, and the haze value is sharply increased, which leads to a decrease in transparency. can

In addition, it was confirmed through experiments that the silica-based filler added together with the polyamide resin can improve the surface hardness of the polymer film obtained from the polyamide resin composition, as well as increase transparency by reducing yellowing denaturation. completed.

In particular, the silica-based filler has a refractive index of about 1.45, which is lower than that of the polyamide resin (refractive index: 1.66), so that when the silica-based filler is added, the total refractive index of the polyamide resin composition of the embodiment or the polymer film obtained therefrom is reduced, The transmittance is improved, the yellow index (YI) is reduced, and the rainbow phenomenon can be prevented by narrowing the refractive index difference with the hard coating layer (refractive index: 1.55) during hard coating.

Specifically, the polyamide resin may satisfy an average particle diameter of individual crystals measured by a small-angle X-ray scattering device of 8.0 nm or less. The polyamide resin may comprise a plurality of individual crystals. The average particle diameter of the individual crystals contained in the polyamide resin can be obtained by checking the particle sizes of all crystals included in the polyamide resin, and calculating the number average particle size by dividing the sum of these particle sizes by the number of individual crystals.

The average particle diameter of the individual crystals is a scattering pattern obtained by irradiating X-rays with an energy of 10 KeV to 20 KeV, or 10 KeV to 14 KeV, or 16 KeV to 20 KeV in a small-angle X-ray scattering device using a solid sphere model. model) and can be measured through analysis equipment.

The irradiated X-rays may be irradiated with, for example, X-rays having an energy of 10 KeV to 14 KeV and X-rays having an energy of 16 KeV to 20 KeV.

내지 30

온도에서, 소각 X선 산란 장치를 이용하여 10 KeV 내지 20 KeV 에너지의 X선을 조사하여 측정되는 결과일 수 있다. 상기 소각 X선 산란 장치 내에서 검출기로서, 이미지 판(imaging Plate), 위치-민감성 검출기(PSPC; Position-sensitive detector) 등이 사용 가능하다.The scattering pattern, which is data obtained from the small-angle X-ray scattering device, is 20

to 30

At temperature, it may be a result measured by irradiating X-rays of 10 KeV to 20 KeV energy using a small-angle X-ray scattering device. As a detector in the small-angle X-ray scattering apparatus, an imaging plate, a position-sensitive detector (PSPC), or the like can be used.

Thereafter, analysis of the average particle size of the individual crystals may be performed through an analysis equipment separately mounted inside or outside the small-angle X-ray scattering device. An example of the small-angle X-ray scattering device may include a PLS 9A beamline, and an example of the analysis device may include a computer program NIST SANS package.

^{Specifically, the average particle diameter of the individual crystals is a plot of the wavenumber q (unit: Å -1} ) and the scattering intensity I (unit: au) obtained by fitting the shape of the individual crystals contained in the sample to a solid sphere model. The diameter distribution curve of the crystal obtained by convolution with the Schulz-Zimm distribution can be obtained through calculation of the computer program (NIST SANS package).

The crystals may be a group of individual crystals having a particle diameter of 0.1 nm to 15 nm, and individual crystals included in this group may have an average particle diameter of 0.8 nm or less. More specifically, 95%, or 99% of the individual crystals included in the group may have a particle size of 0.8 nm or less. That is, the majority of said individual crystals are 0.8 nm or less, or 7 nm or less, or 0.1 nm to 8.0 nm, or 0.1 nm to 7 nm, or 1 nm to 8 nm, or 1 nm to 7 nm, or 3 nm to 8 nm. As it has a particle diameter of nm, or 3 nm to 7 nm, or 5 nm to 6.8 nm, the average particle diameter of individual crystals may also satisfy the above-mentioned range.

More specifically, the average particle diameter of the individual crystals measured by the small-angle X-ray scattering device is 8.0 nm or less, or 7 nm or less, or 0.1 nm to 8.0 nm, or 0.1 nm to 7 nm, or 1 nm to 8 nm, or 1 nm to 7 nm, or 3 nm to 8 nm, or 3 nm to 7 nm, or 5 nm to 6.8 nm.

Specifically, when X-rays are irradiated to a polyamide resin sample using the small-angle X-ray scattering device, a small-angle X-ray scattering pattern is secured through a detector, and when it is analyzed through an analysis device, it is contained in the polyamide resin sample The average semi-diameter (R _c ) value of individual crystals can be obtained. Through this, the average particle diameter of the individual crystals can be finally obtained by calculating a double value _{of the average half diameter (R c ) of the aforementioned individual crystals.}

More specifically, referring to the crystal structure of the polyamide resin of one embodiment described in FIG. 1 below, the polyamide resin is an amorphous polymer present between individual crystals together with a plurality of individual crystals (1). Consisting of chains (3), a particle size (2) can be defined for each individual crystal.

Meanwhile, the individual crystal 1 may be formed by gathering polyamide resin chains in a bundle. In particular, the length of the individual crystals can grow through the overlap between the crystalline polymer blocks contained in the polyamide resin, and it is difficult to specify the shape of the individual overlapped crystals, but it is approximately spherulite by three-dimensional growth. It can be considered to have a structure, a lamellar structure by two-dimensional growth, or a structure intermediate between three-dimensional and two-dimensional.

Preferably, the polyamide resin may have a dimension number of 3.0 or more, or 3.0 to 4.0, of individual crystals measured by a small-angle X-ray scattering device. The dimensional number of the individual crystals of the polyamide resin is a spherical scattering pattern obtained by irradiating X-rays having an energy of 10 KeV to 20 KeV, or 10 KeV to 14 KeV, or 16 KeV to 20 KeV in a small-angle X-ray scattering device. It can be measured through analysis equipment by fitting it to a solid sphere model. The small-angle X-ray scattering device and the analysis thereof include the above-mentioned contents in the average particle diameter of the individual crystals.

Meanwhile, the polyamide resin may further include an amorphous polymer chain existing between individual crystals having an average particle diameter of 8.0 nm or less. More specifically, referring to the crystal structure of the polyamide resin of one embodiment described in FIG. 1 below, the polyamide resin is an amorphous polymer present between individual crystals together with a plurality of individual crystals (1). It may consist of a chain (3).

The amorphous polymer chain suppresses the growth of the average particle size of the individual crystals described above, and the polyamide resin may satisfy the average particle size of the individual crystals measured by a small-angle X-ray scattering device of 8.0 nm or less.

In this case, the distance between the individual crystals having an average particle diameter of 8.0 nm or less may be 0.1 nm to 100 nm, or 1 nm to 100 nm, or 30 nm to 100 nm. The distance between the individual crystals having an average particle diameter of 8.0 nm or less may also be measured by a small-angle X-ray scattering device.

In the polyamide resin, examples of specific components of individual crystals having an average particle diameter of 8.0 nm or less as measured by a small-angle X-ray scattering device are not particularly limited, and various aromatic amide repeating units used for preparing the crystalline polyamide resin are limited. can be applied without

To give an example of a component of an individual crystal having an average particle diameter of 8.0 nm or less as measured by the small-angle X-ray scattering device, a first aromatic amide repeating unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound may include Polymer chains composed of the first aromatic amide repeating unit may be gathered into bundles to form individual crystals having an average particle diameter of 8.0 nm or less.

Specific examples of the 1,4-aromatic diacyl compound include terephthaloyl chloride or terephthalic acid. In addition, examples of the aromatic diamine monomer include 2,2'-bis(trifluoromethyl)-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'-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 (4,4-diaminooctafluorobiphenyl), m-phenylenediamine (m-phenylenediamine), p-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-aminophenoxy) benzene (1,3-bis (4- aminophenoxy)benzene), m-xylylenediamine, p-xylylenediamine, and 4,4'-diaminobenzanilide selected from the group consisting of One or more types can be mentioned.

Preferably, the 1,4-aromatic diacyl compound comprises terephthaloyl chloride or terephthalic acid, and the aromatic diamine compound is 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine may include.

More specifically, the individual crystals having an average particle diameter of 8.0 nm or less may include a repeating unit represented by the following Chemical Formula 1 or a first polyamide segment including a block consisting of the repeating unit.

[Formula 1]

In Formula 1, 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.

In Formula 1, Ar ₁ 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 2,2′-bis(trifluoro methyl) -4,4'-biphenylene group.

More specifically, in Formula 1, Ar ₁ may be a divalent organic functional group derived from an aromatic diamine monomer, and specific examples of the aromatic diamine monomer include 2,2'-bis(trifluoromethyl)-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'-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 (4,4-diaminooctafluorobiphenyl), m-phenylenediamine ( m-phenylenediamine), p-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 ), 1,3-bis (4-aminophenoxy) benzene (1,3-bis (4-aminophenoxy) benzene), and 4,4'-diaminobenzanilide (4,4'-diaminobenzanilide) consisting of at least one selected from the group may be mentioned. 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 (2,2'-dimethyl-4,4'-diaminobenzidine).

The first polyamide segment may include a block including the repeating unit represented by Formula 1 or the repeating unit represented by Formula 1 above.

Specific examples of the repeating unit represented by the formula (1) include a repeating unit represented by the following formula (1-1).

[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 the amidation reaction of terephthaloyl chloride or terephthalic acid and an aromatic diamine monomer. It is a repeating unit, and due to its linear molecular structure, chain packing and alignment can be kept constant in the polymer, and the surface hardness and mechanical properties of the polyamide film can be improved.

Specific examples of the 1,4-aromatic diacyl compound include terephthaloyl chloride or terephthalic acid. In addition, examples of the aromatic diamine monomer include 2,2'-bis(trifluoromethyl)-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'-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 (4,4-diaminooctafluorobiphenyl), m-phenylenediamine (m-phenylenediamine), p-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-aminophenoxy) benzene (1,3-bis (4- aminophenoxy)benzene), m-xylylenediamine, p-xylylenediamine, and 4,4'-diaminobenzanilide selected from the group consisting of One or more types can be mentioned.

Preferably, the 1,4-aromatic diacyl compound comprises terephthaloyl chloride or terephthalic acid, and the aromatic diamine compound is 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine may include.

The number average molecular weight of the first polyamide segment is from 100 g/mol to 5000 g/mol, or from 100 g/mol to 3000 g/mol, or from 100 g/mol to 2500 g/mol, or from 100 g/mol to 2450 g/mol. When the number average molecular weight of the first polyamide segment is increased to more than 5000 g/mol, as the chain of the first polyamide segment becomes excessively long, the crystallinity of the polyamide resin may increase, and thus high It may be difficult to secure transparency by having a haze value. Although an example of a method for measuring the number average molecular weight of the first polyamide segment is not limited, for example, it may be confirmed through small-angle X-ray scattering (SAXS) analysis.

The first polyamide segment may be represented by Formula 5 below.

[Formula 5]

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 Formula 5, when a is 1, Formula 5 may be a repeating unit represented by Formula 1 above. In Formula 5, when a is 2 to 5, Formula 5 may be a block composed of the repeating unit represented by Formula 1 above. In Formula 5, _{the description of Ar 1} includes the contents described above in Formula 1 above.

Based on all the repeating units contained in the polyamide resin, the proportion of the repeating unit represented by Formula 1 is 40 mol% to 95 mol%, 50 mol% to 95 mol%, or 60 mol% to 95 mol%, or from 70 mol% to 95 mol%, or from 50 mol% to 90 mol%, or from 50 mol% to 85 mol%, or from 60 mol% to 85 mol%, or from 70 mol% to 85 mol%, or from 80 mol% to 85 mole %, or 82 mole % to 85 mole %.

As such, the polyamide resin containing the repeating unit represented by Chemical Formula 1 in the above content may secure a sufficient level of molecular weight to secure excellent mechanical properties.

In addition, in the polyamide resin, examples of specific components of the amorphous polymer chain present between the individual crystals having an average particle diameter of 8.0 nm or less are not particularly limited, and various aromatic amides used in the preparation of the amorphous polyamide resin The repeating unit can be applied without limitation.

An example of an amorphous polymer chain component existing between individual crystals having an average particle diameter of 8.0 nm or less as measured by the small-angle X-ray scattering device is derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound a second aromatic amide repeating unit, or a third aromatic amide repeating unit derived from a combination of a 1,3-aromatic diacyl compound and an aromatic diamine compound, or a mixture thereof. Polymer chains composed of the above-described second aromatic amide repeating unit or third aromatic amide repeating unit may implement amorphous characteristics.

Specific examples of the 1,2-aromatic diacyl compound include phthaloyl chloride or phthalic acid. In addition, specific examples of the 1,3-aromatic diacyl compound may include isophthaloyl chloride or isophthalic acid. Examples of the aromatic diamine monomer include 2,2'-bis(trifluoromethyl)-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'-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 (4,4-diaminooctafluorobiphenyl), m-phenylenediamine (m-phenylenediamine), p-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-aminophenoxy) benzene (1,3-bis (4-aminophenoxy) One selected from the group consisting of benzene), m-xylylenediamine, p-xylylenediamine, and 4,4'-diaminobenzanilide more can be mentioned.

Preferably, the 1,2-aromatic diacyl compound comprises phthaloyl chloride or phthalic acid, the 1,3-aromatic diacyl compound comprises isophthaloyl chloride or isophthalic acid, and the aromatic diamine compound comprises: 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine.

More specifically, the amorphous polymer chain present between individual crystals having an average particle diameter of 8.0 nm or less including the first polyamide segment including the repeating unit represented by the formula (1) or a block consisting of the repeating unit is represented by the following formula (2) It may include a second polyamide segment including a repeating unit represented by or a block consisting of the repeating unit.

[Formula 2]

In Formula 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.

In Formula 2, Ar ₂ 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 2,2'-bis(trifluoro methyl) -4,4'-biphenylene group.

More specifically, in Formula 2, Ar ₂ may be a divalent organic functional group derived from an aromatic diamine monomer, and specific examples of the aromatic diamine monomer include 2,2'-bis(trifluoromethyl)-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'-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 (4,4-diaminooctafluorobiphenyl), m-phenylenediamine ( m-phenylenediamine), p-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 ), 1,3-bis (4-aminophenoxy) benzene (1,3-bis (4-aminophenoxy) benzene), and 4,4'-diaminobenzanilide (4,4'-diaminobenzanilide) consisting of at least one selected from the group may be mentioned. 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 (2,2'-dimethyl-4,4'-diaminobenzidine).

The second polyamide segment may include a block composed of the repeating unit represented by the formula (2) or the repeating unit represented by the formula (2).

More specifically, the repeating unit represented by the formula (2) may include a repeating unit represented by the following formula (2-1); or a repeating unit represented by the following formula 2-2; One type of repeating unit may be included.

[Formula 2-1]

[Formula 2-2]

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. A detailed description of Ar ₂ includes the details described above in Formula 2 above.

The repeating unit represented by Formula 2-1 is a repeating unit formed by the amidation reaction of isophthaloyl chloride or isophthalic acid with an aromatic diamine monomer, and the repeating unit represented by Formula 2-2 is phthaloyl chloride or phthalic acid and an aromatic It is a repeating unit formed by the amidation reaction of a diamine monomer.

Specific examples of the repeating unit represented by Formula 2-1 may include a repeating unit represented by Formula 2-4 below.

[Formula 2-4]

Specific examples of the repeating unit represented by Formula 2-2 include a repeating unit represented by Formula 2-5 below.

[Formula 2-5]

Meanwhile, the second polyamide segment may be represented by the following formula (6).

[Formula 6]

In Formula 6, 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, and b is an integer of 1 to 3, or 1 to 2 . In Formula 6, when b is 1, Formula 6 may be a repeating unit represented by Formula 2 above. In Formula 6, when b is 2 to 3, Formula 6 may be a block composed of the repeating unit represented by Formula 2 above.

The repeating unit represented by Formula 2 is a repeating unit formed by the amidation reaction of isophthaloyl chloride, isophthalic acid or phthaloyl chloride, phthalic acid and an aromatic diamine monomer, and due to the curved molecular structure, chain packing and It has a property of disturbing alignment, and by increasing the amorphous area in the polyamide resin, it is possible to improve the optical properties and bending strength of the polyamide film. In addition, by being included in the polyamide resin together with the repeating unit represented by Chemical Formula 1, the molecular weight of the polyamide resin may be increased.

Based on all the repeating units contained in the polyamide resin, the proportion of the repeating unit represented by Formula 2 is 5 mol% to 60 mol%, 5 mol% to 50 mol%, or 5 mol% to 40 mol%, or from 5 mol% to 30 mol%, or from 10 mol% to 50 mol%, or from 15 mol% to 50 mol%, or from 15 mol% to 40 mol%, or from 15 mol% to 30 mol%, or from 15 mol% to 20 mol %, or 15 mol % to 18 mol %.

As such, the polyamide resin containing the repeating unit represented by Chemical Formula 2 in the above content inhibits the length growth of a 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.

More specifically, based on all the repeating units contained in the polyamide resin, the content of the repeating unit represented by Formula 1 is 60 mol% to 95 mol%, or 70 mol% to 95 mol%, or 50 mol% to 90 mol%, or from 50 mol% to 85 mol%, or from 60 mol% to 85 mol%, or from 70 mol% to 85 mol%, or from 80 mol% to 85 mol%, or from 82 mol% to 85 mol%; , wherein 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%, alternatively from 15 mol% to 30 mol%, alternatively from 15 mol% to 20 mol%, alternatively from 15 mol% to 18 mol%.

That is, the polyamide resin increases the molar content of the repeating unit represented by the formula (1), and the polyamide film according to the chain packing and alignment in the polymer by the linear molecular structure of the repeating unit represented by the formula (1). While maximizing the effect of improving surface hardness and mechanical properties, even though the repeating unit represented by Formula 2 has a relatively small molar content, it inhibits the length growth of a chain composed of only a specific repeating unit represented by Formula 1, thereby determining the resin The properties can be lowered, and thus, excellent transparency can be secured by having a low haze value.

Meanwhile, the first polyamide segment and the second polyamide segment may form a main chain including a cross repeating unit represented by Formula 3 below. That is, the first polyamide segment included in the individual crystals having an average particle diameter of 8.0 nm or less measured by the small-angle X-ray scattering device is the second polyamide segment included in the amorphous polymer chain present between the individual crystals and A cross repeating unit represented by the following Chemical Formula 3 may be formed.

Accordingly, the polyamide resin of one embodiment has a structure in which a plurality of individual crystals and amorphous polymer chains are repeated, as shown in the crystal structure shown in FIG. 1 below, and the continuous size growth of only individual crystals can be suppressed. . Through this, the individual crystals may have an average particle diameter measured by a small-angle X-ray scattering device to be reduced to 8.0 nm or less.

[Formula 3]

In Formula 3, A is the first polyamide segment, and B is the second polyamide segment.

Specifically, as shown in Formula 3, the main chain of the polyamide resin comprises a first polyamide segment derived from terephthaloyl chloride or terephthalic acid and a second polyamide segment derived from isophthaloyl chloride, isophthalic acid or phthaloyl chloride, and phthalic acid. Polyamide segments may alternately form polymeric chains with each other. That is, the second polyamide segment is positioned between the first polyamide segments, and may serve to inhibit the length growth of the first polyamide segment.

The second polyamide segment is included in the amorphous polymer chain existing between the individual crystals having an average particle diameter of 8.0 nm or less, and the first polyamide segment is included in the individual crystals having an average particle diameter of 8.0 nm or less. Because it is included, in the polyamide resin, the amorphous polymer chain is positioned between individual crystals having an average particle diameter of 8.0 nm or less, and can serve to inhibit the size growth of individual crystals. This can also be confirmed through the crystal structure shown in Figure 1 below.

As such, when the size growth of the individual crystals is suppressed, the haze value of the polyamide resin can be significantly lowered while the crystal properties of the individual crystals are reduced, so that excellent transparency can be realized.

On the other hand, as shown in Formula 3, the main chain of the polyamide resin has a first polyamide segment derived from terephthaloyl chloride or terephthalic acid and a second polyamide segment derived from isophthaloyl chloride, isophthalic acid or phthaloyl chloride, and phthalic acid. The fact that the polyamide segments alternately form a polymer chain appears to be due to the formation of a melt-kneaded complex in the polyamide resin manufacturing method of the present invention, which will be described later.

As a more specific example, the cross-repeating unit represented by Formula 3 may be a repeating unit represented by Formula 4 below.

[Formula 4]

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 as or different from each other, and are each independently an integer of 1 to 5, or 1 to 3;

In the above formula (4), the crystalline polymer block (derived from terephthaloyl chloride or terephthalic acid) having a number of repeating units of a1 or a2 is an individual crystal having an average particle diameter of 8.0 nm or less as measured by the small-angle X-ray scattering device. can be achieved In addition, in Formula 4, the amorphous polymer block having the number of repeating units of b1 or b2 (derived from isophthaloyl chloride, isophthalic acid or phthaloyl chloride, phthalic acid) is produced by the small-angle X-ray scattering device. It is possible to form an amorphous polymer chain existing between individual crystals having a measured average particle diameter of 8.0 nm or less.

That is, the polyamide resin may include a first polyamide segment including a repeating unit represented by Chemical Formula 1 or a block thereof; and a second polyamide segment including the repeating unit represented by the formula (2) or a block consisting of the repeating unit represented by the formula (2), wherein the first polyamide segment and the second polyamide segment include the cross repeating unit represented by the formula (3) can form a main chain.

The present inventors found that as the average particle diameter of individual crystals decreases to 8.0 nm or less, as in the polyamide resin of one embodiment, a polymer block (hereinafter, The invention was completed after confirming through experiments that a transparent polyamide resin could be realized by reducing the crystallinity of the polyamide resin by minimizing the length growth of the first polyamide segment).

Specifically, the main chain of the polyamide resin is a crystalline polymer block derived from terephthaloyl chloride or terephthalic acid (hereinafter, the first polyamide segment) and isophthaloyl chloride, isophthalic acid or phthaloyl chloride, derived from phthalic acid. Amorphous polymer blocks (second polyamide segments) may alternately form a polymer chain. That is, the second polyamide segment is positioned between the first polyamide segments, and may serve to inhibit the length growth of the first polyamide segment.

In this case, the first polyamide segment is included in individual crystals of the polyamide resin to express crystal properties, and the second polyamide segment is included in an amorphous polymer chain between the individual crystals to express amorphous properties. do.

Therefore, when the length growth of the first polyamide segment is suppressed, the average particle diameter of individual crystals measured by a small-angle X-ray scattering device is measured to be relatively small, and the polyamide resin has a crystal characteristic of the first polyamide segment. Since the haze value can be significantly lowered while decreasing, excellent transparency can be realized.

Conversely, when the length growth inhibitory effect of the first polyamide segment by the second polyamide segment is decreased and the length growth of the first polyamide segment is excessively progressed, the individual crystals measured by the small-angle X-ray scattering device The average particle diameter is measured to be relatively large, and the transparency of the polyamide resin may be deteriorated while the haze value of the first polyamide segment is increased and the haze value is rapidly increased.

Nevertheless, the polyamide resin may have a sufficient level of weight average molecular weight, thereby achieving a sufficient level of mechanical properties.

Meanwhile, the polyamide resin may have a degree of crystallinity measured by a small-angle X-ray scattering device of 20% or less, or 1% to 20%. The crystallinity of the polyamide resin is determined by irradiating X-rays having an energy of 10 KeV to 20 KeV, or 10 KeV to 14 KeV, or 16 KeV to 20 KeV in a small-angle X-ray scattering device using a solid sphere model. model) and can be measured through analysis equipment. The small-angle X-ray scattering device and the analysis thereof include the above-mentioned contents in the average particle diameter of the individual crystals.

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 550000 g/mol.

The high weight average molecular weight of the polyamide resin appears to be due to the formation of a melt-kneaded complex in the polyamide resin manufacturing method according to another embodiment of the present invention, which will be described later. When the weight average molecular weight of the polyamide resin is reduced to less than 330000 g/mol, there is a problem in that mechanical properties such as flexibility and pencil hardness are reduced.

The molecular weight distribution of the polyamide resin may be 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 such a narrow molecular weight distribution, the polyamide resin may have improved mechanical properties such as flexural properties and hardness properties. When the molecular weight distribution of the polyamide resin is excessively wide beyond 3.0, there is a limit in that it is difficult to improve the above-described mechanical properties to a sufficient level.

The polyamide resin has a haze measured by ASTM D1003 of 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 %, alternatively from 0.50% to 1.00%, alternatively from 0.80% to 1.00%, alternatively from 0.81% to 0.97%. When the haze measured by ASTM D1003 of the polyamide resin is increased to more than 3.0%, opacity is increased and it is difficult to secure a sufficient level of transparency.

Preferably, the polyamide resin has a weight average molecular weight of at least 330000 g/mol, at least 420000 g/mol, or at least 500000 g/mol, or from 330000 g/mol to 1000000 g/mol, or from 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 550000 g/mol , at the same time a haze measured by ASTM D1003 of 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 (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 300000 cps, or 100000 cps to 200000 cps, or 110000 cps to 174000 cps. When the relative viscosity of the polyamide resin (measured according to ASTM D 2196 standard) is reduced to less than 45000 cps, in the film forming process using the polyamide resin, the moldability decreases and the efficiency of the molding process decreases. have.

Examples of the method for preparing the polyamide resin include: melt-kneading a compound represented by the following Chemical Formula 7 and a compound represented by the following Chemical Formula 8, and solidifying the melt-kneaded product to form a composite; and reacting the complex with an aromatic diamine monomer.

[Formula 7]

[Formula 8]

In Formulas 7 to 8, X is a halogen or a hydroxyl group.

The present inventors, as in the production method of the polyamide resin, when the compound represented by the formula 7 and the compound represented by the formula 8 are mixed at a temperature higher than the melting point, the compound represented by the formula 7 and the formula 8 A complex of uniformly mixed monomers can be prepared through melting of the compound represented by , the amide repeating unit derived from the compound represented by the above formula (8), or blocks consisting of it, can be alternately polymerized, and the invention has been completed.

That is, the polyamide resin of the embodiment can be obtained by the method for preparing the polyamide resin.

Specifically, since the compound represented by Formula 7 and the compound represented by Formula 8 each exhibit different aspects in solubility and reactivity due to chemical structural differences, the compound represented by Formula 7 even if they are simultaneously added As the amide repeating unit derived from

Accordingly, in the polyamide resin manufacturing method, the compound represented by Formula 7 and the compound represented by Formula 8 are not simply physically mixed, but through the formation of a complex by melt-kneading at a temperature higher than their respective melting points, Each monomer was induced to react relatively equally with the aromatic diamine monomer.

On the other hand, when synthesizing the existing polyamide resin, the compound represented by the formula 7 and the compound represented by the formula 8 are dissolved in a solvent and then reacted with the aromatic diamine monomer in a solution state. There was a limit in that the molecular weight of the finally synthesized polyamide resin decreased due to the hybridization with As the amide repeating unit is formed predominantly, a long block is formed, thereby increasing the crystallinity of the polyamide resin and making it difficult to secure transparency.

Therefore, in the polyamide resin manufacturing method, the composite obtained by melt-kneading the compound represented by the formula 7 and the compound represented by the formula 8 is heated at a temperature lower than the respective melting point (-10 °C to +30 °C, or 0 °C). It was confirmed that the molecular weight of the finally synthesized polyamide resin was improved by reacting it with an aromatic diamine monomer dissolved in an organic solvent in the form of a solid powder through cooling at a temperature of 30 ° C. to +30 ° C. or 10 ° C. to 30 ° C. Through this, it was confirmed through the experiment that excellent mechanical properties were secured.

Specifically, the method for preparing the polyamide resin may include melt-kneading the compound represented by Formula 7 and the compound represented by Formula 8, and solidifying the melt-kneaded product to form a composite.

In the compound represented by Formula 7, X is a halogen or a hydroxyl group. Preferably, in Formula 7, X is chlorine. Specific examples of the compound represented by Formula 7 may include terephthaloyl chloride or terephthalic acid.

The compound represented by Formula 7 may form the repeating unit represented by Formula 1 through the amidation reaction of the aromatic diamine monomer, and due to the linear molecular structure, chain packing and alignment in the polymer are kept constant. and can improve the surface hardness and mechanical properties of the polyamide film.

In the compound represented by the above formula (8), X is a halogen or a hydroxyl group. Preferably, in Formula 8, X is chlorine. Specific examples of the compound represented by Formula 8 may include phthaloyl chloride, phthalic acid, isophthaloyl chloride, or isophthalic acid.

The compound represented by Formula 8 can form the repeating unit represented by Formula 2 by the amidation reaction of the aromatic diamine monomer, and due to the curved molecular structure, it is a compound that interferes with chain packing and alignment in the polymer. It has a character, and by increasing the amorphous area in the polyamide resin, it is possible to improve the optical properties and bending strength of the polyamide film. In addition, since 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.

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 mixing the compound represented by 8 at a temperature above the melting point.

As such, without simply physically mixing the compound represented by the formula 7 and the compound represented by the formula 8, through the formation of a complex by melt-kneading at a temperature higher than the respective melting point, each monomer is an aromatic diamine monomer and can be induced to react relatively equally.

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 repeating unit derived from the compound represented by the formula 7 is predominantly formed to form a long block, The crystallinity of the polyamide resin is increased, and the limitation that it is difficult to secure transparency is overcome, and as in the above embodiment, the first polyamide segment and the second polyamide segment are alternately represented by Formula 3 It is possible to form a main chain including the indicated cross-repeating unit.

In this case, based on 100 parts by weight of the compound represented by the formula 7, 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 may be mixed. Through this, a technical effect of increasing transmittance and clarity may be realized. With respect to 100 parts by weight of the compound represented by Formula 7, when the compound represented by Formula 8 is mixed in less than 5 parts by weight, it becomes opaque and technical problems of increasing hazeness occur, With respect to 100 parts by weight of the compound represented, when the compound represented by Formula 8 is excessively mixed in excess of 60 parts by weight, a technical problem in which physical properties (hardness, tensile strength, etc.) decrease may occur.

In addition, in solidifying the melt-kneaded material to form a composite, the solidification means a physical change in which the melt-kneaded material in a molten state is cooled to a temperature below the melting point to be solidified, and the composite formed thereby is in a solid state can More preferably, the composite may be a solid powder obtained through an additional pulverization process.

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 product to form a complex, the compound represented by the formula 7 and the compound represented by the formula 8 mixing the compound at a temperature of 50° C. or higher; and cooling the resultant of the mixing step.

The terephthaloyl chloride has a melting point of 81.3 °C to 83 °C, the isophthaloyl chloride has a melting point of 43 °C to 44 °C, and the 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 above formula (7) Since the temperature condition is higher than the melting point of both the compound represented by and the compound represented by Formula 8, melt-kneading may proceed.

In the step of cooling the result of the mixing step, by leaving the result of the melt-kneading step at 5 ° C. or less, or -10 ° C. to 5 ° C., or -5 ° C. to 5 ° C. Since the temperature condition is lower than the melting point of both the compound and the compound represented by Formula 8, a more uniform solid powder can be obtained through cooling.

On the other hand, after the step of cooling the result of the mixing step, the step of pulverizing the result of the cooling step may be further included. Through the pulverization step, the composite of the solid content may be prepared in the form of a powder, and the powder obtained after the pulverization step may have an average particle diameter of 1 mm to 10 mm.

Specifically, the pulverizer used for pulverizing to such a particle size is a pin mill, a hammer mill, a screw mill, a roll mill, a disc mill, a jog. A mill (jog mill), sieve (sieve), jaw crusher, etc. may be used, but is not limited to the above-described example.

As such, by reacting the molten mixture of the compound represented by Formula 7 and the compound represented by Formula 8 with the aromatic diamine monomer in the form of solid content, specifically solid powder, through cooling at a temperature lower than the melting point, the formula Excellent mechanical properties of the polyamide resin are secured by improving the molecular weight of the finally synthesized polyamide resin by minimizing the deterioration of the compound represented by 7 and the compound represented by the formula 8 due to moisture or mixing with a solvent can be

In addition, in the method for preparing the polyamide resin, after melt-kneading the compound represented by Formula 7 and the compound represented by Formula 8, and solidifying the melt-kneaded product to form a composite, the composite is mixed with an aromatic diamine monomer It may include a step of reacting with.

The reaction in the step of reacting the complex with the aromatic diamine monomer may be performed under an inert gas atmosphere under a temperature condition of minus 25 °C to 25 °C, or a temperature condition 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 (2,2'-dimethyl-4,4'-diaminobenzidine), 4,4'-diaminodiphenyl sulfone (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 (4,4-diaminooctafluorobiphenyl), m-phenylenediamine, p-phenylenediamine, 4,4'-oxydi Aniline (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 (1,3-bis (4 -aminophenoxy)benzene), m-xylylenediamine (m-xylylenediamine), p-xylylenediamine (p-xylylenediamine) and 4,4'-diaminobenzanilide from the group consisting of (4,4'-diaminobenzanilide) It may include one or more selected.

More preferably, as the aromatic diamine monomer, 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine (2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine; TFDB), 2,2'-dimethyl-4,4'-diaminobenzidine (2,2'-dimethyl-4,4'-diaminobenzidine), m-xylylenediamine, or p-xylylene Diamine (p-xylylenediamine) may be used.

More specifically, the step of reacting the complex with the aromatic diamine monomer may include dissolving the aromatic diamine monomer in an organic solvent to prepare a diamine solution; and adding the complex powder to the diamine solution.

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 in a dissolved state in the organic solvent. Examples of the solvent are not particularly limited, but for example, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-di Ethylacetamide, 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, etc. general general-purpose organic solvents can be used without limitation. .

In the step of adding the complex powder to the diamine solution, the complex powder is reacted with the aromatic diamine monomer dissolved in the diamine solution. Accordingly, by improving the molecular weight of the finally synthesized polyamide resin by minimizing the deterioration of the compound represented by the formula 7 and the compound represented by the formula 8 due to moisture or mixing with a solvent, the Excellent mechanical properties can be secured.

The composite powder can be prepared in the form of a powder of the composite powder through the step of pulverizing the result of the cooling step after the step of cooling the result of the mixing step, and the powder obtained after the pulverizing step has an average particle diameter of 1 mm to 10 mm.

Meanwhile, the polyamide resin composition of the embodiment may include a silica-based filler. The silica-based filler may be added to the polyamide resin composition of the embodiment together with the polyamide resin to improve the surface hardness of the polymer film obtained from the polyamide resin composition, and to minimize yellowing.

In particular, the silica-based filler has a refractive index of about 1.45, which is lower than that of the polyamide resin (refractive index: 1.66), so that when the silica-based filler is added, the total refractive index of the polyamide resin composition of the embodiment or the polymer film obtained therefrom is reduced, The transmittance is improved, the yellow index (YI) is reduced, and the effect of preventing the rainbow phenomenon can be realized by narrowing the refractive index difference with the hard coating layer (refractive index: 1.55) during hard coating.

The silica-based filler is a nano silica particle having a diameter of 0.1 nm or more and 500 nm or less, or 0.1 nm or more and 300 nm or less, or 0.1 nm or more and 100 nm or less, or 0.1 nm or more and 50 nm or less, or 10 nm or more and 15 nm or less. may include. The silica-based filler is used by adding nano silica particles having a diameter of 0.1 nm or more and 500 nm or less alone, or a dispersion of 0.1 nm or more and 500 nm or less dispersed in an organic solvent is added. The specific type and content of the organic solvent used for preparing the dispersion is not limited, and a method widely known in the field of inorganic particle dispersion is applicable.

However, examples of the organic solvent used in the nano silica particle dispersion include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N, N-diethylacetamide, N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, dimethylsulfoxide, acetone, N-methyl-2-pyrrolidone, N-ethyl-2- An organic solvent such as pyrrolidone, tetrahydrofuran, chloroform, gamma-butyrolactone, ethyl lactate, methyl 3-methoxypropionate, methyl isobutyl ketone, toluene, xylene, methanol, and ethanol may be used.

The nano silica particle dispersion may have a solid content of 1% or more and 50% or less, or 10% or more and 50% or less, or 10% or more and 30% or less, and the solid content may include the nano silica particles. If necessary, the nano-silica particle dispersion may further contain a dispersing agent to increase dispersibility.

The nano silica particles may include a predetermined functional group substituted on the surface in order to be more easily dispersed in an organic solvent. Examples of organic functional groups that can be substituted on the surface of the nano-silica particles are not particularly limited, for example, a (meth) acrylate group, a vinyl group, a hydroxyl group, an amine group, an allyl group, an epoxy group, an isocyanate group, an amine group, Alternatively, fluorine or the like may be substituted on the surface of the nano-silica particles.

The shape of the nano silica particles is not particularly limited, and for example, may have various shapes such as hollow, solid, spherical, elliptical, rod-shaped, or irregular shape. The hollow nano silica particle means a particle having an empty space on the surface and/or inside of the inorganic particle. The solid nano silica particle means a particle in which an empty space does not exist therein.

The said nano silica particle diameter can be measured by the dynamic light scattering method, a laser diffraction method, a centrifugal sedimentation method, FFF (Field Flow Fractionation) method, a pore electrical resistance method, etc., for example. For example, when the shape of the nano silica particles is rod-shaped or amorphous, the length of the largest dimension may satisfy the particle diameter of the above range.

The silica-based filler may be contained in an amount of 50 parts by weight or less, or 1 part by weight or more and 50 parts by weight or less, or 3 parts by weight or more and 50 parts by weight or less, or 20 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the polyamide resin. can When the silica-based filler is contained in an excessively small amount compared to the polyamide resin, it is difficult to sufficiently realize the effect of inhibiting surface hardness and yellowing of the silica-based filler by the silica-based filler. In addition, when the silica-based filler is contained in an excessive amount compared to the polyamide resin, it is difficult to sufficiently ensure transparency such as haze or transmittance of the polymer film increases, and mechanical properties such as flexibility may decrease.

The silica-based filler may have a refractive index of 1.4 or more and 1.5 or less, and the polyamide resin may have a refractive index of 1.6 or more and 1.7 or less. That is, the refractive index of the silica-based filler is smaller than the refractive index of the polyamide resin, and when the silica-based filler is added, the total refractive index of the polyamide resin composition of one embodiment or the polymer film obtained therefrom is reduced, and the total transmittance is improved, The yellow index (YI) is reduced, and the rainbow phenomenon can be prevented by narrowing the difference in refractive index with the hard coating layer (refractive index: 1.55) during hard coating.

2. Polymer Film

According to another embodiment of the present invention, there is provided a polymer film including a cured product of the polyamide resin composition of the embodiment. The cured product means a material obtained through a drying process and/or a curing process of the polyamide resin composition of the other embodiment.

The content regarding the polyamide resin composition includes all of the content described above in the embodiment.

In the case of manufacturing a polymer film using the polyamide resin composition of the embodiment, excellent optical and mechanical properties can be realized, and at the same time, flexibility is provided, so that it can be used as a material for various molded articles. For example, the polymer 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 polymer film is not particularly limited, but can be freely adjusted within, for example, 0.01 μm or more and 1000 μm or less. When the thickness of the polymer film increases or decreases by a specific value, physical properties measured in the polymer film may also change by a specific value.

Specifically, the polymer film has a haze value of 3.0% or less, or 1.5% or less, or 1.00% or less, or 0.85% or less, measured according to ASTM D1003 for a specimen having a thickness of 50 ± 5 μm. , or 0.10% or more and 3.0% or less, or 0.10% or more and 1.5% or less, or 0.10% or more and 1.00% or less, or 0.10% or more and 0.70% or less, or 0.27% or more and 0.67% or less. When the haze measured by ASTM D1003 of the polymer film increases to more than 3.0%, opacity is increased and it is difficult to secure a sufficient level of transparency.

And, the polymer film has a yellow index value (yellow index, YI) measured according to ASTM E313 for a specimen having a thickness of 50 ± 5 μm, 4.0 or less, or 3.0 or less, or 0.5 or more and 4.0 or less, or 0.5 or more and 3.0 or less, or 1.97 or more and 2.26 or less. When the yellow index value (yellow index, YI) measured according to ASTM E313 of the polymer film increases to more than 4.0, opacity increases and it is difficult to secure a sufficient level of transparency.

In addition, the polymer film has a transmittance (T, @550nm) of 89% or more, or 89% or more and 92% or less, or 89.29% or more for a specimen having a thickness of 50 ± 5 μm for a 550 nm wavelength visible light. 90.36% or less.

In addition, the polymer film may have a tensile modulus of 7.5 GPa or more, or 7.5 GPa or more and 10 GPa or less, or 7.84 GPa or more and 8.36 GPa or less for a specimen having a thickness of 50 ± 5 µm, measured according to ISO 527-3. have.

And, the polymer film has a tensile strength of 240 MPa or more, or 240 MPa or more and 270 MPa or less, or 245 MPa to 266 MPa for a specimen having a thickness of 50 ± 5 μm, measured according to ISO 527-3. have.

In addition, the polymer film may have an elongation of 15% or more, or 15% or more and 25% or less, or 17% or more and 20% or less, for a specimen having a thickness of 50 ± 5 μm, measured according to ISO 527-3. .

And, the polymer film, the bending strength measured for a specimen having a thickness of 50 ± 5 μm (at a speed of 175 rpm, an angle of 135°, a radius of curvature of 0.8 mm, and the number of reciprocating bending at break at a load of 250 g) The value may be 10000 Cycles or more, or 10000 Cycles or more and 100000 Cycles or less, or 10000 Cycles or more and 20000 Cycles or less.

In addition, the polymer film has a pencil hardness value of 1H or more, 2H or more, or 1 H or more and 4H or less, or 2 H or more, measured according to ASTM D3363 for a specimen having a thickness of 50 ± 5 μm. 4H or less.

The polymer film may be prepared by a conventional method such as a dry method or a wet method using the polyamide resin composition of the embodiment. For example, the polymer film may be obtained by coating the polyamide resin composition of the embodiment on an arbitrary support to form a film, and evaporating a solvent from the film to dry it, and if necessary, the polymer film Stretching and heat treatment may be further performed.

Specifically, the polymer film is formed by applying the polyamide resin composition to a substrate to form a coating film; drying the coating film; and curing the dried coating film by heat treatment.

A method of applying the polyamide resin composition to the substrate is not particularly limited, and for example, methods such as screen printing, offset printing, flexographic printing, and inkjet printing may be used.

In addition, the polyamide resin composition may be applied to the substrate in a state of being dissolved or dispersed in an organic solvent. Specific examples of the organic solvent include toluene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl Pyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3- Ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoa Milk ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether Acetate etc. are mentioned. These may be used alone or may be used in combination.

In addition, an additive capable of improving film thickness uniformity or surface smoothness, or improving adhesion to a substrate may be further included. Examples of such additives include various solvents, surfactants, silane-based compounds, dielectrics or crosslinking compounds.

The drying of the coating film may be carried out by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 50 °C to 150 °C, or 50 °C to 100 °C.

In the step of curing the dried coating film by heat treatment, the heat treatment may be carried out by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, etc. can

3. Resin laminate

According to another embodiment of the invention, the substrate including the polymer film of the other embodiment; and a hard coating layer formed on at least one surface of the substrate.

The substrate may include the polyamide resin of the one embodiment, and may include the polymer film of the other embodiment. The content regarding the polyamide resin may include all of the above-described contents in the one embodiment, and the contents regarding the polymer film may include all of the above-described contents in the other 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 or both surfaces of the substrate. When the hard coating layer is formed on only one surface of the substrate, the opposite surface of the substrate is made of a polyimide-based, polycarbonate-based, polyester-based, polyalkyl (meth)acrylate-based, polyolefin-based and polycyclic olefin-based polymer. A polymer film including one or more polymers selected from the group may be formed.

The hard coating layer may have a thickness of 0.1 μm or more and 100 μm or less.

The hard coating layer can be used without great limitation as long as it is a known material 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 photocurable resin included in the hard coating layer is a polymer of a photocurable compound that can cause a polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional 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 the physical properties of the hard coating layer. Alternatively, the photocurable compound is pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hepta ( Meth)acrylate, tripentaerythritol hepta(meth)acrylate, torylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane polyethoxy tri(meth) ) may be at least one selected from the group consisting of acrylates.

The inorganic particles may be, for example, metal atoms such as silica, aluminum, titanium, zinc, or oxides and nitrides thereof, and each independently silica particles, aluminum oxide particles, titanium oxide particles, or zinc oxide particles, etc. can be used. have.

The inorganic particles may have an average radius of 100 nm or less, or 5 nm or more and 100 nm or less. The type of the organic particles is also not limited, and for example, polymer particles having an average particle diameter of 10 nm or more and 100 μm or less may be used.

The resin laminate can be used as a substrate or cover window of a display device, and has high flexibility and bending durability along with high light transmittance and low haze characteristics, so that it can be used as a substrate or cover window of a flexible display device. That is, a display device including the resin laminate or a flexible display device including the resin laminate may be implemented.

According to the present invention, a polyamide resin composition with improved optical properties such as yellowness, transmittance, and refractive index while improving transparency while suppressing excessive growth of a crystalline polymer chain length, and a polymer film using the same and a resin laminate may be provided.

1 shows a schematic diagram of the crystal structure of the polyamide resin obtained in Example 1 (1).
^{Figure 2 shows the 13} C-NMR spectrum of the polyamide resin obtained in (1) of Example 1.

The invention is described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

<Preparation Example: Preparation of acyl chloride complex>

Preparation Example 1

In a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, nitrogen injector, dropping funnel, and temperature controller, 549.4 g (2.704 mol) of terephthaloyl chloride (TPC; melting point: 83 ° C.) and 120.6 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 acyl chloride (specifically, A complex of terephthaloyl chloride and isophthaloyl chloride) was prepared.

Thereafter, the acyl chloride complex was crushed with a jaw crusher to prepare a powder having an average particle diameter of 5 mm.

<Example: Preparation of polyamide resin and polymer film>

Example 1

(1) polyamide resin

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 setting the temperature of the reactor to 0 °C, 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine (2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine , TFDB) was dissolved in 14.153 g (0.0442 mol).

Here, 8.972 g (0.0442 mol) of the acyl chloride complex powder obtained in Preparation Example 1 was added and stirred, and the amide formation reaction was carried out at 0° C. for 12 hours.

After completion of the reaction, N,N-dimethylacetamide (N,N-dimethylacetamide, DMAc) was added to dilute the solid content to 5% or less, precipitated with 1 L of methanol, and the precipitated solid was filtered. Thereafter, the polyamide resin in the form of a solid was prepared by drying it in a vacuum at 100° C. for 6 hours or more.

^{Through 13} C-NMR as shown in FIG. 2, the polyamide resin obtained in (1) of Example 1 contains 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 repeating units were contained.

(2) Polyamide resin composition

Dissolving the polyamide resin (refractive index: 1.66) obtained in (1) of Example 1 in N,N-dimethylacetamide (N,N-dimethylacetamide) to prepare a polymer solution of about 10% (w/V), Nanosilica (DMAC-ST, manufacturer: Nissan Chemical, particle diameter: 10-15 nm, refractive index: 1.45, 20% in N,N-dimethylacetamide (DMAC)) is added in 20 parts by weight (20 parts by weight) based on 100 parts by weight of polyamide resin. phr) to prepare a polyamide resin composition.

(3) polymer film

The polyamide resin composition obtained in (2) of Example 1 was applied on a polyimide base film (UPILEX-75s, UBE), and the thickness was uniformly controlled using a film applicator.

Thereafter, after drying in a Matiz oven at 80° C. for 15 minutes, and curing at 250° C. for 30 minutes while flowing nitrogen, it was peeled off from the base film to obtain a polymer film.

Example 2

Nanosilica (DMAC-ST, manufacturer: Nissan Chemical, particle size: 10-15 nm, 20% in N,N-dimethylacetamide (DMAC)) is added in an amount of 30 parts by weight (30 phr) based on 100 parts by weight of polyamide resin Except for the above, a polyamide resin, a polyamide resin composition, and a polymer film were prepared in the same manner as in Example 1.

Example 3

Nanosilica (DMAC-ST, manufacturer: Nissan Chemical, particle diameter: 10-15 nm, 20% in N,N-dimethylacetamide (DMAC)) is added in an amount of 40 parts by weight (40 phr) based on 100 parts by weight of polyamide resin Except for the above, a polyamide resin, a polyamide resin composition, and a polymer film were prepared in the same manner as in Example 1.

<Comparative Example: Preparation of polyamide resin and polymer film>

Comparative Example 1

(1) polyamide resin

Instead of the acyl chloride complex powder obtained in Preparation Example 1, 7.358 g (0.0362 mol) of terephthaloyl chloride (TPC) and 1.615 g (0.0080 mol) of isophthaloyl chloride (IPC) were simultaneously added to the amide A polyamide resin was prepared in the same manner as in Example 1 (1), except that the formation reaction was performed.

(2) polymer film

The polyamide resin obtained in (1) of Comparative 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.

Then, after drying for 15 minutes in a 80 ℃ Matiz oven, and after curing at 250 ℃ for 30 minutes while flowing nitrogen, peeled from the base film to obtain a polymer film.

Comparative Example 2

(1) polyamide resin

Instead of the acyl chloride complex powder obtained in Preparation Example 1, 7.358 g (0.0362 mol) of terephthaloyl chloride (TPC) was first added, followed by an interval of about 5 minutes, and sequentially isophthaloyl chloride (isophthaloyl chloride) , IPC) was added to prepare a polyamide resin in the same manner as in Example 1 (1), except that the amide formation reaction was carried out by adding 1.615 g (0.0080 mol).

(2) polymer film

A polymer film was prepared in the same manner as in (2) of Comparative Example 1, except that the polyamide resin obtained in (1) of Comparative Example 2 was used instead of the polyamide resin obtained in (1) of Comparative Example 1 prepared.

Comparative Example 3

(1) polyamide resin

Instead of the acyl chloride complex powder obtained in Preparation Example 1, 1.615 g (0.0080 mol) of isophthaloyl chloride (IPC) was first added, followed by an interval of about 5 minutes, and sequentially terephthaloyl chloride (terephthaloyl chloride) was added. , TPC), 7.358 g (0.0362 mol) of the polyamide resin was prepared in the same manner as in Example 1 (1), except that the amide formation reaction was carried out.

(2) polymer film

A polymer film was prepared in the same manner as in (2) of Comparative 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 Comparative Example 1 prepared.

<Experimental Example 1>

Using small-angle X-ray scattering (SAXS), the properties of individual crystals contained in the polyamide resins obtained in Examples and Comparative Examples were measured by the following method, and the results are shown in the table below. 1 is shown.

Using the polymer films obtained in Examples and Comparative Examples, samples were prepared in a size of 1 cm in width * 1 cm in length, and a small-angle X-ray scattering device (PLS at 23 ° C., having a camera length of 2.5 m and 6.5 m). -9A USAXS beam line), set the sample, irradiate X-rays with energies of 11.1 KeV and 19.9 KeV to obtain a scattering pattern, and then analyze the small-angle X-ray scattering device (NIST SANS package) The average particle diameter (2Rc), dimensionality, and crystallinity of individual crystals were obtained by analyzing the scattering pattern.

Specifically, the analysis of the average particle diameter, dimensionality, and crystallinity of the individual crystals is performed through a computer program (NIST SANS package) using data obtained from a small-angle X-ray scattering device (PLS 9A beamline), ^{More specifically, the average particle diameter of the individual crystals is a plot of the wavenumber q (unit: Å −1} ) and the scattering intensity I (unit: au) obtained by fitting the shape of the individual crystals contained in the sample to a solid sphere model. The diameter distribution curve of the crystal obtained by convolution with the Schulz-Zimm distribution can be obtained through calculation of the computer program (NIST SANS package).

Average grain size of crystals (nm) dimensionality Crystallinity (%) Example 1 5.0 3.7 Less than 20% difficult to measure Example 2 5.0 3.7 Less than 20% difficult to measure Example 3 5.0 3.7 Less than 20% difficult to measure Comparative Example 1 8.4 4.0 Less than 20% difficult to measure Comparative Example 2 13.4 3.2 24 Comparative Example 3 8.1 - Less than 20% difficult to measure

As shown in Table 1 above, while the average particle diameter of individual crystals contained in the polyamide resin obtained in Example was measured as small as 5 nm to 6.8 nm, the average of individual crystals contained in the polyamide resin obtained in Comparative Example 1 The particle diameter was 8.4 nm, the average particle diameter of the individual crystals contained in the polyamide resin obtained in Comparative Example 2 was 13.4 nm, and the average particle diameter of the individual crystals contained in the polyamide resin obtained in Comparative Example 3 was 7.8 nm. In addition, it can be seen that the crystallinity of the polyamide resin obtained in Example was less than 20%, showing low crystallinity, while the crystallinity of the polyamide resin obtained in Comparative Example 2 was 24%, which was increased compared to the Example. Through this, the polyamide resin obtained in the above example was terephthaloyl chloride (TPC) and 2,2'-bis(trifluoromethyl)-4,4'-biphenyldiamine (2,2). It was confirmed that the length growth of the crystalline block composed of repeating units obtained by the amide reaction of '-bis(trifluoromethyl)-4,4'-biphenyldiamine, TFDB) was inhibited compared to the comparative example.

<Experimental Example 2>

The following properties were measured or evaluated for the polyamide resin or polymer film obtained in Examples and Comparative Examples, and the results are shown in Table 2 below.

(1) Thickness: The thickness of the polymer film was measured using a thickness measuring device.

(2) Yellow index (Y.I.): The yellow index of the polymer film was measured according to ASTM E313 using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES).

(3) Light transmittance: Total light transmittance of the polymer film was measured using a Shimadzu UV-2600 UV-vis spectrometer. Among the measurement results, transmittance (T, @388nm) for ultraviolet light with a wavelength of 388 nm and transmittance for visible light with a wavelength of 550 nm (T, @550nm) were shown.

(4) Haze: The haze value of the polymer film was measured according to the measurement method of ASTM D1003 using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES).

(5) Flexibility: The bending strength of the polymer film was evaluated using an MIT-type folding endurance tester. Specifically, when a specimen of a polymer film (1 cm * 7 cm) is loaded into a bending strength tester and fractured by bending at an angle of 135°, a radius of curvature of 0.8 mm and a load of 250 g at a speed of 175 rpm on the left and right sides of the specimen. The number of reciprocating bending cycles (cycle) was measured.

(6) Tensile modulus, tensile strength and elongation: Modulus (GPa), strength (MPa) and elongation (%) were measured according to ISO 527-3 using Universal Testing Systems (Instron® 3360).

(7) Pencil hardness: The pencil hardness of the polymer film was measured according to the measurement method of ASTM D3363 using a Pencil Hardness Tester. Specifically, after fixing pencils of various hardnesses to the tester and scratching the polymer film, the degree of scratching on the polymer film was observed with the naked eye or a microscope. A value corresponding to the hardness was evaluated as the pencil hardness of the polymer film.

The pencil hardness 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 higher the number, the higher the hardness.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Thickness (㎛) 50 50 50 51 51 50 Y.I. 2.26 2.17 1.97 8.55 25.10 4.59 T(%)@550nm 89.29 89.83 90.36 85.63 75.94 87.57 Haze (%) 0.27 0.46 0.67 3.43 24.21 1.61 Flexibility (Cycle) 11524 11183 10412 5210 785 4513 Tensile Modulus (GPa) 7.84 8.09 8.36 7.4 - - Tensile strength (MPa) 266 253 245 - - - Elongation (%) 20 19 17 11 - - pencil hardness 3H 3H 3H 1H F 1H

Looking at Table 2, in the case of the polymer film obtained from the polyamide resin of the example prepared using the acyl chloride complex powder according to Preparation Example 1, a low yellow index of 1.97 to 2.26 at a thickness of about 50 μm, 0.27% to It was confirmed that excellent transparency could be secured through a low haze value of 0.67% and a high transmittance (@550nm) of 89.29% to 90.36%, a high tensile modulus of 7.84 GPa to 8.36 GPa, and a high tensile strength of 245 MPa to 266 MPa It was confirmed that excellent mechanical properties were secured through strength, high elongation of 17% to 20%, high pencil hardness of 3H grade, and breaking strength at 10412 to 11524 reciprocating bending cycles. On the other hand, polyamide resin In the case of the polymer film obtained from the polyamide resins of Comparative Examples 1, 2, and 3 in which the acyl chloride complex powder according to Preparation Example 1 was not used at all in the synthesis process, and the TPC powder and IPC powder were added simultaneously or sequentially, At a thickness of approximately 50 μm, the yellow index was 4.59 to 25.10, the haze value was 1.61% to 24.21%, and the transmittance (@550nm) was increased to 75.94% to 87.57%, confirming that the transparency was poor. In Comparative Examples 1, 2, and 3, due to the difference in solubility and reactivity between the TPC powder and the IPC powder, the block by TPC was excessively formed and the crystallinity of the polyamide resin was increased.

In addition, it was confirmed that it had poor mechanical properties compared to the examples through the low pencil hardness of 1F to 1H grade and the bending resistance to break at 785 to 5210 reciprocal bending cycles.

1: Individual decision
2: Average particle size of individual crystals
3: Amorphous polymer chain

Claims (20)

a polyamide resin in which an average particle diameter of individual crystals measured by a small-angle X-ray scattering device is 8.0 nm or less, and an amorphous polymer chain exists between individual crystals having an average particle diameter of 8.0 nm or less; and
A polyamide resin composition comprising a silica-based filler.
According to claim 1,
The average particle diameter of the individual crystals is measured through analysis equipment by fitting a scattering pattern obtained by irradiating X-rays having an energy of 10 KeV to 20 KeV in the small-angle X-ray scattering device with a solid sphere model. , a polyamide resin composition.
According to claim 1,
The distance between the individual crystals having an average particle diameter of 8.0 nm or less is 0.1 nm or more and 100 nm or less, the polyamide resin composition.
According to claim 1,
The polyamide resin composition, wherein the individual crystals having an average particle diameter of 8.0 nm or less include a first aromatic amide repeating unit derived from a combination of a 1,4-aromatic diacyl compound and an aromatic diamine compound.
According to claim 1,
The polyamide resin composition, wherein the individual crystals having an average particle diameter of 8.0 nm or less include a first polyamide segment including a repeating unit represented by the following Chemical Formula 1, or a block consisting of the repeating unit.
[Formula 1]

In Formula 1, 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.
6. The method of claim 5,
The first polyamide segment has a number average molecular weight of 100 g/mol or more and 5000 g/mol or less, a polyamide resin composition.
6. The method of claim 5,
A polyamide resin composition comprising 40 mol% or more and 95 mol% or less of the first polyamide segment based on all repeating units contained in the polyamide resin.
According to claim 1,
The polyamide resin composition has a crystallinity of 20% or less as measured by a small-angle X-ray scattering apparatus.
According to claim 1,
The amorphous polymer chain is a second aromatic amide repeating unit derived from a combination of a 1,2-aromatic diacyl compound and an aromatic diamine compound, or a combination of a 1,3-aromatic diacyl compound and an aromatic diamine compound. A polyamide resin composition comprising a third aromatic amide repeating unit.
According to claim 1,
Between the individual crystals having an average particle diameter of 8.0 nm or less, an amorphous polymer chain is
A polyamide resin composition comprising a second polyamide segment including a repeating unit represented by the following formula (2) or a block consisting of the repeating unit:
[Formula 2]

In Formula 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.
11. The method of claim 10,
The content of the repeating unit represented by the formula (2) is 5 mol% or more and 60 mol% or less, based on all repeating units contained in the polyamide resin.
6. The method of claim 5,
The amorphous polymer chain existing between individual crystals having an average particle diameter of 8.0 nm or less including the repeating unit represented by Formula 1 or the first polyamide segment including a block consisting of the same is,
A polyamide resin composition comprising a second polyamide segment including a repeating unit represented by the following formula (2) or a block consisting of the repeating unit:
[Formula 2]

In Formula 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.
13. The method of claim 12,
A polyamide resin composition, wherein the first polyamide segment and the second polyamide segment form a main chain including a cross repeating unit represented by the following formula (3):
[Formula 3]

In Formula 3,
A is the first polyamide segment,
B is the second polyamide segment.
14. The method of claim 13,
The cross-repeating unit represented by the formula (3) is a repeating unit represented by the following formula (4), a polyamide resin composition:
[Formula 4]

In the above 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,
a1 and a2 are each independently an integer of 1 to 10,
b1 and b2 are each independently an integer of 1 to 5;
13. The method of claim 12,
Based on all the repeating units contained in the polyamide resin, the content of the repeating unit represented by the formula (1) is 60 mol% to 95 mol%, and the content of the repeating unit represented by the formula (2) is 5 mol% to 40 mol% %, the polyamide resin composition.
According to claim 1,
The silica-based filler is
A polyamide resin composition comprising nano silica particles having a diameter of 0.1 nm or more and 500 nm or less.
According to claim 1,
The silica-based filler is contained in an amount of 50 parts by weight or less based on 100 parts by weight of the polyamide resin, the polyamide resin composition.
According to claim 1,
The silica-based filler has a refractive index of 1.4 or more and 1.5 or less, and the polyamide resin has a refractive index of 1.6 or more and 1.7 or less.
A polymer film comprising a cured product of the polyamide resin composition of claim 1 .
A substrate comprising the polymer film of claim 19; and
A resin laminate comprising a; a hard coating layer formed on at least one surface of the substrate.

Images