KR20190056172A - Plastic laminated film - Google Patents

Abstract

The present invention relates to a plastic stacked film having excellent scratch resistance and UV blocking properties, which comprises: a core layer including a polyamideimide resin or polyamide resin; and outer layers including a polyamideimide resin, and separately stacked on both surfaces of the core layer.

Description

Plastic laminated film {PLASTIC LAMINATED FILM}

The present invention relates to a plastic laminated film comprising a polyamideimide resin or a polyamide resin.

As interest in electronic devices that can bend or bend as one of the next generation display technologies increases, development of materials that can replace glass substrates to protect display devices is required.

Cover films of flexible or foldable devices are required to have colorless transparency such as glass and excellent physical properties such as hardness, bending strength, dimensional stability, chemical resistance, moisture resistance and weather resistance.

In recent years, polyimide-based polymers have been attracting attention as materials satisfying such characteristics, and polyamideimides having a polyamide unit structure introduced into polyimide for improving the hardness of the polyimide have been proposed.

However, the polyamide-imide exhibits a tendency to easily haze as the thickness of the polyamide-imide film is increased due to its high crystallinity. In addition, the polyamide imide has low weather resistance to UV, and when exposed to UV for a long time, the yellow index increases and yellowing of the film occurs.

In the polyamide-imide series films, yellow index and mechanical properties are known to be in a trade-off relationship. For example, the lower the yellow index of the film is, the higher the transmittance is, but the UV blocking property is lowered, and the amorphous region is increased, and the mechanical properties are relatively lowered. On the other hand, the higher the mechanical strength such as the surface hardness and the modulus of the film, the higher the yellow index value due to the development of the crystalline region and the charge transfer complex (CTC).

Accordingly, development of a plastic film having optical properties and mechanical properties at a level that can replace glass as a material for displays and window covers of various electronic devices is required.

The present invention is to provide a plastic laminated film that is colorless and transparent, but can exhibit excellent scratch resistance and ultraviolet shielding properties.

According to the present invention,

A core layer comprising a polyamide-imide resin or a polyamide resin, and

Wherein the outer layer layers include a polyamide-imide resin and are laminated on both sides of the core layer,

A plastic laminated film comprising:

The core layer having a yellow index of less than 1.5 measured according to ASTM E313 and a pencil hardness of at least 4B measured according to ASTM D3363 for a specimen of thickness 50 +/- 2 mu m;

The outer layers had a yellow index of less than 4.5 measured according to ASTM E313, a pencil hardness of at least 2H grade measured according to ASTM D3363, and 20.0% of ultraviolet light at 388 nm, Having a transmittance of less than < RTI ID = 0.0 >

A plastic laminated film is provided.

Hereinafter, a plastic laminated film according to an embodiment of the present invention will be described in detail.

It is to be understood that the terminology is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention, unless explicitly stated herein.

The singular forms as used herein include plural forms as long as the phrases do not expressly contradict it.

Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components, and / And the like.

In this specification, terms including ordinals such as 'first' and 'second' are used for the purpose of distinguishing one element from another, and are not limited by the ordinal number. For example, within the scope of the present invention, a first component may also be referred to as a second component, and similarly, a second component may be named as a first component.

On the other hand, as a result of continuous research by the present inventors, it has been confirmed that the plastic laminated film formed by laminating three layers satisfying the following characteristics can exhibit excellent scratch resistance and ultraviolet shielding properties, colorless and transparent.

Particularly, the plastic laminated film can secure both the optical property and the mechanical property which are in a trade-off relationship, and can provide excellent performance compared with a film composed of a single layer of equivalent thickness or a laminated film which does not satisfy the above- can do.

According to one embodiment of the invention,

A core layer comprising a polyamide-imide resin or a polyamide resin, and

Wherein the outer layer layers include a polyamide-imide resin and are laminated on both sides of the core layer,

A plastic laminated film comprising:

The core layer having a yellow index of less than 1.5 measured according to ASTM E313 and a pencil hardness of at least 4B measured according to ASTM D3363 for a specimen of thickness 50 +/- 2 mu m;

The outer layers had a yellow index of less than 4.5 measured according to ASTM E313, a pencil hardness of at least 2H grade measured according to ASTM D3363, and 20.0% of ultraviolet light at 388 nm, Having a transmittance of less than < RTI ID = 0.0 >

A plastic laminated film is provided.

The plastic laminated film according to this embodiment includes a core layer and outer layers laminated on both sides of the core layer.

That is, the plastic laminated film has a three-layer structure including a first outer layer 2 / a core layer 1 / a second outer layer 2 'which are sequentially stacked as shown in Fig.

The core layer has a relatively good optical property such as yellow index, haze and visible light transmittance as compared with the outer layers. In addition, each of the outer layers has relatively excellent mechanical properties such as scratch resistance, and excellent ultraviolet shielding properties, as compared with the core layer.

The plastic laminated film including the core layer and the outer layers laminated with the above structure is excellent in both ultraviolet shielding property and dimensional stability while satisfying the optical and mechanical properties required for the display and window cover materials of various electronic apparatuses .

According to an embodiment of the invention, the core layer comprises a polyamideimide resin or a polyamide resin, and the outer layers each comprise a polyamideimide resin. Preferably, the core layer and the outer layer each comprise a polyamideimide resin, which may be advantageous for the development of more reliable characteristics.

In the plastic laminated film, the core layer has a yellow index of less than 1.5, measured according to ASTM E313, for specimens having a thickness of 50 +/- 2 mu m. Specifically, the core layer has a hardness of less than or equal to 1.5 or less than or equal to 1.4, And having a yellow index of 1.1 or more or 1.2 or more is preferable for the expression of the above-mentioned characteristics.

The core layer has a pencil hardness of 4B or more as measured according to ASTM D3363 for a specimen having a thickness of 50 占 占 퐉. Specifically, the core layer may be a 4B grade or more or a 3B grade or more measured by the above conditions; And pencil hardness less than or equal to grade B or less than grade 2B.

On the other hand, in the plastic laminated film, the outer layer layers each have a pencil hardness of 2H grade or higher measured according to ASTM D3363 for a specimen having a thickness of 50 +/- 2 mu m. Specifically, each of the outer layers may be at least 2H grade or at least 3H grade measured by the above conditions; And having a pencil hardness of 5H or less or 4H or less is preferable for the development of the above-mentioned properties.

In particular, the outer layers exhibit a transmittance of 20.0% or less with respect to ultraviolet rays of 388 nm wavelength in a specimen having a thickness of 50 ± 2 μm. Specifically, the outer layers are not more than 20.0%, or less than 18.0%, or less than 15.0%, or less than 10.0%, or less than 5.0%, respectively, of ultraviolet rays having a wavelength of 388 nm; And a transmittance of 1.0% or more, or 1.5% or more, or 2.0% or more is preferable for the development of the above-mentioned characteristics.

The outer layers have a yellow index of less than 4.5 measured according to ASTM E313 for specimens each having a thickness of 50 +/- 2 mu m. Specifically, the outer layers are each 4.5 or less, or 4.4 or less, or 4.3 or less, or 4.2 or less, measured according to the above conditions; And a yellow index of 2.0 or higher, or 2.5 or higher, or 3.0 or higher, or 3.1 or higher.

On the other hand, according to the embodiment of the present invention, by changing the composition of the monomers constituting the resin contained in each layer, the core layer and the outer layer that satisfy the above-mentioned characteristics can be provided.

For example, the core layer that meets the above-mentioned properties may comprise from 40 to 55 mole percent of an aromatic diamine monomer, from 0.5 to 5 mole percent of an aromatic dianhydride monomer, and from 40 to 55 mole percent of an aromatic dicarbonyl monomer And a polyamideimide resin which is an imide of a copolymerized polyamic acid.

And, the outer layers meeting the above-mentioned characteristics each independently comprise 40 to 55 mol% of an aromatic diamine monomer, 10 to 15 mol% of an aromatic dianhydride monomer and 30 to 45 mol% of an aromatic dicarbonyl monomer And a polyamideimide resin which is an imide of a copolymerized polyamic acid.

The polyamic acid may be a block copolymer or a random copolymer.

For example, the polyamic acid block copolymer may comprise a first unit structure derived from copolymerization of the aromatic dianhydride monomer and the aromatic dianhydride monomer; And a second unit structure derived from copolymerization of the aromatic diamine monomer and the aromatic dicarbonyl monomer.

The polyamic acid random copolymer may have a unit structure in which the aromatic diamine monomer, the aromatic dianhydride monomer, and the aromatic dicarbonyl monomer each form an amide bond and are randomly copolymerized.

This polyamic acid forms a polyamideimide copolymer having imide bond and amide bond simultaneously by imidization.

According to an embodiment of the present invention, in the polyamide-imide resin contained in the core layer and the outer layers, the aromatic dicarbonyl monomer has a molecular weight of 60.0 Mol% or more may be preferable for forming a copolymer having colorless transparency and excellent mechanical properties.

Preferably, the aromatic dicarbonyl monomer is present in an amount of at least 60.0 mol%, or at least 65.0 mol%, or at least 70.0 mol%, or at least 75.0 mol%, based on the total moles of the aromatic dianhydride monomer and the aromatic dicarbonyl monomer. Or more.

Specifically, in the polyamide-imide resin contained in the outer layers, the aromatic dicarbonyl monomer is contained in an amount of 60.0 mol% or more, or 65.0 mol% or less, based on the total moles of the aromatic dianhydride monomer and the aromatic dicarbonyl monomer. Or more, or 70.0 mol% or more, or 75.0 mol% or more; And not more than 90.0 mol%, or not more than 85.0 mol%, or not more than 80.0 mol%, is preferable for the development of the above-mentioned characteristics.

In the polyamide-imide resin contained in the core layer, the aromatic dicarbonyl monomer may be present in an amount of 80.0 mol% or more, or 85.0 mol% or more, Or 90.0 mol% or more, or 95 mol% or more; And 99.5 mol% or less, or 99.0 mol% or less, or 98.5 mol% or less is preferable for the development of the above-mentioned characteristics.

According to an embodiment of the present invention, the aromatic diamine monomer, the aromatic dianhydride monomer, and the aromatic dicarbonyl monomer for forming the polyamide-imide resin may be compounds that are conventional in the art And can be applied without any specific limitation.

Specific examples of the aromatic diamine monomer include, but are not limited to, 2,2'-bis (trifluoromethyl) -4,4'-bis (trifluoromethyl) '-biphenyldiamine, 4,4'-diaminodiphenyl sulfone, 4,4'- (9-fluorenylidene) dianiline (4,4'- dianiline, bis (4- (4-aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine ', 5,5'-tetrachlorobenzidine), 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, m-phenylenediamine p-phenylenediamine, 4,4'-oxydianiline, 2,2'-dimethyl-4,4'-diaminobie, Bis (4- (4-aminophenoxy) phenyl) propane (2,2-bis [4- (4-aminophenoxy) phenyl] ] propane, 1,3-bis (4-aminophenoxy) benzene (1,3-bis (4-a minophenoxy) benzene, and 4,4'-diaminobenzanilide can be preferably used.

Examples of the aromatic dianhydride monomer include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-biphenyltetracarboxylic dianhydride, (Hexafluoroisopropylidene) diphthalic anhydride, 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (4,4'- (2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride), benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxyl Benzophenone tetracarboxylic dianhydride, oxydiphthalic anhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclobutane- tetracarboxylic dianhydride), cyclopentane At least one compound selected from the group consisting of cyclopentane tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, and bis (3,4-dicarboxyphenyl) sulfone dianhydride Can be preferably used.

Examples of the aromatic dicarbonyl monomer include terephthaloyl chloride, isophthaloyl chloride, biphenyldicarbonyl chloride, terephthalic acid, pyridine-2 2,5-dicarbonyl chloride, pyridine-2,5-dicarboxylic acid, pyrimidine-2,5-dicarbonyl chloride, 2,5-dicarbonyl chloride, pyrimidine-2,5-dicarboxylic acid, 4,4'-biphenyldicarbonyl chloride, and 4,4'-biphenyldicarboxylic acid may be preferably used.

On the other hand, the polymerization conditions for forming the polyamic acid copolymerized with the aromatic diamine monomer, the aromatic dianhydride monomer and the aromatic dicarbonyl monomer are not particularly limited.

Preferably, the polymerization for the formation of the polyamic acid can be carried out by solution polymerization under an inert atmosphere at 0 to 100 캜.

Examples of the solvent for forming the polyamic acid include N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone, N-methyl-2-pyrrolidone, tetrahydrofuran, chloroform, gamma-butyrolactone Can be used.

Imidization after the formation of the polyamic acid can be performed thermally or chemically. For example, compounds such as acetic anhydride, pyridine may be used for chemical imidization.

The polyamide resin that may be contained in the core layer may be formed by a conventional method using the above-mentioned monomers appropriately.

According to an embodiment of the present invention, the polyamide-imide resin and the polyamide resin contained in the core layer and the outer layers may each independently have a weight-average molecular weight of 10,000 to 1,000,000 g / mol, or 10,000 to 500,000 g / mol, / mol. < / RTI >

Preferably, the resin contained in the core layer has a weight average molecular weight of 10,000 to 100,000 g / mol, or 10,000 to 50,000 g / mol, or 10,000 to 30,000 g / mol, or 10,000 to 20,000 g / mol, It may be advantageous for the expression of one characteristic.

On the other hand, the core layer and the outer layer may be prepared by a conventional method such as a dry method or a wet method using the resin. For example, the core layer and the outer layer may be obtained by coating a solution containing the resin on an arbitrary support to form a film, and drying the film by evaporating the solvent from the film.

The plastic laminated film according to the embodiment of the present invention can be manufactured by laminating the core layer and the outer layer obtained by the above-described method in the order of the first outer layer / core layer / second outer layer and pressing them.

The plastic laminated film may be formed by coating a resin solution for forming the outer layers on a support and drying the same to form a first outer layer and then forming a core layer on the first outer layer, Coating a resin solution and drying to form a core layer, and forming a second outer layer on the core layer in a similar manner.

If necessary, stretching and heat treatment for the plastic laminated film can be performed.

On the other hand, according to the embodiment of the present invention, the plastic laminated film having the total thickness of 30 to 100 mu m may be advantageous for securing the optical and mechanical properties at the same time.

Specifically, the plastic laminated film has a thickness of 30 占 퐉 or more, 40 占 퐉 or more, 50 占 퐉 or more; And may have a total thickness of 100 μm or less, or 90 μm or less, or 80 μm or less, or 70 μm or less.

In the plastic laminated film, it is preferable that the core layer and the one outer layer have a thickness ratio of 1: 0.1 to 1: 0.5 for the above-described characteristics.

Specifically, the core layer and the one outer layer may have a ratio of 1: 0.1 or more, 1: 0.2 or more, or 1: 0.3 or more; And may have a thickness ratio of 1: 0.5 or less, or 1: 0.4 or less. As a non-limiting example, a plastic laminated film having a total thickness of 50 占 퐉 may include the core layer having a thickness of 30 占 퐉 and the outer layers each having a thickness of 10 占 퐉 laminated on both sides of the core layer.

According to the embodiment of the present invention, the plastic laminated film has a structure including the core layer and the outer layers which satisfy the above-mentioned characteristics, and thus can exhibit excellent scratch resistance and ultraviolet shielding properties while being colorless and transparent.

Specifically, the plastic laminated film may exhibit a yellow index of 3.0 or less, measured according to ASTM E313, for a specimen having a thickness of 50 +/- 2 mu m.

Preferably, the plastic laminated film has a Young's modulus of 3.0 or less, or 2.9 or less, or 2.8 or less, And a yellow index of 2.0 or more, or 2.1 or more, or 2.2 or more.

The plastic laminated film can exhibit a transmittance of 20.0% or less with respect to ultraviolet rays of 388 nm wavelength in a specimen of 50 ± 2 μm. Preferably, the plastic laminated film is 20.0% or less, or 19.0% or less, or 18.0% or less of the ultraviolet light of 388 nm wavelength; And a transmittance of 1.0% or more, or 5.0% or more, or 10.0% or more.

The plastic laminated film can exhibit a transmittance of 88.0% or more with respect to visible light at a wavelength of 550 nm in a specimen of 50 2 탆. Preferably, the plastic laminated film is at least 88.0% or at least 88.5% of the visible light at a wavelength of 550 nm; And a transmittance of 90.0% or less, or 89.5% or less, or 89.0% or more.

The plastic laminated film may exhibit a pencil hardness of 2H grade or higher measured according to ASTM D3363 for a specimen having a thickness of 50 +/- 2 mu m. Preferably, the plastic laminated film has a grade of 2H or higher or a grade of 3H or higher as measured under the above conditions; And pencil hardness less than or equal to 5H or less than or equal to 4H.

The plastic laminated film has a linear thermal expansion coefficient (CTE) of 12.0 ppm / ° C or less for a specimen of 50 ± 2 μm, and can exhibit excellent dimensional stability. Preferably, the plastic laminated film has a thickness of less than or equal to 12.0 ppm / 占 폚, or 11.9 ppm / 占 폚 or less, or 11.8 ppm / 占 폚 or less, And may have a coefficient of linear thermal expansion of 10.0 ppm / ° C or higher or 10.5 ppm / ° C or higher.

The plastic laminated film according to the present invention is colorless and transparent, yet has excellent scratch resistance and ultraviolet shielding properties and can be suitably used as a cover film for various flexible or foldable devices.

1 is a sectional view of a plastic laminated film according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. However, the following embodiments are intended to illustrate the invention, but the invention is not limited thereto.

Manufacturing example  One

(Production of Resin for Outer Layer A)

42.5 g of N, N-dimethylacetamide (N, N-dimethylacetamide) was charged with slowly blowing nitrogen into a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel and a temperature controller , The temperature of the reactor was adjusted to 25 ° C, and then 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine , TFDB) (4.3354 g, 0.0136 mol). While keeping the temperature of the solution at 25 占 폚, 0.8804 g (0.003 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) ), And the mixture was stirred and reacted for a predetermined time.

Then, after the temperature of the solution was cooled to -10 DEG C, 0.3314 g (0.001632 mol) of isophthaloyl chloride (IPC) and 1.9329 g (0.00952 mol) of terephthaloyl chloride (TPC) And stirred to obtain a polyamic acid solution having a solid content of 15% by weight.

N, N-dimethylacetamide was added to the polyamic acid solution to dilute the solid content to 5 wt% or less, and the solid content was precipitated with 10 L of methanol. The precipitated solids were filtered and dried at 100 DEG C under vacuum for 6 hours or more to obtain a polyamide-imide resin in the form of a solid (weight average molecular weight: about 88,213 g / mol).

Manufacturing example  2

(Production of Resin for Outer Layer B)

42.5 g of N, N-dimethylacetamide (N, N-dimethylacetamide) was charged with slowly blowing nitrogen into a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel and a temperature controller , The temperature of the reactor was adjusted to 25 ° C, and then 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine , TFDB) (4.362 g, 0.01362 mol). While maintaining the temperature of the solution at 25 占 폚, 1.2023 g (0.004086 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) ), And the mixture was stirred and reacted for a predetermined time.

Then, after the temperature of the solution was cooled to -10 DEG C, 1.9358 g (0.00953 mol) of terephthaloyl chloride (TPC) was added and stirred to obtain a polyamic acid solution having a solid content of 15 wt% .

N, N-dimethylacetamide was added to the polyamic acid solution to dilute the solid content to 5 wt% or less, and the solid content was precipitated with 10 L of methanol. The precipitated solids were filtered and dried at 100 DEG C under vacuum for 6 hours or more to obtain a polyamide-imide resin in the form of solid (weight average molecular weight: about 102,488 g / mol).

Manufacturing example  3

(Production of resin for core layer C)

42.5 g of N, N-dimethylacetamide (N, N-dimethylacetamide) was charged with slowly blowing nitrogen into a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel and a temperature controller , The temperature of the reactor was adjusted to 25 ° C, and then 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine , TFDB) (4.556 g, 0.01422 mol). 0.0558 g (0.000284 mol) of cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA) was added while maintaining the temperature of the solution at 25 占 폚, And the mixture was stirred for a predetermined time to dissolve and react.

After the temperature of the solution was cooled to -10 DEG C, 2.8883 g (0.01423 mol) of isophthaloyl chloride (IPC) was added and stirred, and a polyamic acid solution having a solid content of 15 wt% .

N, N-dimethylacetamide was added to the polyamic acid solution to dilute the solid content to 5 wt% or less, and the solid content was precipitated with 10 L of methanol. The precipitated solids were filtered and then dried at 100 DEG C under vacuum for 6 hours or more to obtain a polyamide-imide resin in the form of solid (weight average molecular weight: about 13,157 g / mol).

Manufacturing example  4

(Production of resin for core layer D)

42.5 g of N, N-dimethylacetamide (N, N-dimethylacetamide) was charged with slowly blowing nitrogen into a 1000 mL 4-neck round flask (reactor) equipped with a stirrer, a nitrogen injector, a dropping funnel and a temperature controller , The temperature of the reactor was adjusted to 25 ° C, and then 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine , TFDB) (4.4528 g, 0.0139 mol). 0.3089 g (0.000695 mol) of 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added while keeping the temperature of the solution at 25 ° C After that, the mixture was stirred for a predetermined time to dissolve and react.

After the temperature of the solution was cooled to -10 캜, 2.7383 g (0.013488 mol) of isophthaloyl chloride (IPC) was added and stirred, and a polyamic acid solution having a solid content of 15 wt% .

N, N-dimethylacetamide was added to the polyamic acid solution to dilute the solid content to 5 wt% or less, and the solid content was precipitated with 10 L of methanol. The precipitated solids were filtered and then dried at 100 DEG C under vacuum for 6 hours or more to obtain a polyamide-imide resin in the form of solid (weight average molecular weight: about 16,157 g / mol).

Comparative Example  One

The resin for outer layer A obtained in Preparation Example 1 was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 12% (w / v). The polymer solution was poured into a plastic substrate (UPILEX-75s, UBE Co.), the thickness of the polymer solution was uniformly controlled using a film applicator, dried in a Matze oven at 80 DEG C for 15 minutes, And cured for 30 minutes to obtain a film having a thickness of 50.0 mu m peeled from the substrate.

Comparative Example  2

A film having a thickness of 50.0 탆 was obtained in the same manner as in Comparative Example 1, except that the resin for the outer layer B obtained in Production Example 2 was used in place of the resin for the outer layer A obtained in Production Example 1. [

Comparative Example  3

A film having a thickness of 50.0 탆 was obtained in the same manner as in Comparative Example 1, except that the resin for the core layer C obtained in Production Example 3 was used in place of the resin for the outer layer A obtained in Production Example 1. [

Comparative Example  4

A film having a thickness of 50.0 탆 was obtained in the same manner as in Comparative Example 1, except that the resin for the core layer D obtained in Production Example 4 was used in place of the resin for the outer layer A obtained in Production Example 1. [

Example  One

(1) A resin solution for outer layer A obtained in Preparation Example 1 was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 12% (w / v). The polymer solution was poured into a plastic substrate (UPILEX-75s, UBE Co.), the thickness of the polymer solution was uniformly controlled using a film applicator, dried in a Matze oven at 80 DEG C for 15 minutes, And cured for 30 minutes to form a first outer layer having a thickness of 10.0 탆.

(2) The resin for core layer C obtained in Preparation Example 3 was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 12% (w / v). The polymer solution was poured onto the first outer layer and the polymer solution was uniformly adjusted in thickness using a film applicator. The polymer solution was dried in a Matze oven at 80 DEG C for 15 minutes, cured at 250 DEG C for 30 minutes while flowing nitrogen Thereby forming a core layer having a thickness of 30.0 占 퐉.

(3) A solution containing the resin for the outer layer A prepared above was poured on the core layer, the thickness of the polymer solution was uniformly adjusted using a film applicator, dried in a Matze oven at 80 DEG C for 15 minutes, Followed by curing at 250 DEG C for 30 minutes to form a second outer layer having a thickness of 10.0 mu m.

(4) A laminated film having a thickness of 50.0 占 퐉 in which the first outer layer (A) / the core layer (C) / the second outer layer (A) were sequentially laminated was peeled off from the plastic substrate.

Example  2

(1) A polymer solution of about 12% (w / v) was prepared by dissolving the resin for outer layer B obtained in Preparation Example 2 in N, N-dimethylacetamide. The polymer solution was poured into a plastic substrate (UPILEX-75s, UBE Co.), the thickness of the polymer solution was uniformly controlled using a film applicator, dried in a Matze oven at 80 DEG C for 15 minutes, And cured for 30 minutes to form a first outer layer having a thickness of 10.0 탆.

(2) The resin for core layer C obtained in Preparation Example 3 was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 12% (w / v). The polymer solution was poured onto the first outer layer and the polymer solution was uniformly adjusted in thickness using a film applicator. The polymer solution was dried in a Matze oven at 80 DEG C for 15 minutes, cured at 250 DEG C for 30 minutes while flowing nitrogen Thereby forming a core layer having a thickness of 30.0 占 퐉.

(3) A solution containing the resin for the outer layer B prepared above was poured onto the core layer, the thickness of the polymer solution was uniformly adjusted using a film applicator, dried in a Matze oven at 80 DEG C for 15 minutes, Followed by curing at 250 DEG C for 30 minutes to form a second outer layer having a thickness of 10.0 mu m.

(4) A laminated film having a thickness of 50.0 占 퐉 in which the first outer layer (B) / the core layer (C) / the second outer layer (B) were sequentially laminated was peeled off from the plastic substrate.

Example  3

(1) A resin solution for outer layer A obtained in Preparation Example 1 was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 12% (w / v). The polymer solution was poured into a plastic substrate (UPILEX-75s, UBE Co.), the thickness of the polymer solution was uniformly controlled using a film applicator, dried in a Matze oven at 80 DEG C for 15 minutes, And cured for 30 minutes to form a first outer layer having a thickness of 10.0 탆.

(2) The resin for core layer D obtained in Preparation Example 4 was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 12% (w / v). The polymer solution was poured onto the first outer layer and the polymer solution was uniformly adjusted in thickness using a film applicator. The polymer solution was dried in a Matze oven at 80 DEG C for 15 minutes, cured at 250 DEG C for 30 minutes while flowing nitrogen Thereby forming a core layer having a thickness of 30.0 占 퐉.

(3) A solution containing the resin for the outer layer A prepared above was poured on the core layer, the thickness of the polymer solution was uniformly adjusted using a film applicator, dried in a Matze oven at 80 DEG C for 15 minutes, Followed by curing at 250 DEG C for 30 minutes to form a second outer layer having a thickness of 10.0 mu m.

(4) A laminated film having a thickness of 50.0 占 퐉 in which the first outer layer (A) / the core layer (D) / the second outer layer (A) were laminated successively from the plastic substrate was peeled off.

Example  4

(1) A polymer solution of about 12% (w / v) was prepared by dissolving the resin for outer layer B obtained in Preparation Example 2 in N, N-dimethylacetamide. The polymer solution was poured into a plastic substrate (UPILEX-75s, UBE Co.), the thickness of the polymer solution was uniformly controlled using a film applicator, dried in a Matze oven at 80 DEG C for 15 minutes, And cured for 30 minutes to form a first outer layer having a thickness of 10.0 탆.

(2) The resin for core layer D obtained in Preparation Example 4 was dissolved in N, N-dimethylacetamide to prepare a polymer solution of about 12% (w / v). The polymer solution was poured onto the first outer layer and the polymer solution was uniformly adjusted in thickness using a film applicator. The polymer solution was dried in a Matze oven at 80 DEG C for 15 minutes, cured at 250 DEG C for 30 minutes while flowing nitrogen Thereby forming a core layer having a thickness of 30.0 占 퐉.

(3) A solution containing the resin for the outer layer B prepared above was poured onto the core layer, the thickness of the polymer solution was uniformly adjusted using a film applicator, dried in a Matze oven at 80 DEG C for 15 minutes, Followed by curing at 250 DEG C for 30 minutes to form a second outer layer having a thickness of 10.0 mu m.

(4) A laminated film having a thickness of 50.0 占 퐉 in which the first outer layer (B) / the core layer (D) / the second outer layer (B) were sequentially laminated was peeled off from the plastic substrate.

Test Example

The following properties of the films according to the Examples and Comparative Examples were measured or evaluated, and the results are shown in Table 1 below.

(1) Yellow index (YI): The yellow index of the film was measured according to the method of ASTM E313 using a COH-400 Spectrophotometer (NIPPON DENSHOKU INDUSTRIES).

(2) Transmittance: The total light transmittance of the film was measured using a UV-VIS-NIR Spectrophotometer (SolidSpec-3700, SHIMADZU). The transmittance (T,%, @ 388 nm) for ultraviolet light of 388 nm wavelength and the transmittance (T,%, @ 550 nm) for visible light of 550 nm wavelength are shown in Table 1 below.

(3) Pencil Hardness: The pencil hardness of the film was measured according to the measurement method of ASTM D3363 using Pencil Hardness Tester. Specifically, when a pencil having various hardnesses is fixed to the tester and scratches on the film, the degree of occurrence of scratches on the film is visually observed by a microscope or a microscope. When the scratches are not scratched by more than 70% of the total number of scratches, The corresponding values were evaluated for the pencil path of the film.

(4) Thermal Expansion Coefficient (CTE): 2940 TMA V2.4E Using a TMA method (IPC-TM-650 2.4.24.5) with a temperature profile of 50 to 250 ° C and a heating rate of 10 ° C / linear thermal expansion coefficient (ppm / 캜).

Y.I. T (%)
@ 388nm T (%)
@ 550nm Pencil hardness CTE
(ppm / DEG C) Example 1 (ACA) 2.3 17.0 88.9 3H 10.8 Example 2 (BC-B) 2.8 13.0 88.8 3H 11.7 Example 3 (ADA) 2.2 18.0 88.8 3H 11.0 Example 4 (B-D-B) 2.7 13.0 88.8 3H 11.8 Comparative Example 1 (A) 3.2 18.0 88.2 3H 17.8 Comparative Example 2 (B) 4.2 4.0 88.1 3H 22.4 Comparative Example 3 (C) 1.4 83.0 90.1 3B 16.8 Comparative Example 4 (D) 1.3 85.0 89.8 3B 17.8

Referring to Table 1, it was confirmed that the laminated film according to the Examples had a yellow index of 2.8 or less and a visible light transmittance of 88.8% or more, thus having optically colorless transparent characteristics. In addition, the laminated film according to the above examples exhibited a pencil hardness of 3H grade, a UV transmittance of 20% or less at 388 nm wavelength, and a coefficient of linear thermal expansion of 11.8 ppm / ° C or less, and exhibited excellent scratch resistance, It was confirmed to have stability.

1: core layer
2: first outer layer
2 ': second outer layer

Claims (11)

A core layer comprising a polyamide-imide resin or a polyamide resin, and
Wherein the outer layer layers include a polyamide-imide resin and are laminated on both sides of the core layer,
A plastic laminated film comprising:
The core layer having a yellow index of less than 1.5 measured according to ASTM E313 and a pencil hardness of at least 4B measured according to ASTM D3363 for a specimen of thickness 50 +/- 2 mu m;
The outer layers had a yellow index of less than 4.5 measured according to ASTM E313, a pencil hardness of at least 2H grade measured according to ASTM D3363, and 20.0% of ultraviolet light at 388 nm, Having a transmittance of less than < RTI ID = 0.0 >
Plastic laminated film.
The method according to claim 1,
Wherein the core layer and the outer layers each comprise a polyamideimide resin.
The method according to claim 1,
The core layer comprises a polyamide which is an imide of polyamic acid copolymerized with from 40 to 55 mol% of aromatic diamine monomer, from 0.5 to 5 mol% of aromatic dianhydride monomer and from 40 to 55 mol% of aromatic dicarbonyl monomer A mid resin;
Wherein said outer layers are each independently selected from the group consisting of 40 to 55 mole percent of an aromatic diamine monomer, 10 to 15 mole percent of an aromatic dianhydride monomer, and 30 to 45 mole percent of an aromatic dicarbonyl monomer, Lt; RTI ID = 0.0 > polyamide < / RTI >
Plastic laminated film.
The method of claim 3,
The aromatic diamine monomers are each independently selected from the group consisting of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine, 2,2'-bis (trifluoromethyl) 4,4'-diaminodiphenyl sulfone, 4,4'- (9-fluorenylidene) dianiline, bis (4,4'- (4- (4-aminophenoxy) phenyl) sulfone), 2,2 ', 5,5'-tetrachlorobenzidine (2,2', 5,5 2,7-diaminofluorene, 4,4-diaminooctafluorobiphenyl, m-phenylenediamine, and the like. , p-phenylenediamine, 4,4'-oxydianiline, 2,2'-dimethyl-4,4'-diaminobiphenyl (2,2'- bis (4-aminophenoxy) phenyl] propane, 1, 2-bis [4- (4-aminophenoxy) phenyl] , 3-bis (4-aminophenoxy) benzene, 1,3-bis And at least one compound selected from the group consisting of 4,4'-diaminobenzanilide,
Plastic laminated film.
The method of claim 3,
The aromatic dianhydride monomers are each independently selected from the group consisting of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4' - ( Hexafluoroisopropylidene diphthalic anhydride, 2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (2, 4'- , 2'-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, But are not limited to, benzophenone tetracarboxylic dianhydride, oxydiphthalic anhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride ), Cyclopentane At least one compound selected from the group consisting of cyclopentane tetracarboxylic dianhydride and bis (3,4-dicarboxyphenyl) sulfone dianhydride. ,
Plastic laminated film.
The method of claim 3,
The aromatic dicarbonyl monomer may be selected from the group consisting of terephthaloyl chloride, isophthaloyl chloride, biphenyldicarbonyl chloride, terephthalic acid, pyridine-2,5-dicarboxylic acid Pyridine-2,5-dicarboxylic acid, pyrimidine-2,5-dicarbonyl chloride, pyridine-2,5-dicarboxylic acid, dicarbonyl chloride, pyrimidine-2,5-dicarboxylic acid, 4,4'-biphenyldicarbonyl chloride, and 4,4 ' - (4,4'-biphenyldicarboxylic acid).
Plastic laminated film.
The method according to claim 1,
Wherein the polyamideimide resin and the polyamide resin each independently have a weight average molecular weight of 10,000 to 1,000,000 g / mol.
The method according to claim 1,
A plastic laminated film having a total thickness of 30 to 100 占 퐉.
The method according to claim 1,
Wherein the core layer and the one outer layer have a thickness ratio of 1: 0.1 to 1: 0.5.
The method according to claim 1,
The plastic laminated film had a yellow index of less than 3.0 measured according to ASTM E313 for a specimen having a thickness of 50 +/- 2 mu m, a transmittance of 20.0% or less for ultraviolet light of 388 nm wavelength, And a transmittance of 88.0% or more with respect to visible light of the plastic laminated film.
The method according to claim 1,
The plastic laminated film has a plastic hardness of at least 2H and a linear thermal expansion coefficient (CTE) of 12.0 ppm / DEG C or less, measured according to ASTM D3363 for a specimen having a thickness of 50 +/- 2 mu m Laminated film.

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