WO2019135500A1

WO2019135500A1 - Aromatic poly(amide-imide) copolymer film and production method therefor

Info

Publication number: WO2019135500A1
Application number: PCT/KR2018/015472
Authority: WO
Inventors: 유비오; 박순용; 박영석; 최일환; 태영지; 박관열
Original assignee: 주식회사 엘지화학
Priority date: 2018-01-03
Filing date: 2018-12-07
Publication date: 2019-07-11

Abstract

The present invention relates to an aromatic poly(amide-imide) copolymer film having high retardation and exhibiting a low moisture absorption rate, and a production method therefor.

Description

Title of the Invention

Process for producing an aromatic poly (amide-imide) copolymer film phase

TECHNICAL FIELD

Cross-reference with related application (s)

This application claims priority to Korean Patent Application No. 10-2018-0000881, filed January 3, 2018,

Claims priority to Korean Patent Application No. 10-2018-0153913, filed December 3, 2018, the entire contents of which are incorporated herein by reference.

The present invention relates to an aromatic poly (amide-imide) copolymer film and a process for producing the same.

TECHNICAL BACKGROUND OF THE INVENTION

The aromatic polyimide resin is a polymer having mostly an amorphous structure and exhibits excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to its rigid chain structure. Such a polyimide resin is widely used as an electric / electronic material. However, the polyimide resin has a limitation in use due to the limitation of the deep brown color due to the formation of the charge transfer complex (CTC) of the TI electrons present in the imide chain.

A method of restricting the movement of TI electrons by introducing a strong electron attracting group such as a trifluoromethyl (-CF3 ₎ group in order to solve the above limitation and obtain a colorless transparent polyimide resin; A method in which a sulfone (-SO _{2 -)} group, an ether (-O-) group or the like is introduced into the main chain to form a bending structure to reduce the formation of the bending structure; Or a method of inhibiting the resonance structure formation of TI electrons by introducing an aliphatic cyclic compound.

However, the polyimide resin according to the above proposals is difficult to exhibit sufficient heat resistance by a bending structure or an aliphatic cyclic compound, and a film produced using the polyimide resin still has a limit to exhibit poor mechanical properties.

Recently, aromatic poly (amide-imide) copolymers having a polyamide unit structure have been developed to improve the scratch resistance of polyimide. However, when a polyamide unit structure is introduced into polyimide, the scratch resistance is improved, but there is a limit to securing the UV shielding function. 2019/135500 1 »(: 1 ^ 1 {2018/015472

Therefore, there is a continuing need for the development of aromatic poly (amide-imide) copolymers which can improve scratch resistance and mechanical properties while improving the \ N shielding function.

DISCLOSURE OF THE INVENTION

[Problem to be solved]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a resin composition which exhibits excellent scratch resistance and mechanical properties

And to provide an aromatic poly (amide-imide) copolymer film having improved shielding function.

The present invention also provides a process for producing the aromatic poly (amide-imide) copolymer film.

MEANS FOR SOLVING THE PROBLEMS

In the specification, a retardation (射1 ₁₎ in the thickness direction with respect to the 550 ™ having a wavelength of 3000 ₁₁₁₎ ₁ or more, to the water absorption according to general formula 1, not more than 3.6%, an aromatic poly (amide-imide) copolymer A coalescing film is provided.

[Formula 1]

Water Absorption Rate (%) = (^ 1- ^ 2) * 100 I Bip 2

(Amide-imide) copolymer film is impregnated with ultrapure water for 24 hours, and after the 2 'S phase impregnation, the aromatic poly (amide-imide) This is the weight measured by drying for 30 minutes.

Also disclosed herein is a process for the production of aromatic poly (amide-imide) copolymers by reacting an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic dicarbonyl monomer to form an aromatic poly (amide-imide) copolymer; (Amide-imide) copolymer film obtained by dissolving the aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms, A manufacturing method is provided.

Aromatic polyester according to the specific implementation of the invention below (amide-imide) is decided More ^{specifically,} description will be given to the copolymer film and a production method thereof. According to one embodiment of the present invention, An aromatic poly (amide-imide) copolymer film having a retardation (Rth) of 3,000 nm or more and a water absorption rate according to the general formula (1) of 3.6% or less can be provided. The present inventors have found that a polymer film produced by using an aromatic poly (amide-imide) copolymer formed from an aromatic monomer and applying the production method described later exhibits a retardation in the thickness direction with respect to a wavelength of 550 nm Rth) of 3,000 ran or more and a water absorption rate according to the following general formula (1) is 3.6% or less.

The aromatic poly (amide-imide) copolymer film of this embodiment may have a retardation (Rth) in the thickness direction of 3,000 ran or more, or 3,000 nm to 4,500 nm in a thickness direction at a wavelength of 550 nm in an unstretched state, The index and the haze value are lowered and the mechanical strength can be improved and the water absorption property can be lowered according to the orientation of the polymer inside the film.

The aromatic poly (amide-imide) copolymer film of the embodiment may have a water absorption rate of 3.6% or less, or 2.0 to 3.6% according to the general formula 1. The retardation (Rth) value in the thickness direction The yellow index and the haze value are lowered and the mechanical strength can be improved according to the orientation of the polymer in the film and the water absorption can be lowered.

The retardation (Rth) in the thickness direction can be confirmed by a commonly known measuring method and measuring device. For example, as a device for measuring the retardation (Rth) in the thickness direction, Axoscan, a prism coupler (trade name) manufactured by AXOMETRICS, and the like can be given. As a measurement condition of the retardation (Rth) in the thickness direction, the refractive index (589 nm) of the polyamide-imide resin film was input to the measuring apparatus, and the temperature was 25 ° C and the humidity was 40% , The retardation in the thickness direction of the polyamide-imide resin film was measured using light having a wavelength of 590 nm, and the measured retardation value (measured value by automatic measurement (automatic calculation) of the measuring apparatus) Based on the thickness of the film. In addition, the size of the polyimide film of the measurement sample 2019/135500 1 »(: 1 ^ 1 {2018/015472

(Diameter: about ₁ ^ ₁ ) of the stage, it is not particularly limited, but it may be a size of 76 mm long, 52 mm wide, and 13 mm thick.

Further, the value of the refractive index (589 " of the polyamide-imide resin film) used in the measurement of the retardation in the thickness direction (the value of the refractive index of the polyamide-imide resin film is preferably the same as that of the polyamide-imide resin film forming the film to be the object of measurement of retardation An amidimide resin film is formed on the surface of the substrate, and then the unoriented film is used as a measurement sample (and when the film to be measured is an unstretched film, the film can be used as a measurement sample as it is) ), A refractive index measuring apparatus (product name: manufactured by Atago Co., Ltd., product name: 쌨-11) was used, and a light source of 589 ₁ was used, and at a temperature of 23 째 C (In the direction perpendicular to the thickness direction) of the light _guide 589 ₁₁₁₁₁ .

In addition, when the sample to be measured is unstretched, the refractive index in the in-plane direction of the film becomes constant in any direction in the plane, and by measuring the refractive index, the inherent refractive index of the polyamide-imide resin film can be measured In addition, the refractive index in the direction of the delay axis in the plane is denoted by the refractive index in the in-plane direction perpendicular to the direction of the retardation axis, and the other equals =% because the measurement sample is unstretched. Thus, the inherent refractive index (589) of the polyamide-imide resin film is measured using an unoriented film, and the obtained measurement value is used for the measurement of the retardation in the thickness direction described above. In here, the size of the polyamide-imide resin film, a film of the test sample is, if the size that can be used in the refractive index jeukjeong device is not particularly limited, and a side 1 (Payne square (length and breadth 10 _11), the size of a thickness of 13 .

A polymeric resin film having an internal structure which is generally rigid (^ (1)) may have a relatively high haze or yellowness or a low light transmittance. On the other hand, the aromatic poly (amide-imide) copolymer film of the embodiment exhibits retardation (1 ₁ ) in the thickness direction as described above, and has a crystalline rigid (? % Or less, thereby preventing water penetration and the like, and accordingly, it can have a low haze value and a high transmittance. For this reason, the aromatic poly (amide-imide) 2019/135500 1 »(: 1 ^ 1 {2018/015472

Copolymer films can have higher mechanical strength while having lower yellow index and haze values.

More specifically, the aromatic poly (amide-imide) copolymer film may have a thickness in the range of 1 _/ ^ ₁ to 100 _/ film and may have a haze of 2% or less and a visible light transmittance of 98% or more in this thickness range have. On the other hand, in the aromatic poly (amide-imide) copolymer film of the embodiment, after forming a copolymer using a predetermined aromatic monomer, the copolymer formed in accordance with a production method described later is mixed with an amide containing an aliphatic group having 3 or more carbon atoms Soluble in a solvent and coating the same, and may have the above-described characteristics depending on such monomer selection and a specific production method.

Specifically, the aromatic poly (amide-imide) copolymer film may comprise an aromatic poly (amide-imide) copolymer between an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic dicarbonyl monomer, The aromatic poly (amide-imide) copolymer may be an imide of an aromatic diamine monomer, an aromatic dianhydride monomer, and a polyamic acid copolymerized with an aromatic dicarbonyl monomer.

More specifically, in the aromatic poly (amide-imide) copolymer, the repeating unit derived from the aromatic dicarbonyl monomer has a total moles of repeating units derived from the aromatic dianhydride monomer and the aromatic dicarbonyl monomer Based on the total weight of the composition. The repeating unit derived from the aromatic dicarbonyl monomer may be a copolymer of 10 to 60 mol% of 4,4'-biphenyldicarbonyl repeating units; 10 to 50 mol% of isopthaloyl repeating units; And 20 to 70 mol% of terephthaloyl repeating units. According to the specific composition of the aromatic poly (amide-imide) copolymer, a polymer film exhibiting excellent scratch resistance and high mechanical properties and having an excellent shielding function can be prepared. More specifically, The aromatic poly (amide-imide) copolymer film of this embodiment has improved mechanical properties as well as improved mechanical properties

And has a colorless transparent optical property 2019/135500 1 »(: 1 ^ 1 {2018/015472

. The aromatic poly (amide-imide) copolymer contained in the aromatic poly (amide-imide) copolymer film of the embodiment may be a block copolymer or a random copolymer.

For example, the aromatic poly (amide-imide) copolymer comprises 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.

In the aromatic poly (amide-imide) copolymer, the aromatic poly (amide-imide) copolymer is obtained by copolymerizing the aromatic diamine monomer, the aromatic dianhydride monomer and the aromatic dicarbonyl monomer, And may include randomly copolymerized unit structures. Such a polyamic acid forms an aromatic poly (amide-imide) copolymer having imide bond and amide bond simultaneously by imidization.

As described above, in the aromatic poly (amide-imide) copolymer, the repeating unit derived from the aromatic dicarbonyl monomer has a total of repeating units derived from the aromatic dianhydride monomer and the aromatic dicarbonyl monomer And may be contained in an amount of 51 mol% or more based on the molar amount. When the repeating unit derived from the aromatic dicarbonyl monomer is contained in an amount of less than 51 mol% based on the total moles of repeating units derived from the aromatic dianhydride monomer and the aromatic dicarbonyl monomer, the aromatic poly (amide- Imide) copolymer film, the optical properties such as surface hardness, elastic modulus, mechanical properties such as tensile strength, yellow index, and transmittance may be lowered.

The maximum value of the content of the repeating units derived from the aromatic dicarbonyl monomer relative to the total moles of the repeating units derived from the aromatic dianhydride monomer and the aromatic dicarbonyl monomer is not particularly limited, Or less, or 85 mol% or less, or 80 mol% or less have.

The aromatic dicarbonyl monomer may be selected from the group consisting of 4,4'-biphenyldi carbonyl chloride (BPC), isophthaloyl chloride (I PC) and terephthaloyl chloride (terephthaloyl chloride ide, TPC).

The isopthaloyl chloride (IPC) and the terephthaloyl chloride (TPC) are compounds in which two carbonyl groups are bonded at the position of meta or para to the central phenylene group.

When such isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC) are used as the aromatic dicarbonyl monomer, it is advantageous to improve the processability due to the meta bond in the copolymer and to improve the mechanical properties due to the para bond , But there is a limit to securing the UV-cut performance.

When 4,4'-biphenyldicarbonyl chloride (BPC), which is an aromatic dicarbonyl monomer and a compound having two carbonyl groups bonded to the central biphenylene group in a para position, is additionally used, As the 4'-biphenyldicarbonyl chloride (BPC) has a higher crystallinity than isopthaloyl chloride (IPC) and terephthaloyl chloride (TPC), the hardness of the aromatic poly (amide- imide) And at the same time increase the UV-cut slope. Also, in the aromatic poly (amide-imide) copolymer, the repeating unit derived from the aromatic dicarbonyl monomer may be a repeating unit derived from 10 to 60 mol% of 4,4'-biphenyldicarbonyl repeating unit; 10 to 50 mol% of isopthaloyl repeating units; And 20 to 7 mole% terephthaloyl repeating units. (BPC), isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC), which form the aromatic dicarbonyl monomer, and aromatic poly (amide -Imide) copolymer, it is possible to improve the hardness and mechanical properties while improving transparency and yellowness of the copolymer and improve the ultraviolet shielding function. Particularly, when the 4,4'-biphenyldicarbonyl chloride (BPC) is contained in an amount of less than 10 mol% based on the total molar amount of the aromatic dicarbonyl monomer, the scratch resistance and mechanical properties are not effectively improved. If it is contained in an amount exceeding 60 mol%, there may be a problem that the haze of the film after coating and curing is high. Accordingly, the 4,4'-biphenyldicarbonyl chloride (BPC) is present in an amount of 10 mol% or more, 12 mol% or more, or 14 mol% or more, based on the total moles of the aromatic dicarbonyl monomer. Or less, and 60 mol% or less, or 55 mol% or less.

Also, the isophthaloyl chloride (IPC) is present in an amount of 10 mol% or more, or 14 mol% or more, based on the total moles of the aromatic dicarbonyl monomer. And may be contained in an amount of 50 mol% or less.

Also, the terephthaloyl chloride (TPC) may be used in an amount of 20 mol% or more, 35 mol% or more, and preferably 20 mol% or more, based on the total moles of the aromatic dicarbonyl monomer. Or less, and 60 mol% or less, or 55 mol% or less.

The molar ratio of the aromatic dianhydride monomer to the aromatic dicarbonyl monomer in the aromatic poly (amide-imide) copolymer may be from 1: 0.95 to 1: 1.05. Specifically, in the aromatic poly (amide-imide) copolymer, the molar ratio of (aromatic dianhydride monomer) to (aromatic dianhydride monomer and aromatic dicarbonyl monomer) may be 1: 1.

As described above, in the aromatic poly (amide-imide) copolymer according to one embodiment, only when the composition of the aromatic dicarbonyl monomer simultaneously satisfies the above-mentioned two conditions, excellent hardness and mechanical properties and excellent scratch resistance High grade pencil hardness) and excellent UY shielding capability.

The aromatic diamine monomer may be selected from the group consisting of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (tr ifuoromethyl) -4,4'- , TFDB), 1,3-cyclohexanediamine (13CHD), or meta-methylenediamine (mMDA). The use of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (TFDB) as the aromatic diamine monomer improves hardness and maintains a low yellow index 2019/135500 1 »(: 1 ^ 1 {2018/015472

.

The aromatic dianhydride monomer may be 3,3 ', 4,4'-diphenyltetracarboxylic acid dianhydride (3,3', 4,4'-biphenyl tetracarboxylic acid dianhydride, BPDA) , Cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA), or 2,2-bis (3,4-dicarboxyphenyl) nucleus fluoropropane dianhydride (2, 2 '-bis (3,4-di carboxypheny 1) hexa f 1 uor opr opane di anhydride, 6FDA). Of these, 3,3 ', 4,4'-biphenyl tetracarboxylic acid dianhydride (3,3', 4,4'-biphenyl tetracarboxylic acid dianhydride) or cyclobutane - The use of 1,2,3,4-tetracarboxylic dianhydride (Cyclobutane-1,2,3,4-tetracarboxylic dianhydride) has been found to improve the hardness, UV-shielding, UV weatherability and chemical imidization desirable.

On the other hand, the aromatic poly (amide-imide) copolymer film is dispersed in the polymer base material containing the aromatic poly (amide-imide) copolymer.

Examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, benzoate compounds, cyanoacrylate compounds, salicylic ester compounds, oxybenzophenone compounds, triazine compounds, and inorganic compounds , But the present invention is not limited to these.

Examples of the benzotriazole compound include 2- (-hydroxyphenyl) benzotriazole, 2- (-hydroxy-5'-methylphenyl) benzotriazole, 2-

Phenyl) - 5-carboxylic acid butyl ester benzotriazole, 2- _{(2'-hydroxy-5-methylphenyl)} - _{5,6-dichloro-benzotriazole,} 2- (2-hydroxy-5-methyl Phenyl-5-ethylsulfone benzotriazole, 2- (7-hydroxy-5'-t-butylphenyl) Benzotriazole, 2- (2-hydroxy-t-aminophenyl) benzotriazole, 2- (2-hydroxy-3 ', 5'- 3 ', 5-dimethylphenyl) -5 (2-methylphenyl) benzotriazole, 2- (2-stearyloxy- (2-hydroxy-3'5-di-1-butylphenyl) -5- (2-hydroxy-5-carboxylate) benzotriazole ethyl ester, 2- 2019/135500 1 »(: 1 ^ 1 {2018/015472

Chloro-benzotriazole, ₂ _ (2-hydroxy-3-methyl-5-N-butylphenyl) - 5-chloro-benzotriazole, 2- (2-hydroxy-不-1; -butyl-methyl-phenyl) - 5-chloro-benzotriazole, 2- (2-hydroxy-丁-methoxyphenyl) benzotriazole, 2- (2-hydroxy-不,丁-di-t-butylphenyl) _{-5-chloro-benzotriazole,} _2- ( ₂ -hydroxy-5'-cyclohexylphenyl) benzotriazole, 2- (2-hydroxy-4'-dimethylphenyl) 5-carboxylic acid butyl ester benzotriazole, 2- (2-hydroxy-4-dichlorophenyl) benzotriazole, 2- (-hydroxy- (2-hydroxy-5-methoxyphenyl) -5-methylbenzotriazole, 2-hydroxy-4-octoxyphenyl) benzotriazole, 2- - - methyl Carbonyl) - 5-carboxylic acid ester benzotriazole, 2- (2-acetoxymethyl-phenyl) can be exemplified by benzoin azoles such as Triton.

Examples of the benzophenone-based compounds include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-41-octoxybenzophenone, 2-hydroxy- Carboxybenzophenone, 2,2-dihydroxy-4,4-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,

Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzophenone, 2,2,4,4-tetrahydroxybenzophenone, 2,5- dihydroxy- 4-hydroxy-5-benzoylphenyl) methane, and the like can be given as examples of the bis (2-methoxybenzophenone).

Examples of the benzoate compound include phenylysarsylate, 4-biphenylsulfate, 2,5-1-butyl-4-hydroxybenzoic acid _11- nuclear decyl ester, 2,4-di- 3, 5-di-t-butyl-4-hydroxybenzoate, and the like.

As the cyanoacrylate compound, ethyl-2-cyano-3,3-diphenylacrylate can be exemplified. Examples of the salicylic ester compounds include phenyl salicylate and 4-butylphenyl salicylate.

Examples of oxybenzophenone compounds include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-tetra-oxybenzophenone.

As the triazine compound, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [(infuracyl) oxy] -phenol can be exemplified. 2019/135500 1 »(: 1 ^ 1 {2018/015472

Examples of the inorganic compound include titanium oxide, zinc oxide, cerium oxide, iron oxide, barium sulfate and the like.

The specific examples of the benzotriazole-based, benzophenone is preferable to use one of the nongye and specifically, 2- (2'-hydroxy-5 'O _ ₆₁寸octylphenyl) benzotriazole [2- (2'-( Urine [« _7- 5'-1 ₆₁ _° _{-0 7} 1 _61¾ , 1: ratio ₆₁₁₂₀₁ : _{1 320} 1 _6] and octadecyl-3- (3,5- ) -propionate [0 8 acid ₆₀ 1-3- (3, 5-obtain and寸_1 ₆₁₎ ₁₁₁ 1- 4-one (1 _{10 1)} 1 _{16] ¾ ^} 1) _ ₁₎ ₁ 1 Ke _{011 6]} may be further included.

Such an aromatic compound may be added during the production of the aromatic poly (amide-imide) copolymer film, whereby the yellow index and haze of the aromatic poly (amide-imide) copolymer film may be lowered and the mechanical properties The moisture absorption characteristics can be improved.

The 2- (2'-hydroxy-5 ^1-la卜octylphenyl) benzotriazole [2- (2 '-取打5' Ah 611: -0 (: 1 11) 1161¾1) 5611201: 1 2016] and Octadecyl-3- (3,5-di- ₆ -hexyl-4-hydroxyphenyl) -propionate [ 1) 1 ratio 71-4-

Wherein the aromatic compound is selected from the group consisting of aromatic poly (amide-imide) copolymers having a weight average molecular weight of from 0.001 to 10 parts by weight .

The aromatic poly (amide-imide) copolymer is from 10,000 to 1,000, 000 for細₀ 1, or 50,000 to 1,000,000 seedlings / ₁₁₁₀ 1, or 50,000 to 500,000 / ₁₁₁₀ 1, or 50,000 to 300,000 _§細₀ 1 parts by weight of May have an average molecular weight.

Specifically, the aromatic poly (amide-imide) copolymer is a

Pursuant to 03 363 25 to 55 _ a pencil hardness haese measured for the specimens having a thickness of {} (1 _{11 633)} may be equal to or greater than the rating ¾.

In addition, the aromatic poly (amide-imide)

The tensile strength measured for a specimen having a thickness of 25 to 55 according to the condition 38 is 180

Or more, 200

Or higher than 220 Wa. The higher the tensile strength is, the better the mechanical properties are, and the upper limit is not limited. However, for example, 300 Wa or less, 280

Or less, or less than or equal to 270 minutes. 2019/135500 1 »(: 1 ^ 1 {2018/015472

The aromatic poly (amide-imide) copolymer may have a tensile elongation of 18% or more as measured on a specimen having a thickness of 25 to 55 占 based on Showa 38. Preferably, the tensile elongation may be 20% or more, 22% or more, or 25% or more. The higher the tensile elongation is, the better the mechanical properties are, and the upper limit is not limited. For example, it may be 35% or less, 33% or less, or 30% or less.

The aromatic poly (amide-imide) copolymer was measured for a specimen having a thickness of 25 to 55 in Table 424, and the transmittance

And may be 2.80 or more in the range of 10 to 80%. Also,

The 0 wavelength (the wavelength when the transmittance is less than 1%) may be 353 11111 to 355 ₁ ?. According to another embodiment of the present invention, there is provided a process for producing an aromatic poly (amide-imide) copolymer comprising reacting an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic dicarbonyl monomer to form an aromatic poly (amide-imide) copolymer; And an aromatic poly (amide-imide) copolymer of the above-described embodiment, which comprises coating a coating liquid formed by dissolving the aromatic poly (amide imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms, A process for producing a coalesced film can be provided. (Amide-imide) copolymer by reacting an aromatic dianhydride monomer, an aromatic dianhydride monomer and an aromatic dicarbonyl monomer, dissolving the aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms, An aromatic poly (amide-imide) copolymer film having the above-mentioned characteristics can be provided.

The specific contents of the aromatic diamine monomer, the aromatic dianhydride monomer and the aromatic dicarbonyl monomer are as described above.

The polymerization conditions for forming the aromatic poly (amide-imide) copolymer are not particularly limited. For example, a polyamic acid is formed using the aromatic diamine monomer, the aromatic dianhydride monomer, and the aromatic dicarbonyl monomer And imidizing it to form the copolymer. The polymerization for the formation of the polyamic acid can be carried out by solution polymerization under an inert atmosphere of from 0 to 100. Examples of the solvent for forming the polyamic acid include - Dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, acetone, N-methyl-2-pyrrolidone, tetrahydrofuran, chloroform, gamma-butyrolactone and the like can be used. Imidization after the formation of the polyamic acid can be performed thermally or chemically. For example, compounds such as acetyl anhydride, pyridines can be used for chemical imidization. On the other hand, as described above, an aromatic poly (amide-imide) copolymer prepared by coating a substrate with a coating solution formed by dissolving the aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms The film may have a retardation (Rth) in the thickness direction of 3,000 nm or more and a water absorption rate according to the general formula (1) of 3.6% or less with respect to a wavelength of 550 nm in an unstretched state. In addition, the aromatic poly (amide-imide) copolymer film may have a haze of 2% or less and a visible light transmittance of 98% or more at a thickness of Urn to 100 // m.

The properties of such an aromatic poly (amide-imide) copolymer film appear to be attributed to the use of the above-mentioned amide solvent including an aliphatic group having 3 or more carbon atoms. More specifically, the amide solvent containing an aliphatic group having 3 or more carbon atoms increases the solubility of the poly (amide-imide) polymer, and may have a more advantageous effect on the orientation of the polymer when the coating is dried. The films formed from the copolymers can have properties such as low yellow index, haze index, high mechanical strength, and low hygroscopicity. Specific examples of the amide solvent including the aliphatic group having 3 or more carbon atoms include methyl 3-methoxypropionate, 3-methoxy-N, N-dimethylopropionamide N, N-dimethylpropionamide) and N, N-dimethylpropionamide (N, N-dimethylpropionamide). Also, as described above, the aromatic poly (amide-imide) copolymer film may have the above-described characteristics depending on the specific monomers used in the synthesis of the aromatic poly (amide-imide) copolymer and the content thereof have. Specifically, the aromatic dicarbonyl monomer may be contained in an amount of 51 mol% or more based on the total moles of the aromatic dianhydride monomer and the aromatic dicarbonyl monomer. Also, the aromatic dicarbonyl monomer may include 10 to 60 mol% of 4,4'-biphenyldicarbonyl chloride; 10 to 50 mol% of isophthaloyl chlorides; And 20 to 70 mol% of terephthaloyl chloride. The coating solution formed by dissolving the above aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms is 2- (-hydroxy-5'-tert-octylphenyl) benzotriazole [2- Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) di-tert-butyl-4-hydroxyphenyl) -propionate] may further include at least one aromatic compound.

These aromatic compounds can be dispersed in the polymeric substrate comprising the aromatic poly (amide-imide) copolymer in the finally produced aromatic poly (amide-imide) copolymer film, and thus the aromatic poly (amide- Imide) copolymers can have properties such as low yellow index, haze index, high mechanical strength, and low hygroscopicity. The method of coating the coating liquid formed by dissolving the aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms is not particularly limited. For example, Coating methods and apparatuses commonly known in the art can be used.

The type of the substrate is not limited, and examples include various organic or inorganic substrates, glass substrates, paper substrates, polymer substrates, metal substrates, and the like. 【Effects of the Invention】 2019/135500 1 »(: 1 ^ 1 {2018/015472

The aromatic poly (amide-imide) copolymer according to the present invention exhibits excellent scratch resistance and mechanical properties

It is possible to provide a polyamide-imide film having an improved shielding function.

DETAILED DESCRIPTION OF THE INVENTION

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

[Examples and Comparative Examples: Production of poly (amide-imide) copolymer film] Comparative Example 1

Nitrogen was passed through a 1001 4- _l½- liter round-bottomed flask (reactor) equipped with a stirrer, a nitrogen inlet, a dropping funnel, a temperature controller and a condenser

Dimethylacetamide (0 · 42.5 _§) was filled, the temperature of the reactor was adjusted to 25 ° (:

2, - (trifluoromethyl) bis-4,4'-biphenyl-diamine as the _{01 ^ 1®) 4.3413 0.0135¾ 0 1} ) for making and dissolved in a solution of 25 ° (: it was maintained at.

Here cyclobutane-1,2, 3,4-tetracarboxylic dianhydride犯then added with Yoshi 0.0213 0.0001 ₀ 1 mi), and stirred for a period of time to dissolve and react. -10 and the temperature of the solution (after cooling to, biphenyl-dimethyl carbonyl chloride犯tt) 1.5136 (0.00542¾ ₀₎ for the child port and phthaloyl chloride (0.5505 I (0.00271. 1), it gave the chloride奸的) In the agitation 1.0734 _§ (0.0052¾ ₀ 1) respectively terephthaloyl. A polyamic acid solution having a solid content of 15% by weight was obtained.

The polyamic acid solution was poured into the polyamic acid solution to dilute to a solid content of 5% or less and precipitated with methanol (1). The precipitated solids were filtered and dried at 100 ° C for 6 hours or longer to obtain a solid A poly (amide-imide) copolymer (acid # 1) was obtained. A weight average molecular weight of about 147,

211/11101).

The obtained poly (amide-imide) copolymer (0) at time # 1) was dissolved in dimethyl propionamide, 1 - [1] _11161; 1 ₁₇ 1 ₁ ) ₁ (1 ₀₁₁₃₁ (1 ₆ ) to prepare a polymer solution of about 15%. The polymer solution was applied onto a plastic substrate (11 eggs) (-75 ₃ , \ BE 2019/135500 1 »(: 1 ^ 1 {2018/015472

The polymer solution was uniformly adjusted in thickness using a film applicator, dried in a Matze oven for 10 minutes at room temperature, cured at 250 ° C for 30 minutes while flowing nitrogen, 50.0 < / RTI > Example 1

Polyester obtained in Comparative Example 1 (amide-imide) copolymer (on # 1) 100 parts by weight compared to the aromatic compound, 0 ^ ₃ ₍₁₆₀₇ 1-3- (3, 5 - (^ O _{61. !;} . Technique - Liver -

1 _¾ line _{_{1 '( «: / 1)}} 1 16] ¾ 1) _ 1) 1' (1 _{1 6} (1 _3110« 1076) 5 parts by weight of one company, 1 I-dimethyl-propionamide A--) 1 _{11 161:} 1 ₁₇ 1 _131'0 a polymer solution of about 15 ¾> was prepared by dissolving in _{011 311} ^ line _6).

The polymer solution was poured into a plastic substrate (75 cm ₃ ), and the thickness of the polymer solution was uniformly adjusted using a film applicator.

After drying in a Matiz oven for 10 minutes, the coating was cured for 30 minutes at 250 ° C with nitrogen flow,

A film was obtained. Example 2

(100 parts by weight) of the poly (amide-imide) copolymer obtained in the above Comparative Example 1 ! ·: - 1) 1 -4-1¾ year 1 ( «71) 1161171): 1) 10 011 6 (1 ₈₁₁₀ 1010) 5 parts by weight of N, N - dimethyl-propionamide (1: 1 _11161;] ₁ 1 ₁₎ _{1 'every} 1 _{011 311} ^ of about 15 _{\ ¥ 1} dissolved in _(16); to thereby prepare a polymer solution in%.

The polymer solution was applied onto a plastic substrate (egg ratio: 75

The polymer solution was uniformly adjusted in thickness using a film applicator and dried in a Matiz oven at 80 for 10 minutes. Then, 250

And cured for 30 minutes to obtain a time film having a thickness of 50.0 peeled from the substrate. Example 3

The aromatic compound, 100 parts by weight of the poly (amide-imide) copolymer (acid # 1) obtained in Comparative Example 1, 2019/135500 1 »(: 1 ^ 1 {2018/015472

1) 1 - 1 - 1 - 4, and 11 (1): 11) were dissolved in 5 parts by weight of 1-dimethylpropionamide (1: 1) 1 _{11161; ] 17} 1 ₁₎ a polymer solution of about 15 _\付¾> was prepared by dissolving in _one piece 1 11 _0113111 _6).

The polymer solution was poured into a plastic substrate (75 比 in comparative form) and the polymer solution was uniformly adjusted in thickness using a film applicator. The polymer solution was dried in a Matiz oven for 20 minutes at 60 캜, (&Quot;:") for 30 minutes to peel off the substrate to a thickness of 50.0

A film was obtained. Comparative Example 2

Equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a condenser

100 ₁ 4 - _11% Nitrogen Nitrogen was passed through a round flask (reactor)

And dissolved by the solution 25 ° (:... And was kept at this after the commitment with a table for 0.0201 (0.000 ^ _0: 1), followed by stirring for a period of time to dissolve and the reaction and -10 ° the solution temperature ( after cooling to, 1 tt 0.5355 John (US ₀ .00263 1), gave 2.44 _§ tt by stirring by the addition of ₍₀ .01¾ ₁₀ 1), respectively, the concentration of solid content is to obtain a polyamic acid solution of 15% by weight.

The polyamic acid solution was poured into the polyamic acid solution to dilute to a solid content of 5% or less and precipitated with methanol (1). The precipitated solids were filtered and dried at 100 ° C (for 6 hours or more under vacuum to obtain poly (Amide-imide) copolymer (Si # 2) was obtained. The weight average molecular weight of the amide-imide copolymer was about 154,197.

The above poly (amide-imide) copolymer (acid # 2) was dissolved in N, N-dimethylpropionamide, 1 - [- ^ _1161; 1 _¾ 1 _{1) 101)} 1 ₀₁₁₃₁ 1 ₆₎ to prepare a polymer solution of about 15%. The polymer solution

The polymer solution was uniformly adjusted in thickness using a film applicator, dried in a Matze oven at 120 ° C for 15 minutes, cured at 250 ° C for 30 minutes while flowing nitrogen, And obtained a film having a thickness of 49.8 占₁ . 2019/135500 Example 1 (1 ^ {2018/015472 Example 4

The aromatic compound 0 8 (1 ₆₀ 1-3- (3,5- (11-1 _{61 '} )) was added to 100 parts by weight of the poly (amide-imide) copolymer obtained in the above Comparative Example 2 _One; The Yagi-san-

1 _¾ year 1 Yes) 1161 _¾ 1) - _! 01 011 6 (1 3110 1076) 5 parts by weight of 1, or 1 four-dimethyl propionamide _{control, 1 ^ - [) 1 11161} ± 1 1 1) from about 15 ¾ dissolved in 1 _"Ke 1 _{01 131} _(16)> of the To prepare a polymer solution.

The polymer solution

The polymer solution was uniformly adjusted to a thickness of 80 μm using a film applicator, dried in a Matiz oven for 10 minutes, and then cured for 30 minutes at 250 ° C. with flowing nitrogen, A film having a thickness of 50.0 _ peeled from the substrate was obtained. Example 5

Aromatic compounds were prepared from 100 parts by weight of the poly (amide-imide) copolymer (( _0- ? 1) # 2) obtained in Comparative Example 2, 3,5- -1611; - 1-4-1 _¾ year 1 ( «:, 1) 11 611: 1) 1) 1 [011 6 (1 (休1010) 5 parts by weight of N, N - dimethyl-propionamide 0 _11161: 1; a polymer solution of about 15% was prepared and dissolved in 1 ₁₇ 1 ₁₎ ₁ sheet 1 _{01 131} _(16).

The polymer solution plastic substrate ^{(1] 1 3 11止}} (- 75 3, is poured into a byemyo Co.) using a film applicator of uniformly controlling the thickness of the polymer solution was 80 ° (: dried at Matiz oven for 10 minutes After curing for 30 minutes at 250 DEG C with flowing nitrogen, the thickness peeled from the substrate was 50.0

A film was obtained. Example 6

The poly (amide-imide) copolymer ((: ₀ gauge # 2) obtained in Comparative Example 2, which is an aromatic compound, ₆₁技₃ LA 1 ₁₁ ^ 1: ₀ 11 _{_{3 (3- (3,5- -1 61 ·}} †; -

1) 1-4-117 (11, ¥) 1½1 _¾ , 1) _! ) 1_ (1011, 6 (1 greater than 110. 1010) 5 parts by weight of N, N - dimethyl-propionamide (1: [^ _11161;] ₁₇ 1 ₁₎ ₁ (1 _{011 311} ^ _{16) to about 15 _\% dissolved in To prepare a polymer solution.

The polymer solution was poured into a plastic substrate and the thickness of the polymer solution was uniformly adjusted using a film applicator. 2019/135500 1 »(: 1 ^ 1 {2018/015472

After drying in a Matiz oven for 20 minutes, the film was cured at 250 ° C for 30 minutes while flowing nitrogen to obtain a Si film having a thickness of 50.0 _/ peel peeled from the substrate. Test Example

(1) The retardation 0¾1 ₁₎ in the thickness direction with respect to a wavelength of 550 ₁ ^ ₁

(Retardation in the thickness direction)) was measured using a polymer film (length: 76 占, width: 52 占 and thickness: 13 占_/ L) prepared in each example and each comparative example as it is as a measurement sample

(Refractive index with respect to light of 550? Of the film obtained by measurement of the above-mentioned refractive index) of each polymer film was input, and then the temperature was changed to 25. ( 1, and humidity: 40%, light having a wavelength of 590 ₁₁₁₁₁ was used and the retardation measured in the thickness direction was measured, and then the obtained retardation measurement value in the thickness direction (measured value obtained by automatic measurement of the measuring apparatus) was used , And converting it into a retardation value _per 10 mm of the thickness of the film

(2) Water absorption rate

The water absorption rate was calculated according to the following general formula (1).

[Formula 1]

Water Absorption Rate () = (11-12) _{* 100} / 썪 2

In the general formula 1, silver is a weight determined by impregnating the aromatic poly (amide-imide) copolymer film with ultrapure water for 24 hours,

2 is a weight measured by drying the aromatic poly (amide-imide) copolymer film after the impregnation at 150 ° for 30 minutes.

: 11 ¥ 2600) according to the method of measuring the film thickness (X) and

And the slope was measured.

The slope (/) was measured in the range of 10 to 80% transmittance

The group was expressed as the wavelength when the transmittance was less than 1%. 2019/135500 1 »(: 1 ^ 1 {2018/015472

[Table 1]

The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1, (Amide - imide) copolymer film has a relatively high 1 - slope and has excellent shielding function and colorless transparent optical characteristics.

In contrast, the poly (amide-imide) copolymer films of the comparative examples have relatively low

It has been confirmed that the shielding function is low due to inclination.

Claims

Claims: What is claimed is: 1. A liquid crystal display device having a retardation in a thickness direction of 3,000 or more and a water absorption rate according to the following general formula (1) Aromatic poly (amide-imide) copolymer film of 3.6% or less:

[Formula 1]

Water absorption rate ") = 1 2) _{* 100} /

In the general formula (1), 1 denotes a weight determined by impregnating the aromatic poly (amide-imide) copolymer film with ultrapure water for 24 hours,

After the impregnation, the aromatic poly (amide-imide) copolymer film was dried at 150 ° C for 30 minutes.

[Claim 2]

The method according to claim 1,

The aromatic poly (amide-imide) copolymer film has a film thickness of from 3,000 11111 to 4,500 (in the thickness direction retarder 1 against the wavelength of 550 ₁₁₁₁₁ )

ego,

(Amide-imide) copolymer film according to the above general formula (1) has a water absorption rate of 2.0 to 3.6%.

[3]

The method according to claim 1,

(Amide-imide) copolymer film having a slope (ert / () of 2.80 or more in the range of 10 to 80% of transmittance, measured on a specimen having a thickness of 25 to 55 based on the specimen 424).

[4]

The method according to claim 1,

The aromatic poly (amide-imide) copolymer film comprises an aromatic poly (amide-imide) copolymer comprising an aromatic poly (amide-imide) copolymer between an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic dicarbonyl monomer. Imide) copolymer film.

[Claim 5]

5. The method of claim 4,

, The aromatic poly (amide-imide) copolymer charge,

The repeating unit derived from the aromatic dicarbonyl monomer is contained in an amount of 51 mol% or more based on the total moles of the aromatic dianhydride monomer and the repeating unit derived from the aromatic dicarbonyl monomer,

The repeating unit derived from the aromatic dicarbonyl monomer has 10 to 60 mol% of 4,4'-biphenyldicarbonyl repeating units; 10 to 50 mol% of isopthaloyl repeating units and 20 to 70 mol% of terephthaloyl repeating units.

Aromatic poly (amide-imide) copolymer films.

[Claim 6]

5. The method of claim 4,

The aromatic diamine monomer may be selected from the group consisting of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2,2'-bis (tr ifuoromethyl) Including,

The aromatic dianhydride monomer may be selected from the group consisting of 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride or cyclobutane-1,2,3 , And 4-tetracarboxylic dianhydride. 2. A film according to claim 1, wherein the aromatic poly (amide-imide) copolymer is a poly (amide-imide) copolymer.

7.

5. The method of claim 4,

(2'-hydroxy-5'-tert-octylphenyl) benzotriazole [2- (2'-hydroxyphenyl) benzotriazole] is dispersed in a polymer base material containing the aromatic poly (amide-

Hydroxy-5 '-tert-octylphenyl) benzotriazole and octadecyl-3- (3,5-di tert-butyl-4-hydroxyphenyl) -propionate [Oct adecyl-3- -tert-butyl ^~ 4 - 2019/135500 1 »(: 1 ^ 1 {2018/015472

_{_{] 17 (1 1 ( «:}} 71) 1 ½11 1) - 1) 1 (¾ ^ 011 6] , further comprising an aromatic compound selected one or more from the group consisting of aromatic poly (amide-imide) copolymer film .

[8]

The method according to claim 1,

The aromatic poly (amide-imide) copolymer film having a retardation ₍₁₁₎ of more than 3000] ₁ in the thickness direction with respect to a wavelength of 550 ₁ ™ in non-stretched state, the aromatic poly (amide-imide) copolymer film.

[Claim 9]

The method according to claim 1,

The aromatic poly (amide-imide) copolymer film has a thickness of 1 to 100 mu m,

Having a haze of not more than 2% and a visible light transmittance of not less than 98%

Aromatic poly (amide-imide) copolymer films.

Claim 10

Reacting an aromatic diamine monomer, an aromatic dianhydride monomer and an aromatic dicarbonyl monomer to form an aromatic poly (amide-imide) copolymer; And

And coating the substrate with a coating solution formed by dissolving the aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms.

A process for producing an aromatic poly (amide-imide) copolymer film according to claim 1.

Claim 11

11. The method of claim 10,

Amide solvent containing the aliphatic group having 3 or more carbon atoms is 3-methoxy or _ 1, 1-dimethyl-propionamide _{_{(3- 161: 1 1 (休}} 7- : 1 _{1116 71} <1 _{6 0113111)} or

_Propionamide - [^ ₁₁₁₆₁ ; 1 ₁₇ 1 ₁ ) ₁ 1 ₀₁₁₃₁₁ ^ (1 ₆ ), aromatic A process for producing a poly (amide-imide) copolymer film.

Claim 12

11. The method of claim 10,

Wherein the aromatic dicarbonyl monomer is contained in an amount of 51 mol% or more based on the total moles of the aromatic dianhydride monomer and the aromatic dicarbonyl monomer,

Wherein the aromatic dicarbonyl monomer comprises 10 to 60 mol% of 4,4'-biphenyl di carbonyl chloride; 10 to 50 mol% of isophthaloyl chlorides; And 20 to 70 mol% of terephthaloyl chlorides, based on the total weight of the copolymer.

Claim 13

11. The method of claim 10,

The coating liquid formed by dissolving the aromatic poly (amide-imide) copolymer in an amide solvent containing an aliphatic group having 3 or more carbon atoms,

5-tert-octylphenyl) benzotriazole and octadecyl-3 (3,5-di-tert-octylphenyl) at least one aromatic compound selected from the group consisting of tert-butyl-4-hydroxyphenyl) -propionate [Oct adecy 1, 3-di- tert -butyl-4-hydroxyphenyl) (Amide-imide) copolymer film.