KR101676534B1 - Thermoplastic Resin comprising Polyimide - Google Patents

Abstract

상기 화학식 1에서 X, Y₁, Y₂, R₁ 내지 R₃, m 및 n 은 본 명세서 중에서 정의한 바와 동일하다.The present invention relates to a polyimide having a repeating unit represented by the following general formula (1) and having a glass transition temperature (T _g ) of 120 to 190 ° C and a melt flow index (MI) of 1 to 30 g / min or a thermoplastic resin Lt; / RTI >
[Chemical Formula 1]

In Formula 1, X, Y ₁ , Y ₂ , R ₁ to R ₃ , m and n are the same as defined in the present specification.

Description

A thermoplastic resin containing polyimide (Thermoplastic Resin comprising Polyimide)

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition containing polyimide and a method for producing the same, and more particularly to a thermoplastic resin composition capable of extrusion molding.

Background Art [0002] With the recent trend toward higher performance, higher functionality, and miniaturization of electronic devices, there has been an increasing demand for miniaturization and weight reduction of electronic components used in electronic devices. In addition, the materials of electronic parts are required to have more characteristics such as heat resistance, mechanical strength, electrical characteristics and the like, and a semiconductor device packaging method and a wiring board on which the semiconductor device is packaged are required to have high density, high performance and high performance.

Polyimide has high heat resistance, flame retardancy, and excellent electrical insulation, and is widely used for electric and electronic applications. Generally, polyimides are prepared by thermal imidization or chemical imidization of precursor polyamic acid produced by the polycondensation reaction of an acid anhydride component and a diamine component.

Polyimide is superior in reliability and stability to polyamic acid, which is a precursor thereof, but has a disadvantage of low solubility and coating property to a solvent. On the other hand, polyamic acid has superior solubility and coating properties than polyimide, but the problem that the carboxyl group (-COOH) or amide bond (-CONH-) contained in the polyamic acid molecule lowers the long-term reliability and stability of the polyamic acid Cause.

Accordingly, there is a need for a molecular design capable of simultaneously satisfying both the solubility and coating properties of polyamic acid and the excellent reliability of polyimide.

Korean Patent Publication No. 2007-0031023 (published on March 19, 2007)

It is an object of the present invention to provide a thermoplastic resin containing polyimide having excellent optical and mechanical properties together with melt flow characteristics and glass transition temperature suitable for extrusion molding.

Another object of the present invention is to provide an extrusion molding method using the thermoplastic resin.

Another object of the present invention is to provide a display substrate manufactured by the extrusion molding method using the thermoplastic resin.

Another object of the present invention is to provide a three-dimensional printed matter produced using the thermoplastic resin.

The present invention relates to a polyimide having a repeating unit represented by the following general formula (1) and having a glass transition temperature (T _g ) of 120 ° C. to 190 ° C. and a melt flow index (MI) of 1 to 30 g / A thermoplastic resin containing a precursor is provided.

 [Chemical Formula 1]

Wherein X ₁ and X ₂ are each independently an aromatic or alicyclic divalent organic group derived from an acid anhydride, Y ₁ and Y ₂ are each independently an aromatic or alicyclic divalent group derived from a diamine And m and n are numbers from 0 to 1 representing the mole fraction.

In the formula 1, at least one of X ₁ and X ₂ is an aromatic or alicyclic divalent organic group derived from an acid anhydride containing an ether group, an ester group, or a combination thereof in a molecule, Or at least one of Y ₁ and Y ₂ is an aromatic or alicyclic divalent organic group, in the range of 20 to 100 mol% based on the total mols of the tetravalent organic group, May be included in an amount of 20 to 100 mol% based on the total molar amount.

In one embodiment, the divalent organic groups derived from the diaminediphatic polyamines can be included at about 0 to about 80 mole percent, based on the total moles of divalent organic-derived divalent organic groups.

In one embodiment, the polyamine may be a polyether diamine.

In one embodiment, the polyamine may be a polysiloxane diamine.

In one embodiment, at least one of X ₁ and X ₂ may be a tetravalent organic group derived from an acid anhydride of formula (3a) or (3b):

[Chemical Formula 3]

(3b)

R ₂₁ and R ₂₂ each independently represent a single bond, -O-, -CR ₂₃ R ₂₄ -, -C (= O) -, -C (= O) O-, -C = O) NH-, -S-, -SO-, -SO ₂ -, a monocyclic or polycyclic cycloalkylene group having 6 to 18 carbon atoms, a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms, , Wherein R ₂₃ and R ₂₄ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a haloalkyl group having 1 to 10 carbon atoms.

In formula (1), X ₁ and X ₂ are selected from the group consisting of the functional groups represented by the following formulas (4a) to (4p), provided that at least one of X ₁ and X ₂ is selected from the group consisting of the functional groups represented by the following formulas Lt; RTI ID = 0.0 >

Wherein R ₂₃ and R ₂₄ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a haloalkyl group having 1 to 10 carbon atoms.

In formula (1), Y ₁ and Y ₂ may each independently be a divalent organic group selected from the group consisting of functional groups represented by the following formulas (6a) to (6q).

In one embodiment, the polyimide contained in the thermoplastic resin may be one prepared by chemically or thermally imidizing a polyimide precursor of Formula 8:

[Chemical Formula 8]

X ₁ and X ₂ are each independently an aromatic or alicyclic divalent organic group derived from an acid anhydride, Y ₁ and Y ₂ are each independently an aromatic or alicyclic divalent group derived from a diamine And m and n are numbers from 0 to 1 representing the mole fraction.

In one embodiment, the thermoplastic resin may comprise polyimide or a precursor thereof in an amount of about 5 to about 50 weight percent based on the total weight of solids.

 In one embodiment, the thermoplastic resin may have an intrinsic viscosity of from about 200 to about 25,000 cP.

In order to solve the other problems of the present invention, there is provided an extrusion molding method using the thermoplastic resin.

In one embodiment, the extrusion molding method may be such that the heating process is performed at a temperature of about 180 to about 350 < 0 > C.

In order to solve still another problem of the present invention, there is provided a film produced by extrusion molding the thermoplastic resin.

The film can be used as a display substrate.

Further, according to the present invention, a method of three-dimensionally printing using the thermoplastic resin and a three-dimensional printed matter are provided.

Other details of the embodiments of the present invention are included in the following detailed description.

The thermoplastic resin containing the polyimide or a precursor thereof according to the present invention has thermal and melting properties suitable for extrusion molding, as well as excellent transparency and mechanical properties, and is useful for the production of a molded article by extrusion molding or three-dimensional printing.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description.

It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

In the present specification, all the compounds or functional groups may be substituted or unsubstituted, unless otherwise specified. Herein, the term "substituted" means that at least one hydrogen contained in the compound or the functional group is a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, Substituted with a substituent selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, a carboxylic acid group, an aldehyde group, an epoxy group, a cyano group, a nitro group, an amino group, a sulfonic acid group and derivatives thereof.

In the present specification, unless otherwise specified, the term "a combination thereof" means a compound wherein at least two functional groups are a single bond, a double bond, a triple bond, an alkylene group having 1 to 10 carbon atoms (for example, methylene (-CH ₂ -), ethylene (-CH ₂ CH ₂ -), etc.), a fluoroalkylene group having 1 to 10 carbon atoms (for example, fluoromethylene (-CF ₂ -), perfluoroethylene (-CF ₂ CF ₂ -) and the like) , A cycloalkylene group having 4 to 18 carbon atoms (e.g., cyclohexene group), an arylene group having 6 to 12 carbon atoms (e.g., phenylene group), a heteroatom such as N, O, P, (-C═O-), an ether group (-O-), an ester group (-COO-), -S-, -NH- or -N = N- Or the like), or that two or more functional groups are condensed and connected to each other.

The present invention relates to a thermoplastic resin composition comprising a polyimide having a repeating unit represented by the following general formula (1) and having a glass transition temperature (T _g ) of 120 to 190 캜 and a melt flow index (MI) of 1 to 30 g / Resin.

[Chemical Formula 1]

In Formula 1,

X ₁ and X ₂ are each independently an aromatic or alicyclic divalent organic group derived from an acid anhydride, and may be the same or different from each other.

Y ₁ and Y ₂ are each independently an aromatic or alicyclic divalent organic group derived from a diamine and may be the same or different from each other,

and m and n are numbers from 0 to 1 representing the molar fraction.

Specifically, in Formula 1, X ₁ and X ₂ are each independently an aromatic or alicyclic tetravalent organic group derived from a tetracarboxylic dianhydride, and more specifically, an aromatic tetravalent organic group represented by the following general formulas (2a) to (2d) An alicyclic divalent organic group containing a structure of a cycloalkane having 3 to 12 carbon atoms, an alicyclic divalent organic group represented by the following formula (2e), and combinations thereof:

(2a)

(2b)

[Chemical Formula 2c]

(2d)

 [Formula 2e]

In Formula 2a through 2e, R ₁₁ to R ₁₇ are each independently a fluoroalkyl group having 1 to 10 carbon alkyl group or a C 1 -C 10, a1 is an integer of 0 or 2, b1 is in the range of 0 to 4 integer, c1 is an integer of 0 to 8, d1 and e1 are each independently an integer of 0 to 3, f1, and g1 is an integer from 0 to 9, each independently, and a ₁₁ and a ₁₂ represents a single bond, each independently, -O- _{, -CR 18 R 19 -, -C} (= O) -, -C (= O) O-, -C (= O) NH-, -S-, -SO-, -SO 2 -, C 6 -C A monocyclic or polycyclic arylene group having 6 to 18 carbon atoms (e.g., a phenylene group, a naphthalene group, etc.), and a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms Wherein R ₁₈ and R ₁₉ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a haloalkyl group having 1 to 10 carbon atoms (for example, triple A methyl group, a trifluoromethyl group, a trifluoromethyl group, a trifluoromethyl group,

At least one of X ₁ and X ₂ is a divalent aromatic or alicyclic group derived from an acid dianhydride containing an ether group, an ester group or a combination thereof in the molecule, Can be a tetravalent organic group derived from an acid dianhydride of 3a or 3b:

[Chemical Formula 3]

(3b)

R ₂₁ and R ₂₂ each independently represent a single bond, -O-, -CR ₂₃ R ₂₄ -, -C (= O) -, -C (= O) O-, -C = O) NH-, -S-, -SO- , -SO 2 - , the carbon number of 6 or multi-part type of polycyclic cycloalkyl group of 1 to 18 (for example, a cyclohexylene group and the like), having 6 to 18 carbon atoms (For example, phenylene group, naphthalene group and the like), and combinations thereof, wherein R ₂₃ and R ₂₄ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms Alkyl group having 1 to 10 carbon atoms, and haloalkyl group having 1 to 10 carbon atoms (e.g., trifluoromethyl group and the like).

The tetravalent organic group of an aromatic or aliphatic ring derived from an acid dianhydride containing an intramolecular ether group, an ester group, or a combination thereof may be present in an amount of 20 mol% or more, or 50 mol% or more, or 100 Mol% or less. Preferably an acid dihydrate containing an ether group in the molecular structure.

More specifically, X ₁ and X ₂ in the formula (1) are selected from the group consisting of the functional groups represented by the following formulas (4a) to (4p), provided that at least one of X ₁ and X ₂ is a functional group Lt; / RTI > may be a tetravalent organic group selected from:

Y ₁ and Y ₂ each independently represent an aromatic divalent organic group represented by the following general formulas (5a) to (5d), an alicyclic divalent organic group represented by the following general formula (5e), a cycloalkanediyl group having 4 to 18 carbon atoms And a divalent organic group selected from the group consisting of combinations thereof.

[Chemical Formula 5a]

[Chemical Formula 5b]

[Chemical Formula 5c]

[Chemical Formula 5d]

[Chemical Formula 5e]

In formulas (5a) to (5e), R ₃₁ to R ₃₇ are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms, a3, d3 and e3 are each independently 0 4 integer, b3 is the integer 0 to 6, c3 is an integer of 0 to 3, and f3 and g3 is an integer from 0 to 10, each independently, and a ₃₁ and a ₃₂ represents a single bond, -O, each independently _{-, -CR 38 R 39 -,} -C (= O) -, -C (= O) O-, -C (= O) NH-, -S-, -SO-, -SO 2 -, -O (CH ₂ CH ₂ O) _p -, a monocyclic or polycyclic cycloalkylene group having 6 to 18 carbon atoms (such as a cyclohexylene group), a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms for example, phenylene group, naphthalene group and the like) and is selected from the group consisting of, wherein R ₃₈ and R ₃₉ represent an alkyl group having 1 to 10 carbon atoms and hydrogen atoms, having 1 to 10 carbon atoms, each independently Haloalkyl group will be selected from the group consisting of (e. G., A methyl group such as trifluoromethyl), p is an integer of 1 to 44.

More specifically, Y ₁ and Y ₂ may each independently be a divalent organic group selected from the group consisting of the following functional groups represented by the following formulas (6a) to (6q).

When at least one of Y ₁ and Y ₂ is an aromatic or alicyclic divalent organic group, it is preferably 20 mol% or more, or 50 mol% or more, and 100 mol% or less, based on the total moles of divalent organic- .

The diamine may further include a polyamine, specifically, a polyamine such as a polyetheramine or a polysiloxane diamine. The polyamine can contribute to the improvement of fluidity when the resin is heated. The polyamine may include 80 mol% or less, or 50 mol% or less, or 5 to 35 mol% or 5 to 20 mol% of the total diamine.

Polyether amines are also referred to as polyoxyalkylene diamines, and among them, preferable ones are represented by the following formulas, but are not limited thereto.

NH ₂ [(CH ₂ ) ₂ O]] _n (CH ₂ ) ₂ NH ₂

In the above formula, n is an integer of 1 or more, and may be 10 or less. Preferably from 1 to 5.

Specific examples of the polyetheramine include D-230 (D-400, D-2000, D-4000, ED-600, ED-900, ED-2000, EDR-148) manufactured by San Techno Chemical Co., Ltd.; Polyether amines (D-230, D-400, D-2000) manufactured by BASF.

The polysiloxanediamine may be represented by the following formula.

Wherein R ₄₁ to R ₄₈ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a phenyl group, and x and y are each independently an integer of 1 to 15.

Specific examples thereof include, but are not limited to, polysiloxanediamine (X-22-9409) manufactured by Shin-Etsu.

The polyimide-containing thermoplastic resin may be prepared by chemically imidizing a polyimide precursor of the following formula (VIII) in the presence of a tertiary amine at a temperature of 130 ° C or higher, or in a vacuum or an inert gas atmosphere at a temperature of 150 to 380 ° C Can be prepared by heating:

[Chemical Formula 8]

In Formula 8, X ₁ , X ₂ , Y ₁ , Y ₂ , m and n are the same as defined above.

The polyimide precursor of Formula 8 may be prepared by a process comprising the step of polymerizing an acid dianhydride and a diamine. The acid dianhydride and the diamine may be used without limitation as long as they can provide the organic group described above with respect to Formula 1, and thus a detailed description thereof will be omitted.

By having a molecular structure comprising a polyimide ether group, an ester group, or combination thereof made from a composition as described above, it may have a high decomposition temperature and a low glass transition temperature (T _g).

The thermoplastic resin containing the polyimide of formula (1) or a precursor thereof according to the present invention is characterized by a glass transition temperature (T _g ) of 120 ° C. to 190 ° C. and a melt flow index (MI) of 1 to 30 g / min . In addition, the thermoplastic resin according to the present invention has a thermal decomposition temperature of 310 ° C or higher, which is advantageous for a melting process such as extrusion molding because of a large difference between a glass transition temperature and a thermal decomposition temperature.

The polycondensation reaction of the acid dianhydride and the diamine can be carried out according to a usual polymerization method for producing a polyimide precursor such as solution polymerization, for example, solution polymerization and melt polymerization.

At this time, the polymerization reaction may be carried out under anhydrous conditions, and the temperature during the polymerization reaction may be 25 to 50 ° C, preferably 40 to 45 ° C.

Specific examples of the organic solvent include N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N, N-dimethylformamide (DEAc), N, N-dimethylmethoxyacetamide, dimethylsulfoxide, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylurea, N-methylcaprolactam Bis (2-methoxyethoxy) ethane, bis [2-methoxyethoxy] ethane, Amide such as poly (ethylene glycol) methacrylate (PEGMA), gamma-butyrolactone (GBL), equamide M100 (Idemitsu Kosan Co., Ltd.) Based solvent, water, and a mixture thereof.

The molten polymerisation can be carried out by conducting a melt polycondensation reaction of diamine and acid dianhydride under a catalyst to a suitable flow rate (MI) to obtain a molten polyimide precursor composition.

The polyimide precursor produced by the above-described preparation method may have a weight average molecular weight of 1,000 g / mol to 500,000 g / mol, preferably 20,000 g / mol to 500,000 g / mol. If the weight average molecular weight of the polyimide precursor is less than 20,000 g / mol, it may be difficult to obtain the effect of the present invention.

Next, the imidization to the polyimide precursor may be carried out according to a method of imidization to a polyimide precursor.

Specifically, after the addition of a tertiary amine such as pyridine or triethylamine to the polymerization solution of the polyimide precursor, the chemical imidization may be carried out at a temperature of 130 ° C or higher, or in a vacuum atmosphere or an inert atmosphere such as nitrogen, Thermal imidization may be performed in which heat treatment is performed at a temperature of 150 to 380 占 폚. The polyimide obtained after the chemical imidization is soluble, and when the polymerization solution is cooled to 100 캜 or less, the polyimide precipitates while becoming insoluble in the polymerization solvent. As a result, the polyimide can be easily obtained only by washing the precipitate.

It is preferable that the polyimide or the precursor thereof produced by the above process is included in an amount of 5 to 50% by weight based on the total weight of the solid content of the thermoplastic resin.

The solvent used for preparing the polyimide by the chemical imidization may be the same as the organic solvent used in the production of the polyimide precursor by the solvent polymerization. Specific examples thereof include NMP, DMAc, DMF, DEAc, PEGMA , GBL, amide-based solvents such as Equamide M100, Idemitsu Kosan Co., Ltd., water, and mixtures thereof.

The solvent may also be included in an amount such that the thermoplastic resin composition has a viscosity of 200 to 25,000 cP. If the viscosity of the thermoplastic resin composition is less than 200 cP or the content of the organic solvent is excessively large because the content of the organic solvent is too small, the viscosity of the thermoplastic resin composition exceeding 25,000 cP may lower the fairness in the production of the display substrate.

Next, the thermoplastic resin produced by the above-mentioned method may be advantageous in extrusion molding due to its wide thermal properties such that the difference between the heat transfer temperature (T _g ) and the thermal decomposition temperature. From the thermal characteristics, it is possible to control not only a wide temperature range but also a thermally stable manufacturing process in the production of molding by extrusion molding. The step of extruding the thermoplastic resin may be performed at 150 to 310 ° C, and a molded article having excellent heat resistance and mechanical strength within the above range, and having high transparency and low retardation can be obtained.

The extrusion molding can be carried out according to a conventional method.

In the extrusion molding step using the thermoplastic resin according to the present invention, the thermoplastic resin supplied to the extrusion head can be heated in the region between T _g and the thermal decomposition temperature. For example, it may be melted and extruded at a temperature of 150 to 310 ° C, preferably 170 to 290 ° C. In the case of a thermoplastic resin by melt polymerization, it may be put into a molten state in an extrusion head and the extrusion process may be possible immediately.

The thermoplastic resin according to the present invention has a melt flow index (MI) of 1 to 30 g / min in the above-mentioned melting process, so that it is possible to provide an optimum flow flow index suitable for extrusion. For extrusion molding, the heat flow should be excellent. If the heat flow is low, the film does not flow down in the compressor, which makes it difficult to form the film. As a result, the process time becomes longer and the process cost increases.

In addition, the thermoplastic resin of the present invention is expected to be free from molding problems such as melt fracture at a proper melting point, to be uniformly molded at the time of retention, to have excellent long-term durability, and to have excellent appearance and thermal stability of a molded article.

When the thermoplastic resin composition contains a polyimide precursor, an imidization reaction occurs in the polyimide precursor in the heating step. The imidization rate of the polyimide precursor may be 90% or more, preferably 98% or more, by the heating process as described above.

A film, a display substrate, a three-dimensional printed matter, or the like can be formed from the thermoplastic resin composition containing the polyimide by using the extrusion molding method as described above.

The method of producing a film or a display substrate by extrusion molding can be used without limitations as long as it is used in film extrusion molding in the industry. For example, the step of extruding the support of the thermoplastic resin; Cooling the thermoplastic resin applied on the support; And a peeling step on the formed film.

 At this time, the thermoplastic resin composition may be extruded into a film, and it may be preferable to control the extrusion conditions so that the thermoplastic resin composition extruded into a film has a thickness of 40 to 200 占 퐉.

The display substrate produced by the above-mentioned production method exhibits high transparency, low retardation, excellent heat resistance, and mechanical properties by including the polyimide film of Formula 1 or a polyimide film produced using the precursor thereof. Specifically, the polyimide film may have a light transmittance of 550 to 80% at a thickness of 5 to 50 탆. The polyimide film may have a retardation in the plane direction and a thickness direction of 80 nm or less, preferably 0.001 to 80 nm. The polyimide film may have a tensile strength of 50 to 500 MPa and may have an elongation at break of 4 to 100%.

Due to the excellent properties of the polyimide film as described above, it can be applied to a display substrate, specifically, a display substrate for a flexible device requiring high transparency and isotropy such as an OLED, an LCD, an electronic paper, and a solar cell have.

Meanwhile, the thermoplastic resin according to the present invention can also be used as a modeling material for three-dimensional printing. The three-dimensional printing using the polymer resin is substantially similar to the extrusion molding process, so that the method for producing the three-dimensional printed material can be used without limitation as long as it is a conventional method used in the industry.

Specifically, the method includes: supplying a thermoplastic resin composition to an extrusion head of an extrusion-based lamination type deposition system; Melting the supplied thermoplastic resin composition in an extrusion head in an extrusion head; Extruding the melted thermoplastic resin composition; And cooling the extruded thermoplastic material, but the present invention is not limited thereto.

A cooling step in the manufacture sculpture by the extrusion molding is essential to cooling below T _m or T _g to impart when the thermoplastic resin is extruded, dimensionally stable, this cooling is to the extrudate passed through a water tank or, Cooling water spraying, air cooling, and the like. However, the present invention is not limited thereto.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Abbreviations used in the following examples are as follows.

BPADA: 4,4'-bisphenol A dianhydride (4,4'-bisphenol A dianhydride)

MBCHA: 4,4'-methylenebis (cyclohexylamine) (4,4'-methylenebis (cyclohexylamine))

DMAc: N, N-Dimethylacetamide (N, N-dimethylacetamide)

Example 1

0.033 mol of diamine MBCHA and 0.004 mol of poly (propyleneglycol) bis (2-aminopropyl ether) (Polyetheramine D400, BASF) were dissolved in 20 g of DMAc and 11.2 g of toluene, 0.038 mol of acid dianhydride BPADA was added, For 6 hours to prepare a polyamic acid solution and then polymerized at 170 DEG C for 6 hours to prepare a solution for forming a polyimide film.

The polyimide solution was precipitated by dropping in 1 L of methanol, and then vacuum dried at 200 ° C for 2 hours and 30 minutes to prepare a polyimide polymer powder.

Example 2

(0.038 mol) of diamine MBCHA and 0.004 mol of poly (propylene glycol) bis (2-aminopropyl ether) (Polyetheramine D230, BASF) were dissolved in 20 g of DMAc and 11.2 g of toluene, And the mixture was stirred at 50 ° C for 6 hours to prepare a polyamic acid solution and then polymerized at 170 ° C for 6 hours to prepare a solution for forming a polyimide film.

The polyimide solution was precipitated by dropping in 1 L of methanol, and then vacuum dried at 200 ° C for 2 hours and 30 minutes to prepare a polyimide polymer powder.

Example 3

0.038 mol of diamine MBCHA and 0.008 mol of poly (propyleneglycol) bis (2-aminopropyl ether) (Polyetheramine D230, BASF) were dissolved in 20 g of DMAc and 11.2 g of toluene, and the acid dianhydride BPADA (0.038 mol) And the mixture was stirred at 50 ° C for 6 hours to prepare a polyamic acid solution and then polymerized at 170 ° C for 6 hours to prepare a solution for forming a polyimide film.

The polyimide solution was precipitated by dropping in 1 L of methanol, and then vacuum dried at 200 ° C for 2 hours and 30 minutes to prepare a polyimide polymer powder.

Example 4

0.029 mol of diamine MBCHA and 0.012 mol of poly (propyleneglycol) bis (2-aminopropyl ether) (Polyetheramine D230, Basf) were dissolved in 20 g of DMAc and 11.2 g of toluene. BPADA (0.038 mol) C for 6 hours to prepare a polyamic acid solution and then polymerized at 170 DEG C for 6 hours to prepare a solution for forming a polyimide film.

The polyimide solution was precipitated by dropping in 1 L of methanol, and then vacuum dried at 200 ° C for 2 hours and 30 minutes to prepare a polyimide polymer powder.

Example 5

(0.038 mol) of diamine MBCHA and 0.00192 mol of polysiloxane diamine (X-22-9409, Shin-Etsu) were dissolved in 20 g of DMAc and 11.2 g of toluene, and acid dianhydride BPADA (0.038 mol) And stirred for a time to prepare a polyamic acid solution. The solution was then polymerized at 170 DEG C for 6 hours to prepare a solution for forming a polyimide film.

The polyimide solution was precipitated by dropping in 1 L of methanol, and then vacuum dried at 200 ° C for 2 hours and 30 minutes to prepare a polyimide polymer powder.

Comparative Example 1

4,4'-methylenebis (cyclohexylamine) (MBCHA, 0.05 mol) was dissolved in 40 g of DMAc, 4,4'-bisphenol A dianhydride (BPADA, 0.05 mol) was added as a second monomer, The mixture was stirred at 50 DEG C for 6 hours to prepare a polyamic acid solution, and then polymerized at 170 DEG C for 6 hours to prepare a solution for forming a polyimide film.

The polyimide solution was precipitated by dropping in 1 L of methanol, followed by vacuum drying at 200 캜 for 2 hours and 30 minutes to prepare a polyimide polymer powder.

Test Example 1

In order to measure the melt flow index required for extrusion molding, the polyimide powder prepared in Examples 1 to 5 and Comparative Example 1 was measured by the following method.

The polyimide powders of Examples 32 to 37 were dried at 250 DEG C for 3 hours, pre-heated at MI, and dried to measure 5 to 10 g of PEI159 powder, which was introduced into the hopper. The weight was increased to 10 kg, then the pressure was applied for 5 minutes, and the flow rate was measured. The results are shown in Table 7 below.

≪ MI measurement condition >

PEI 139: 270 ~ 290 ℃, 10kg difficult to measure (300 ℃, 10kg)

PEI 249 to 254: Measured at 270 DEG C, 10 kg

PEI 254: Measurement after left in MI nozzle for 30 minutes

T _g (° C) CTE T _d0.1% MI (g / min) DSC TMA Example 1 165 163 163 330 4.4 Example 2 179 173 148 345 2.3 Example 3 163 159 168 316 10.0 Example 4 148 145 163 324 24.8 Example 5 169 170 145 333 4.5 Comparative Example 1 205 210 70 318 0.1

As a result of the experiment, as shown in Table 1, Comparative Example 1 shows a low heat flow rate of 0.1 g / min at 300 ° C. This is because the polyimide of Comparative Example 1 had a rigid structure and lacked flexibility. On the other hand, the polyimides of Examples 1 to 5 having improved flexibility while maintaining isotropy exhibited a remarkably high melt flow index. From the results of Examples 1 to 5, it can be seen that the heat flowability can be controlled according to the amount of diamine added to improve the flexibility.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (16)

A thermoplastic resin comprising a polyimide having a repeating unit represented by the following formula (1) and having a glass transition temperature (T _g ) of 120 to 190 캜 and a melt flow index (MI) of 1 to 30 g /
[Chemical Formula 1]

In Formula 1,
X ₁ and X ₂ are each independently an aromatic or alicyclic divalent organic group derived from an acid anhydride,
Y ₁ and Y ₂ are each independently be an aliphatic divalent strange organic derived from a diamine, Y ₁ and Y either a _divalent polyoxyalkylene diamine or the divalent organic group derived from a polysiloxane diamine, And
m and n are numbers that are greater than 0 and less than 1, representing the mole fraction. The method according to claim 1,
In the formula (1), at least one of X ₁ and X ₂ is an aromatic or alicyclic divalent organic group derived from an acid anhydride containing an ether group, an ester group or a combination thereof in a molecule, 4 is contained in an amount of 20 to 100 mol% based on the total molar amount of the organic group. The method according to claim 1,
Wherein the diamine comprises a divalent organic group derived from a polyoxyalkylene diamine or a polysiloxane diamine in an amount of from greater than 0 to 80 mole percent based on the total moles of dicarboxylic-derived divalent organic groups. delete delete The method according to claim 1,
Wherein at least one of X ₁ and X ₂ in the general formula (1) is a tetravalent organic group derived from an acid anhydride of the following general formula (3a) or (3b):
[Chemical Formula 3]

(3b)

In the above formulas (3a) and (3b)
R ₂₁ and R ₂₂ are each independently a single bond, -O-, -CR ₂₃ R ₂₄ -, -C (═O) -, -C (═O) O-, -C S-, -SO-, -SO ₂ -, a monocyclic or polycyclic cycloalkylene group having 6 to 18 carbon atoms, a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms, and combinations thereof. And each of R ₂₃ and R ₂₄ is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a haloalkyl group having 1 to 10 carbon atoms. The method according to claim 1,
Wherein X ₁ and X ₂ are selected from the group consisting of the functional groups represented by the following formulas (4a) to (4p), provided that at least one of X ₁ and X ₂ is selected from the group consisting of the functional groups represented by the following formulas Thermoplastic resin which is an organic group:

Wherein R ₂₃ and R ₂₄ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a haloalkyl group having 1 to 10 carbon atoms. The method according to claim 1,
Wherein the alicyclic divalent organic group is selected from the group consisting of functional groups represented by the following formulas (6f) to (6i):

The method according to claim 1,
Wherein the polyimide is prepared by chemically imidizing or thermally imidizing a polyimide precursor of formula (8): < EMI ID =
[Chemical Formula 8]

In Formula 8,
X ₁ and X ₂ are each independently an aromatic or alicyclic divalent organic group derived from an acid anhydride,
Y ₁ and Y ₂ are each independently an aliphatic organic Kii are, Y ₁ and Y ₂ is any one of polyester derived from a diamine polyoxyalkylene diamine or the divalent organic group derived from a polysiloxane diamine, and
m and n are numbers that are greater than 0 and less than 1, representing the mole fraction. The method according to claim 1,
And a polyimide or a precursor thereof in an amount of 5 to 50% by weight based on the total weight of the solid content. The method according to claim 1,
A thermoplastic resin having an intrinsic viscosity of 200 to 25,000 cP. A method of extrusion molding using the thermoplastic resin according to claim 1. A film produced by extrusion molding the thermoplastic resin according to claim 1. A display substrate produced by extrusion molding the thermoplastic resin according to claim 1. A method for three-dimensional printing using the thermoplastic resin according to claim 1. A three-dimensional printed matter produced using the thermoplastic resin according to claim 1.