KR101598667B1 - Glass-polymer composite substrate and method for manufacturing same - Google Patents

Abstract

상기 화학식 1에서 X, Y₁, Y₂, R₁ 내지 R₃, m, n 및 z는 본 명세서 중에서 정의한 바와 동일하다.The present invention relates to a glass-polymer composite substrate exhibiting excellent heat resistance, chemical resistance and mechanical properties together with high transparency and low retardation, and exhibiting excellent adhesion even under high temperature and high humidity, and a process for producing the glass- And a polymer layer located on at least one side of the glass substrate and comprising a polyimide of the following formula:
[Chemical Formula 1]

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

Description

GLASS-POLYMER COMPOSITE SUBSTRATE AND METHOD FOR MANUFACTURING SAME [0002]

The present invention relates to a glass-polymer composite substrate and a method for producing the glass-polymer composite substrate, and more particularly, to a glass-polymer composite substrate having excellent transparency and low retardation as well as excellent heat resistance, chemical resistance and mechanical properties, - polymer composite substrate and a method for producing the same.

Flexible devices are typically manufactured on the basis of high temperature thin film transistor (TFT) processes. The process temperature may vary depending on the type of the semiconductor layer, the insulating film, and the barrier layer included in the device during the manufacture of the flexible device, but usually a temperature of about 300 to 500 ° C is required in the TFT process. However, the polymer material capable of withstanding such a processing temperature is extremely limited, and polyimide known to have excellent heat resistance is mainly used.

Polyimide is a polymer synthesized by the reaction of an acid anhydride with a diamine or a diisocyanate, and is superior to a polymer having heat resistance, chemical resistance, mechanical properties, and electrical insulating properties. However, when the polyimide is bonded instantaneously at a high temperature due to the imide ring and the aromatic structure, the adhesion to the cross section to be bonded is low because the high temperature flowability is poor, and furthermore, There is a problem in that it is further intensified after the exposure in FIG.

Korean Patent Publication No. 2009-0057414 (published on Jun. 5, 2009)

An object of the present invention is to provide a glass-polymer composite substrate exhibiting excellent heat resistance, chemical resistance and mechanical properties together with high transparency and low retardation, and exhibiting excellent adhesion even under high temperature and high humidity, and a process for producing the same.

A glass-polymer composite substrate according to one aspect of the present invention comprises a glass substrate and a polymer layer disposed on at least one side of the glass substrate and including a polyimide of the following formula:

[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 dianhydride, provided that at least one of X ₁ and X ₂ is an ether group, an ester group, An aromatic or alicyclic divalent organic group derived from an acid dianhydride containing a functional group selected from the group consisting of a divalent aliphatic group,

Y ₁ and Y ₂ are each independently an aromatic, alicyclic or aliphatic divalent organic group derived from a diamine, provided that at least one of Y ₁ and Y ₂ is composed of an ether group, an ester group, Aromatic, alicyclic or aliphatic divalent organic group derived from a diamine containing a functional group selected from the group consisting of a divalent organic group derived from a diamine in an amount of 20 to 100 mol%

m and n are each independently an integer of 1 or more.

In Formula 1, at least one of X ₁ and X ₂ may be a tetravalent organic group derived from any one selected from the group consisting of acid dianhydrides represented by the following Chemical Formulas 3a to 3d:

Wherein R ₂₁ to R ₂₄ each independently represents a single bond, -O-, -CR ₂₅ R ₂₆ -, -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, And R ₂₅ and R ₂₆ 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, And p is an integer of 1 to 44. [

In addition, at least one of X ₁ and X ₂ in formula (I) has 4 is selected from the group consisting of functional groups having the structure of Formula 4a to 4l at least one of X ₁ and X ₂ are to be organic date:

In Formula 1, at least one of Y ₁ and Y ₂ may be a divalent organic group derived from a diamine selected from the group consisting of the following Formulas 6a to 6e:

In formulas (6a) to (6d), R ₅₁ to R ₅₄ each independently represents a single bond, -O-, -CR ₅₅ R ₅₆ -, -C (═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, And R ₅₅ and R ₅₆ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms And p is an integer of 1 to 44, and q is an integer of 1 to 8.

In formula (1), at least one of Y ₁ and Y ₂ may be a divalent organic group selected from the group consisting of functional groups represented by the following formulas (7a) to (7p)

In the above formula, q is an integer of 1 to 8.

The polyimide may have a polyimide precursor having an imidization ratio of 90% or more.

In the glass-polymer composite substrate, the polymer layer may have a light transmittance of 400 to 100% at a thickness of 1 to 10 mu m.

The polymer layer may have a retardation in the plane direction and a thickness direction of 0.001 to 100 nm.

Further, the polymer layer may have a tensile strength of 50 to 500 MPa and a elongation at break of 10 to 100%.

The polymer layer may exhibit an adhesive strength of 30 N / cm or more to the glass substrate under conditions of high temperature and high humidity, 100 DEG C, 100% RH, and 6 days.

A display substrate according to another aspect of the present invention includes the aforementioned glass-polymer composite substrate.

According to another aspect of the present invention, there is provided a method for manufacturing a glass-polymer composite substrate, comprising: preparing a composition comprising the polyimide of Formula 1 or a precursor thereof; The composition is coated on at least one surface of a glass substrate and cured to form a polymer layer, or the composition is coated on one side of a support and dried to form a coating layer, which is laminated on one side of the glass substrate, Thereby forming a polymer layer.

In the process for producing the glass-polymer composite substrate, the polyimide is chemically imidized in the presence of a tertiary amine at a temperature of 130 ° C or higher, or in a vacuum or an inert gas atmosphere, Lt; RTI ID = 0.0 > 380 C: < / RTI >

[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 dianhydride, provided that at least one of X ₁ and X ₂ is an ether group, an ester group, An aromatic or alicyclic divalent organic group derived from an acid dianhydride containing a functional group selected from the group consisting of a divalent aliphatic group,

Y ₁ and Y ₂ are each independently an aromatic, alicyclic or aliphatic divalent organic group derived from a diamine, provided that at least one of Y ₁ and Y ₂ is composed of an ether group, an ester group, Aromatic, alicyclic or aliphatic divalent organic group derived from a diamine containing a functional group selected from the group consisting of a divalent organic group derived from a diamine in an amount of 20 to 100 mol%

m and n are each independently an integer of 1 or more.

Also, the polyimide precursor may be prepared by polymerizing an acid dianhydride and a diamine, wherein the acid dianhydride is an acid dianhydride containing a functional group selected from the group consisting of an ether group, an ester group, Wherein the content of the acid dianhydride-derived tetravalent organic group containing a functional group selected from the group consisting of an ether group, an ester group and a combination thereof in the molecule with respect to the total moles of acid anhydride-derived tetravalent organic groups in the polyester precursor is from 20 to 100 mol %, And the diamine containing a functional group selected from the group consisting of an ether group, an ester group, and a combination thereof in the molecule is used as the diamine in the total molar amount of the diamine-derived divalent organic group in the polyimide precursor A functional group selected from the group consisting of an intramolecular ether group, an ester group, and combinations thereof It was derived from the diamine to react together in an amount such that the amount of the organic group of 20 to 100mol% may be produced.

In addition, the composition may include polyimide or a precursor thereof in an amount of 5 to 50 wt% based on the total weight of the composition based on the solid content.

In addition, the composition may have a viscosity of 200 to 25,000 cP.

Also, the curing process may be performed by heat treatment at a temperature of 150 to 380 ° C.

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

The glass-polymer composite substrate according to the present invention exhibits excellent heat resistance, chemical resistance and mechanical properties together with high transparency and low retardation, and exhibits excellent adhesion even under high temperature and high humidity. As a result, it is useful as a substrate in a display device requiring transparency and isotropy such as flexible transparent display, OLED flexible light, 3D polarizer film and the like.

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 -) and the like), 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., a 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 a heteroalkylene group containing one or more heteroatom (s)), or two or more functional groups are condensed and connected to each other.

The present invention provides a glass-polymer composite substrate comprising a glass substrate, and a polymer layer disposed on at least one side of the glass substrate, the polymer layer comprising a polyimide of the following general formula:

[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 dianhydride, provided that at least one of X ₁ and X ₂ is an ether group, an ester group, An aromatic or alicyclic divalent organic group derived from an acid dianhydride containing a functional group selected from the group consisting of a divalent aliphatic group,

Y ₁ and Y ₂ are each independently an aromatic, alicyclic or aliphatic divalent organic group derived from a diamine, provided that at least one of Y ₁ and Y ₂ is composed of an ether group, an ester group, Aromatic, alicyclic or aliphatic divalent organic group derived from a diamine containing a functional group selected from the group consisting of a divalent organic group derived from a diamine in an amount of 20 to 100 mol%

m and n are each independently an integer of 1 or more.

The present invention also provides a display substrate comprising the glass-polymer composite substrate.

The present invention also relates to a process for preparing a polyimide of formula 1 or a precursor thereof; The composition is coated on at least one surface of a glass substrate and cured to form a polymer layer, or the composition is coated on one side of a support and dried to form a coating layer, which is laminated on one side of the glass substrate, Thereby forming a polymer layer. The present invention also provides a method for producing a glass-polymer composite substrate.

Hereinafter, a glass-polymer composite substrate according to an embodiment of the invention, a method of manufacturing the glass-polymer composite substrate, and a display substrate including the glass-polymer composite substrate will be described in detail.

According to one embodiment of the present invention, there is provided a glass-polymer composite substrate comprising a glass base material and a polymer layer located on at least one side of the glass base material and comprising a polyimide of the following general formula (1).

In the above-mentioned glass-polymer composite substrate, the glass base material is not only excellent in transparency but also excellent in heat and chemical stability.

Specifically, it is preferable that the glass base material has a thickness of 10 to 500 탆.

Further, a polymer layer containing a polyimide of the following formula 1 may be formed on at least one surface of the glass substrate.

[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 dianhydride, provided that at least one of X ₁ and X ₂ is an ether group, an ester group, An aromatic or alicyclic divalent organic group derived from an acid dianhydride containing a functional group selected from the group consisting of a divalent aliphatic group,

Y ₁ and Y ₂ are each independently an aromatic, alicyclic or aliphatic divalent organic group derived from a diamine, provided that at least one of Y ₁ and Y ₂ is composed of an ether group, an ester group, Aromatic alicyclic or aliphatic divalent organic group derived from diamines containing a functional group selected from the group consisting of 20 to 100 mol% based on the total moles of divalent organic-derived divalent organic groups, and

m and n are numbers representing the molar ratio of the respective repeating units, and may be independently an integer of 1 or more.

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 -, -O [ CH ₂ CH ₂ O] _p -, a monocyclic or polycyclic cycloalkylene group having 6 to 18 carbon atoms (e.g., cyclohexylene group and the like), a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms A phenylene group, a naphthalene group, etc.), and combinations thereof, 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 (example Surface, is selected from the group consisting of a methyl group, etc.), trifluoromethyl, p may be an integer of from 1 to 44.

In addition, at least one of X ₁ and X ₂ as described above may be an aromatic or aliphatic cyclic organic group derived from an acid dianhydride containing a functional group selected from the group consisting of an ether group, an ester group, , Specifically acid dianhydrides of the following formulas (3a) to (3d):

Wherein R ₂₁ to R ₂₄ each independently represents a single bond, -O-, -CR ₂₅ R ₂₆ -, -C (═O) -, -C (═O) O-, -C = O) NH-, -S-, -SO- , -SO 2 -, -O [CH 2 CH 2 O] p -, a cycloalkylene group of part formula or polycyclic of 6 to 18 carbon atoms (for example, Cyclohexylene group, etc.), a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms (e.g., a phenylene group, a naphthalene group, etc.), and combinations thereof, wherein R ₂₅ and R ₂₆ 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, trifluoromethyl group and the like), and p may be an integer of 1 to 44 .

More specifically, at least one of X < _{1 >} and X < ₂ > may be a tetravalent organic group selected from the group consisting of functional groups having the structures of the following formulas (4a)

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 A divalent organic group selected from the group consisting of an alicyclic divalent organic group, a divalent organic group represented by the following formula (5f), a divalent organic group represented by the following formula (5g), and combinations thereof:

[Chemical Formula 5a]

[Chemical Formula 5b]

[Chemical Formula 5c]

[Chemical Formula 5d]

[Chemical Formula 5e]

[Chemical Formula 5f]

[Chemical Formula 5g]

In formulas (5a) to (5g), 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 A ₃₃ is - [CR _a R _b -CH ₂ O] q-, wherein R ₃₈ to R ₄₀ , R _a, and R _{a are each} independently selected from the group consisting of _a hydrogen atom, R _b is within a independently represents a hydrogen atom, a C 1 each Will be selected from the group consisting of the 10-alkyl group and having 1 to 10 carbon atoms in the haloalkyl group (e. G., Such as a trifluoromethyl group), p is an integer from 1 to 44, q is an integer from 1 to 8, 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.

Also, at least one of Y ₁ and Y ₂ is a divalent aromatic or aliphatic cyclic organic group derived from a diamine containing a functional group selected from the group consisting of an ether group, an ester group and a combination thereof, Specifically, it may be a divalent organic group derived from a diamine selected from the group consisting of the following formulas (6a) to (6e):

In formulas (6a) to (6e), R ₅₁ to R ₅₄ each independently represents a single bond, -O-, -CR ₅₅ R ₅₆ -, -C (= O) -, -C = O) NH-, -S-, -SO- , -SO 2 -, -O [CH 2 CH 2 O] p -, a cycloalkylene group of part formula or polycyclic of 6 to 18 carbon atoms (for example, Cyclohexylene group and the like), a monocyclic or polycyclic arylene group having 6 to 18 carbon atoms (e.g., a phenylene group, a naphthalene group and the like), and a combination thereof, wherein R ₅₅ and R ₅₆ 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, trifluoromethyl group and the like), and p is 1 to 44 And q may be an integer of 1 to 8.

More specifically, at least one of Y < ₁ > and Y < ₂ > may be a divalent organic group selected from the group consisting of functional groups having the structures of the following formulas (7a)

In the above formula, q may be an integer of 1 to 8.

The polyimide of the formula (1) having the above structure is obtained by reacting a tetravalent organic group of an aromatic or aliphatic ring derived from an acid dianhydride containing a functional group selected from the group consisting of an ether group, an ester group, Based on the total moles of the dianhydrides derived from the acid dianhydride in the precursor, and at the same time, an aromatic group derived from a diamine containing a functional group selected from the group consisting of an ether group, an ester group, , Alicyclic or aliphatic divalent organic groups of 20 to 100 mol% based on the total moles of diamine-derived divalent organic groups in the polyimide precursor. With such optimum contents, it is possible to obtain a diimine-derived divalent organic group containing an ether or ester group and an acid or a dianhydride-derived divalent organic group containing an ether or ester group, thereby exhibiting excellent heat resistance, chemical resistance and mechanical And can exhibit excellent adhesive force even under high temperature and high humidity.

The glass-polymer composite substrate may be prepared by preparing a composition comprising the polyimide of Formula 1 or a precursor thereof; The composition is coated on at least one surface of a glass substrate and cured to form a polymer layer, or the composition is coated on one side of a support and dried to form a coating layer, which is laminated on one side of the glass substrate, To thereby form a polymer layer.

In detail, step 1 is a step of preparing a composition comprising the polyimide or a precursor thereof.

The composition may be prepared by dissolving the polyimide or precursor of Formula 1 in a solvent, or a solution containing a polyimide precursor obtained as a result of the polycondensation reaction of an acid dianhydride and diamine is used as a composition for forming a polymer layer .

The polyimide of Formula 1 may be prepared by adding a tertiary amine (for example, pyridine or triethylamine) to a polymerization solution of a polyimide precursor of Formula 8 and then chemically imidizing the polymer at a temperature of 130 ° C or higher, Or by thermal imidization at a temperature of 150 to 380 [deg.] C in a vacuum or an inert gas atmosphere:

[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 method comprising the step of polymerizing an acid dianhydride and a diamine, wherein the acid dianhydride (hereinafter, simply referred to as a first acid dianhydride) An acid dianhydride (hereinafter, simply referred to as a second acid dianhydride) containing a functional group selected from the group consisting of an ether group, an ester group, and a combination thereof in the molecule is reacted with a polyhydric precursor in the total moles of acid anhydride- Is used in an amount such that the content of the acid dianhydride-derived tetravalent organic group-containing functional group selected from the group consisting of an ether group, an ester group, and a combination thereof is from 20 to 100 mol% Hereinafter simply referred to as a first diamine), a functional group selected from the group consisting of an ether group, an ester group, (Hereinafter, simply referred to as a second diamine) is contained in the polyimide precursor with a functional group selected from the group consisting of an intramolecular ether group, an ester group, and a combination thereof in the total moles of the diamine-derived divalent organic group Is used in an amount such that the content of the diamine-derived divalent organic group is from 20 to 100 mol%.

Specifically, the first acid dianhydride which can be used in preparing the polyimide precursor of Formula 8 may be a tetracarboxylic dianhydride having an aromatic or alicyclic tetravalent organic group, wherein the aromatic or alicyclic di The same as described above. More specifically, the first acid dianhydride is selected from the group consisting of 4,4'-oxydiphthalic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetra Cyclohexanetetracarboxylic dianhydride, bicyclopentanetetracarboxylic dianhydride, cyclopropane tetracarboxylic dianhydride, 3,3 ', 4'-cyclohexanetetracarboxylic dianhydride, , 4,4'-benzophenone tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride , 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3 , 5,6-pyridine tetracarboxylic dianhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3' 4'-tetracarboxylic dianhydride, and mixtures thereof.

The second acid dianhydride which can be used in the preparation of the polyimide precursor of Formula 8 is an acid dianhydride containing a functional group selected from the group consisting of ether, ester and combinations thereof, The mountain of 3d can be water diarrhea:

In the above formulas (3a) to (3d), R ₂₁ to R ₂₄ are the same as defined above.

More specifically, the second acid dianhydride is 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) Phenyl] propane dianhydride, ethylene glycol bis (4-trimellitic anhydride), 2,2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) , 4,4'-oxydiphthalic anhydride, 5-isobenzofurancarboxylic acid 1,3-dihydro-1,3-dioxo-5,5 '- (1,4-phenylene) And a mixture thereof.

The first diamine that can be used in the preparation of the polyimide precursor of Formula 8 is specifically a diamine containing an intramolecular alicyclic or aliphatic divalent organic group, wherein the aromatic or alicyclic divalent organic group is as described above same. More specifically, the first diamine may include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diamino Benzophenone, 4,4'-bis (4-aminophenylsulfonyl) diphenyl ether, 3,3'-diaminodiphenyl ether, 3,3-diaminodiphenyl sulfide, 3,3'-diamino Diphenyl sulfone, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-methylenebis (cyclohexylamine) or 3,3'-diaminobenzophenone, And the like.

Among them, the first diamine may preferably be a diamine containing a divalent functional group selected from the group consisting of the following formulas (9a) to (9j)

The second diamine usable in the preparation of the polyimide precursor of formula (8) is a diamine containing a functional group selected from the group consisting of ether, ester and combinations thereof, It can be a diamine selected from the group:

In the general formulas (6a) to (6d), R ₅₁ to R ₅₄ , and q are as defined above.

More specifically, the second diamine is at least one selected from the group consisting of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- , 4,3'-bis (4-aminophenoxy) biphenyl, bis [4- (4 (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ) Phenyl] ether, 4,4'-bis (4-aminothiophenoxy) diphenyl sulfone, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, Phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl-1,1,1 , 3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 4,4'-bis Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (Aminophenoxy) phenyl] ether, 4,4'-bis (3-aminophenylsulfonyl) diphenyl ether, 4,4'- Bis [4- (3-aminophenoxy) benzoyl] benzene, and mixtures thereof.

Of these, the diamines preferably comprise a divalent organic group selected from the group consisting of functional groups having the structures of the following formulas (7a) to (7p):

In the above formula, q may be an integer of 1 to 8.

The above-mentioned polymerization reaction can be carried out according to a usual polymerization method for producing a polyimide precursor such as solution polymerization. Specifically, it can be carried out by dissolving the first and second diamines in an organic solvent, and then adding the first and second acid dianhydrides to the resulting mixed solution to effect polymerization reaction.

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, 2- (2-methoxyethoxy) ether, poly (ethylene glycol) methacrylate (PEGMA), gamma-butyrolactone (GBL), amides such as Ek (Equamide ^® M100, Idemitsu Kosan Co., Ltd) Amide-based solvents, water, and mixtures thereof.

Also, in the polyimide precursor in which the first and second diamines and the first and second acid dianhydrides used in the polymerization reaction are finally prepared, the content ratio of the second diamine and the second acid to the anhydride- It may be desirable to be used in consideration.

The polyimide precursor prepared by the above production method may have a weight average molecular weight of 10,000 g / mol or more, more preferably 10,000 to 100,000 g / mol. If the weight average molecular weight of the polyimide precursor is less than 10,000 g / mol, the mechanical properties may deteriorate.

The composition for forming the polymer layer may be prepared by dissolving the polyimide of formula (1) or the polyimide precursor of formula (8) prepared in the same manner as described above in a solvent. At this time, the solvent as may be used to advance the same as the organic solvent used upon producing the polyimide precursor by solvent polymerization, specifically, NMP, DMAc, DMF, DEAc, PEGMA, GBL, Ek amide (Equamide ^® M100, Idemitsu Kosan Co., Ltd), water, and a mixture thereof.

The solvent may also be included in an amount such that the composition has a viscosity of from 200 to 25,000 cP. In the case where the content of the organic solvent is too small and the viscosity of the polyimide precursor composition is less than 200 cp or the content of the organic solvent is excessively large and the viscosity of the polyimide precursor composition exceeds 25,000 cp, There is a possibility that the processability in manufacturing is lowered.

When a solution containing the polyimide precursor obtained as a result of the polymerization reaction of the acid dianhydride and the diamine is used as the composition for forming the polymer layer, the polyimide or the precursor thereof is preferably added in an amount of 5 to 100 parts by weight, 50% by weight.

Step 2 is a step of preparing a glass-polymer composite substrate by forming a polymer layer on at least one surface of the organic substrate using the composition prepared in Step 1. [

The method of forming the polymer layer may include a method of directly applying a polyimide precursor composition to at least one surface of a glass substrate and curing the coating composition or applying the composition to one side of a support and drying the coated layer to form a coating layer, Followed by post-curing to form a polymer layer.

When the composition for forming the polymer layer is directly applied to at least one surface of the glass substrate, the coating process may be performed according to a conventional coating method, and specifically, a spin coating method, a bar coating method, a roll coating method, A knife method, a gravure method, a reverse roll method, a kiss roll method, a doctor blade method, a spray method, a dipping method, a brushing method or the like may be used and may be carried out by a solvent casting method.

The coating amount of the composition may be applied in an amount such that the thickness of the final polyimide film is 1 to 10 mu m.

The curing process may be performed by a heat treatment at a temperature of 150 to 380 ° C, or may be performed by a multi-step heating process at various temperatures within the temperature range.

By the curing process as described above, an imidization reaction occurs in the polyimide precursor, and a polyimide film is formed. The imidization rate of the polyimide precursor may be 90% or more, preferably 98% or more, by the above curing treatment.

As another method, in the case of coating the above composition on one side of a support to form a coating layer, and then laminating the coating layer on at least one side of the glass substrate and then curing, the polyimide film formed on the support is laminated to the glass substrate Except that the above-mentioned process is further carried out.

The laminating process may be performed according to a conventional laminating method such as heat transfer.

The glass-polymer composite substrate produced by the above-described production method exhibits excellent heat resistance, chemical resistance and mechanical properties together with a high transparency and a low retardation by including the polymer layer of the polyimide of the formula (1) And exhibits excellent adhesion. Specifically, the polymer layer may have a light transmittance of 400 to 100% at a thickness of 1 to 10 mu m. The polyimide film may have a retardation in the plane direction and a thickness direction of 0.001 to 100 nm. The polymer layer also has a tensile strength of 50 to 500 MPa and may have an elongation at break of 10 to 100%. In addition, the polymer layer prior adhesive strength test represents a significant improvement in adhesion of can not be measured degree, specifically, for the adhesiveness evaluation glass substrate in the high temperature and high humidity, 100 ℃, 100% RH, the 6-day conditions It may exhibit an adhesive force of 30 N / cm or more. As described above, the polymer layer can be directly formed on the glass substrate without forming a separate adhesive layer in the production of the glass-polymer composite substrate due to the excellent adhesive force of the polymer layer. As a result, The problem can be prevented.

Due to such excellent properties, the glass-polymer composite substrate is useful as a substrate in a display device requiring transparency and isotropy such as a flexible transparent display, an OLED flexible light, and a 3D polarizer film. In particular, in the case of OLED flexible lighting, when a glass substrate is manufactured by a batch type, the productivity is lowered, the thickness of the glass substrate is increased and the weight is increased. In order to solve this problem, the glass substrate is used in a roll- However, such a problem can be solved when the glass-polymer composite substrate is applied.

Accordingly, according to another embodiment of the present invention, there is provided a display substrate comprising the above glass-polymer composite substrate.

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.

Example  One

(3-aminophenoxy) benzene (1,3-B3APB, 0.039 mol) and 2,2'-bis (trifluoromethyl) -4,4'- diaminobiphenyl (TFMB, 0.004 mol) was dissolved in 80 g of DMAc, and 5-isobenzofurancarboxylic acid, 1,3-dihydro-1,3-dioxo-5,5 '- (1,4- phenylene) ester (TAHQ, 0.044 mol ) Was added and 50 g of DMAc was polymerized at 50 캜 for 24 hours to prepare a solution containing polyamic acid.

The resulting polyamic acid polymer-containing solution was added at a mole ratio of 0.5 mol of a curing agent to the solid content, and the mixture was mixed at 1400 rpm for 10 minutes in a paste mixer to prepare a composition for forming a polyimide film.

The composition prepared above was bar coated on a glass substrate to a thickness of 1 to 3 탆. Subsequently, the glass substrate was subjected to a heat treatment for 3 minutes on a hot plate at 210 DEG C to perform a curing process. After completion of the curing process, a film adhered to the glass substrate was obtained.

Example 2

(TFMB, 0.037 mol) was dissolved in 30 g of DMAc, and ethylene glycol bis (4-trimellitic anhydride) (TMBG- 100, 0.037 mol) was added, and the mixture was polymerized in 30 g of DMAc at 50 DEG C for 24 hours to prepare a solution containing polyamic acid.

The resulting polyamic acid polymer-containing solution was added with 0.5 mol of a curing agent based on the molar ratio to the solids content, and the mixture was mixed at 1400 rpm for 10 minutes in a paste mixer to prepare a composition for forming a polyimide film.

The composition prepared above was bar coated on a glass substrate to a thickness of 1 to 3 탆. Subsequently, the glass substrate was subjected to a heat treatment for 3 minutes on a hot plate at 210 DEG C to perform a curing process. After completion of the curing process, a film adhered to the glass substrate was obtained.

Example 3

Ethylene glycol bis (4-trimellitic anhydride) (TMEG-100, 0.037 mol) was added and dissolved in 50 g of DMAc. 4,4'-methylenebis (cyclohexylamine) (MBCHA, 0.037 mol) was added And the mixture was stirred at 0 ° C for 1 hour and then polymerized at 50 ° C for 24 hours to prepare a solution containing polyamic acid.

The resulting polyamic acid polymer-containing solution was added with 0.5 mol of a curing agent based on the molar ratio to the solids content, and the mixture was mixed with a paste mixer at 1400 rpm for 10 minutes to prepare a composition for forming a polyimide film.

The composition prepared above was bar coated on a glass substrate to a thickness of 1 to 3 탆. Subsequently, the glass substrate was subjected to a heat treatment for 3 minutes on a hot plate at 210 DEG C to perform a curing process. After completion of the curing process, a film adhered to the glass substrate was obtained.

Example 4

Bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB, 0.004 mol) and 1,3-bis (3-aminophenoxy) benzene Was dissolved in 30 g of NMP, and 5-isobenzofurancarboxylic acid, 1,3-dihydro-1,3-dioxo-5,5 '- (1,4-phenylene) ester (TAHQ, 0.044 mol) And 300 g of NMP was added thereto. The mixture was stirred at 50 ° C for 6 hours, 12.6 g of toluene was added, and the mixture was polymerized at 180 ° C for 24 hours to prepare a solution for forming a polyimide film.

The composition prepared above was bar coated on a glass substrate to a thickness of 1 to 3 탆. Subsequently, the glass substrate was subjected to a heat treatment for 3 minutes on a hot plate at 210 DEG C to perform a curing process. After completion of the curing process, a film adhered to the glass substrate was obtained.

Example 5

(TFMB, 0.049 mol) was dissolved in 40 g of NMP and ethylene glycol bis (4-trimellitic anhydride) (TMEG- 100, 0.049 mol) was added, and the mixture was added to 30 g of NMP and stirred at 50 ° C for 6 hours. Then, 13.8 g of toluene was added and polymerization was carried out at 180 ° C for 24 hours to prepare a composition for forming a polyimide film.

The composition prepared above was bar coated on a glass substrate to a thickness of 1 to 3 탆. Subsequently, the glass substrate was subjected to a heat treatment for 3 minutes on a hot plate at 210 DEG C to perform a curing process. After completion of the curing process, a film adhered to the glass substrate was obtained.

Example 6

(4-trimellitic anhydride) (TMEG-100, 0.037 mol) was dissolved in 30 g of NMP and 4,4'-methylenebis (cyclohexylamine) (MBCHA, 0.037 mol) , And the mixture was stirred at 0 ° C for 1 hour and at 50 ° C for 6 hours. Then, 11.8 g of toluene was added and polymerization was carried out at 180 ° C for 24 hours to prepare a composition for forming a polyimide film.

The composition prepared above was bar coated on a glass substrate to a thickness of 1 to 3 탆. Subsequently, the glass substrate was subjected to a heat treatment for 3 minutes on a hot plate at 210 DEG C to perform a curing process. After completion of the curing process, a film adhered to the glass substrate was obtained.

Comparative Example 1

4,4'-Methylenebis (2-methylcyclohexylamine) (TFMB, 0.084 mol) was dissolved in 100 g of anhydrous DMAc and 3,3 ', 4,4'- biphenyltetracarboxylic dianhydride (BPDA, 0.085 mol) was added and stirred at 40 DEG C for 24 hours to prepare a solution containing polyamic acid. The reaction proceeded under anhydrous conditions.

The resulting polyamic acid polymer-containing solution was added with 0.5 mol of a curing agent based on the molar ratio to the solids content, and the mixture was mixed with a paste mixer at 1400 rpm for 10 minutes to prepare a composition for forming a polyimide film.

The composition prepared above was bar coated on a glass substrate to a thickness of 1 to 3 탆. Subsequently, the glass substrate was subjected to a heat treatment for 3 minutes on a hot plate at 210 DEG C to perform a curing process. After completion of the curing process, a film adhered to the glass substrate was obtained.

Comparative Example 2

4,4'-methylenebis (2-methylcyclohexylamine) (TFMB, 0.064 mol) was dissolved in 100 g of anhydrous DMAc, 4,4'-oxydiptalic anhydride (ODPA, 0.064 mol) And stirred for a time to prepare a solution containing polyamic acid. The reaction proceeded under anhydrous conditions.

The resultant polyamic acid polymer-containing solution was added with 0.5 mol of a curing agent based on the molar ratio, and the mixture was mixed at 1400 rpm for 10 minutes in a paste mixer to prepare a composition for forming a polyimide film.

The composition prepared above was bar coated on a glass substrate to a thickness of 1 to 3 탆. Subsequently, the glass substrate was subjected to a heat treatment for 3 minutes on a hot plate at 210 DEG C to perform a curing process. After completion of the curing process, a film adhered to the glass substrate was obtained.

The diamine and acid dianhydride components used in Examples and Comparative Examples are as follows.

Diamine Acid anhydride Example 1 1,3-B3APB / TFMB TAHQ Example 2 TFMB TMEG Example 3 MBCHA TMEG Example 4 1,3-B3APB / TFMB TAHQ Example 5 TFMB TMEG Example 6 MBCHA TMEG Comparative Example 1 TFMB BPDA Comparative Example 2 TFMB ODPA

Manufacturing example  One

The solution containing the polyamic acid solution prepared in Examples 1 to 6 and the polyamic acid prepared in Comparative Example was adjusted to have a solid content weight percentage of 10,000 cP, Respectively. Each of the glass substrates coated with the polyamic acid solution was held on a hot plate at 210 DEG C for 3 minutes to perform a curing process.

After completion of the curing process, the glass substrate was immersed in a 10% hydrofluoric acid solution to dissolve the glass substrate, and the formed film was peeled off and dried in an oven at 100 ° C to produce a polyimide film.

Manufacturing example  2

The solutions containing the polyamic acid polymer complexes prepared in Examples 1 to 3 were each adjusted to have a weight percentage of solids of 10,000 cP and then spin-coated on glass substrates with a thickness of 10 탆. The glass substrate coated with the solution of Example 1 and the comparative example was placed in an oven and heated at a rate of 2 ° C / min, followed by heating at 80 ° C for 15 minutes, at 150 ° C for 30 minutes, at 220 ° C for 30 minutes, , And the curing process was carried out at 350 ° C for 1 hour. After completion of the curing process, the glass substrate was immersed in a 10% hydrofluoric acid solution to dissolve the glass substrate, and the formed film was removed and dried in an oven at 100 ° C. to produce a polyimide film.

Test Example  One: Imidization rate

The physical properties of the film depend on the imidization rate due to the curing of the polyamic acid, which is the precursor of the polyimide. That is, if the imidization rate is not completely progressed, the mechanical properties will be greatly reduced.

Thus, the polyamic acid precursor solution prepared in Examples 1 to 6 and Comparative Example 1 was subjected to thermal imidization at 210 DEG C for 3 minutes and then subjected to chemical imidization using a curing agent, And evaluated according to the following formula. In the case of Comparative Example 1, thermal imidization was performed by curing in an oven at 210 ° C for 1 hour:

[Equation 1]

The imidization rate was calculated using the following equation based on the results of AT-IR measurement of films made according to the curing conditions.

Imidization rate (%) = (A1386 / A1501) sample / (A1386 / A1501) Completely imaged X100

In the above formula (1), A1386 represents the C-N stretching motion of the C-N st imide ring group, and A1501 represents the aromatic st. Aromatic C-C stretching movement.

When polyimide rings are made by thermal and chemical reactions in polyamic acid, the -COOH-NH- of the polyamic acid forms a ring with the water leaving the C-N bond. As a result, as the imidization progresses, the COOH and N-H peaks decrease and the C-N peak increases. However, the benzene ring included in the polymer structure was calculated by calculating the area change ratio of A1386 based on the benzene peak A1501, which is constant in the calculation of the imidization rate, regardless of the imide reaction.

 The results are shown in Table 2 below.

Reference value Thermal imidization Chemical imidization Example 1 100.0 99.1 99.2 Example 2 100.0 99.0 99.3 Example 3 100.0 99.1 99.2 Example 4 100.0 98.9 99.1 Example 5 100.0 99.5 99.1 Example 6 100.0 99.0 98.9 Comparative Example 1 100.0 30.4 Not soluble

As shown in Table 2, in Examples 1 to 3, the thermal imidization rate is 99 or more. These results are in accordance with the structural characteristics. Since Examples 1 to 3 have a flexible structure, the heat transfer temperature of the polymer is relatively low, so that the imidization can proceed effectively due to a short heat treatment at a temperature higher than the heat transfer temperature.

In Examples 4 to 6, the imidization rate is 99% or more by proceeding the chemical imide reaction in an NMP solvent. Due to such a structure, soluble polyimide is not soluble in common solvents and can exhibit high chemical resistance even in a semiconductor cleaning agent.

In addition, in Examples 1 to 6, the polymerization time was shortened by the polymerization of soluble polyimide one pot method and the physical properties were sufficiently maintained even after curing at 210 ° C for 3 minutes after polymerization. From these results, it can be seen that Examples 1 to 6 have a PAA curing time, which can reduce the overall process time.

On the other hand, since the structure of Comparative Example 1 is considerably rigid, the heat transfer temperature is high, and therefore the imidization rate is only 30% at the heat curing temperature at 210 캜. As a result, since the structure of Comparative Example 1 in which the imidization is completely completed has a structure having high chemical resistance which does not dissolve in any solvent, it is difficult to transmit an imide reaction by a chemical reaction. It was confirmed that Comparative Examples 2 to 3 were the same as those of Comparative Example 1.

Test Example  2: Evaluation of physical properties of polyimide film

The polyamic acid solutions of Examples 1 to 6 were prepared as follows to prepare films, and then physical properties of the films were measured in the following manner. The results are shown in Table 3 below.

Specifically, the solution containing the polyamic acid solution prepared in Examples 1 to 6 and the polyamic acid prepared in Comparative Example was adjusted to have a solid content weight percentage of 10,000 cP, Respectively. Each of the glass substrates coated with the polyamic acid solution was held on a hot plate at 210 DEG C for 3 minutes to perform a curing process.

After completion of the curing process, the glass substrate was immersed in a 10% hydrofluoric acid solution to dissolve the glass substrate, and the formed film was peeled off and dried in an oven at 100 ° C to produce a polyimide film.

To in Table 3, T is TESA-HITEGAUGES, heat transfer temperature (Tg) of DSC, the thermal decomposition temperature (Td1%) is TGA, coefficient of thermal expansion (CTE) is TMA, the thickness retardation (R _th), and a plane direction retardation (Ro ) Was measured by Axoscan, T ₅₅₀ by UV-Vis spectrum, and tensile strength and elongation at break by UTM according to KS M ISO 527 measurement method.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 T (占 퐉) 9.8 11 9.1 10.5 10.2 10.7 12 14 Tg (占 폚) 180 210 177 180 210 177 320 300 Td1% (占 폚) 450 400 390 450 400 390 470 454 CTE (ppm) 56 70 82 56 70 82 23 41.8 R _th (nm) -30 -37 -15 -30 -37 -15 440 183 Ro (nm) 0.19 0.45 0.41 0.19 0.45 0.41 2.3 0.23 T ₅₅₀ 87.9 88.9 89.4 87.9 88.9 89.4 88 89 Elongation at break
(%) 123 128 49 123 128 49 5.7 6.2 The tensile strength
(kgf / mm ² ) 107 84.9 99.1 107 84.9 99.1 82.5 75.6

As shown in Table 3, the polyimides of Examples 1 to 6 had a low thermal transition temperature (Tg) of 180 to 210 ° C, while the thermal decomposition temperature Td1% was 390 to 450 ° C, which was considerably higher than the heat transfer temperature Excellent thermal stability. Also, Rth representing the birefringence value in the thickness direction exhibited isotropy of 30 nm or less. In addition, it can be confirmed that the two factors of light have a high transparency at 90% and a strong and flexible physical property because the elongation is about 50% or more while maintaining a proper stretching strength. This property prevents cracking of the thin film glass substrate during the continuous roll process and prevents the process from stopping due to the broken pieces entering into the roll.

On the other hand, in Comparative Examples 1 and 2, due to the rigid structure, the heat transfer temperature is considerably high and the heat stability is also excellent. However, the rigid structure tends to have a crystalline structure because it increases packing densities between molecules. As a result, the Rth value is considerably high, and the film has anisotropic physical properties, resulting in bending of light, which is not suitable for use as an optical film. In addition, the elongation and the stretching strength of Comparative Examples 1 and 2 are considerably low because the imidization reaction did not sufficiently proceed at 210 DEG C for 3 minutes.

Test Example  3. Adhesion test

The films formed on the glass substrates in Examples 1 to 6 were cut at intervals of 5 mm from the top and bottom and left and right sides, and then the substrates were allowed to stand in hot water at 90 캜 for 3 days by dipping. Three days later, the substrate was taken out and the film was peeled off from the cut end to confirm the degree of peeling off the substrate.

Comparative Examples 1 and 2 were also carried out in the same manner as above to carry out an adhesion test.

As a result, in Examples 1 to 6, the adhesiveness was very excellent, so that peeling did not occur from the cut surface even when it was immersed in hot water for 3 days. In addition, the adhesiveness of the film cured in the polyimide state produced by the chemical reaction with the film cured in the polyimide precursor polyimide state remained the same without changing the adhesion to the glass substrate. However, in the case of Comparative Examples 1 and 2, the film was separated from the substrate after being cured for 3 hours and floated in water.

This difference is due to the fact that the structures of Examples 1 to 6 have an ester group and an ether group, which can form hydrogen bonds with the surface of the glass substrate and maintain excellent adhesiveness. In addition, the adhesiveness can be the same not only on the glass substrate but also on the metal substrate.

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 (17)

Glass substrate, and
A glass-polymer composite substrate comprising a polymer layer located on at least one side of the glass substrate and comprising a polyimide of formula 1:
[Chemical Formula 1]

In Formula 1,
m and n are each independently an integer of 1 or more,
X ₁ and X ₂ are each independently an aromatic or alicyclic divalent organic group derived from an acid dianhydride, provided that at least one of X ₁ and X ₂ is an ether group, an ester group, An aromatic or alicyclic divalent organic group derived from an acid dianhydride containing a functional group selected from the group consisting of a divalent aliphatic group,
Y ₁ and Y ₂ are each independently an aromatic, alicyclic or aliphatic divalent organic group derived from a diamine, provided that at least one of Y ₁ and Y ₂ is selected from the group consisting of the following formulas (6a) to (6e) The divalent organic group derived from diamine is contained in an amount of 20 to 100 mol% based on the total moles of divalent organic groups derived from the diamine,

In formulas (6a) to (6d), R ₅₁ to R ₅₄ each independently represents a single bond, -O-, -CR ₅₅ R ₅₆ -, -C (═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, And R ₅₅ and R ₅₆ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms And p is an integer of 1 to 44, and q is an integer of 1 to 8. The method according to claim 1,
Wherein at least one of X ₁ and X ₂ in Formula 1 is a tetravalent organic group derived from any one selected from the group consisting of acid dianhydrides of the following Chemical Formulas 3a to 3d:

Wherein R ₂₁ to R ₂₄ each independently represents a single bond, -O-, -CR ₂₅ R ₂₆ -, -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, And R ₂₅ and R ₂₆ 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, And p is an integer of 1 to 44. [ The method according to claim 1,
At least one of X ₁ and X ₂ in the formula (1), X ₁ and X ₂ in at least one to the glass 4 is selected from the group consisting of functional groups having the structure of Formula 4a to 4l will organic group-polymer composite substrate :

delete The method according to claim 1,
Wherein at least one of Y ₁ and Y ₂ in the general formula (1) is a divalent organic group selected from the group consisting of functional groups having the following general formulas (7a) to (7p)

In the above formula, q is an integer of 1 to 8. The method according to claim 1,
Wherein the polyimide has an imidization ratio of 90% or more of the polyimide precursor. The method according to claim 1,
Wherein the polymer layer has a light transmittance of 10 to 100% at a thickness of 1 to 10 mu m and a thickness of 400 nm. The method according to claim 1,
Wherein the polymer layer has a retardation in a plane direction and a thickness direction of 0.001 to 100 nm. The method according to claim 1,
Wherein the polymer layer has a tensile strength of 50 to 500 MPa and a elongation at break of 10 to 100%. The method according to claim 1,
Wherein the polymer layer exhibits an adhesive strength of 30 N / cm or more to a glass substrate under conditions of high temperature and high humidity, 100 DEG C and 100% RH for 6 days. A display substrate comprising a glass-polymer composite substrate according to any one of claims 1 to 3 and 5 to 10. Preparing a composition comprising a polyimide of formula 1 or a precursor thereof; And,
The composition is coated on at least one surface of a glass substrate and then cured to form a polymer layer. Alternatively, the composition is coated on one surface of a support and dried to form a coating layer, which is laminated on one side of the glass substrate, Polymer composite substrate comprising the steps of:
[Chemical Formula 1]

In Formula 1,
m and n are each independently an integer of 1 or more,
X ₁ and X ₂ are each independently an aromatic or alicyclic divalent organic group derived from an acid dianhydride, provided that at least one of X ₁ and X ₂ is an ether group, an ester group, An aromatic or alicyclic divalent organic group derived from an acid dianhydride containing a functional group selected from the group consisting of a divalent aliphatic group,
Y ₁ and Y ₂ are each independently an aromatic, alicyclic or aliphatic divalent organic group derived from a diamine, provided that at least one of Y ₁ and Y ₂ is selected from the group consisting of the following formulas (6a) to (6e) The divalent organic group derived from diamine is contained in an amount of 20 to 100 mol% based on the total moles of divalent organic groups derived from the diamine,

In formulas (6a) to (6d), R ₅₁ to R ₅₄ each independently represents a single bond, -O-, -CR ₅₅ R ₅₆ -, -C (═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, And R ₅₅ and R ₅₆ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms And p is an integer of 1 to 44, and q is an integer of 1 to 8. 13. The method of claim 12,
The polyimide is prepared by chemically imidizing a polyimide precursor of the following formula (8) in the presence of a tertiary amine at a temperature of 130 ° C or higher, or by thermally imidizing it at a temperature of 150 to 380 ° C in a vacuum or an inert gas atmosphere ≪ RTI ID = 0.0 > 1, < / RTI >
[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 dianhydride, provided that at least one of X ₁ and X ₂ is an ether group, an ester group, An aromatic or alicyclic divalent organic group derived from an acid dianhydride containing a functional group selected from the group consisting of a divalent aliphatic group,
Y ₁ and Y ₂ are each independently an aromatic, alicyclic or aliphatic divalent organic group derived from a diamine, provided that at least one of Y ₁ and Y ₂ is composed of an ether group, an ester group, Aromatic, alicyclic or aliphatic divalent organic group derived from a diamine containing a functional group selected from the group consisting of a divalent organic group derived from a diamine in an amount of 20 to 100 mol%
m and n are each independently an integer of 1 or more. 14. The method of claim 13,
Wherein the polyimide precursor is obtained by polymerizing an acid dianhydride and a diamine, wherein the acid dianhydride comprises an acid dianhydride containing a functional group selected from the group consisting of ether groups, ester groups, The content of an acid dianhydride-derived aromatic or alicyclic divalent organic group containing a functional group selected from the group consisting of an ether group, an ester group, and a combination thereof in the molecule relative to the total moles of an acid anhydride- And 20 to 100 mol%, and the diamine containing a functional group selected from the group consisting of an ether group, an ester group, and a combination thereof in the molecule is used as the diamine in the polyimide precursor, Selected from the group consisting of intramolecular ether groups, ester groups and combinations thereof relative to the total moles of the device By weight based on the total amount of the diamine-containing divalent organic group-containing functional group and the diamine-containing divalent organic group-containing functional group is 20 to 100 mol%. 13. The method of claim 12,
Wherein the composition comprises polyimide or a precursor thereof in an amount of 5 to 50 wt% based on the total weight of the composition based on the solid content. 13. The method of claim 12,
Wherein the composition has a viscosity of 200 to 25,000 cP. 13. The method of claim 12,
Wherein the curing step is carried out by heat treatment at a temperature of 150 to 380 占 폚.